[Title 40 CFR ]
[Code of Federal Regulations (annual edition) - July 1, 2001 Edition]
[From the U.S. Government Printing Office]

[[Page i]]

Part 60 (Appendices)

Revised as of July 1, 2001

Protection of Environment

Containing a codification of documents of general
applicability and future effect
As of July 1, 2001
With Ancillaries
Published by
Office of the Federal Register
National Archives and Records
Administration

A Special Edition of the Federal Register

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----------------------------------------------------------
As of July 1, 2001
Title 40, Part 60
Revised as of July 1, 2000
Is Replaced by Two Volumes
Title 60, (Sec. 60.1 to End)
and
Title 60 (Appendices)

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Table of Contents

Page
Explanation................................................. v

Title 40:
Chapter I--Environmental Protection Agency 3
Finding Aids:
Material Incorporated by Reference...................... 681
Table of CFR Titles and Chapters........................ 685
Alphabetical List of Agencies Appearing in the CFR...... 703
List of CFR Sections Affected........................... 713

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----------------------------

Cite this Code: CFR
To cite the regulations in
this volume use title,
part and appendix letter.
Thus, 40 CFR 60,
appendices refers to title
40, part 60, appendix A.

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EXPLANATION

The Code of Federal Regulations is a codification of the general and
permanent rules published in the Federal Register by the Executive
departments and agencies of the Federal Government. The Code is divided
into 50 titles which represent broad areas subject to Federal
regulation. Each title is divided into chapters which usually bear the
name of the issuing agency. Each chapter is further subdivided into
parts covering specific regulatory areas.
Each volume of the Code is revised at least once each calendar year
and issued on a quarterly basis approximately as follows:

Title 1 through Title 16.................................as of January 1
Title 17 through Title 27..................................as of April 1
Title 28 through Title 41...................................as of July 1
Title 42 through Title 50................................as of October 1

The appropriate revision date is printed on the cover of each
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LEGAL STATUS

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HOW TO USE THE CODE OF FEDERAL REGULATIONS

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OMB CONTROL NUMBERS

The Paperwork Reduction Act of 1980 (Pub. L. 96-511) requires
Federal agencies to display an OMB control number with their information
collection request.

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Many agencies have begun publishing numerous OMB control numbers as
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OBSOLETE PROVISIONS

Provisions that become obsolete before the revision date stated on
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INCORPORATION BY REFERENCE

What is incorporation by reference? Incorporation by reference was
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This material, like any other properly issued regulation, has the force
of law.
What is a proper incorporation by reference? The Director of the
Federal Register will approve an incorporation by reference only when
the requirements of 1 CFR part 51 are met. Some of the elements on which
approval is based are:
(a) The incorporation will substantially reduce the volume of
material published in the Federal Register.
(b) The matter incorporated is in fact available to the extent
necessary to afford fairness and uniformity in the administrative
process.
(c) The incorporating document is drafted and submitted for
publication in accordance with 1 CFR part 51.
Properly approved incorporations by reference in this volume are
listed in the Finding Aids at the end of this volume.
What if the material incorporated by reference cannot be found? If
you have any problem locating or obtaining a copy of material listed in
the Finding Aids of this volume as an approved incorporation by
reference, please contact the agency that issued the regulation
containing that incorporation. If, after contacting the agency, you find
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Register, National Archives and Records Administration, Washington DC
20408, or call (202) 523-4534.

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The Federal Register Index is issued monthly in cumulative form.
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A List of CFR Sections Affected (LSA) is published monthly, keyed to
the revision dates of the 50 CFR titles.

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REPUBLICATION OF MATERIAL

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Raymond A. Mosley,
Director,
Office of the Federal Register.

July 1, 2001.

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THIS TITLE

Title 40--Protection of Environment is composed of twenty-eight
volumes. The parts in these volumes are arranged in the following order:
parts 1-49, parts 50-51, part 52 (52.01-52.1018), part 52 (52.1019-End),
parts 53-59, part 60 (60.1-End), part 60 (Appendices), parts 61-62, part
63 (63.1-63.599), part 63 (63.600-1-63.1199), part 63 (63.1200-End),
parts 64-71, parts 72-80, parts 81-85, part 86 (86.1-86.599-99) part 86
(86.600-1-End), parts 87-99, parts 100-135, parts 136-149, parts 150-
189, parts 190-259, parts 260-265, parts 266-299, parts 300-399, parts
400-424, parts 425-699, parts 700-789, and part 790 to End. The contents
of these volumes represent all current regulations codified under this
title of the CFR as of July 1, 2001.

Chapter I--Environmental Protection Agency appears in all twenty-
four volumes. A Pesticide Tolerance Commodity/Chemical Index and Crop
Grouping Commodities Index appear in parts 150-189. A Toxic Substances
Chemical--CAS Number Index appears in parts 700-789 and part 790 to End.
Redesignation Tables appear in the volumes containing parts 50-51, parts
150-189, and parts 700-789. Regulations issued by the Council on
Environmental Quality appear in the volume containing part 790 to End.
The OMB control numbers for title 40 appear in Sec. 9.1 of this chapter.

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[[Page 1]]

TITLE 40--PROTECTION OF ENVIRONMENT

(This book contains part 60)

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Part

chapter i--Environmental Protection Agency (Continued)...... 60

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CHAPTER I--ENVIRONMENTAL PROTECTION AGENCY

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SUBCHAPTER C--AIR PROGRAMS (CONTINUED)
Part Page
60 Appendix A to part 60--Test methods......... 5

Editorial Notes: 1. Subchapter C--Air Programs is contained in volumes
40 CFR parts 50-51, part 52.01-52.1018, part 52.1019-end, parts 53-59,
part 60 (60.1-end), part 60 (Appendices), parts 61-62, part 63 (63.1-
63.599), part 63 (63.600-63.1199), part (63.1200-End), parts 64-71,
parts 72-80, parts 81-85, part 86 (86.1-86.599-99), part 86 (86.600 to
end) and parts 87-99.

2. Nomenclature changes to chapter I appear at 65 FR 47324, 47325,
Aug. 2, 2000.

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SUBCHAPTER C--AIR PROGRAMS (CONTINUED)

PART 60--STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES (Continued)--Table of Contents

Appendix A-1 to Part 60--Test Methods 1 through 2F
Appendix A-2 to Part 60--Test Methods 2G through 3C
Appendix A-3 to Part 60--Test Methods 4 through 5I
Appendix A-4 to Part 60--Test Methods 6 through 10B
Appendix A-5 to Part 60--Test Methods 11 through 15A
Appendix A-6 to Part 60--Test Methods 16 through 18
Appendix A-7 to Part 60--Test Methods 19 through 25E
Appendix A-8 to Part 60--Test Methods 26 through 29
Appendix B to Part 60--Performance Specifications
Appendix C to Part 60--Determination of Emmission Rate Change
Appendix D to Part 60--Required Emission Inventory Information
Appendix E to Part 60 [Reserved]
Appendix F to Part 60--Quality Assurance Procedures
Appendix G to Part 60--Provisions for an Alternative Method of
Demonstrating Compliance with 40 CFR 60.43 for the Newton
Power Station of Central Illinois Public Service Company
Appendix H to Part 60 [Reserved]
Appendix I to Part 60--Removable Label and Owner's Manual

Authority: 42 U.S.C. 7401-7601.

Source: 36 FR 24877, Dec. 23, 1971, unless otherwise noted.

Appendix A-1 to Part 60--Test Methods 1 through 2F

Method 1--Sample and velocity traverses for stationary sources
Method 1A--Sample and velocity traverses for stationary sources with
small stacks or ducts
Method 2--Determination of stack gas velocity and volumetric flow rate
(Type S pitot tube)
Method 2A--Direct measurement of gas volume through pipes and small
ducts
Method 2B--Determination of exhaust gas volume flow rate from gasoline
vapor incinerators
Method 2C--Determination of gas velocity and volumetric flow rate in
small stacks or ducts (standard pitot tube)
Method 2D--Measurement of gas volume flow rates in small pipes and ducts
Method 2E--Determination of landfill gas production flow rate
Method 2F--Determination of Stack Gas Velocity and Volumetric Flow Rate
With Three-Dimensional Probes
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It

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should be clearly understood that unless otherwise identified all such
methods and changes must have prior approval of the Administrator. An
owner employing such methods or deviations from the test methods without
obtaining prior approval does so at the risk of subsequent disapproval
and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the the degree of detail should be similar to the detail contained
in the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 1--Sample and Velocity Traverses for Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material is incorporated by reference from other
methods in this part. Therefore, to obtain reliable results, persons
using this method should have a thorough knowledge of at least the
following additional test method: Method 2.

1.0 Scope and Application

1.1 Measured Parameters. The purpose of the method is to provide
guidance for the selection of sampling ports and traverse points at
which sampling for air pollutants will be performed pursuant to
regulations set forth in this part. Two procedures are presented: a
simplified procedure, and an alternative procedure (see Section 11.5).
The magnitude of cyclonic flow of effluent gas in a stack or duct is the
only parameter quantitatively measured in the simplified procedure.
1.2 Applicability. This method is applicable to gas streams flowing
in ducts, stacks, and flues. This method cannot be used when: (1) the
flow is cyclonic or swirling; or (2) a stack is smaller than 0.30 meter
(12 in.) in diameter, or 0.071 m\2\ (113 in.\2\) in cross-sectional
area. The simplified procedure cannot be used when the measurement site
is less than two stack or duct diameters downstream or less than a half
diameter upstream from a flow disturbance.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.
Note: The requirements of this method must be considered before
construction of a new facility from which emissions are to be measured;
failure to do so may require subsequent alterations to the stack or
deviation from the standard procedure. Cases involving variants are
subject to approval by the Administrator.

2.0 Summary of Method

2.1 This method is designed to aid in the representative
measurement of pollutant emissions and/or total volumetric flow rate
from a stationary source. A measurement site where the effluent stream
is flowing in a known direction is selected, and the cross-section of
the stack is divided into a number of equal areas. Traverse points are
then located within each of these equal areas.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies.

6.1 Apparatus. The apparatus described below is required only when
utilizing the alternative site selection procedure described in Section
11.5 of this method.
6.1.1 Directional Probe. Any directional probe, such as United
Sensor Type DA Three-Dimensional Directional Probe, capable of measuring
both the pitch and yaw angles of gas flows is acceptable. Before using
the probe, assign an identification number to the directional probe, and
permanently mark or engrave the number on the body of the probe. The
pressure holes of directional probes are susceptible to plugging when
used

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in particulate-laden gas streams. Therefore, a procedure for cleaning
the pressure holes by ``back-purging'' with pressurized air is required.
6.1.2 Differential Pressure Gauges. Inclined manometers, U-tube
manometers, or other differential pressure gauges (e.g., magnehelic
gauges) that meet the specifications described in Method 2, Section 6.2.
Note: If the differential pressure gauge produces both negative and
positive readings, then both negative and positive pressure readings
shall be calibrated at a minimum of three points as specified in Method
2, Section 6.2.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Procedure

11.1 Selection of Measurement Site.
11.1.1 Sampling and/or velocity measurements are performed at a
site located at least eight stack or duct diameters downstream and two
diameters upstream from any flow disturbance such as a bend, expansion,
or contraction in the stack, or from a visible flame. If necessary, an
alternative location may be selected, at a position at least two stack
or duct diameters downstream and a half diameter upstream from any flow
disturbance.
11.1.2 An alternative procedure is available for determining the
acceptability of a measurement location not meeting the criteria above.
This procedure described in Section 11.5 allows for the determination of
gas flow angles at the sampling points and comparison of the measured
results with acceptability criteria.
11.2 Determining the Number of Traverse Points.
11.2.1 Particulate Traverses.
11.2.1.1 When the eight- and two-diameter criterion can be met, the
minimum number of traverse points shall be: (1) twelve, for circular or
rectangular stacks with diameters (or equivalent diameters) greater than
0.61 meter (24 in.); (2) eight, for circular stacks with diameters
between 0.30 and 0.61 meter (12 and 24 in.); and (3) nine, for
rectangular stacks with equivalent diameters between 0.30 and 0.61 meter
(12 and 24 in.).
11.2.1.2 When the eight- and two-diameter criterion cannot be met,
the minimum number of traverse points is determined from Figure 1-1.
Before referring to the figure, however, determine the distances from
the measurement site to the nearest upstream and downstream
disturbances, and divide each distance by the stack diameter or
equivalent diameter, to determine the distance in terms of the number of
duct diameters. Then, determine from Figure 1-1 the minimum number of
traverse points that corresponds: (1) to the number of duct diameters
upstream; and (2) to the number of diameters downstream. Select the
higher of the two minimum numbers of traverse points, or a greater
value, so that for circular stacks the number is a multiple of 4, and
for rectangular stacks, the number is one of those shown in Table 1-1.
11.2.2 Velocity (Non-Particulate) Traverses. When velocity or
volumetric flow rate is to be determined (but not particulate matter),
the same procedure as that used for particulate traverses (Section
11.2.1) is followed, except that Figure 1-2 may be used instead of
Figure 1-1.
11.3 Cross-Sectional Layout and Location of Traverse Points.
11.3.1 Circular Stacks.
11.3.1.1 Locate the traverse points on two perpendicular diameters
according to Table 1-2 and the example shown in Figure 1-3. Any equation
(see examples in References 2 and 3 in Section 16.0) that gives the same
values as those in Table 1-2 may be used in lieu of Table 1-2.
11.3.1.2 For particulate traverses, one of the diameters must
coincide with the plane containing the greatest expected concentration
variation (e.g., after bends); one diameter shall be congruent to the
direction of the bend. This requirement becomes less critical as the
distance from the disturbance increases; therefore, other diameter
locations may be used, subject to the approval of the Administrator.
11.3.1.3 In addition, for elliptical stacks having unequal
perpendicular diameters, separate traverse points shall be calculated
and located along each diameter. To determine the cross-sectional area
of the elliptical stack, use the following equation:

Square Area = D1 x D2 x 0.7854

Where: D1 = Stack diameter 1

D2 = Stack diameter 2
11.3.1.4 In addition, for stacks having diameters greater than 0.61
m (24 in.), no traverse points shall be within 2.5 centimeters (1.00
in.) of the stack walls; and for stack diameters equal to or less than
0.61 m (24 in.), no traverse points shall be located within 1.3 cm (0.50
in.) of the stack walls. To meet these criteria, observe the procedures
given below.
11.3.2 Stacks With Diameters Greater Than 0.61 m (24 in.).
11.3.2.1 When any of the traverse points as located in Section
11.3.1 fall within 2.5 cm (1.0 in.) of the stack walls, relocate them
away from the stack walls to: (1) a distance of 2.5 cm (1.0 in.); or (2)
a distance equal to the nozzle inside diameter, whichever is larger.
These relocated traverse points (on each

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end of a diameter) shall be the ``adjusted'' traverse points.
11.3.2.2 Whenever two successive traverse points are combined to
form a single adjusted traverse point, treat the adjusted point as two
separate traverse points, both in the sampling and/or velocity
measurement procedure, and in recording of the data.
11.3.3 Stacks With Diameters Equal To or Less Than 0.61 m (24 in.).
Follow the procedure in Section 11.3.1.1, noting only that any
``adjusted'' points should be relocated away from the stack walls to:
(1) a distance of 1.3 cm (0.50 in.); or (2) a distance equal to the
nozzle inside diameter, whichever is larger.
11.3.4 Rectangular Stacks.
11.3.4.1 Determine the number of traverse points as explained in
Sections 11.1 and 11.2 of this method. From Table 1-1, determine the
grid configuration. Divide the stack cross-section into as many equal
rectangular elemental areas as traverse points, and then locate a
traverse point at the centroid of each equal area according to the
example in Figure 1-4.
11.3.4.2 To use more than the minimum number of traverse points,
expand the ``minimum number of traverse points'' matrix (see Table 1-1)
by adding the extra traverse points along one or the other or both legs
of the matrix; the final matrix need not be balanced. For example, if a
4 x 3 ``minimum number of points'' matrix were expanded to 36 points,
the final matrix could be 9 x 4 or 12 x 3, and would not necessarily
have to be 6 x 6. After constructing the final matrix, divide the
stack cross-section into as many equal rectangular, elemental areas as
traverse points, and locate a traverse point at the centroid of each
equal area.
11.3.4.3 The situation of traverse points being too close to the
stack walls is not expected to arise with rectangular stacks. If this
problem should ever arise, the Administrator must be contacted for
resolution of the matter.
11.4 Verification of Absence of Cyclonic Flow.
11.4.1 In most stationary sources, the direction of stack gas flow
is essentially parallel to the stack walls. However, cyclonic flow may
exist (1) after such devices as cyclones and inertial demisters
following venturi scrubbers, or (2) in stacks having tangential inlets
or other duct configurations which tend to induce swirling; in these
instances, the presence or absence of cyclonic flow at the sampling
location must be determined. The following techniques are acceptable for
this determination.
11.4.2 Level and zero the manometer. Connect a Type S pitot tube to
the manometer and leak-check system. Position the Type S pitot tube at
each traverse point, in succession, so that the planes of the face
openings of the pitot tube are perpendicular to the stack cross-
sectional plane; when the Type S pitot tube is in this position, it is
at ``0 deg. reference.'' Note the differential pressure (p)
reading at each traverse point. If a null (zero) pitot reading is
obtained at 0 deg. reference at a given traverse point, an acceptable
flow condition exists at that point. If the pitot reading is not zero at
0 deg. reference, rotate the pitot tube (up to 90 deg. yaw
angle), until a null reading is obtained. Carefully determine and record
the value of the rotation angle () to the nearest degree. After
the null technique has been applied at each traverse point, calculate
the average of the absolute values of ; assign values
of 0 deg. to those points for which no rotation was required, and
include these in the overall average. If the average value of
is greater than 20 deg., the overall flow condition in the stack is
unacceptable, and alternative methodology, subject to the approval of
the Administrator, must be used to perform accurate sample and velocity
traverses.
11.5 The alternative site selection procedure may be used to
determine the rotation angles in lieu of the procedure outlined in
Section 11.4.
11.5.1 Alternative Measurement Site Selection Procedure. This
alternative applies to sources where measurement locations are less than
2 equivalent or duct diameters downstream or less than one-half duct
diameter upstream from a flow disturbance. The alternative should be
limited to ducts larger than 24 in. in diameter where blockage and wall
effects are minimal. A directional flow-sensing probe is used to measure
pitch and yaw angles of the gas flow at 40 or more traverse points; the
resultant angle is calculated and compared with acceptable criteria for
mean and standard deviation.

Note: Both the pitch and yaw angles are measured from a line passing
through the traverse point and parallel to the stack axis. The pitch
angle is the angle of the gas flow component in the plane that INCLUDES
the traverse line and is parallel to the stack axis. The yaw angle is
the angle of the gas flow component in the plane PERPENDICULAR to the
traverse line at the traverse point and is measured from the line
passing through the traverse point and parallel to the stack axis.

11.5.2 Traverse Points. Use a minimum of 40 traverse points for
circular ducts and 42 points for rectangular ducts for the gas flow
angle determinations. Follow the procedure outlined in Section 11.3 and
Table 1-1 or 1-2 for the location and layout of the traverse points. If
the measurement location is determined to be acceptable according to the
criteria in this alternative procedure, use the same traverse point
number and locations for sampling and velocity measurements.
11.5.3 Measurement Procedure.
11.5.3.1 Prepare the directional probe and differential pressure
gauges as recommended

[[Page 9]]

by the manufacturer. Capillary tubing or surge tanks may be used to
dampen pressure fluctuations. It is recommended, but not required, that
a pretest leak check be conducted. To perform a leak check, pressurize
or use suction on the impact opening until a reading of at least 7.6 cm
(3 in.) H2O registers on the differential pressure gauge,
then plug the impact opening. The pressure of a leak-free system will
remain stable for at least 15 seconds.
11.5.3.2 Level and zero the manometers. Since the manometer level
and zero may drift because of vibrations and temperature changes,
periodically check the level and zero during the traverse.
11.5.3.3 Position the probe at the appropriate locations in the gas
stream, and rotate until zero deflection is indicated for the yaw angle
pressure gauge. Determine and record the yaw angle. Record the pressure
gauge readings for the pitch angle, and determine the pitch angle from
the calibration curve. Repeat this procedure for each traverse point.
Complete a ``back-purge'' of the pressure lines and the impact openings
prior to measurements of each traverse point.
11.5.3.4 A post-test check as described in Section 11.5.3.1 is
required. If the criteria for a leak-free system are not met, repair the
equipment, and repeat the flow angle measurements.
11.5.4 Calibration. Use a flow system as described in Sections
10.1.2.1 and 10.1.2.2 of Method 2. In addition, the flow system shall
have the capacity to generate two test-section velocities: one between
365 and 730 m/min (1,200 and 2,400 ft/min) and one between 730 and 1,100
m/min (2,400 and 3,600 ft/min).
11.5.4.1 Cut two entry ports in the test section. The axes through
the entry ports shall be perpendicular to each other and intersect in
the centroid of the test section. The ports should be elongated slots
parallel to the axis of the test section and of sufficient length to
allow measurement of pitch angles while maintaining the pitot head
position at the test-section centroid. To facilitate alignment of the
directional probe during calibration, the test section should be
constructed of plexiglass or some other transparent material. All
calibration measurements should be made at the same point in the test
section, preferably at the centroid of the test section.
11.5.4.2 To ensure that the gas flow is parallel to the central
axis of the test section, follow the procedure outlined in Section 11.4
for cyclonic flow determination to measure the gas flow angles at the
centroid of the test section from two test ports located 90 deg. apart.
The gas flow angle measured in each port must be 2 deg. of
0 deg.. Straightening vanes should be installed, if necessary, to meet
this criterion.
11.5.4.3 Pitch Angle Calibration. Perform a calibration traverse
according to the manufacturer's recommended protocol in 5 deg.
increments for angles from -60 deg. to +60 deg. at one velocity in each
of the two ranges specified above. Average the pressure ratio values
obtained for each angle in the two flow ranges, and plot a calibration
curve with the average values of the pressure ratio (or other suitable
measurement factor as recommended by the manufacturer) versus the pitch
angle. Draw a smooth line through the data points. Plot also the data
values for each traverse point. Determine the differences between the
measured data values and the angle from the calibration curve at the
same pressure ratio. The difference at each comparison must be within
2 deg. for angles between 0 deg. and 40 deg. and within 3 deg. for
angles between 40 deg. and 60 deg..
11.5.4.4 Yaw Angle Calibration. Mark the three-dimensional probe to
allow the determination of the yaw position of the probe. This is
usually a line extending the length of the probe and aligned with the
impact opening. To determine the accuracy of measurements of the yaw
angle, only the zero or null position need be calibrated as follows:
Place the directional probe in the test section, and rotate the probe
until the zero position is found. With a protractor or other angle
measuring device, measure the angle indicated by the yaw angle indicator
on the three-dimensional probe. This should be within 2 deg. of 0 deg..
Repeat this measurement for any other points along the length of the
pitot where yaw angle measurements could be read in order to account for
variations in the pitot markings used to indicate pitot head positions.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

L = length.
n = total number of traverse points.
Pi = pitch angle at traverse point i, degree.
Ravg = average resultant angle, degree.
Ri = resultant angle at traverse point i, degree.
Sd = standard deviation, degree.

W = width.
Yi = yaw angle at traverse point i, degree.
12.2 For a rectangular cross section, an equivalent diameter
(De) shall be calculated using the following equation, to
determine the upstream and downstream distances:
[GRAPHIC] [TIFF OMITTED] TR17OC00.037

12.3 If use of the alternative site selection procedure (Section
11.5 of this method) is required, perform the following calculations
using the equations below: the resultant angle at each traverse point,
the average resultant angle, and the standard deviation. Complete the
calculations retaining at least one extra significant figure beyond that
of

[[Page 10]]

the acquired data. Round the values after the final calculations.
12.3.1 Calculate the resultant angle at each traverse point:
[GRAPHIC] [TIFF OMITTED] TR17OC00.038

12.3.2 Calculate the average resultant for the measurements:
[GRAPHIC] [TIFF OMITTED] TR17OC00.039

12.3.3 Calculate the standard deviations:
[GRAPHIC] [TIFF OMITTED] TR17OC00.040

12.3.4 Acceptability Criteria. The measurement location is
acceptable if Ravg 20 deg. and Sd
10 deg..

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Determining Dust Concentration in a Gas Stream, ASME Performance
Test Code No. 27. New York. 1957.
2. DeVorkin, Howard, et al. Air Pollution Source Testing Manual. Air
Pollution Control District. Los Angeles, CA. November 1963.
3. Methods for Determining of Velocity, Volume, Dust and Mist
Content of Gases. Western Precipitation Division of Joy Manufacturing
Co. Los Angeles, CA. Bulletin WP-50. 1968.
4. Standard Method for Sampling Stacks for Particulate Matter. In:
1971 Book of ASTM Standards, Part 23. ASTM Designation D 2928-71.
Philadelphia, PA. 1971.
5. Hanson, H.A., et al. Particulate Sampling Strategies for Large
Power Plants Including Nonuniform Flow. USEPA, ORD, ESRL, Research
Triangle Park, NC. EPA-600/2-76-170. June 1976.
6. Entropy Environmentalists, Inc. Determination of the Optimum
Number of Sampling Points: An Analysis of Method 1 Criteria.
Environmental Protection Agency. Research Triangle Park, NC. EPA
Contract No. 68-01-3172, Task 7.
7. Hanson, H.A., R.J. Davini, J.K. Morgan, and A.A. Iversen.
Particulate Sampling Strategies for Large Power Plants Including
Nonuniform Flow. USEPA, Research Triangle Park, NC. Publication No. EPA-
600/2-76-170. June 1976. 350 pp.
8. Brooks, E.F., and R.L. Williams. Flow and Gas Sampling Manual.
U.S. Environmental Protection Agency. Research Triangle Park, NC.
Publication No. EPA-600/2-76-203. July 1976. 93 pp.
9. Entropy Environmentalists, Inc. Traverse Point Study. EPA
Contract No. 68-02-3172. June 1977. 19 pp.
10. Brown, J. and K. Yu. Test Report: Particulate Sampling Strategy
in Circular Ducts. Emission Measurement Branch. U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711. July 31, 1980. 12
pp.
11. Hawksley, P.G.W., S. Badzioch, and J.H. Blackett. Measurement of
Solids in Flue Gases. Leatherhead, England, The British Coal Utilisation
Research Association. 1961. pp. 129-133.
12. Knapp, K.T. The Number of Sampling Points Needed for
Representative Source Sampling. In: Proceedings of the Fourth National
Conference on Energy and Environment. Theodore, L. et al. (ed). Dayton,
Dayton Section of the American Institute of Chemical Engineers. October
3-7, 1976. pp. 563-568.
13. Smith, W.S. and D.J. Grove. A Proposed Extension of EPA Method 1
Criteria. Pollution Engineering. XV (8):36-37. August 1983.
14. Gerhart, P.M. and M.J. Dorsey. Investigation of Field Test
Procedures for Large Fans. University of Akron. Akron, OH. (EPRI
Contract CS-1651). Final Report (RP-1649-5). December 1980.
15. Smith, W.S. and D.J. Grove. A New Look at Isokinetic Sampling--
Theory and Applications. Source Evaluation Society Newsletter. VIII
(3):19-24. August 1983.

[[Page 11]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[GRAPHIC] [TIFF OMITTED] TR17OC00.041

Table 1-1 Cross-Section Layout for Rectangular Stacks
------------------------------------------------------------------------
Number of tranverse points layout Matrix
------------------------------------------------------------------------
9...................................... 3 x 3
12..................................... 4 x 3
16..................................... 4 x 4
20..................................... 5 x 4
25..................................... 5 x 5
30..................................... 6 x 5
36..................................... 6 x 6
42..................................... 7 x 6
49..................................... 7 x 7
------------------------------------------------------------------------

[[Page 12]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.042

Table 1-2.--Location of Traverse Points in Circular Stacks
[Percent of stack diameter from inside wall to tranverse point]
--------------------------------------------------------------------------------------------------------------------------------------------------------
Number of traverse points on a diameter
Traverse point number on a diameter -----------------------------------------------------------------------------------------------
2 4 6 8 10 12 14 16 18 20 22 24
--------------------------------------------------------------------------------------------------------------------------------------------------------
1....................................................... 14.6 6.7 4.4 3.2 2.6 2.1 1.8 1.6 1.4 1.3 1.1 1.1
2....................................................... 85.4 25.0 14.6 10.5 8.2 6.7 5.7 4.9 4.4 3.9 3.5 3.2
3....................................................... 75.0 29.6 19.4 14.6 11.8 9.9 8.5 7.5 6.7 6.0 5.5
4....................................................... 93.3 70.4 32.3 22.6 17.7 14.6 12.5 10.9 9.7 8.7 7.9
5....................................................... 85.4 67.7 34.2 25.0 20.1 16.9 14.6 12.9 11.6 10.5

[[Page 13]]

6....................................................... 95.6 80.6 65.8 35.6 26.9 22.0 18.8 16.5 14.6 13.2
7....................................................... 89.5 77.4 64.4 36.6 28.3 23.6 20.4 18.0 16.1
8....................................................... 96.8 85.4 75.0 63.4 37.5 29.6 25.0 21.8 19.4
9....................................................... 91.8 82.3 73.1 62.5 38.2 30.6 26.2 23.0
10...................................................... 97.4 88.2 79.9 71.7 61.8 38.8 31.5 27.2
11...................................................... 93.3 85.4 78.0 70.4 61.2 39.3 32.3
12...................................................... 97.9 90.1 83.1 76.4 69.4 60.7 39.8
13...................................................... 94.3 87.5 81.2 75.0 68.5 60.2
14...................................................... 98.2 91.5 85.4 79.6 73.8 67.7
15...................................................... 95.1 89.1 83.5 78.2 72.8
16...................................................... 98.4 92.5 87.1 82.0 77.0
17...................................................... 95.6 90.3 85.4 80.6
18...................................................... 98.6 93.3 88.4 83.9
19...................................................... 96.1 91.3 86.8
20...................................................... 98.7 94.0 89.5
21...................................................... 96.5 92.1
22...................................................... 98.9 94.5
23...................................................... 96.8
24...................................................... 99.9
--------------------------------------------------------------------------------------------------------------------------------------------------------

[GRAPHIC] [TIFF OMITTED] TR17OC00.043

[[Page 14]]

[GRAPHIC] [TIFF OMITTED] TC15NO91.220

Method 1A--Sample and Velocity Traverses for Stationary Sources With
Small Stacks or Ducts

1.0 Scope and Application

1.1 Measured Parameters. The purpose of the method is to provide
guidance for the selection of sampling ports and traverse points at
which sampling for air pollutants will be performed pursuant to
regulations set forth in this part.
1.2 Applicability. The applicability and principle of this method
are identical to Method 1, except its applicability is limited to stacks
or ducts. This method is applicable to flowing gas streams in ducts,
stacks, and flues of less than about 0.30 meter (12 in.) in diameter, or
0.071 m ² (113 in.²) in cross-sectional area, but
equal to or greater than about 0.10 meter (4 in.) in diameter, or 0.0081
m ² (12.57 in.²) in cross-sectional area. This
method cannot be used when the flow is cyclonic or swirling.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 The method is designed to aid in the representative measurement
of pollutant emissions and/or total volumetric flow rate from a
stationary source. A measurement site or a pair of measurement sites
where the effluent stream is flowing in a known direction is (are)
selected. The cross-section of the stack is divided into a number of
equal areas. Traverse points are then located within each of these equal
areas.
2.2 In these small diameter stacks or ducts, the conventional
Method 5 stack assembly (consisting of a Type S pitot tube attached to a
sampling probe, equipped with a nozzle and thermocouple) blocks a
significant portion of the cross-section of the duct and causes
inaccurate measurements. Therefore, for particulate matter (PM) sampling
in small stacks or ducts, the gas velocity is measured using a standard
pitot tube downstream of the actual emission sampling site. The straight
run of duct between the PM sampling and velocity measurement sites
allows the flow profile, temporarily disturbed by the presence of the
sampling probe, to redevelop and stabilize.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

[[Page 15]]

6.0 Equipment and Supplies [Reserved]

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Procedure

11.1 Selection of Measurement Site.
11.1.1 Particulate Measurements--Steady or Unsteady Flow. Select a
particulate measurement site located preferably at least eight
equivalent stack or duct diameters downstream and 10 equivalent
diameters upstream from any flow disturbances such as bends, expansions,
or contractions in the stack, or from a visible flame. Next, locate the
velocity measurement site eight equivalent diameters downstream of the
particulate measurement site (see Figure 1A-1). If such locations are
not available, select an alternative particulate measurement location at
least two equivalent stack or duct diameters downstream and two and one-
half diameters upstream from any flow disturbance. Then, locate the
velocity measurement site two equivalent diameters downstream from the
particulate measurement site. (See Section 12.2 of Method 1 for
calculating equivalent diameters for a rectangular cross-section.)
11.1.2 PM Sampling (Steady Flow) or Velocity (Steady or Unsteady
Flow) Measurements. For PM sampling when the volumetric flow rate in a
duct is constant with respect to time, Section 11.1.1 of Method 1 may be
followed, with the PM sampling and velocity measurement performed at one
location. To demonstrate that the flow rate is constant (within 10
percent) when PM measurements are made, perform complete velocity
traverses before and after the PM sampling run, and calculate the
deviation of the flow rate derived after the PM sampling run from the
one derived before the PM sampling run. The PM sampling run is
acceptable if the deviation does not exceed 10 percent.
11.2 Determining the Number of Traverse Points.
11.2.1 Particulate Measurements (Steady or Unsteady Flow). Use
Figure 1-1 of Method 1 to determine the number of traverse points to use
at both the velocity measurement and PM sampling locations. Before
referring to the figure, however, determine the distances between both
the velocity measurement and PM sampling sites to the nearest upstream
and downstream disturbances. Then divide each distance by the stack
diameter or equivalent diameter to express the distances in terms of the
number of duct diameters. Then, determine the number of traverse points
from Figure 1-1 of Method 1 corresponding to each of these four
distances. Choose the highest of the four numbers of traverse points (or
a greater number) so that, for circular ducts the number is a multiple
of four; and for rectangular ducts, the number is one of those shown in
Table 1-1 of Method 1. When the optimum duct diameter location criteria
can be satisfied, the minimum number of traverse points required is
eight for circular ducts and nine for rectangular ducts.
11.2.2 PM Sampling (Steady Flow) or only Velocity (Non-Particulate)
Measurements. Use Figure 1-2 of Method 1 to determine number of traverse
points, following the same procedure used for PM sampling as described
in Section 11.2.1 of Method 1. When the optimum duct diameter location
criteria can be satisfied, the minimum number of traverse points
required is eight for circular ducts and nine for rectangular ducts.
11.3 Cross-sectional Layout, Location of Traverse Points, and
Verification of the Absence of Cyclonic Flow. Same as Method 1, Sections
11.3 and 11.4, respectively.

12.0 Data Analysis and Calculations [Reserved]

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 1, Section 16.0, References 1 through 6, with the
addition of the following:
1. Vollaro, Robert F. Recommended Procedure for Sample Traverses in
Ducts Smaller Than 12 Inches in Diameter. U.S. Environmental Protection
Agency, Emission Measurement Branch, Research Triangle Park, North
Carolina. January 1977.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 16]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.044

Method 2--Determination of Stack Gas Velocity and Volumetric Flow Rate
(Type S Pitot Tube)

1.0 Scope and Application.

1.1 This method is applicable for the determination of the average
velocity and the volumetric flow rate of a gas stream.
1.2 This method is not applicable at measurement sites that fail to
meet the criteria of Method 1, Section 11.1. Also, the method cannot be
used for direct measurement in cyclonic or swirling gas streams; Section
11.4 of Method 1 shows how to determine cyclonic or swirling flow
conditions. When unacceptable conditions exist, alternative procedures,
subject to the approval of the Administrator, must be employed to
produce accurate flow rate determinations. Examples of such alternative
procedures are: (1) to install straightening vanes; (2) to calculate the
total volumetric flow rate stoichiometrically, or (3) to move to another
measurement site at which the flow is acceptable.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method.

2.1 The average gas velocity in a stack is determined from the gas
density and from measurement of the average velocity head with a Type S
(Stausscheibe or reverse type) pitot tube.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Specifications for the apparatus are given below. Any other
apparatus that has been demonstrated (subject to approval of the
Administrator) to be capable of meeting the specifications will be
considered acceptable.
6.1 Type S Pitot Tube.
6.1.1 Pitot tube made of metal tubing (e.g., stainless steel) as
shown in Figure 2-1. It is recommended that the external tubing diameter
(dimension Dt, Figure 2-2b) be between 0.48 and 0.95 cm (\3/
16\ and \3/8\ inch). There shall be an equal distance from the base of
each leg of the pitot tube to its face-opening plane (dimensions
PA and PB, Figure 2-2b); it is recommended that
this distance be between 1.05 and 1.50 times the external tubing
diameter. The face openings of the pitot tube shall, preferably, be
aligned as shown in Figure 2-2; however, slight misalignments of the
openings are permissible (see Figure 2-3).
6.1.2 The Type S pitot tube shall have a known coefficient,
determined as outlined in Section 10.0. An identification number shall
be assigned to the pitot tube; this number shall be permanently marked
or engraved on

[[Page 17]]

the body of the tube. A standard pitot tube may be used instead of a
Type S, provided that it meets the specifications of Sections 6.7 and
10.2. Note, however, that the static and impact pressure holes of
standard pitot tubes are susceptible to plugging in particulate-laden
gas streams. Therefore, whenever a standard pitot tube is used to
perform a traverse, adequate proof must be furnished that the openings
of the pitot tube have not plugged up during the traverse period. This
can be accomplished by comparing the velocity head (p)
measurement recorded at a selected traverse point (readable p
value) with a second p measurement recorded after ``back
purging'' with pressurized air to clean the impact and static holes of
the standard pitot tube. If the before and after p measurements
are within 5 percent, then the traverse data are acceptable. Otherwise,
the data should be rejected and the traverse measurements redone. Note
that the selected traverse point should be one that demonstrates a
readable p value. If ``back purging'' at regular intervals is
part of a routine procedure, then comparative p measurements
shall be conducted as above for the last two traverse points that
exhibit suitable p measurements.
6.2 Differential Pressure Gauge. An inclined manometer or
equivalent device. Most sampling trains are equipped with a 10 in.
(water column) inclined-vertical manometer, having 0.01 in.
H20 divisions on the 0 to 1 in. inclined scale, and 0.1 in.
H20 divisions on the 1 to 10 in. vertical scale. This type of
manometer (or other gauge of equivalent sensitivity) is satisfactory for
the measurement of p values as low as 1.27 mm (0.05 in.)
H20. However, a differential pressure gauge of greater
sensitivity shall be used (subject to the approval of the
Administrator), if any of the following is found to be true: (1) the
arithmetic average of all p readings at the traverse points in
the stack is less than 1.27 mm (0.05 in.) H20; (2) for
traverses of 12 or more points, more than 10 percent of the individual
p readings are below 1.27 mm (0.05 in.) H20; or (3)
for traverses of fewer than 12 points, more than one p reading
is below 1.27 mm (0.05 in.) H20. Reference 18 (see Section
17.0) describes commercially available instrumentation for the
measurement of low-range gas velocities.
6.2.1 As an alternative to criteria (1) through (3) above, Equation
2-1 (Section 12.2) may be used to determine the necessity of using a
more sensitive differential pressure gauge. If T is greater than 1.05,
the velocity head data are unacceptable and a more sensitive
differential pressure gauge must be used.
Note: If differential pressure gauges other than inclined manometers
are used (e.g., magnehelic gauges), their calibration must be checked
after each test series. To check the calibration of a differential
pressure gauge, compare p readings of the gauge with those of a
gauge-oil manometer at a minimum of three points, approximately
representing the range of p values in the stack. If, at each
point, the values of p as read by the differential pressure
gauge and gauge-oil manometer agree to within 5 percent, the
differential pressure gauge shall be considered to be in proper
calibration. Otherwise, the test series shall either be voided, or
procedures to adjust the measured p values and final results
shall be used, subject to the approval of the Administrator.
6.3 Temperature Sensor. A thermocouple, liquid-filled bulb
thermometer, bimetallic thermometer, mercury-in-glass thermometer, or
other gauge capable of measuring temperatures to within 1.5 percent of
the minimum absolute stack temperature. The temperature sensor shall be
attached to the pitot tube such that the sensor tip does not touch any
metal; the gauge shall be in an interference-free arrangement with
respect to the pitot tube face openings (see Figure 2-1 and Figure 2-4).
Alternative positions may be used if the pitot tube-temperature gauge
system is calibrated according to the procedure of Section 10.0.
Provided that a difference of not more than 1 percent in the average
velocity measurement is introduced, the temperature gauge need not be
attached to the pitot tube. This alternative is subject to the approval
of the Administrator.
6.4 Pressure Probe and Gauge. A piezometer tube and mercury- or
water-filled U-tube manometer capable of measuring stack pressure to
within 2.5 mm (0.1 in.) Hg. The static tap of a standard type pitot tube
or one leg of a Type S pitot tube with the face opening planes
positioned parallel to the gas flow may also be used as the pressure
probe.
6.5 Barometer. A mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.54 mm (0.1 in.) Hg.

Note: The barometric pressure reading may be obtained from a nearby
National Weather Service station. In this case, the station value (which
is the absolute barometric pressure) shall be requested and an
adjustment for elevation differences between the weather station and
sampling point shall be made at a rate of minus 2.5 mm (0.1 in.) Hg per
30 m (100 ft) elevation increase or plus 2.5 mm (0.1 in.) Hg per 30 m
(100 ft.) for elevation decrease.

6.6 Gas Density Determination Equipment. Method 3 equipment, if
needed (see Section 8.6), to determine the stack gas dry molecular
weight, and Method 4 (reference method) or Method 5 equipment for
moisture content determination. Other methods may be used subject to
approval of the Administrator.
6.7 Calibration Pitot Tube. When calibration of the Type S pitot
tube is necessary

[[Page 18]]

(see Section 10.1), a standard pitot tube shall be used for a reference.
The standard pitot tube shall, preferably, have a known coefficient,
obtained either (1) directly from the National Institute of Standards
and Technology (NIST), Gaithersburg MD 20899, (301) 975-2002, or (2) by
calibration against another standard pitot tube with an NIST-traceable
coefficient. Alternatively, a standard pitot tube designed according to
the criteria given in Sections 6.7.1 through 6.7.5 below and illustrated
in Figure 2-5 (see also References 7, 8, and 17 in Section 17.0) may be
used. Pitot tubes designed according to these specifications will have
baseline coefficients of 0.99 0.01.
6.7.1 Standard Pitot Design.
6.7.1.1 Hemispherical (shown in Figure 2-5), ellipsoidal, or
conical tip.
6.7.1.2 A minimum of six diameters straight run (based upon D, the
external diameter of the tube) between the tip and the static pressure
holes.
6.7.1.3 A minimum of eight diameters straight run between the
static pressure holes and the centerline of the external tube, following
the 90 deg. bend.
6.7.1.4 Static pressure holes of equal size (approximately 0.1 D),
equally spaced in a piezometer ring configuration.
6.7.1.5 90 deg. bend, with curved or mitered junction.
6.8 Differential Pressure Gauge for Type S Pitot Tube Calibration.
An inclined manometer or equivalent. If the single-velocity calibration
technique is employed (see Section 10.1.2.3), the calibration
differential pressure gauge shall be readable to the nearest 0.127 mm
(0.005 in.) H20. For multivelocity calibrations, the gauge
shall be readable to the nearest 0.127 mm (0.005 in.) H20 for
p values between 1.27 and 25.4 mm (0.05 and 1.00 in.)
H20, and to the nearest 1.27 mm (0.05 in.) H20 for
p values above 25.4 mm (1.00 in.) H20. A special,
more sensitive gauge will be required to read p values below
1.27 mm (0.05 in.) H20 (see Reference 18 in Section 16.0).

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Set up the apparatus as shown in Figure 2-1. Capillary tubing
or surge tanks installed between the manometer and pitot tube may be
used to dampen p fluctuations. It is recommended, but not
required, that a pretest leak-check be conducted as follows: (1) blow
through the pitot impact opening until at least 7.6 cm (3.0 in.)
H20 velocity head registers on the manometer; then, close off
the impact opening. The pressure shall remain stable for at least 15
seconds; (2) do the same for the static pressure side, except using
suction to obtain the minimum of 7.6 cm (3.0 in.) H20. Other
leak-check procedures, subject to the approval of the Administrator, may
be used.
8.2 Level and zero the manometer. Because the manometer level and
zero may drift due to vibrations and temperature changes, make periodic
checks during the traverse (at least once per hour). Record all
necessary data on a form similar to that shown in Figure 2-6.
8.3 Measure the velocity head and temperature at the traverse
points specified by Method 1. Ensure that the proper differential
pressure gauge is being used for the range of p values
encountered (see Section 6.2). If it is necessary to change to a more
sensitive gauge, do so, and remeasure the p and temperature
readings at each traverse point. Conduct a post-test leak-check
(mandatory), as described in Section 8.1 above, to validate the traverse
run.
8.4 Measure the static pressure in the stack. One reading is
usually adequate.
8.5 Determine the atmospheric pressure.
8.6 Determine the stack gas dry molecular weight. For combustion
processes or processes that emit essentially CO2,
O2, CO, and N2, use Method 3. For processes
emitting essentially air, an analysis need not be conducted; use a dry
molecular weight of 29.0. For other processes, other methods, subject to
the approval of the Administrator, must be used.
8.7 Obtain the moisture content from Method 4 (reference method, or
equivalent) or from Method 5.
8.8 Determine the cross-sectional area of the stack or duct at the
sampling location. Whenever possible, physically measure the stack
dimensions rather than using blueprints. Do not assume that stack
diameters are equal. Measure each diameter distance to verify its
dimensions.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1-10.4..................... Sampling Ensure accurate
equipment measurement of stack
calibration. gas flow rate,
sample volume.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Type S Pitot Tube. Before its initial use, carefully examine
the Type S pitot tube top, side, and end views to verify that the face
openings of the tube are aligned within the specifications illustrated
in Figures 2-2 and 2-3. The pitot tube shall not be used if it fails to
meet these alignment specifications. After verifying the face opening
alignment,

[[Page 19]]

measure and record the following dimensions of the pitot tube: (a) the
external tubing diameter (dimension Dt, Figure 2-2b); and (b)
the base-to-opening plane distances (dimensions PA and
PB, Figure 2-2b). If Dt is between 0.48 and 0.95
cm \3/16\ and \3/8\ in.), and if PA and PB are
equal and between 1.05 and 1.50 Dt, there are two possible
options: (1) the pitot tube may be calibrated according to the procedure
outlined in Sections 10.1.2 through 10.1.5, or (2) a baseline (isolated
tube) coefficient value of 0.84 may be assigned to the pitot tube. Note,
however, that if the pitot tube is part of an assembly, calibration may
still be required, despite knowledge of the baseline coefficient value
(see Section 10.1.1). If Dt, PA, and PB
are outside the specified limits, the pitot tube must be calibrated as
outlined in Sections 10.1.2 through 10.1.5.
10.1.1 Type S Pitot Tube Assemblies. During sample and velocity
traverses, the isolated Type S pitot tube is not always used; in many
instances, the pitot tube is used in combination with other source-
sampling components (e.g., thermocouple, sampling probe, nozzle) as part
of an ``assembly.'' The presence of other sampling components can
sometimes affect the baseline value of the Type S pitot tube coefficient
(Reference 9 in Section 17.0); therefore, an assigned (or otherwise
known) baseline coefficient value may or may not be valid for a given
assembly. The baseline and assembly coefficient values will be identical
only when the relative placement of the components in the assembly is
such that aerodynamic interference effects are eliminated. Figures 2-4,
2-7, and 2-8 illustrate interference-free component arrangements for
Type S pitot tubes having external tubing diameters between 0.48 and
0.95 cm (\3/16\ and \3/8\ in.). Type S pitot tube assemblies that fail
to meet any or all of the specifications of Figures 2-4, 2-7, and 2-8
shall be calibrated according to the procedure outlined in Sections
10.1.2 through 10.1.5, and prior to calibration, the values of the
intercomponent spacings (pitot-nozzle, pitot-thermocouple, pitot-probe
sheath) shall be measured and recorded.

Note: Do not use a Type S pitot tube assembly that is constructed
such that the impact pressure opening plane of the pitot tube is below
the entry plane of the nozzle (see Figure 2-6B).

10.1.2 Calibration Setup. If the Type S pitot tube is to be
calibrated, one leg of the tube shall be permanently marked A, and the
other, B. Calibration shall be performed in a flow system having the
following essential design features:
10.1.2.1 The flowing gas stream must be confined to a duct of
definite cross-sectional area, either circular or rectangular. For
circular cross sections, the minimum duct diameter shall be 30.48 cm (12
in.); for rectangular cross sections, the width (shorter side) shall be
at least 25.4 cm (10 in.).
10.1.2.2 The cross-sectional area of the calibration duct must be
constant over a distance of 10 or more duct diameters. For a rectangular
cross section, use an equivalent diameter, calculated according to
Equation 2-2 (see Section 12.3), to determine the number of duct
diameters. To ensure the presence of stable, fully developed flow
patterns at the calibration site, or ``test section,'' the site must be
located at least eight diameters downstream and two diameters upstream
from the nearest disturbances.

Note: The eight- and two-diameter criteria are not absolute; other
test section locations may be used (subject to approval of the
Administrator), provided that the flow at the test site has been
demonstrated to be or found stable and parallel to the duct axis.

10.1.2.3 The flow system shall have the capacity to generate a
test-section velocity around 910 m/min (3,000 ft/min). This velocity
must be constant with time to guarantee steady flow during calibration.
Note that Type S pitot tube coefficients obtained by single-velocity
calibration at 910 m/min (3,000 ft/min) will generally be valid to
3 percent for the measurement of velocities above 300 m/min
(1,000 ft/min) and to 6 percent for the measurement of
velocities between 180 and 300 m/min (600 and 1,000 ft/min). If a more
precise correlation between the pitot tube coefficient, (Cp),
and velocity is desired, the flow system should have the capacity to
generate at least four distinct, time-invariant test-section velocities
covering the velocity range from 180 to 1,500 m/min (600 to 5,000 ft/
min), and calibration data shall be taken at regular velocity intervals
over this range (see References 9 and 14 in Section 17.0 for details).
10.1.2.4 Two entry ports, one for each of the standard and Type S
pitot tubes, shall be cut in the test section. The standard pitot entry
port shall be located slightly downstream of the Type S port, so that
the standard and Type S impact openings will lie in the same cross-
sectional plane during calibration. To facilitate alignment of the pitot
tubes during calibration, it is advisable that the test section be
constructed of Plexiglas^TM or some other transparent
material.
10.1.3 Calibration Procedure. Note that this procedure is a general
one and must not be used without first referring to the special
considerations presented in Section 10.1.5. Note also that this
procedure applies only to single-velocity calibration. To obtain
calibration data for the A and B sides of the Type S pitot tube, proceed
as follows:
10.1.3.1 Make sure that the manometer is properly filled and that
the oil is free from contamination and is of the proper density.

[[Page 20]]

Inspect and leak-check all pitot lines; repair or replace if necessary.
10.1.3.2 Level and zero the manometer. Switch on the fan, and allow
the flow to stabilize. Seal the Type S pitot tube entry port.
10.1.3.3 Ensure that the manometer is level and zeroed. Position
the standard pitot tube at the calibration point (determined as outlined
in Section 10.1.5.1), and align the tube so that its tip is pointed
directly into the flow. Particular care should be taken in aligning the
tube to avoid yaw and pitch angles. Make sure that the entry port
surrounding the tube is properly sealed.
10.1.3.4 Read pstd, and record its value in a
data table similar to the one shown in Figure 2-9. Remove the standard
pitot tube from the duct, and disconnect it from the manometer. Seal the
standard entry port.
10.1.3.5 Connect the Type S pitot tube to the manometer and leak-
check. Open the Type S tube entry port. Check the manometer level and
zero. Insert and align the Type S pitot tube so that its A side impact
opening is at the same point as was the standard pitot tube and is
pointed directly into the flow. Make sure that the entry port
surrounding the tube is properly sealed.
10.1.3.6 Read ps, and enter its value in the
data table. Remove the Type S pitot tube from the duct, and disconnect
it from the manometer.
10.1.3.7 Repeat Steps 10.1.3.3 through 10.1.3.6 until three pairs
of p readings have been obtained for the A side of the Type S
pitot tube.
10.1.3.8 Repeat Steps 10.1.3.3 through 10.1.3.7 for the B side of
the Type S pitot tube.
10.1.3.9 Perform calculations as described in Section 12.4. Use the
Type S pitot tube only if the values of A and
B are less than or equal to 0.01 and if the absolute
value of the difference between Cp(A) and Cp(B) is
0.01 or less.
10.1.4 Special Considerations.
10.1.4.1 Selection of Calibration Point.
10.1.4.1.1 When an isolated Type S pitot tube is calibrated, select
a calibration point at or near the center of the duct, and follow the
procedures outlined in Section 10.1.3. The Type S pitot coefficients
measured or calculated, (i.e. Cp(A) and Cp(B))
will be valid, so long as either: (1) the isolated pitot tube is used;
or (2) the pitot tube is used with other components (nozzle,
thermocouple, sample probe) in an arrangement that is free from
aerodynamic interference effects (see Figures 2-4, 2-7, and 2-8).
10.1.4.1.2 For Type S pitot tube-thermocouple combinations (without
probe assembly), select a calibration point at or near the center of the
duct, and follow the procedures outlined in Section 10.1.3. The
coefficients so obtained will be valid so long as the pitot tube-
thermocouple combination is used by itself or with other components in
an interference-free arrangement (Figures 2-4, 2-7, and 2-8).
10.1.4.1.3 For Type S pitot tube combinations with complete probe
assemblies, the calibration point should be located at or near the
center of the duct; however, insertion of a probe sheath into a small
duct may cause significant cross-sectional area interference and
blockage and yield incorrect coefficient values (Reference 9 in Section
17.0). Therefore, to minimize the blockage effect, the calibration point
may be a few inches off-center if necessary. The actual blockage effect
will be negligible when the theoretical blockage, as determined by a
projected-area model of the probe sheath, is 2 percent or less of the
duct cross-sectional area for assemblies without external sheaths
(Figure 2-10a), and 3 percent or less for assemblies with external
sheaths (Figure 2-10b).
10.1.4.2 For those probe assemblies in which pitot tube-nozzle
interference is a factor (i.e., those in which the pitot-nozzle
separation distance fails to meet the specifications illustrated in
Figure 2-7A), the value of Cp(s) depends upon the amount of
free space between the tube and nozzle and, therefore, is a function of
nozzle size. In these instances, separate calibrations shall be
performed with each of the commonly used nozzle sizes in place. Note
that the single-velocity calibration technique is acceptable for this
purpose, even though the larger nozzle sizes (>0.635 cm or \1/4\ in.)
are not ordinarily used for isokinetic sampling at velocities around 910
m/min (3,000 ft/min), which is the calibration velocity. Note also that
it is not necessary to draw an isokinetic sample during calibration (see
Reference 19 in Section 17.0).
10.1.4.3 For a probe assembly constructed such that its pitot tube
is always used in the same orientation, only one side of the pitot tube
need be calibrated (the side which will face the flow). The pitot tube
must still meet the alignment specifications of Figure 2-2 or 2-3,
however, and must have an average deviation () value of 0.01 or
less (see Section 10.1.4.4).
10.1.5 Field Use and Recalibration.
10.1.5.1 Field Use.
10.1.5.1.1 When a Type S pitot tube (isolated or in an assembly) is
used in the field, the appropriate coefficient value (whether assigned
or obtained by calibration) shall be used to perform velocity
calculations. For calibrated Type S pitot tubes, the A side coefficient
shall be used when the A side of the tube faces the flow, and the B side
coefficient shall be used when the B side faces the flow. Alternatively,
the arithmetic average of the A and B side coefficient values may be
used, irrespective of which side faces the flow.
10.1.5.1.2 When a probe assembly is used to sample a small duct,
30.5 to 91.4 cm (12 to 36 in.) in diameter, the probe sheath sometimes
blocks a significant part of the duct cross-

[[Page 21]]

section, causing a reduction in the effective value of Cp(s).
Consult Reference 9 (see Section 17.0) for details. Conventional pitot-
sampling probe assemblies are not recommended for use in ducts having
inside diameters smaller than 30.5 cm (12 in.) (see Reference 16 in
Section 17.0).
10.1.5.2 Recalibration.
10.1.5.2.1 Isolated Pitot Tubes. After each field use, the pitot
tube shall be carefully reexamined in top, side, and end views. If the
pitot face openings are still aligned within the specifications
illustrated in Figure 2-2 and Figure 2-3, it can be assumed that the
baseline coefficient of the pitot tube has not changed. If, however, the
tube has been damaged to the extent that it no longer meets the
specifications of Figure 2-2 and Figure 2-3, the damage shall either be
repaired to restore proper alignment of the face openings, or the tube
shall be discarded.
10.1.5.2.2 Pitot Tube Assemblies. After each field use, check the
face opening alignment of the pitot tube, as in Section 10.1.5.2.1.
Also, remeasure the intercomponent spacings of the assembly. If the
intercomponent spacings have not changed and the face opening alignment
is acceptable, it can be assumed that the coefficient of the assembly
has not changed. If the face opening alignment is no longer within the
specifications of Figure 2-2 and Figure 2-3, either repair the damage or
replace the pitot tube (calibrating the new assembly, if necessary). If
the intercomponent spacings have changed, restore the original spacings,
or recalibrate the assembly.
10.2 Standard Pitot Tube (if applicable). If a standard pitot tube
is used for the velocity traverse, the tube shall be constructed
according to the criteria of Section 6.7 and shall be assigned a
baseline coefficient value of 0.99. If the standard pitot tube is used
as part of an assembly, the tube shall be in an interference-free
arrangement (subject to the approval of the Administrator).
10.3 Temperature Sensors.
10.3.1 After each field use, calibrate dial thermometers, liquid-
filled bulb thermometers, thermocouple-potentiometer systems, and other
sensors at a temperature within 10 percent of the average absolute stack
temperature. For temperatures up to 405 deg.C (761 deg.F), use an ASTM
mercury-in-glass reference thermometer, or equivalent, as a reference.
Alternatively, either a reference thermocouple and potentiometer
(calibrated against NIST standards) or thermometric fixed points (e.g.,
ice bath and boiling water, corrected for barometric pressure) may be
used. For temperatures above 405 deg.C (761 deg.F), use a reference
thermocouple-potentiometer system calibrated against NIST standards or
an alternative reference, subject to the approval of the Administrator.
10.3.2 The temperature data recorded in the field shall be
considered valid. If, during calibration, the absolute temperature
measured with the sensor being calibrated and the reference sensor agree
within 1.5 percent, the temperature data taken in the field shall be
considered valid. Otherwise, the pollutant emission test shall either be
considered invalid or adjustments (if appropriate) of the test results
shall be made, subject to the approval of the Administrator.
10.4 Barometer. Calibrate the barometer used against a mercury
barometer.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
Section 8.0).

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature.

A = Cross-sectional area of stack, m\2\ (ft\2\).
Bws = Water vapor in the gas stream (from Method 4 (reference
method) or Method 5), proportion by volume.
Cp = Pitot tube coefficient, dimensionless.
Cp(s) = Type S pitot tube coefficient, dimensionless.
Cp(std) = Standard pitot tube coefficient; use 0.99 if the
coefficient is unknown and the tube is designed according to
the criteria of Sections 6.7.1 to 6.7.5 of this method.
De = Equivalent diameter.
K = 0.127 mm H2O (metric units). 0.005 in. H2O
(English units).
Kp = Velocity equation constant.
L = Length.
Md = Molecular weight of stack gas, dry basis (see Section
8.6), g/g-mole (lb/lb-mole).
Ms = Molecular weight of stack gas, wet basis, g/g-mole (lb/
lb-mole).
n = Total number of traverse points.
Pbar = Barometric pressure at measurement site, mm Hg (in.
Hg).
Pg = Stack static pressure, mm Hg (in. Hg).
Ps = Absolute stack pressure (Pbar +
Pg), mm Hg (in. Hg),
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Qsd = Dry volumetric stack gas flow rate corrected to
standard conditions, dscm/hr (dscf/hr).
T = Sensitivity factor for differential pressure gauges.
Ts = Stack temperature, deg.C ( deg.F).
Ts(abs) = Absolute stack temperature, deg.K ( deg.R).
= 273 + Ts for metric units,
= 460 + Ts for English units.
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Vs = Average stack gas velocity, m/sec (ft/sec).
W = Width.
p = Velocity head of stack gas, mm H2O (in.
H20).

[[Page 22]]

pi = Individual velocity head reading at traverse
point ``i'', mm (in.) H2O.
pstd = Velocity head measured by the standard pitot
tube, cm (in.) H2O.
ps = Velocity head measured by the Type S pitot
tube, cm (in.) H2O.
3600 = Conversion Factor, sec/hr.
18.0 = Molecular weight of water, g/g-mole (lb/lb-mole).

12.2 Calculate T as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.045

12.3 Calculate De as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.046

12.4 Calibration of Type S Pitot Tube.
12.4.1 For each of the six pairs of p readings (i.e.,
three from side A and three from side B) obtained in Section 10.1.3,
calculate the value of the Type S pitot tube coefficient according to
Equation 2-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.047

12.4.2 Calculate Cp(A), the mean A-side coefficient, and
Cp(B), the mean B-side coefficient. Calculate the difference
between these two average values.
12.4.3 Calculate the deviation of each of the three A-side values
of Cp(s) from Cp(A), and the deviation of each of
the three B-side values of Cp(s) from Cp(B), using
Equation 2-4:
[GRAPHIC] [TIFF OMITTED] TR17OC00.048

12.4.4 Calculate the average deviation from the mean, for
both the A and B sides of the pitot tube. Use Equation 2-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.049

12.5 Molecular Weight of Stack Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.050

12.6 Average Stack Gas Velocity.
[GRAPHIC] [TIFF OMITTED] TR17OC00.051

[GRAPHIC] [TIFF OMITTED] TR17OC00.052

[GRAPHIC] [TIFF OMITTED] TR17OC00.053

12.7 Average Stack Gas Dry Volumetric Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.054

[[Page 23]]

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Mark, L.S. Mechanical Engineers' Handbook. New York. McGraw-Hill
Book Co., Inc. 1951.
2. Perry, J.H., ed. Chemical Engineers' Handbook. New York. McGraw-
Hill Book Co., Inc. 1960.
3. Shigehara, R.T., W.F. Todd, and W.S. Smith. Significance of
Errors in Stack Sampling Measurements. U.S. Environmental Protection
Agency, Research Triangle Park, N.C. (Presented at the Annual Meeting of
the Air Pollution Control Association, St. Louis, MO., June 14-19,
1970).
4. Standard Method for Sampling Stacks for Particulate Matter. In:
1971 Book of ASTM Standards, Part 23. Philadelphia, PA. 1971. ASTM
Designation D 2928-71.
5. Vennard, J.K. Elementary Fluid Mechanics. New York. John Wiley
and Sons, Inc. 1947.
6. Fluid Meters--Their Theory and Application. American Society of
Mechanical Engineers, New York, N.Y. 1959.
7. ASHRAE Handbook of Fundamentals. 1972. p. 208.
8. Annual Book of ASTM Standards, Part 26. 1974. p. 648.
9. Vollaro, R.F. Guidelines for Type S Pitot Tube Calibration. U.S.
Environmental Protection Agency, Research Triangle Park, N.C. (Presented
at 1st Annual Meeting, Source Evaluation Society, Dayton, OH, September
18, 1975.)
10. Vollaro, R.F. A Type S Pitot Tube Calibration Study. U.S.
Environmental Protection Agency, Emission Measurement Branch, Research
Triangle Park, N.C. July 1974.
11. Vollaro, R.F. The Effects of Impact Opening Misalignment on the
Value of the Type S Pitot Tube Coefficient. U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park,
NC. October 1976.
12. Vollaro, R.F. Establishment of a Baseline Coefficient Value for
Properly Constructed Type S Pitot Tubes. U.S. Environmental Protection
Agency, Emission Measurement Branch, Research Triangle Park, NC.
November 1976.
13. Vollaro, R.F. An Evaluation of Single-Velocity Calibration
Technique as a Means of Determining Type S Pitot Tube Coefficients. U.S.
Environmental Protection Agency, Emission Measurement Branch, Research
Triangle Park, NC. August 1975.
14. Vollaro, R.F. The Use of Type S Pitot Tubes for the Measurement
of Low Velocities. U.S. Environmental Protection Agency, Emission
Measurement Branch, Research Triangle Park, NC. November 1976.
15. Smith, Marvin L. Velocity Calibration of EPA Type Source
Sampling Probe. United Technologies Corporation, Pratt and Whitney
Aircraft Division, East Hartford, CT. 1975.
16. Vollaro, R.F. Recommended Procedure for Sample Traverses in
Ducts Smaller than 12 Inches in Diameter. U.S. Environmental Protection
Agency, Emission Measurement Branch, Research Triangle Park, NC.
November 1976.
17. Ower, E. and R.C. Pankhurst. The Measurement of Air Flow, 4th
Ed. London, Pergamon Press. 1966.
18. Vollaro, R.F. A Survey of Commercially Available Instrumentation
for the Measurement of Low-Range Gas Velocities. U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park,
NC. November 1976. (Unpublished Paper).
19. Gnyp, A.W., et al. An Experimental Investigation of the Effect
of Pitot Tube-Sampling Probe Configurations on the Magnitude of the S
Type Pitot Tube Coefficient for Commercially Available Source Sampling
Probes. Prepared by the University of Windsor for the Ministry of the
Environment, Toronto, Canada. February 1975.

[[Page 24]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.055

[[Page 25]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.056

[[Page 26]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.057

[[Page 27]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.058

[GRAPHIC] [TIFF OMITTED] TR17OC00.059

PLANT

DATE

RUN NO.

[[Page 28]]

STACK DIA. OR DIMENSIONS, m (in.)

BAROMETRIC PRESS., mm Hg (in. Hg)

CROSS SECTIONAL AREA, m\2\ (ft\2\)

OPERATORS

PITOT TUBE I.D. NO.

AVG. COEFFICIENT, Cp =

LAST DATE CALIBRATED

------------------------------------------------------------------------

-------------------------------------------------------------------------

------------------------------------------------------------------------

SCHEMATIC OF STACK CROSS SECTION

--------------------------------------------------------------------------------------------------------------------------------------------------------
Stack temperature
Traverse Pt. No. Vel. Hd., p ----------------------------------------------- Pg mm Hg (in. Hg) (p)\1/2\
mm (in.) H2O Ts, deg.C ( deg.F) Ts, deg.K ( deg.R)
--------------------------------------------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------
Average(1)
--------------------------------------------------------------------------------------------------------------------------------------------------------

Figure 2-6. Velocity Traverse Data

[[Page 29]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.060

[GRAPHIC] [TIFF OMITTED] TR17OC00.061

[[Page 30]]

PITOT TUBE IDENTIFICATION NUMBER:

DATE:

CALIBRATED BY:

``A'' Side Calibration
----------------------------------------------------------------------------------------------------------------
Pstd cm P(s) cm Deviation Cp(s)--
Run No. H2O (in H2O) H2O (in H2O) Cp(s) Cp(A)
----------------------------------------------------------------------------------------------------------------
1
----------------------------------------------------------------------------------------------------------------
2
----------------------------------------------------------------------------------------------------------------
3
----------------------------------------------------------------------------------------------------------------
Cp, avg
(SIDE A)
----------------------------------------------------------------------------------------------------------------

``B'' Side Calibration
----------------------------------------------------------------------------------------------------------------
Pstd cm P(s) cm Deviation Cp(s)--
Run No. H2O (in H2O) H2O (in H2O) Cp(s) Cp(B)
----------------------------------------------------------------------------------------------------------------
1
----------------------------------------------------------------------------------------------------------------
2
----------------------------------------------------------------------------------------------------------------
3
----------------------------------------------------------------------------------------------------------------
Cp, avg
(SIDE B)
----------------------------------------------------------------------------------------------------------------

[GRAPHIC] [TIFF OMITTED] TR17OC00.062

[Cp, avg (side A)--Cp, avg (side B)]*
*Must be less than or equal to 0.01

Figure 2-9. Pitot Tube Calibration Data

[[Page 31]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.063

Method 2A--Direct Measurement of Gas Volume Through Pipes and Small
Ducts

1.0 Scope and Application

1.1 This method is applicable for the determination of gas flow
rates in pipes and small ducts, either in-line or at exhaust positions,
within the temperature range of 0 to 50 deg.C (32 to 122 deg.F).
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas volume meter is used to measure gas volume directly.
Temperature and pressure measurements are made to allow correction of
the volume to standard conditions.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

[[Page 32]]

and health practices and determine the applicability of regulatory
limitations prior to performing this test method.

6.0 Equipment and Supplies

Specifications for the apparatus are given below. Any other
apparatus that has been demonstrated (subject to approval of the
Administrator) to be capable of meeting the specifications will be
considered acceptable.
6.1 Gas Volume Meter. A positive displacement meter, turbine meter,
or other direct measuring device capable of measuring volume to within 2
percent. The meter shall be equipped with a temperature sensor (accurate
to within 2 percent of the minimum absolute temperature) and
a pressure gauge (accurate to within 2.5 mm Hg). The
manufacturer's recommended capacity of the meter shall be sufficient for
the expected maximum and minimum flow rates for the sampling conditions.
Temperature, pressure, corrosive characteristics, and pipe size are
factors necessary to consider in selecting a suitable gas meter.
6.2 Barometer. A mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg.
Note: In many cases, the barometric reading may be obtained from a
nearby National Weather Service station, in which case the station value
(which is the absolute barometric pressure) shall be requested and an
adjustment for elevation differences between the weather station and
sampling point shall be applied at a rate of minus 2.5 mm (0.1 in.) Hg
per 30 m (100 ft) elevation increase or vice versa for elevation
decrease.
6.3 Stopwatch. Capable of measurement to within 1 second.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Installation. As there are numerous types of pipes and small
ducts that may be subject to volume measurement, it would be difficult
to describe all possible installation schemes. In general, flange
fittings should be used for all connections wherever possible. Gaskets
or other seal materials should be used to assure leak-tight connections.
The volume meter should be located so as to avoid severe vibrations and
other factors that may affect the meter calibration.
8.2 Leak Test.
8.2.1 A volume meter installed at a location under positive
pressure may be leak-checked at the meter connections by using a liquid
leak detector solution containing a surfactant. Apply a small amount of
the solution to the connections. If a leak exists, bubbles will form,
and the leak must be corrected.
8.2.2 A volume meter installed at a location under negative
pressure is very difficult to test for leaks without blocking flow at
the inlet of the line and watching for meter movement. If this procedure
is not possible, visually check all connections to assure leak-tight
seals.
8.3 Volume Measurement.
8.3.1 For sources with continuous, steady emission flow rates,
record the initial meter volume reading, meter temperature(s), meter
pressure, and start the stopwatch. Throughout the test period, record
the meter temperatures and pressures so that average values can be
determined. At the end of the test, stop the timer, and record the
elapsed time, the final volume reading, meter temperature, and pressure.
Record the barometric pressure at the beginning and end of the test run.
Record the data on a table similar to that shown in Figure 2A-1.
8.3.2 For sources with noncontinuous, non-steady emission flow
rates, use the procedure in Section 8.3.1 with the addition of the
following: Record all the meter parameters and the start and stop times
corresponding to each process cyclical or noncontinuous event.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1-10.4..................... Sampling Ensure accurate
equipment measurement of stack
calibration. gas flow rate,
sample volume.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Volume Meter.
10.1.1 The volume meter is calibrated against a standard reference
meter prior to its initial use in the field. The reference meter is a
spirometer or liquid displacement meter with a capacity consistent with
that of the test meter.
10.1.2 Alternatively, a calibrated, standard pitot may be used as
the reference meter in conjunction with a wind tunnel assembly. Attach
the test meter to the wind tunnel so that the total flow passes through
the test meter. For each calibration run, conduct a 4-point traverse
along one stack diameter at a position at least eight diameters of
straight tunnel downstream and two diameters upstream of any bend,
inlet, or air mover. Determine the traverse point locations as specified
in Method 1. Calculate the reference volume using the velocity values
following the procedure in Method 2, the wind tunnel cross-sectional
area, and the run time.

[[Page 33]]

10.1.3 Set up the test meter in a configuration similar to that
used in the field installation (i.e., in relation to the flow moving
device). Connect the temperature sensor and pressure gauge as they are
to be used in the field. Connect the reference meter at the inlet of the
flow line, if appropriate for the meter, and begin gas flow through the
system to condition the meters. During this conditioning operation,
check the system for leaks.
10.1.4 The calibration shall be performed during at least three
different flow rates. The calibration flow rates shall be about 0.3,
0.6, and 0.9 times the rated maximum flow rate of the test meter.
10.1.5 For each calibration run, the data to be collected include:
reference meter initial and final volume readings, the test meter
initial and final volume reading, meter average temperature and
pressure, barometric pressure, and run time. Repeat the runs at each
flow rate at least three times.
10.1.6 Calculate the test meter calibration coefficient as
indicated in Section 12.2.
10.1.7 Compare the three Ym values at each of the flow
rates tested and determine the maximum and minimum values. The
difference between the maximum and minimum values at each flow rate
should be no greater than 0.030. Extra runs may be required to complete
this requirement. If this specification cannot be met in six successive
runs, the test meter is not suitable for use. In addition, the meter
coefficients should be between 0.95 and 1.05. If these specifications
are met at all the flow rates, average all the Ym values from
runs meeting the specifications to obtain an average meter calibration
coefficient, Ym.
10.1.8 The procedure above shall be performed at least once for
each volume meter. Thereafter, an abbreviated calibration check shall be
completed following each field test. The calibration of the volume meter
shall be checked with the meter pressure set at the average value
encountered during the field test. Three calibration checks (runs) shall
be performed using this average flow rate value. Calculate the average
value of the calibration factor. If the calibration has changed by more
than 5 percent, recalibrate the meter over the full range of flow as
described above.

Note: If the volume meter calibration coefficient values obtained
before and after a test series differ by more than 5 percent, the test
series shall either be voided, or calculations for the test series shall
be performed using whichever meter coefficient value (i.e., before or
after) gives the greater value of pollutant emission rate.
10.2 Temperature Sensor. After each test series, check the
temperature sensor at ambient temperature. Use an American Society for
Testing and Materials (ASTM) mercury-in-glass reference thermometer, or
equivalent, as a reference. If the sensor being checked agrees within 2
percent (absolute temperature) of the reference, the temperature data
collected in the field shall be considered valid. Otherwise, the test
data shall be considered invalid or adjustments of the results shall be
made, subject to the approval of the Administrator.
10.3 Barometer. Calibrate the barometer used against a mercury
barometer prior to the field test.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
Section 8.0).

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra decimal figure
beyond that of the acquired data. Round off figures after final
calculation.

12.1 Nomenclature.

f = Final reading.
i = Initial reading.
Pbar = Barometric pressure, mm Hg.
Pg = Average static pressure in volume meter, mm Hg.
Qs = Gas flow rate, m³/min, standard conditions.
s = Standard conditions, 20 deg.C and 760 mm Hg.
Tr = Reference meter average temperature, deg.K ( deg.R).
Tm = Test meter average temperature, deg.K ( deg.R).
Vr = Reference meter volume reading, m³.
Vm = Test meter volume reading, m³.
Ym = Test meter calibration coefficient, dimensionless.
= Elapsed test period time, min.

12.2 Test Meter Calibration Coefficient.
[GRAPHIC] [TIFF OMITTED] TR17OC00.064

12.3 Volume.

[[Page 34]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.065

12.4 Gas Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.066

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Rom, Jerome J. Maintenance, Calibration, and Operation of
Isokinetic Source Sampling Equipment. U.S. Environmental Protection
Agency, Research Triangle Park, NC. Publication No. APTD-0576. March
1972.
2. Wortman, Martin, R. Vollaro, and P.R. Westlin. Dry Gas Volume
Meter Calibrations. Source Evaluation Society Newsletter. Vol. 2, No. 2.
May 1977.
3. Westlin, P.R., and R.T. Shigehara. Procedure for Calibrating and
Using Dry Gas Volume Meters as Calibration Standards. Source Evaluation
Society Newsletter. Vol. 3, No. 1. February 1978.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 2B--Determination of Exhaust Gas Volume Flow Rate From Gasoline
Vapor Incinerators

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should also have a thorough knowledge of at
least the following additional test methods: Method 1, Method 2, Method
2A, Method 10, Method 25A, Method 25B.

1.0 Scope and Application

1.1 This method is applicable for the determination of exhaust
volume flow rate from incinerators that process gasoline vapors
consisting primarily of alkanes, alkenes, and/or arenes (aromatic
hydrocarbons). It is assumed that the amount of auxiliary fuel is
negligible.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Organic carbon concentration and volume flow rate are measured
at the incinerator inlet using either Method 25A or Method 25B and
Method 2A, respectively. Organic carbon, carbon dioxide
(CO2), and carbon monoxide (CO) concentrations are measured
at the outlet using either Method 25A or Method 25B and Method 10,
respectively. The ratio of total carbon at the incinerator inlet and
outlet is multiplied by the inlet volume to determine the exhaust volume
flow rate.

3.0 Definitions

Same as Section 3.0 of Method 10 and Method 25A.

4.0 Interferences

Same as Section 4.0 of Method 10.

5.0 Safety

6.0 Equipment and Supplies

Same as Section 6.0 of Method 2A, Method 10, and Method 25A and/or
Method 25B as applicable, with the addition of the following:
6.1 This analyzer must meet the specifications set forth in Section
6.1.2 of Method 10, except that the span shall be 15 percent
CO2 by volume.

7.0 Reagents and Standards

Same as Section 7.0 of Method 10 and Method 25A, with the following
addition and exceptions:
7.1 Carbon Dioxide Analyzer Calibration. CO2 gases
meeting the specifications set forth in Section 7 of Method 6C are
required.
7.2 Hydrocarbon Analyzer Calibration. Methane shall not be used as
a calibration gas when performing this method.
7.3 Fuel Gas. If Method 25B is used to measure the organic carbon
concentrations at both the inlet and exhaust, no fuel gas is required.

[[Page 35]]

8.0 Sample Collection and Analysis

8.1 Pre-test Procedures. Perform all pre-test procedures (e.g.,
system performance checks, leak checks) necessary to determine gas
volume flow rate and organic carbon concentration in the vapor line to
the incinerator inlet and to determine organic carbon, carbon monoxide,
and carbon dioxide concentrations at the incinerator exhaust, as
outlined in Method 2A, Method 10, and Method 25A and/or Method 25B as
applicable.
8.2 Sampling. At the beginning of the test period, record the
initial parameters for the inlet volume meter according to the
procedures in Method 2A and mark all of the recorder strip charts to
indicate the start of the test. Conduct sampling and analysis as
outlined in Method 2A, Method 10, and Method 25A and/or Method 25B as
applicable. Continue recording inlet organic and exhaust CO2,
CO, and organic concentrations throughout the test. During periods of
process interruption and halting of gas flow, stop the timer and mark
the recorder strip charts so that data from this interruption are not
included in the calculations. At the end of the test period, record the
final parameters for the inlet volume meter and mark the end on all of
the recorder strip charts.
8.3 Post-test Procedures. Perform all post-test procedures (e.g.,
drift tests, leak checks), as outlined in Method 2A, Method 10, and
Method 25A and/or Method 25B as applicable.

9.0 Quality Control

Same as Section 9.0 of Method 2A, Method 10, and Method 25A.

10.0 Calibration and Standardization

Same as Section 10.0 of Method 2A, Method 10, and Method 25A.
Note: If a manifold system is used for the exhaust analyzers, all
the analyzers and sample pumps must be operating when the analyzer
calibrations are performed.
10.1 If an analyzer output does not meet the specifications of the
method, invalidate the test data for the period. Alternatively,
calculate the exhaust volume results using initial calibration data and
using final calibration data and report both resulting volumes. Then,
for emissions calculations, use the volume measurement resulting in the
greatest emission rate or concentration.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
Section 8.0).

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra decimal
figure beyond that of the acquired data. Round off figures after the
final calculation.
12.1 Nomenclature.

Coe = Mean carbon monoxide concentration in system exhaust,
ppm.
(CO2)2 = Ambient carbon dioxide concentration, ppm
(if not measured during the test period, may be assumed to
equal 300 ppm).
(CO2)e = Mean carbon dioxide concentration in
system exhaust, ppm.
HCe = Mean organic concentration in system exhaust as defined
by the calibration gas, ppm.
Hci = Mean organic concentration in system inlet as defined
by the calibration gas, ppm.
Ke = Hydrocarbon calibration gas factor for the exhaust
hydrocarbon analyzer, unitless [equal to the number of carbon
atoms per molecule of the gas used to calibrate the analyzer
(2 for ethane, 3 for propane, etc.)].
Ki = Hydrocarbon calibration gas factor for the inlet
hydrocarbon analyzer, unitless.
Ves = Exhaust gas volume, m\3\.
Vis = Inlet gas volume, m\3\.
Qes = Exhaust gas volume flow rate, m\3\/min.
Qis = Inlet gas volume flow rate, m\3\/min.
= Sample run time, min.
s = Standard conditions: 20 deg.C, 760 mm Hg.

12.2 Concentrations. Determine mean concentrations of inlet
organics, outlet CO2, outlet CO, and outlet organics
according to the procedures in the respective methods and the analyzers'
calibration curves, and for the time intervals specified in the
applicable regulations.
12.3 Exhaust Gas Volume. Calculate the exhaust gas volume as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.067

12.4 Exhaust Gas Volume Flow Rate. Calculate the exhaust gas volume
flow rate as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.210

[[Page 36]]

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Section 16.0 of Method 2A, Method 10, and Method 25A.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 2C--Determination of Gas Velocity and Volumetric Flow Rate in
Small Stacks or Ducts (Standard Pitot Tube)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material is incorporated by reference from other
methods in this part. Therefore, to obtain reliable results, persons
using this method should also have a thorough knowledge of at least the
following additional test methods: Method 1, Method 2.

1.0 Scope and Application

1.1 This method is applicable for the determination of average
velocity and volumetric flow rate of gas streams in small stacks or
ducts. Limits on the applicability of this method are identical to those
set forth in Method 2, Section 1.0, except that this method is limited
to stationary source stacks or ducts less than about 0.30 meter (12 in.)
in diameter, or 0.071 m\2\ (113 in.\2\) in cross-sectional area, but
equal to or greater than about 0.10 meter (4 in.) in diameter, or 0.0081
m\2\ (12.57 in.\2\) in cross-sectional area.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 The average gas velocity in a stack or duct is determined from
the gas density and from measurement of velocity heads with a standard
pitot tube.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Method 2, Section 6.0, with the exception of the following:
6.1 Standard Pitot Tube (instead of Type S). A standard pitot tube
which meets the specifications of Section 6.7 of Method 2. Use a
coefficient of 0.99 unless it is calibrated against another standard
pitot tube with a NIST-traceable coefficient (see Section 10.2 of Method
2).
6.2 Alternative Pitot Tube. A modified hemispherical-nosed pitot
tube (see Figure 2C-1), which features a shortened stem and enlarged
impact and static pressure holes. Use a coefficient of 0.99 unless it is
calibrated as mentioned in Section 6.1 above. This pitot tube is useful
in particulate liquid droplet-laden gas streams when a ``back purge'' is
ineffective.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection and Analysis

8.1 Follow the general procedures in Section 8.0 of Method 2,
except conduct the measurements at the traverse points specified in
Method 1A. The static and impact pressure holes of standard pitot tubes
are susceptible to plugging in particulate-laden gas streams. Therefore,
adequate proof that the openings of the pitot tube have not plugged
during the traverse period must be furnished; this can be done by taking
the velocity head (p) heading at the final traverse point,
cleaning out the impact and static holes of the standard pitot tube by
``back-purging'' with pressurized air, and then taking another
p reading. If the p readings made before and after the
air purge are the same (within 5 percent) the traverse is
acceptable. Otherwise, reject the run. Note that if the p at
the final traverse point is unsuitably low, another point may be
selected. If ``back purging'' at regular intervals is part of the
procedure, then take comparative p readings, as above, for the
last two back purges at which suitably high p readings are
observed.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.0.......................... Sampling Ensure accurate
equipment measurement of stack
calibration. gas velocity head.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Same as Method 2, Sections 10.2 through 10.4.

[[Page 37]]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
Section 8.0).

12.0 Calculations and Data Analysis

Same as Method 2, Section 12.0.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 2, Section 16.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.068

Method 2D--Measurement of Gas Volume Flow Rates in Small Pipes and Ducts

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material is incorporated by reference from other
methods in this part. Therefore, to obtain reliable results, persons
using this method should also have a thorough knowledge of at least the
following additional test methods: Method 1, Method 2, and Method 2A.

1.0 Scope and Application

1.1 This method is applicable for the determination of the
volumetric flow rates of gas streams in small pipes and ducts. It can be
applied to intermittent or variable gas flows only with particular
caution.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 All the gas flow in the pipe or duct is directed through a
rotameter, orifice plate or similar device to measure flow rate or
pressure drop. The device has been previously calibrated in a manner
that insures its proper calibration for the gas being measured. Absolute
temperature and pressure measurements are made to allow correction of
volumetric flow rates to standard conditions.

3.0 Definitions. [Reserved]

4.0 Interferences. [Reserved]

5.0 Safety

5.1 This method may involve hazardous materials, operations, and
equipment. This

[[Page 38]]

test method may not address all of the safety problems associated with
its use. It is the responsibility of the user of this test method to
establish appropriate safety and health practices and determine the
applicability of regulatory limitations prior to performing this test
method.

6.0 Equipment and Supplies

Specifications for the apparatus are given below. Any other
apparatus that has been demonstrated (subject to approval of the
Administrator) to be capable of meeting the specifications will be
considered acceptable.
6.1 Gas Metering Rate or Flow Element Device. A rotameter, orifice
plate, or other volume rate or pressure drop measuring device capable of
measuring the stack flow rate to within 5 percent. The
metering device shall be equipped with a temperature gauge accurate to
within 2 percent of the minimum absolute stack temperature
and a pressure gauge (accurate to within 5 mm Hg). The
capacity of the metering device shall be sufficient for the expected
maximum and minimum flow rates at the stack gas conditions. The
magnitude and variability of stack gas flow rate, molecular weight,
temperature, pressure, dewpoint, and corrosive characteristics, and pipe
or duct size are factors to consider in choosing a suitable metering
device.
6.2 Barometer. Same as Method 2, Section 6.5.
6.3 Stopwatch. Capable of measurement to within 1 second.

7.0 Reagents and Standards. [Reserved]

8.0 Sample Collection and Analysis

8.1 Installation and Leak Check. Same as Method 2A, Sections 8.1
and 8.2, respectively.
8.2 Volume Rate Measurement.
8.2.1 Continuous, Steady Flow. At least once an hour, record the
metering device flow rate or pressure drop reading, and the metering
device temperature and pressure. Make a minimum of 12 equally spaced
readings of each parameter during the test period. Record the barometric
pressure at the beginning and end of the test period. Record the data on
a table similar to that shown in Figure 2D-1.
8.2.2 Noncontinuous and Nonsteady Flow. Use volume rate devices
with particular caution. Calibration will be affected by variation in
stack gas temperature, pressure and molecular weight. Use the procedure
in Section 8.2.1 with the addition of the following: Record all the
metering device parameters on a time interval frequency sufficient to
adequately profile each process cyclical or noncontinuous event. A
multichannel continuous recorder may be used.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.0.......................... Sampling Ensure accurate
equipment measurement of stack
calibration. gas flow rate or
sample volume.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Same as Method 2A, Section 10.0, with the following exception:
10.1 Gas Metering Device. Same as Method 2A, Section 10.1, except
calibrate the metering device with the principle stack gas to be
measured (examples: air, nitrogen) against a standard reference meter. A
calibrated dry gas meter is an acceptable reference meter. Ideally,
calibrate the metering device in the field with the actual gas to be
metered. For metering devices that have a volume rate readout, calculate
the test metering device calibration coefficient, Ym, for
each run shown in Equation 2D-2 Section 12.3.
10.2 For metering devices that do not have a volume rate readout,
refer to the manufacturer's instructions to calculate the Vm2
corresponding to each Vr.
10.3 Temperature Gauge. Use the procedure and specifications in
Method 2A, Section 10.2. Perform the calibration at a temperature that
approximates field test conditions.
10.4 Barometer. Calibrate the barometer to be used in the field
test with a mercury barometer prior to the field test.

11.0 Analytical Procedure.

Sample collection and analysis are concurrent for this method (see
Section 8.0).

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Pbar = Barometric pressure, mm Hg (in. Hg).
Pm = Test meter average static pressure, mm Hg (in. Hg).
Qr = Reference meter volume flow rate reading, m\3\/min
(ft\3\/min).
Qm = Test meter volume flow rate reading, m\3\/min (ft\3\/
min).
Tr = Absolute reference meter average temperature, deg.K
( deg.R).
Tm = Absolute test meter average temperature, deg.K
( deg.R).
Kl = 0.3855 deg.K/mm Hg for metric units, = 17.65 deg.R/in.
Hg for English units.
12.2 Gas Flow Rate.

[[Page 39]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.069

12.3 Test Meter Device Calibration Coefficient. Calculation for
testing metering device calibration coefficient, Ym.
[GRAPHIC] [TIFF OMITTED] TR17OC00.070

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Spink, L.K. Principles and Practice of Flowmeter Engineering. The
Foxboro Company. Foxboro, MA. 1967.
2. Benedict, R.P. Fundamentals of Temperature, Pressure, and Flow
Measurements. John Wiley & Sons, Inc. New York, NY. 1969.
3. Orifice Metering of Natural Gas. American Gas Association.
Arlington, VA. Report No. 3. March 1978. 88 pp.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Plant

Date

Run No.

Sample location

Start

Finish

Operators

Metering device No.

Calibration coefficient

Calibration gas

Date to recalibrate

----------------------------------------------------------------------------------------------------------------
Temperature
Time Flow rate reading Static Pressure ---------------------------------------
[mm Hg (in. Hg)] deg.C ( deg.F) deg.K ( deg.R)
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------
Average
----------------------------------------------------------------------------------------------------------------

Figure 2D-1. Volume Flow Rate Measurement Data

Method 2E--Determination of Landfill Gas Production Flow Rate

[[Page 40]]

method should also have a thorough knowledge of at least the following
additional test methods: Methods 2 and 3C.

1.0 Scope and Application

1.1 Applicability. This method applies to the measurement of
landfill gas (LFG) production flow rate from municipal solid waste
landfills and is used to calculate the flow rate of nonmethane organic
compounds (NMOC) from landfills.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Extraction wells are installed either in a cluster of three or
at five dispersed locations in the landfill. A blower is used to extract
LFG from the landfill. LFG composition, landfill pressures, and orifice
pressure differentials from the wells are measured and the landfill gas
production flow rate is calculated.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 Since this method is complex, only experienced personnel should
perform the test. Landfill gas contains methane, therefore explosive
mixtures may exist at or near the landfill. It is advisable to take
appropriate safety precautions when testing landfills, such as
refraining from smoking and installing explosion-proof equipment.

6.0 Equipment and Supplies

6.1 Well Drilling Rig. Capable of boring a 0.61 m (24 in.) diameter
hole into the landfill to a minimum of 75 percent of the landfill depth.
The depth of the well shall not extend to the bottom of the landfill or
the liquid level.
6.2 Gravel. No fines. Gravel diameter should be appreciably larger
than perforations stated in Sections 6.10 and 8.2.
6.3 Bentonite.
6.4 Backfill Material. Clay, soil, and sandy loam have been found
to be acceptable.
6.5 Extraction Well Pipe. Minimum diameter of 3 in., constructed of
polyvinyl chloride (PVC), high density polyethylene (HDPE), fiberglass,
stainless steel, or other suitable nonporous material capable of
transporting landfill gas.
6.6 Above Ground Well Assembly. Valve capable of adjusting gas
flow, such as a gate, ball, or butterfly valve; sampling ports at the
well head and outlet; and a flow measuring device, such as an in-line
orifice meter or pitot tube. A schematic of the aboveground well head
assembly is shown in Figure 2E-1.
6.7 Cap. Constructed of PVC or HDPE.
6.8 Header Piping. Constructed of PVC or HDPE.
6.9 Auger. Capable of boring a 0.15-to 0.23-m (6-to 9-in.) diameter
hole to a depth equal to the top of the perforated section of the
extraction well, for pressure probe installation.
6.10 Pressure Probe. Constructed of PVC or stainless steel (316),
0.025-m (1-in.). Schedule 40 pipe. Perforate the bottom two-thirds. A
minimum requirement for perforations is slots or holes with an open area
equivalent to four 0.006-m (\1/4\-in.) diameter holes spaced 90 deg.
apart every 0.15 m (6 in.).
6.11 Blower and Flare Assembly. Explosion-proof blower, capable of
extracting LFG at a flow rate of 8.5 m ³/min (300 ft
³/min), a water knockout, and flare or incinerator.
6.12 Standard Pitot Tube and Differential Pressure Gauge for Flow
Rate Calibration with Standard Pitot. Same as Method 2, Sections 6.7 and
6.8.
6.13 Orifice Meter. Orifice plate, pressure tabs, and pressure
measuring device to measure the LFG flow rate.
6.14 Barometer. Same as Method 4, Section 6.1.5.
6.15 Differential Pressure Gauge. Water-filled U-tube manometer or
equivalent, capable of measuring within 0.02 mm Hg (0.01 in.
H2O), for measuring the pressure of the pressure probes.

7.0 Reagents and Standards. Not Applicable

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Placement of Extraction Wells. The landfill owner or operator
may install a single cluster of three extraction wells in a test area or
space five equal-volume wells over the landfill. The cluster wells are
recommended but may be used only if the composition, age of the refuse,
and the landfill depth of the test area can be determined.
8.1.1 Cluster Wells. Consult landfill site records for the age of
the refuse, depth, and composition of various sections of the landfill.
Select an area near the perimeter of the landfill with a depth equal to
or greater than the average depth of the landfill and with the average
age of the refuse between 2 and 10 years old. Avoid areas known to
contain nondecomposable materials, such as concrete and asbestos. Locate
the cluster wells as shown in Figure 2E-2.
8.1.1.1 The age of the refuse in a test area will not be uniform,
so calculate a weighted average age of the refuse as shown in Section
12.2.
8.1.2 Equal Volume Wells. Divide the sections of the landfill that
are at least 2 years old into five areas representing equal volumes.
Locate an extraction well near the center of each area.

[[Page 41]]

8.2 Installation of Extraction Wells. Use a well drilling rig to
dig a 0.6 m (24 in.) diameter hole in the landfill to a minimum of 75
percent of the landfill depth, not to extend to the bottom of the
landfill or the liquid level. Perforate the bottom two thirds of the
extraction well pipe. A minimum requirement for perforations is holes or
slots with an open area equivalent to 0.01-m (0.5-in.) diameter holes
spaced 90 deg. apart every 0.1 to 0.2 m (4 to 8 in.). Place the
extraction well in the center of the hole and backfill with gravel to a
level 0.30 m (1 ft) above the perforated section. Add a layer of
backfill material 1.2 m (4 ft) thick. Add a layer of bentonite 0.9 m (3
ft) thick, and backfill the remainder of the hole with cover material or
material equal in permeability to the existing cover material. The
specifications for extraction well installation are shown in Figure 2E-
3.
8.3 Pressure Probes. Shallow pressure probes are used in the check
for infiltration of air into the landfill, and deep pressure probes are
use to determine the radius of influence. Locate pressure probes along
three radial arms approximately 120 deg. apart at distances of 3, 15,
30, and 45 m (10, 50, 100, and 150 ft) from the extraction well. The
tester has the option of locating additional pressure probes at
distances every 15 m (50 feet) beyond 45 m (150 ft). Example placements
of probes are shown in Figure 2E-4. The 15-, 30-, and 45-m, (50-, 100-,
and 150-ft) probes from each well, and any additional probes located
along the three radial arms (deep probes), shall extend to a depth equal
to the top of the perforated section of the extraction wells. All other
probes (shallow probes) shall extend to a depth equal to half the depth
of the deep probes.
8.3.1 Use an auger to dig a hole, 0.15- to 0.23-m (6-to 9-in.) in
diameter, for each pressure probe. Perforate the bottom two thirds of
the pressure probe. A minimum requirement for perforations is holes or
slots with an open area equivalent to four 0.006-m (0.25-in.) diameter
holes spaced 90 deg. apart every 0.15 m (6 in.). Place the pressure
probe in the center of the hole and backfill with gravel to a level 0.30
m (1 ft) above the perforated section. Add a layer of backfill material
at least 1.2 m (4 ft) thick. Add a layer of bentonite at least 0.3 m (1
ft) thick, and backfill the remainder of the hole with cover material or
material equal in permeability to the existing cover material. The
specifications for pressure probe installation are shown in Figure 2E-5.
8.4 LFG Flow Rate Measurement. Place the flow measurement device,
such as an orifice meter, as shown in Figure 2E-1. Attach the wells to
the blower and flare assembly. The individual wells may be ducted to a
common header so that a single blower, flare assembly, and flow meter
may be used. Use the procedures in Section 10.1 to calibrate the flow
meter.
8.5 Leak-Check. A leak-check of the above ground system is required
for accurate flow rate measurements and for safety. Sample LFG at the
well head sample port and at the outlet sample port. Use Method 3C to
determine nitrogen (N2) concentrations. Determine the
difference between the well head and outlet N2 concentrations
using the formula in Section 12.3. The system passes the leak-check if
the difference is less than 10,000 ppmv.
8.6 Static Testing. Close the control valves on the well heads
during static testing. Measure the gauge pressure (Pg) at
each deep pressure probe and the barometric pressure (Pbar)
every 8 hours (hr) for 3 days. Convert the gauge pressure of each deep
pressure probe to absolute pressure using the equation in Section 12.4.
Record as Pi (initial absolute pressure).
8.6.1 For each probe, average all of the 8-hr deep pressure probe
readings (Pi) and record as Pia (average absolute
pressure). Pia is used in Section 8.7.5 to determine the
maximum radius of influence.
8.6.2 Measure the static flow rate of each well once during static
testing.
8.7 Short-Term Testing. The purpose of short-term testing is to
determine the maximum vacuum that can be applied to the wells without
infiltration of ambient air into the landfill. The short-term testing is
performed on one well at a time. Burn all LFG with a flare or
incinerator.
8.7.1 Use the blower to extract LFG from a single well at a rate at
least twice the static flow rate of the respective well measured in
Section 8.6.2. If using a single blower and flare assembly and a common
header system, close the control valve on the wells not being measured.
Allow 24 hr for the system to stabilize at this flow rate.
8.7.2 Test for infiltration of air into the landfill by measuring
the gauge pressures of the shallow pressure probes and using Method 3C
to determine the LFG N2 concentration. If the LFG
N2 concentration is less than 5 percent and all of the
shallow probes have a positive gauge pressure, increase the blower
vacuum by 3.7 mm Hg (2 in. H2O), wait 24 hr, and repeat the
tests for infiltration. Continue the above steps of increasing blower
vacuum by 3.7 mm Hg (2 in. H2O), waiting 24 hr, and testing
for infiltration until the concentration of N2 exceeds 5
percent or any of the shallow probes have a negative gauge pressure.
When this occurs,reduce the blower vacuum to the maximum setting at
which the N2 concentration was less than 5 percent and the
gauge pressures of the shallow probes are positive.
8.7.3 At this blower vacuum, measure atmospheric pressure
(Pbar) every 8 hr for 24 hr, and record the LFG flow rate
(Qs) and the probe gauge pressures (Pf) for all of
the probes. Convert the gauge pressures of the

[[Page 42]]

deep probes to absolute pressures for each 8-hr reading at Qs
as shown in Section 12.4.
8.7.4 For each probe, average the 8-hr deep pressure probe absolute
pressure readings and record as Pfa (the final average
absolute pressure).
8.7.5 For each probe, compare the initial average pressure
(Pia) from Section 8.6.1 to the final average pressure
(Pfa). Determine the furthermost point from the well head
along each radial arm where Pfa Pia.
This distance is the maximum radius of influence (Rm), which
is the distance from the well affected by the vacuum. Average these
values to determine the average maximum radius of influence
(Rma).
8.7.6 Calculate the depth (Dst) affected by the
extraction well during the short term test as shown in Section 12.6. If
the computed value of Dst exceeds the depth of the landfill,
set Dst equal to the landfill depth.
8.7.7 Calculate the void volume (V) for the extraction well as
shown in Section 12.7.
8.7.8 Repeat the procedures in Section 8.7 for each well.
8.8 Calculate the total void volume of the test wells
(Vv) by summing the void volumes (V) of each well.
8.9 Long-Term Testing. The purpose of long-term testing is to
extract two void volumes of LFG from the extraction wells. Use the
blower to extract LFG from the wells. If a single Blower and flare
assembly and common header system are used, open all control valves and
set the blower vacuum equal to the highest stabilized blower vacuum
demonstrated by any individual well in Section 8.7. Every 8 hr, sample
the LFG from the well head sample port, measure the gauge pressures of
the shallow pressure probes, the blower vacuum, the LFG flow rate, and
use the criteria for infiltration in Section 8.7.2 and Method 3C to test
for infiltration. If infiltration is detected, do not reduce the blower
vacuum, instead reduce the LFG flow rate from the well by adjusting the
control valve on the well head. Adjust each affected well individually.
Continue until the equivalent of two total void volumes (Vv)
have been extracted, or until Vt = 2Vv.
8.9.1 Calculate Vt, the total volume of LFG extracted
from the wells, as shown in Section 12.8.
8.9.2 Record the final stabilized flow rate as Qf and
the gauge pressure for each deep probe. If, during the long term
testing, the flow rate does not stabilize, calculate Qf by
averaging the last 10 recorded flow rates.
8.9.3 For each deep probe, convert each gauge pressure to absolute
pressure as in Section 12.4. Average these values and record as
Psa. For each probe, compare Pia to
Psa. Determine the furthermost point from the well head along
each radial arm where Psa Pia. This
distance is the stabilized radius of influence. Average these values to
determine the average stabilized radius of influence (Rsa).
8.10 Determine the NMOC mass emission rate using the procedures in
Section 12.9 through 12.15.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... LFG flow rate Ensures accurate
meter measurement of LFG
calibration. flow rate and sample
volume
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 LFG Flow Rate Meter (Orifice) Calibration Procedure. Locate a
standard pitot tube in line with an orifice meter. Use the procedures in
Section 8, 12.5, 12.6, and 12.7 of Method 2 to determine the average dry
gas volumetric flow rate for at least five flow rates that bracket the
expected LFG flow rates, except in Section 8.1, use a standard pitot
tube rather than a Type S pitot tube. Method 3C may be used to determine
the dry molecular weight. It may be necessary to calibrate more than one
orifice meter in order to bracket the LFG flow rates. Construct a
calibration curve by plotting the pressure drops across the orifice
meter for each flow rate versus the average dry gas volumetric flow rate
in m\3\/min of the gas.

11.0 Procedures [Reserved]

12.0 Data Analysis and Calculations

12.1 Nomenclature.

A = Age of landfill, yr.
Aavg = Average age of the refuse tested, yr.
Ai = Age of refuse in the ith fraction, yr.
Ar = Acceptance rate, Mg/yr.
CNMOC = NMOC concentration, ppmv as hexane (CNMOC
= Ct/6).
Co = Concentration of N2 at the outlet, ppmv.
Ct = NMOC concentration, ppmv (carbon equivalent) from Method
25C.
Cw = Concentration of N2 at the wellhead, ppmv.
D = Depth affected by the test wells, m.
Dst = Depth affected by the test wells in the short-term
test, m.
e = Base number for natural logarithms (2.718).
f = Fraction of decomposable refuse in the landfill.

[[Page 43]]

fi = Fraction of the refuse in the ith section.
k = Landfill gas generation constant, yr^-1.
Lo = Methane generation potential, m\3\/Mg.
Lo' = Revised methane generation potential to account for the
amount of nondecomposable material in the landfill, m\3\/Mg.
Mi = Mass of refuse in the ith section, Mg.
Mr = Mass of decomposable refuse affected by the test well,
Mg.
Pbar = Atmospheric pressure, mm Hg.
Pf = Final absolute pressure of the deep pressure probes
during short-term testing, mm Hg.
Pfa = Average final absolute pressure of the deep pressure
probes during short-term testing, mm Hg.
Pgf = final gauge pressure of the deep pressure probes, mm
Hg.
Pgi = Initial gauge pressure of the deep pressure probes, mm
Hg.
Pi = Initial absolute pressure of the deep pressure probes
during static testing, mm Hg.
Pia = Average initial absolute pressure of the deep pressure
probes during static testing, mm Hg.
Ps = Final absolute pressure of the deep pressure probes
during long-term testing, mm Hg.
Psa = Average final absolute pressure of the deep pressure
probes during long-term testing, mm Hg.
Qf = Final stabilized flow rate, m\3\/min.
Qi = LFG flow rate measured at orifice meter during the ith
interval, m\3\/min.
Qs = Maximum LFG flow rate at each well determined by short-
term test, m\3\/min.
Qt = NMOC mass emission rate, m\3\/min.
Rm = Maximum radius of influence, m.
Rma = Average maximum radius of influence, m.
Rs = Stabilized radius of influence for an individual well,
m.
Rsa = Average stabilized radius of influence, m.
ti = Age of section i, yr.
tt = Total time of long-term testing, yr.
tvi = Time of the ith interval (usually 8), hr.
V = Void volume of test well, m\3\.
Vr = Volume of refuse affected by the test well, m\3\.
Vt = Total volume of refuse affected by the long-term
testing, m\3\.
Vv = Total void volume affected by test wells, m\3\.
WD = Well depth, m.
= Refuse density, Mg/m\3\ (Assume 0.64 Mg/m\3\ if data are
unavailable).

12.2 Use the following equation to calculate a weighted average age
of landfill refuse.
[GRAPHIC] [TIFF OMITTED] TR17OC00.071

12.3 Use the following equation to determine the difference in
N2 concentrations (ppmv) at the well head and outlet
location.
[GRAPHIC] [TIFF OMITTED] TR17OC00.072

12.4 Use the following equation to convert the gauge pressure
(Pg) of each initial deep pressure probe to absolute pressure
(Pi).
[GRAPHIC] [TIFF OMITTED] TR17OC00.073

12.5 Use the following equation to convert the gauge pressures of
the deep probes to absolute pressures for each 8-hr reading at
Qs.
[GRAPHIC] [TIFF OMITTED] TR17OC00.074

12.6 Use the following equation to calculate the depth
(Dst) affected by the extraction well during the short-term
test.
[GRAPHIC] [TIFF OMITTED] TR17OC00.075

12.7 Use the following equation to calculate the void volume for
the extraction well (V).
[GRAPHIC] [TIFF OMITTED] TR17OC00.076

12.8 Use the following equation to calculate Vt, the
total volume of LFG extracted from the wells.
[GRAPHIC] [TIFF OMITTED] TR17OC00.077

12.9 Use the following equation to calculate the depth affected by
the test well. If using cluster wells, use the average depth of the
wells for WD. If the value of D is greater than the depth of the
landfill, set D equal to the landfill depth.
[GRAPHIC] [TIFF OMITTED] TR17OC00.078

12.10 Use the following equation to calculate the volume of refuse
affected by the test well.
[GRAPHIC] [TIFF OMITTED] TR17OC00.079

12.11 Use the following equation to calculate the mass affected by
the test well.
[GRAPHIC] [TIFF OMITTED] TR17OC00.080

12.12 Modify Lo to account for the nondecomposable
refuse in the landfill.
[GRAPHIC] [TIFF OMITTED] TR17OC00.081

12.13 In the following equation, solve for k (landfill gas
generation constant) by iteration. A suggested procedure is to select a
value for k, calculate the left side of the equation, and if not equal
to zero, select another value for k. Continue this process until

[[Page 44]]

the left hand side of the equation equals zero, 0.001.
[GRAPHIC] [TIFF OMITTED] TR17OC00.082

12.14 Use the following equation to determine landfill NMOC mass
emission rate if the yearly acceptance rate of refuse has been
consistent (10 percent) over the life of the landfill.
[GRAPHIC] [TIFF OMITTED] TR17OC00.083

12.15 Use the following equation to determine landfill NMOC mass
emission rate if the acceptance rate has not been consistent over the
life of the landfill.
[GRAPHIC] [TIFF OMITTED] TR17OC00.084

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Same as Method 2, Appendix A, 40 CFR Part 60.
2. Emcon Associates, Methane Generation and Recovery from Landfills.
Ann Arbor Science, 1982.
3. The Johns Hopkins University, Brown Station Road Landfill Gas
Resource Assessment, Volume 1: Field Testing and Gas Recovery
Projections. Laurel, Maryland: October 1982.
4. Mandeville and Associates, Procedure Manual for Landfill Gases
Emission Testing.
5. Letter and attachments from Briggum, S., Waste Management of
North America, to Thorneloe, S., EPA. Response to July 28, 1988 request
for additional information. August 18, 1988.
6. Letter and attachments from Briggum, S., Waste Management of
North America, to Wyatt, S., EPA. Response to December 7, 1988 request
for additional information. January 16, 1989.

[[Page 45]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.085

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[GRAPHIC] [TIFF OMITTED] TR17OC00.086

[[Page 47]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.087

[[Page 48]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.088

[[Page 49]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.089

Method 2F--Determination of Stack Gas Velocity And Volumetric Flow Rate
With Three-Dimensional Probes

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material has been incorporated from other methods in
this part. Therefore, to obtain reliable results, those using this
method should have a thorough knowledge of at least the following
additional test methods: Methods 1, 2, 3 or 3A, and 4.

1.0 Scope and Application

1.1 This method is applicable for the determination of yaw angle, pitch
angle, axial velocity and the volumetric flow rate of a gas

[[Page 50]]

stream in a stack or duct using a three-dimensional (3-D) probe. This
method may be used only when the average stack or duct gas velocity is
greater than or equal to 20 ft/sec. When the above condition cannot be
met, alternative procedures, approved by the Administrator, U.S.
Environmental Protection Agency, shall be used to make accurate flow
rate determinations.

2.0 Summary of Method

2.1 A 3-D probe is used to determine the velocity pressure and the
yaw and pitch angles of the flow velocity vector in a stack or duct. The
method determines the yaw angle directly by rotating the probe to null
the pressure across a pair of symmetrically placed ports on the probe
head. The pitch angle is calculated using probe-specific calibration
curves. From these values and a determination of the stack gas density,
the average axial velocity of the stack gas is calculated. The average
gas volumetric flow rate in the stack or duct is then determined from
the average axial velocity.

3.0 Definitions

3.1. Angle-measuring Device Rotational Offset (RADO).
The rotational position of an angle-measuring device relative to the
reference scribe line, as determined during the pre-test rotational
position check described in section 8.3.
3.2 Axial Velocity. The velocity vector parallel to the axis of the
stack or duct that accounts for the yaw and pitch angle components of
gas flow. The term ``axial'' is used herein to indicate that the
velocity and volumetric flow rate results account for the measured yaw
and pitch components of flow at each measurement point.
3.3 Calibration Pitot Tube. The standard (Prandtl type) pitot tube
used as a reference when calibrating a 3-D probe under this method.
3.4 Field Test. A set of measurements conducted at a specific unit
or exhaust stack/duct to satisfy the applicable regulation (e.g., a
three-run boiler performance test, a single-or multiple-load nine-run
relative accuracy test).
3.5 Full Scale of Pressure-measuring Device. Full scale refers to
the upper limit of the measurement range displayed by the device. For
bi-directional pressure gauges, full scale includes the entire pressure
range from the lowest negative value to the highest positive value on
the pressure scale.
3.6 Main probe. Refers to the probe head and that section of probe
sheath directly attached to the probe head. The main probe sheath is
distinguished from probe extensions, which are sections of sheath added
onto the main probe to extend its reach.
3.7 ``May,'' ``Must,'' ``Shall,'' ``Should,'' and the imperative
form of verbs.
3.7.1 ``May'' is used to indicate that a provision of this method
is optional.
3.7.2 ``Must,'' ``Shall,'' and the imperative form of verbs (such
as ``record'' or ``enter'') are used to indicate that a provision of
this method is mandatory.
3.7.3 ``Should'' is used to indicate that a provision of this
method is not mandatory, but is highly recommended as good practice.
3.8 Method 1. Refers to 40 CFR part 60, appendix A, ``Method 1--
Sample and velocity traverses for stationary sources.''
3.9 Method 2. Refers to 40 CFR part 60, appendix A, ``Method 2--
Determination of stack gas velocity and volumetric flow rate (Type S
pitot tube).''
3.10 Method 2G. Refers to 40 CFR part 60, appendix A, ``Method 2G--
Determination of stack gas velocity and volumetric flow rate with two-
dimensional probes.''
3.11 Nominal Velocity. Refers to a wind tunnel velocity setting
that approximates the actual wind tunnel velocity to within
1.5 m/sec (5 ft/sec).
3.12 Pitch Angle. The angle between the axis of the stack or duct
and the pitch component of flow, i.e., the component of the total
velocity vector in a plane defined by the traverse line and the axis of
the stack or duct. (Figure 2F-1 illustrates the ``pitch plane.'') From
the standpoint of a tester facing a test port in a vertical stack, the
pitch component of flow is the vector of flow moving from the center of
the stack toward or away from that test port. The pitch angle is the
angle described by this pitch component of flow and the vertical axis of
the stack.
3.13 Readability. For the purposes of this method, readability for
an analog measurement device is one half of the smallest scale division.
For a digital measurement device, it is the number of decimals displayed
by the device.
3.14 Reference Scribe Line. A line permanently inscribed on the
main probe sheath (in accordance with section 6.1.6.1) to serve as a
reference mark for determining yaw angles.
3.15 Reference Scribe Line Rotational Offset (RSLO). The
rotational position of a probe's reference scribe line relative to the
probe's yaw-null position, as determined during the yaw angle
calibration described in section 10.5.
3.16 Response Time. The time required for the measurement system to
fully respond to a change from zero differential pressure and ambient
temperature to the stable stack or duct pressure and temperature
readings at a traverse point.
3.17 Tested Probe. A 3-D probe that is being calibrated.
3.18 Three-dimensional (3-D) Probe. A directional probe used to
determine the velocity pressure and yaw and pitch angles in a flowing
gas stream.

[[Page 51]]

3.19 Traverse Line. A diameter or axis extending across a stack or
duct on which measurements of differential pressure and flow angles are
made.
3.20 Wind Tunnel Calibration Location. A point, line, area, or
volume within the wind tunnel test section at, along, or within which
probes are calibrated. At a particular wind tunnel velocity setting, the
average velocity pressures at specified points at, along, or within the
calibration location shall vary by no more than 2 percent or 0.3 mm
H2O (0.01 in. H2O), whichever is less restrictive,
from the average velocity pressure at the calibration pitot tube
location. Air flow at this location shall be axial, i.e., yaw and pitch
angles within 3 deg.. Compliance with these flow criteria
shall be demonstrated by performing the procedures prescribed in
sections 10.1.1 and 10.1.2. For circular tunnels, no part of the
calibration location may be closer to the tunnel wall than 10.2 cm (4
in.) or 25 percent of the tunnel diameter, whichever is farther from the
wall. For elliptical or rectangular tunnels, no part of the calibration
location may be closer to the tunnel wall than 10.2 cm (4 in.) or 25
percent of the applicable cross-sectional axis, whichever is farther
from the wall.
3.21 Wind Tunnel with Documented Axial Flow. A wind tunnel facility
documented as meeting the provisions of sections 10.1.1 (velocity
pressure cross-check) and 10.1.2 (axial flow verification) using the
procedures described in these sections or alternative procedures
determined to be technically equivalent.
3.22 Yaw Angle. The angle between the axis of the stack or duct and
the yaw component of flow, i.e., the component of the total velocity
vector in a plane perpendicular to the traverse line at a particular
traverse point. (Figure 2F-1 illustrates the ``yaw plane.'') From the
standpoint of a tester facing a test port in a vertical stack, the yaw
component of flow is the vector of flow moving to the left or right from
the center of the stack as viewed by the tester. (This is sometimes
referred to as ``vortex flow,'' i.e., flow around the centerline of a
stack or duct.) The yaw angle is the angle described by this yaw
component of flow and the vertical axis of the stack. The algebraic sign
convention is illustrated in Figure 2F-2.
3.23 Yaw Nulling. A procedure in which a probe is rotated about its
axis in a stack or duct until a zero differential pressure reading
(``yaw null'') is obtained. When a 3-D probe is yaw-nulled, its impact
pressure port (P1) faces directly into the direction of flow
in the stack or duct and the differential pressure between pressure
ports P2 and P3 is zero.
4.0 Interferences. [Reserved]
5.0 Safety.
5.1 This test method may involve hazardous operations and the use
of hazardous materials or equipment. This method does not purport to
address all of the safety problems associated with its use. It is the
responsibility of the user to establish and implement appropriate safety
and health practices and to determine the applicability of regulatory
limitations before using this test method.

6.0 Equipment and Supplies

6.1 Three-dimensional Probes. The 3-D probes as specified in
subsections 6.1.1 through 6.1.3 below qualify for use based on
comprehensive wind tunnel and field studies involving both inter-and
intra-probe comparisons by multiple test teams. Other types of probes
shall not be used unless approved by the Administrator. Each 3-D probe
shall have a unique identification number or code permanently marked on
the main probe sheath. The minimum recommended diameter of the sensing
head of any probe used under this method is 2.5 cm (1 in.). Each probe
shall be calibrated prior to use according to the procedures in section
10. Manufacturer-supplied calibration data shall be used as example
information only, except when the manufacturer calibrates the 3-D probe
as specified in section 10 and provides complete documentation.
6.1.1 Five-hole prism-shaped probe. This type of probe consists of
five pressure taps in the flat facets of a prism-shaped sensing head.
The pressure taps are numbered 1 through 5, with the pressures measured
at each hole referred to as P1, P2, P3,
P4, and P5, respectively. Figure 2F-3 is an
illustration of the placement of pressure taps on a commonly available
five-hole prism-shaped probe, the 2.5-cm (1-in.) DAT probe. (Note:
Mention of trade names or specific products does not constitute
endorsement by the U.S. Environmental Protection Agency.) The numbering
arrangement for the prism-shaped sensing head presented in Figure 2F-3
shall be followed for correct operation of the probe. A brief
description of the probe measurements involved is as follows: the
differential pressure P2-P3 is used to yaw null
the probe and determine the yaw angle; the differential pressure
P4-P5 is a function of pitch angle; and the
differential pressure P1-P2 is a function of total
velocity.
6.1.2 Five-hole spherical probe. This type of probe consists of
five pressure taps in a spherical sensing head. As with the prism-shaped
probe, the pressure taps are numbered 1 through 5, with the pressures
measured at each hole referred to as P1, P2,
P3, P4, and P5, respectively. However,
the P4 and P5 pressure taps are in the reverse
location from their respective positions on the prism-shaped probe head.
The differential pressure P2-P3 is used to yaw
null the probe and determine the yaw angle; the differential pressure
P4-P5 is a function of pitch angle; and the
differential pressure P1-P2 is a function

[[Page 52]]

of total velocity. A diagram of a typical spherical probe sensing head
is presented in Figure 2F-4. Typical probe dimensions are indicated in
the illustration.
6.1.3 A manual 3-D probe refers to a five-hole prism-shaped or
spherical probe that is positioned at individual traverse points and yaw
nulled manually by an operator. An automated 3-D probe refers to a
system that uses a computer-controlled motorized mechanism to position
the five-hole prism-shaped or spherical head at individual traverse
points and perform yaw angle determinations.
6.1.4 Other three-dimensional probes. [Reserved]
6.1.5 Probe sheath. The probe shaft shall include an outer sheath
to: (1) provide a surface for inscribing a permanent reference scribe
line, (2) accommodate attachment of an angle-measuring device to the
probe shaft, and (3) facilitate precise rotational movement of the probe
for determining yaw angles. The sheath shall be rigidly attached to the
probe assembly and shall enclose all pressure lines from the probe head
to the farthest position away from the probe head where an angle-
measuring device may be attached during use in the field. The sheath of
the fully assembled probe shall be sufficiently rigid and straight at
all rotational positions such that, when one end of the probe shaft is
held in a horizontal position, the fully extended probe meets the
horizontal straightness specifications indicated in section 8.2 below.
6.1.6 Scribe lines.
6.1.6.1 Reference scribe line. A permanent line, no greater than
1.6 mm (1/16 in.) in width, shall be inscribed on each manual probe that
will be used to determine yaw angles of flow. This line shall be placed
on the main probe sheath in accordance with the procedures described in
section 10.4 and is used as a reference position for installation of the
yaw angle-measuring device on the probe. At the discretion of the
tester, the scribe line may be a single line segment placed at a
particular position on the probe sheath (e.g., near the probe head),
multiple line segments placed at various locations along the length of
the probe sheath (e.g., at every position where a yaw angle-measuring
device may be mounted), or a single continuous line extending along the
full length of the probe sheath.
6.1.6.2 Scribe line on probe extensions. A permanent line may also
be inscribed on any probe extension that will be attached to the main
probe in performing field testing. This allows a yaw angle-measuring
device mounted on the extension to be readily aligned with the reference
scribe line on the main probe sheath.
6.1.6.3 Alignment specifications. This specification shall be met
separately, using the procedures in section 10.4.1, on the main probe
and on each probe extension. The rotational position of the scribe line
or scribe line segments on the main probe or any probe extension must
not vary by more than 2 deg.. That is, the difference between the
minimum and maximum of all of the rotational angles that are measured
along the full length of the main probe or the probe extension must not
exceed 2 deg..
6.1.7 Probe and system characteristics to ensure horizontal
stability.
6.1.7.1 For manual probes, it is recommended that the effective
length of the probe (coupled with a probe extension, if necessary) be at
least 0.9 m (3 ft.) longer than the farthest traverse point mark on the
probe shaft away from the probe head. The operator should maintain the
probe's horizontal stability when it is fully inserted into the stack or
duct. If a shorter probe is used, the probe should be inserted through a
bushing sleeve, similar to the one shown in Figure 2F-5, that is
installed on the test port; such a bushing shall fit snugly around the
probe and be secured to the stack or duct entry port in such a manner as
to maintain the probe's horizontal stability when fully inserted into
the stack or duct.
6.1.7.2 An automated system that includes an external probe casing
with a transport system shall have a mechanism for maintaining
horizontal stability comparable to that obtained by manual probes
following the provisions of this method. The automated probe assembly
shall also be constructed to maintain the alignment and position of the
pressure ports during sampling at each traverse point. The design of the
probe casing and transport system shall allow the probe to be removed
from the stack or duct and checked through direct physical measurement
for angular position and insertion depth.
6.1.8 The tubing that is used to connect the probe and the
pressure-measuring device should have an inside diameter of at least 3.2
mm (1/8 in.), to reduce the time required for pressure equilibration,
and should be as short as practicable.
6.2 Yaw Angle-measuring Device. One of the following devices shall
be used for measurement of the yaw angle of flow.
6.2.1 Digital inclinometer. This refers to a digital device capable
of measuring and displaying the rotational position of the probe to
within 1 deg.. The device shall be able to be locked into
position on the probe sheath or probe extension, so that it indicates
the probe's rotational position throughout the test. A rotational
position collar block that can be attached to the probe sheath (similar
to the collar shown in Figure 2F-6) may be required to lock the digital
inclinometer into position on the probe sheath.
6.2.2 Protractor wheel and pointer assembly. This apparatus,
similar to that shown in

[[Page 53]]

Figure 2F-7, consists of the following components.
6.2.2.1 A protractor wheel that can be attached to a port opening
and set in a fixed rotational position to indicate the yaw angle
position of the probe's scribe line relative to the longitudinal axis of
the stack or duct. The protractor wheel must have a measurement ring on
its face that is no less than 17.8 cm (7 in.) in diameter, shall be able
to be rotated to any angle and then locked into position on the stack or
duct port, and shall indicate angles to a resolution of 1 deg..
6.2.2.2 A pointer assembly that includes an indicator needle
mounted on a collar that can slide over the probe sheath and be locked
into a fixed rotational position on the probe sheath. The pointer needle
shall be of sufficient length, rigidity, and sharpness to allow the
tester to determine the probe's angular position to within 1 deg. from
the markings on the protractor wheel. Corresponding to the position of
the pointer, the collar must have a scribe line to be used in aligning
the pointer with the scribe line on the probe sheath.
6.2.3 Other yaw angle-measuring devices. Other angle-measuring
devices with a manufacturer's specified precision of 1 deg. or better
may be used, if approved by the Administrator.
6.3 Probe Supports and Stabilization Devices. When probes are used
for determining flow angles, the probe head should be kept in a stable
horizontal position. For probes longer than 3.0 m (10 ft.), the section
of the probe that extends outside the test port shall be secured. Three
alternative devices are suggested for maintaining the horizontal
position and stability of the probe shaft during flow angle
determinations and velocity pressure measurements: (1) Monorails
installed above each port, (2) probe stands on which the probe shaft may
be rested, or (3) bushing sleeves of sufficient length secured to the
test ports to maintain probes in a horizontal position. Comparable
provisions shall be made to ensure that automated systems maintain the
horizontal position of the probe in the stack or duct. The physical
characteristics of each test platform may dictate the most suitable type
of stabilization device. Thus, the choice of a specific stabilization
device is left to the judgment of the testers.
6.4 Differential Pressure Gauges. The pressure (P)
measuring devices used during wind tunnel calibrations and field testing
shall be either electronic manometers (e.g., pressure transducers),
fluid manometers, or mechanical pressure gauges (e.g.,
Magnehelic gauges). Use of electronic
manometers is recommended. Under low velocity conditions, use of
electronic manometers may be necessary to obtain acceptable
measurements.
6.4.1 Differential pressure-measuring device. This refers to a
device capable of measuring pressure differentials and having a
readability of 1 percent of full scale. The device shall be
capable of accurately measuring the maximum expected pressure
differential. Such devices are used to determine the following pressure
measurements: velocity pressure, static pressure, yaw-null pressure, and
pitch-angle pressure. For an inclined-vertical manometer, the
readability specification of 1 percent shall be met
separately using the respective full-scale upper limits of the inclined
and vertical portions of the scales. To the extent practicable, the
device shall be selected such that most of the pressure readings are
between 10 and 90 percent of the device's full-scale measurement range
(as defined in section 3.5). Typical velocity pressure (P1-
P2) ranges for both the prism-shaped probe and the spherical
probe are 0 to 1.3 cm H2O (0 to 0.5 in. H2O), 0 to
5.1 cm H2O (0 to 2 in. H2O), and 0 to 12.7 cm
H2O (0 to 5 in. H2O). The pitch angle
(P4-P5) pressure range is typically -6.4 to +6.4
mm H2O (-0.25 to +0.25 in. H2O) or -12.7 to +12.7
mm H2O (-0.5 to +0.5 in. H2O) for the prism-shaped
probe, and -12.7 to +12.7 mm H2O (-0.5 to +0.5 in.
H2O) or -5.1 to +5.1 cm H2O (-2 to +2 in.
H2O) for the spherical probe. The pressure range for the yaw
null (P2-P3) readings is typically -12.7 to +12.7
mm H2O (-0.5 to +0.5 in. H2O) for both probe
types. In addition, pressure-measuring devices should be selected such
that the zero does not drift by more than 5 percent of the average
expected pressure readings to be encountered during the field test. This
is particularly important under low pressure conditions.
6.4.2 Gauge used for yaw nulling. The differential pressure-
measuring device chosen for yaw nulling the probe during the wind tunnel
calibrations and field testing shall be bi-directional, i.e., capable of
reading both positive and negative differential pressures. If a
mechanical, bi-directional pressure gauge is chosen, it shall have a
full-scale range no greater than 2.6 cm H2O (1 in.
H2O) [i.e., -1.3 to +1.3 cm H2O (-0.5 in. to +0.5
in.)].
6.4.3 Devices for calibrating differential pressure-measuring
devices. A precision manometer (e.g., a U-tube, inclined, or inclined-
vertical manometer, or micromanometer) or NIST (National Institute of
Standards and Technology) traceable pressure source shall be used for
calibrating differential pressure-measuring devices. The device shall be
maintained under laboratory conditions or in a similar protected
environment (e.g., a climate-controlled trailer). It shall not be used
in field tests. The precision manometer shall have a scale gradation of
0.3 mm H2O (0.01 in. H2O), or less, in the range
of 0 to 5.1 cm H2O (0 to 2 in. H2O) and 2.5 mm
H2O (0.1 in. H2O), or less, in the range of 5.1 to
25.4 cm H2O (2 to 10 in. H2O). The manometer shall
have manufacturer's documentation that it meets

[[Page 54]]

an accuracy specification of at least 0.5 percent of full scale. The
NIST-traceable pressure source shall be recertified annually.
6.4.4 Devices used for post-test calibration check. A precision
manometer meeting the specifications in section 6.4.3, a pressure-
measuring device or pressure source with a documented calibration
traceable to NIST, or an equivalent device approved by the Administrator
shall be used for the post-test calibration check. The pressure-
measuring device shall have a readability equivalent to or greater than
the tested device. The pressure source shall be capable of generating
pressures between 50 and 90 percent of the range of the tested device
and known to within 1 percent of the full scale of the
tested device. The pressure source shall be recertified annually.
6.5 Data Display and Capture Devices. Electronic manometers (if
used) shall be coupled with a data display device (such as a digital
panel meter, personal computer display, or strip chart) that allows the
tester to observe and validate the pressure measurements taken during
testing. They shall also be connected to a data recorder (such as a data
logger or a personal computer with data capture software) that has the
ability to compute and retain the appropriate average value at each
traverse point, identified by collection time and traverse point.
6.6 Temperature Gauges. For field tests, a thermocouple or
resistance temperature detector (RTD) capable of measuring temperature
to within 3 deg.C (5 deg.F) of the stack or duct
temperature shall be used. The thermocouple shall be attached to the
probe such that the sensor tip does not touch any metal and is located
on the opposite side of the probe head from the pressure ports so as not
to interfere with the gas flow around the probe head. The position of
the thermocouple relative to the pressure port face openings shall be in
the same configuration as used for the probe calibrations in the wind
tunnel. Temperature gauges used for wind tunnel calibrations shall be
capable of measuring temperature to within 0.6 deg.C
(1 deg.F) of the temperature of the flowing gas stream in
the wind tunnel.
6.7 Stack or Duct Static Pressure Measurement. The pressure-
measuring device used with the probe shall be as specified in section
6.4 of this method. The static tap of a standard (Prandtl type) pitot
tube or one leg of a Type S pitot tube with the face opening planes
positioned parallel to the gas flow may be used for this measurement.
Also acceptable is the pressure differential reading of P1-
Pbar from a five-hole prism-shaped probe (e.g., Type DA or
DAT probe) with the P1 pressure port face opening positioned
parallel to the gas flow in the same manner as the Type S probe.
However, the spherical probe, as specified in section 6.1.2, is unable
to provide this measurement and shall not be used to take static
pressure measurements. Static pressure measurement is further described
in section 8.11.
6.8 Barometer. Same as Method 2, section 2.5.
6.9 Gas Density Determination Equipment. Method 3 or 3A shall be
used to determine the dry molecular weight of the stack gas. Method 4
shall be used for moisture content determination and computation of
stack gas wet molecular weight. Other methods may be used, if approved
by the Administrator.
6.10 Calibration Pitot Tube. Same as Method 2, section 2.7.
6.11 Wind Tunnel for Probe Calibration. Wind tunnels used to
calibrate velocity probes must meet the following design specifications.
6.11.1 Test section cross-sectional area. The flowing gas stream
shall be confined within a circular, rectangular, or elliptical duct.
The cross-sectional area of the tunnel must be large enough to ensure
fully developed flow in the presence of both the calibration pitot tube
and the tested probe. The calibration site, or ``test section,'' of the
wind tunnel shall have a minimum diameter of 30.5 cm (12 in.) for
circular or elliptical duct cross-sections or a minimum width of 30.5 cm
(12 in.) on the shorter side for rectangular cross-sections. Wind
tunnels shall meet the probe blockage provisions of this section and the
qualification requirements prescribed in section 10.1. The projected
area of the portion of the probe head, shaft, and attached devices
inside the wind tunnel during calibration shall represent no more than 4
percent of the cross-sectional area of the tunnel. The projected area
shall include the combined area of the calibration pitot tube and the
tested probe if both probes are placed simultaneously in the same cross-
sectional plane in the wind tunnel, or the larger projected area of the
two probes if they are placed alternately in the wind tunnel.
6.11.2 Velocity range and stability. The wind tunnel should be
capable of maintaining velocities between 6.1 m/sec and 30.5 m/sec (20
ft/sec and 100 ft/sec). The wind tunnel shall produce fully developed
flow patterns that are stable and parallel to the axis of the duct in
the test section.
6.11.3 Flow profile at the calibration location. The wind tunnel
shall provide axial flow within the test section calibration location
(as defined in section 3.20). Yaw and pitch angles in the calibration
location shall be within 3 deg. of 0 deg.. The procedure for
determining that this requirement has been met is described in section
10.1.2.
6.11.4 Entry ports in the wind tunnel test section.
6.11.4.1 Port for tested probe. A port shall be constructed for the
tested probe. The port should have an elongated slot parallel to the

[[Page 55]]

axis of the duct at the test section. The elongated slot should be of
sufficient length to allow attaining all the pitch angles at which the
probe will be calibrated for use in the field. To facilitate alignment
of the probe during calibration, the test section should include a
window constructed of a transparent material to allow the tested probe
to be viewed. This port shall be located to allow the head of the tested
probe to be positioned within the calibration location (as defined in
section 3.20) at all pitch angle settings.
6.11.4.2 Port for verification of axial flow. Depending on the
equipment selected to conduct the axial flow verification prescribed in
section 10.1.2, a second port, located 90 deg. from the entry port for
the tested probe, may be needed to allow verification that the gas flow
is parallel to the central axis of the test section. This port should be
located and constructed so as to allow one of the probes described in
section 10.1.2.2 to access the same test point(s) that are accessible
from the port described in section 6.11.4.1.
6.11.4.3 Port for calibration pitot tube. The calibration pitot
tube shall be used in the port for the tested probe or a separate entry
port. In either case, all measurements with the calibration pitot tube
shall be made at the same point within the wind tunnel over the course
of a probe calibration. The measurement point for the calibration pitot
tube shall meet the same specifications for distance from the wall and
for axial flow as described in section 3.20 for the wind tunnel
calibration location.
6.11.5 Pitch angle protractor plate. A protractor plate shall be
attached directly under the port used with the tested probe and set in a
fixed position to indicate the pitch angle position of the probe
relative to the longitudinal axis of the wind tunnel duct (similar to
Figure 2F-8). The protractor plate shall indicate angles in 5 deg.
increments with a minimum resolution of 2 deg.. The tested
probe shall be able to be locked into position at the desired pitch
angle delineated on the protractor. The probe head position shall be
maintained within the calibration location (as defined in section 3.20)
in the test section of the wind tunnel during all tests across the range
of pitch angles.

7.0 Reagents and Standards. [Reserved]

8.0 Sample Collection and Analysis

8.1 Equipment Inspection and Set-Up

8.1.1 All probes, differential pressure-measuring devices, yaw
angle-measuring devices, thermocouples, and barometers shall have a
current, valid calibration before being used in a field test. (See
sections 10.3.3, 10.3.4, and 10.5 through10.10 for the applicable
calibration requirements.)
8.1.2 Before each field use of a 3-D probe, perform a visual
inspection to verify the physical condition of the probe head according
to the procedures in section 10.2. Record the inspection results on a
form similar to Table 2F-1. If there is visible damage to the 3-D probe,
the probe shall not be used until it is recalibrated.
8.1.3 After verifying that the physical condition of the probe head
is acceptable, set up the apparatus using lengths of flexible tubing
that are as short as practicable. Surge tanks installed between the
probe and pressure-measuring device may be used to dampen pressure
fluctuations provided that an adequate measurement response time (see
section 8.8) is maintained.
8.2 Horizontal Straightness Check. A horizontal straightness check
shall be performed before the start of each field test, except as
otherwise specified in this section. Secure the fully assembled probe
(including the probe head and all probe shaft extensions) in a
horizontal position using a stationary support at a point along the
probe shaft approximating the location of the stack or duct entry port
when the probe is sampling at the farthest traverse point from the stack
or duct wall. The probe shall be rotated to detect bends. Use an angle-
measuring device or trigonometry to determine the bend or sag between
the probe head and the secured end. (See Figure 2F-9.) Probes that are
bent or sag by more than 5 deg. shall not be used. Although this check
does not apply when the probe is used for a vertical traverse, care
should be taken to avoid the use of bent probes when conducting vertical
traverses. If the probe is constructed of a rigid steel material and
consists of a main probe without probe extensions, this check need only
be performed before the initial field use of the probe, when the probe
is recalibrated, when a change is made to the the design or material of
the probe assembly, and when the probe becomes bent. With such probes, a
visual inspection shall be made of the fully assembled probe before each
field test to determine if a bend is visible. The probe shall be rotated
to detect bends. The inspection results shall be documented in the field
test report. If a bend in the probe is visible, the horizontal
straightness check shall be performed before the probe is used.
8.3 Rotational Position Check. Before each field test, and each time
an extension is added to the probe during a field test, a rotational
position check shall be performed on all manually operated probes
(except as noted in section 8.3.5, below) to ensure that, throughout
testing, the angle-measuring device is either: aligned to within
1 deg. of the rotational position of the reference scribe
line; or is affixed to the probe such that the rotational offset of the
device from the reference scribe line is known to within
1 deg.. This check shall consist of direct measurements of
the rotational positions of the reference scribe line and angle-
measuring device sufficient to

[[Page 56]]

verify that these specifications are met. Annex A in section 18 of this
method gives recommended procedures for performing the rotational
position check, and Table 2F-2 gives an example data form. Procedures
other than those recommended in Annex A in section 18 may be used,
provided they demonstrate whether the alignment specification is met and
are explained in detail in the field test report.
8.3.1 Angle-measuring device rotational offset. The tester shall
maintain a record of the angle-measuring device rotational offset,
RADO, as defined in section 3.1. Note that RADO is
assigned a value of 0 deg. when the angle-measuring device is aligned to
within 1 deg. of the rotational position of the reference
scribe line. The RADO shall be used to determine the yaw
angle of flow in accordance with section 8.9.4.
8.3.2 Sign of angle-measuring device rotational offset. The sign of
RADO is positive when the angle-measuring device (as viewed
from the ``tail'' end of the probe) is positioned in a clockwise
direction from the reference scribe line and negative when the device is
positioned in a counterclockwise direction from the reference scribe
line.
8.3.3 Angle-measuring devices that can be independently adjusted
(e.g., by means of a set screw), after being locked into position on the
probe sheath, may be used. However, the RADO must also take
into account this adjustment.
8.3.4 Post-test check. If probe extensions remain attached to the
main probe throughout the field test, the rotational position check
shall be repeated, at a minimum, at the completion of the field test to
ensure that the angle-measuring device has remained within
2 deg. of its rotational position established prior to
testing. At the discretion of the tester, additional checks may be
conducted after completion of testing at any sample port or after any
test run. If the 2 deg. specification is not met, all
measurements made since the last successful rotational position check
must be repeated. Section 18.1.1.3 of Annex A provides an example
procedure for performing the post-test check.
8.3.5 Exceptions.
8.3.5.1 A rotational position check need not be performed if, for
measurements taken at all velocity traverse points, the yaw angle-
measuring device is mounted and aligned directly on the reference scribe
line specified in sections 6.1.6.1 and 6.1.6.3 and no independent
adjustments, as described in section 8.3.3, are made to the device's
rotational position.
8.3.5.2 If extensions are detached and re-attached to the probe
during a field test, a rotational position check need only be performed
the first time an extension is added to the probe, rather than each time
the extension is re-attached, if the probe extension is designed to be
locked into a mechanically fixed rotational position (e.g., through use
of interlocking grooves) that can re-establish the initial rotational
position to within 1 deg..
8.4 Leak Checks. A pre-test leak check shall be conducted before
each field test. A post-test check shall be performed at the end of the
field test, but additional leak checks may be conducted after any test
run or group of test runs. The post-test check may also serve as the
pre-test check for the next group of test runs. If any leak check is
failed, all runs since the last passed leak check are invalid. While
performing the leak check procedures, also check each pressure device's
responsiveness to the changes in pressure.
8.4.1 To perform the leak check, pressurize the probe's
P1 pressure port until at least 7.6 cm H2O (3 in.
H2O) pressure, or a pressure corresponding to approximately
75 percent of the pressure-measuring device's measurement scale,
whichever is less, registers on the device; then, close off the pressure
port. The pressure shall remain stable [2.5 mm
H2O (0.10 in. H2O)] for at least 15
seconds. Check the P2, P3, P4, and
P5 pressure ports in the same fashion. Other leak-check
procedures may be used, if approved by the Administrator.
8.5 Zeroing the Differential Pressure-measuring Device. Zero each
differential pressure-measuring device, including the device used for
yaw nulling, before each field test. At a minimum, check the zero after
each field test. A zero check may also be performed after any test run
or group of test runs. For fluid manometers and mechanical pressure
gauges (e.g., Magnehelic gauges), the
zero reading shall not deviate from zero by more than 0.8 mm
H2O (0.03 in. H2O) or one minor scale
division, whichever is greater, between checks. For electronic
manometers, the zero reading shall not deviate from zero between checks
by more than: 0.3 mm H2O (0.01 in.
H2O), for full scales less than or equal to 5.1 cm
H2O (2.0 in. H2O); or 0.8 mm
H2O (0.03 in. H2O), for full scales
greater than 5.1 cm H2O (2.0 in. H2O). (Note: If
negative zero drift is not directly readable, estimate the reading based
on the position of the gauge oil in the manometer or of the needle on
the pressure gauge.) In addition, for all pressure-measuring devices
except those used exclusively for yaw nulling, the zero reading shall
not deviate from zero by more than 5 percent of the average measured
differential pressure at any distinct process condition or load level.
If any zero check is failed at a specific process condition or load
level, all runs conducted at that process condition or load level since
the last passed zero check are invalid.
8.6 Traverse Point Verification. The number and location of the
traverse points shall be selected based on Method 1 guidelines. The
stack or duct diameter and port nipple lengths, including any extension
of the port

[[Page 57]]

nipples into stack or duct, shall be verified the first time the test is
performed; retain and use this information for subsequent field tests,
updating it as required. Physically measure the stack or duct dimensions
or use a calibrated laser device; do not use engineering drawings of the
stack or duct. The probe length necessary to reach each traverse point
shall be recorded to within 6.4 mm (1/4 in.)
and, for manual probes, marked on the probe sheath. In determining these
lengths, the tester shall take into account both the distance that the
port flange projects outside of the stack and the depth that any port
nipple extends into the gas stream. The resulting point positions shall
reflect the true distances from the inside wall of the stack or duct, so
that when the tester aligns any of the markings with the outside face of
the stack port, the probe's impact port shall be located at the
appropriate distance from the inside wall for the respective Method 1
traverse point. Before beginning testing at a particular location, an
out-of-stack or duct verification shall be performed on each probe that
will be used to ensure that these position markings are correct. The
distances measured during the verification must agree with the
previously calculated distances to within 1/4 in. For manual
probes, the traverse point positions shall be verified by measuring the
distance of each mark from the probe's P1 pressure port. A
comparable out-of-stack test shall be performed on automated probe
systems. The probe shall be extended to each of the prescribed traverse
point positions. Then, the accuracy of the positioning for each traverse
point shall be verified by measuring the distance between the port
flange and the probe's P1 pressure port.
8.7 Probe Installation. Insert the probe into the test port. A
solid material shall be used to seal the port.
8.8 System Response Time. Determine the response time of the probe
measurement system. Insert and position the ``cold'' probe (at ambient
temperature and pressure) at any Method 1 traverse point. Read and
record the probe's P1-P2 differential pressure,
temperature, and elapsed time at 15-second intervals until stable
readings for both pressure and temperature are achieved. The response
time is the longer of these two elapsed times. Record the response time.
8.9 Sampling.
8.9.1 Yaw angle measurement protocol. With manual probes, yaw angle
measurements may be obtained in two alternative ways during the field
test, either by using a yaw angle-measuring device (e.g., digital
inclinometer) affixed to the probe, or using a protractor wheel and
pointer assembly. For horizontal traversing, either approach may be
used. For vertical traversing, i.e., when measuring from on top or into
the bottom of a horizontal duct, only the protractor wheel and pointer
assembly may be used. With automated probes, curve-fitting protocols may
be used to obtain yaw-angle measurements.
8.9.1.1 If a yaw angle-measuring device affixed to the probe is to
be used, lock the device on the probe sheath, aligning it either on the
reference scribe line or in the rotational offset position established
under section 8.3.1.
8.9.1.2 If a protractor wheel and pointer assembly is to be used,
follow the procedures in Annex B of this method.
8.9.1.3 Other yaw angle-determination procedures. If approved by
the Administrator, other procedures for determining yaw angle may be
used, provided that they are verified in a wind tunnel to be able to
perform the yaw angle calibration procedure as described in section
10.5.
8.9.2 Sampling strategy. At each traverse point, first yaw-null the
probe, as described in section 8.9.3, below. Then, with the probe
oriented into the direction of flow, measure and record the yaw angle,
the differential pressures and the temperature at the traverse point,
after stable readings are achieved, in accordance with sections 8.9.4
and 8.9.5. At the start of testing in each port (i.e., after a probe has
been inserted into the flue gas stream), allow at least the response
time to elapse before beginning to take measurements at the first
traverse point accessed from that port. Provided that the probe is not
removed from the flue gas stream, measurements may be taken at
subsequent traverse points accessed from the same test port without
waiting again for the response time to elapse.
8.9.3 Yaw-nulling procedure. In preparation for yaw angle
determination, the probe must first be yaw nulled. After positioning the
probe at the appropriate traverse point, perform the following
procedures.
8.9.3.1 Rotate the probe until a null differential pressure reading
(the difference in pressures across the P2 and P3
pressure ports is zero, i.e., P2 = P3) is
indicated by the yaw angle pressure gauge. Read and record the angle
displayed by the angle-measuring device.
8.9.3.2 Sign of the measured angle. The angle displayed on the
angle-measuring device is considered positive when the probe's impact
pressure port (as viewed from the ``tail'' end of the probe) is oriented
in a clockwise rotational position relative to the stack or duct axis
and is considered negative when the probe's impact pressure port is
oriented in a counterclockwise rotational position (see Figure 2F-10).
8.9.4 Yaw angle determination. After performing the yaw-nulling
procedure in section

[[Page 58]]

8.9.3, determine the yaw angle of flow according to one of the following
procedures. Special care must be observed to take into account the signs
of the recorded angle and all offsets.
8.9.4.1 Direct-reading. If all rotational offsets are zero or if
the angle-measuring device rotational offset (RADO)
determined in section 8.3 exactly compensates for the scribe line
rotational offset (RSLO) determined in section 10.5, then the
magnitude of the yaw angle is equal to the displayed angle-measuring
device reading from section 8.9.3.1. The algebraic sign of the yaw angle
is determined in accordance with section 8.9.3.2.

Note: Under certain circumstances (e.g., testing of horizontal
ducts), a 90 deg. adjustment to the angle-measuring device readings may
be necessary to obtain the correct yaw angles.

8.9.4.2 Compensation for rotational offsets during data reduction.
When the angle-measuring device rotational offset does not compensate
for reference scribe line rotational offset, the following procedure
shall be used to determine the yaw angle:
(a) Enter the reading indicated by the angle-measuring device from
section 8.9.3.1.
(b) Associate the proper algebraic sign from section 8.9.3.2 with
the reading in step (a).
(c) Subtract the reference scribe line rotational offset,
RSLO, from the reading in step (b).
(d) Subtract the angle-measuring device rotational offset,
RADO, if any, from the result obtained in step (c).
(e) The final result obtained in step (d) is the yaw angle of flow.

Note: It may be necessary to first apply a 90 deg. adjustment to the
reading in step (a), in order to obtain the correct yaw angle.

8.9.4.3 Record the yaw angle measurements on a form similar to
Table 2F-3.
8.9.5 Velocity determination. Maintain the probe rotational
position established during the yaw angle determination. Then, begin
recording the pressure-measuring device readings for the impact pressure
(P1-P2) and pitch angle pressure (P4-
P5). These pressure measurements shall be taken over a
sampling period of sufficiently long duration to ensure representative
readings at each traverse point. If the pressure measurements are
determined from visual readings of the pressure device or display, allow
sufficient time to observe the pulsation in the readings to obtain a
sight-weighted average, which is then recorded manually. If an automated
data acquisition system (e.g., data logger, computer-based data
recorder, strip chart recorder) is used to record the pressure
measurements, obtain an integrated average of all pressure readings at
the traverse point. Stack or duct gas temperature measurements shall be
recorded, at a minimum, once at each traverse point. Record all
necessary data as shown in the example field data form (Table 2F-3).
8.9.6 Alignment check. For manually operated probes, after the
required yaw angle and differential pressure and temperature
measurements have been made at each traverse point, verify (e.g., by
visual inspection) that the yaw angle-measuring device has remained in
proper alignment with the reference scribe line or with the rotational
offset position established in section 8.3. If, for a particular
traverse point, the angle-measuring device is found to be in proper
alignment, proceed to the next traverse point; otherwise, re-align the
device and repeat the angle and differential pressure measurements at
the traverse point. In the course of a traverse, if a mark used to
properly align the angle-measuring device (e.g., as described in section
18.1.1.1) cannot be located, re-establish the alignment mark before
proceeding with the traverse.
8.10 Probe Plugging. Periodically check for plugging of the
pressure ports by observing the responses on pressure differential
readouts. Plugging causes erratic results or sluggish responses. Rotate
the probe to determine whether the readouts respond in the expected
direction. If plugging is detected, correct the problem and repeat the
affected measurements.
8.11 Static Pressure. Measure the static pressure in the stack or
duct using the equipment described in section 6.7.
8.11.1 If a Type DA or DAT probe is used for this measurement,
position the probe at or between any traverse point(s) and rotate the
probe until a null differential pressure reading is obtained at
P2-P3. Rotate the probe 90 deg.. Disconnect the
P2 pressure side of the probe and read the pressure
P1-Pbar and record as the static pressure. (Note:
The spherical probe, specified in section 6.1.2, is unable to provide
this measurement and shall not be used to take static pressure
measurements.)
8.11.2 If a Type S probe is used for this measurement, position the
probe at or between any traverse point(s) and rotate the probe until a
null differential pressure reading is obtained. Disconnect the tubing
from one of the pressure ports; read and record the P. For
pressure devices with one-directional scales, if a deflection in the
positive direction is noted with the negative side disconnected, then
the static pressure is positive. Likewise, if a deflection in the
positive direction is noted with the positive side disconnected, then
the static pressure is negative.
8.12 Atmospheric Pressure. Determine the atmospheric pressure at
the sampling elevation during each test run following the procedure
described in section 2.5 of Method 2.

[[Page 59]]

8.13 Molecular Weight. Determine the stack gas dry molecular
weight. For combustion processes or processes that emit essentially
CO2, O2, CO, and N2, use Method 3 or
3A. For processes emitting essentially air, an analysis need not be
conducted; use a dry molecular weight of 29.0. Other methods may be
used, if approved by the Administrator.
8.14 Moisture. Determine the moisture content of the stack gas
using Method 4 or equivalent.
8.15 Data Recording and Calculations. Record all required data on a
form similar to Table 2F-3.
8.15.1 Selection of appropriate calibration curves. Choose the
appropriate pair of F1 and F2 versus pitch angle
calibration curves, created as described in section 10.6.
8.15.2 Pitch angle derivation. Use the appropriate calculation
procedures in section 12.2 to find the pitch angle ratios that are
applicable at each traverse point. Then, find the pitch angles
corresponding to these pitch angle ratios on the ``F1 versus
pitch angle'' curve for the probe.
8.15.3 Velocity calibration coefficient derivation. Use the pitch
angle obtained following the procedures described in section 8.15.2 to
find the corresponding velocity calibration coefficients from the
``F2 versus pitch angle'' calibration curve for the probe.
8.15.4 Calculations. Calculate the axial velocity at each traverse
point using the equations presented in section 12.2 to account for the
yaw and pitch angles of flow. Calculate the test run average stack gas
velocity by finding the arithmetic average of the point velocity results
in accordance with sections 12.3 and 12.4, and calculate the stack gas
volumetric flow rate in accordance with section 12.5 or 12.6, as
applicable.

9.0 Quality Control

9.1 Quality Control Activities. In conjunction with the yaw angle
determination and the pressure and temperature measurements specified in
section 8.9, the following quality control checks should be performed.
9.1.1 Range of the differential pressure gauge. In accordance with
the specifications in section 6.4, ensure that the proper differential
pressure gauge is being used for the range of P values
encountered. If it is necessary to change to a more sensitive gauge,
replace the gauge with a gauge calibrated according to section 10.3.3,
perform the leak check described in section 8.4 and the zero check
described in section 8.5, and repeat the differential pressure and
temperature readings at each traverse point.
9.1.2 Horizontal stability check. For horizontal traverses of a
stack or duct, visually check that the probe shaft is maintained in a
horizontal position prior to taking a pressure reading. Periodically,
during a test run, the probe's horizontal stability should be verified
by placing a carpenter's level, a digital inclinometer, or other angle-
measuring device on the portion of the probe sheath that extends outside
of the test port. A comparable check should be performed by automated
systems.

10.0 Calibration

10.1 Wind Tunnel Qualification Checks. To qualify for use in
calibrating probes, a wind tunnel shall have the design features
specified in section 6.11 and satisfy the following qualification
criteria. The velocity pressure cross-check in section 10.1.1 and axial
flow verification in section 10.1.2 shall be performed before the
initial use of the wind tunnel and repeated immediately after any
alteration occurs in the wind tunnel's configuration, fans, interior
surfaces, straightening vanes, controls, or other properties that could
reasonably be expected to alter the flow pattern or velocity stability
in the tunnel. The owner or operator of a wind tunnel used to calibrate
probes according to this method shall maintain records documenting that
the wind tunnel meets the requirements of sections 10.1.1 and 10.1.2 and
shall provide these records to the Administrator upon request.
10.1.1 Velocity pressure cross-check. To verify that the wind
tunnel produces the same velocity at the tested probe head as at the
calibration pitot tube impact port, perform the following cross-check.
Take three differential pressure measurements at the fixed calibration
pitot tube location, using the calibration pitot tube specified in
section 6.10, and take three measurements with the calibration pitot
tube at the wind tunnel calibration location, as defined in section
3.20. Alternate the measurements between the two positions. Perform this
procedure at the lowest and highest velocity settings at which the
probes will be calibrated. Record the values on a form similar to Table
2F-4. At each velocity setting, the average velocity pressure obtained
at the wind tunnel calibration location shall be within 2
percent or 2.5 mm H2O (0.01 in. H2O), whichever is
less restrictive, of the average velocity pressure obtained at the fixed
calibration pitot tube location. This comparative check shall be
performed at 2.5-cm (1-in.), or smaller, intervals across the full
length, width, and depth (if applicable) of the wind tunnel calibration
location. If the criteria are not met at every tested point, the wind
tunnel calibration location must be redefined, so that acceptable
results are obtained at every point. Include the results of the velocity
pressure cross-check in the calibration data section of the field test
report. (See section 16.1.4.)
10.1.2 Axial flow verification. The following procedures shall be
performed to demonstrate that there is fully developed axial flow within
the calibration location

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and at the calibration pitot tube location. Two testing options are
available to conduct this check.
10.1.2.1 Using a calibrated 3-D probe. A 3-D probe that has been
previously calibrated in a wind tunnel with documented axial flow (as
defined in section 3.21) may be used to conduct this check. Insert the
calibrated 3-D probe into the wind tunnel test section using the tested
probe port. Following the procedures in sections 8.9 and 12.2 of this
method, determine the yaw and pitch angles at all the point(s) in the
test section where the velocity pressure cross-check, as specified in
section 10.1.1, is performed. This includes all the points in the
calibration location and the point where the calibration pitot tube will
be located. Determine the yaw and pitch angles at each point. Repeat
these measurements at the highest and lowest velocities at which the
probes will be calibrated. Record the values on a form similar to Table
2F-5. Each measured yaw and pitch angle shall be within
3 deg. of 0 deg.. Exceeding the limits indicates
unacceptable flow in the test section. Until the problem is corrected
and acceptable flow is verified by repetition of this procedure, the
wind tunnel shall not be used for calibration of probes. Include the
results of the axial flow verification in the calibration data section
of the field test report. (See section 16.1.4.)
10.1.2.2 Using alternative probes. Axial flow verification may be
performed using an uncalibrated prism-shaped 3-D probe (e.g., DA or DAT
probe) or an uncalibrated wedge probe. (Figure 2F-11 illustrates a
typical wedge probe.) This approach requires use of two ports: the
tested probe port and a second port located 90 deg. from the tested
probe port. Each port shall provide access to all the points within the
wind tunnel test section where the velocity pressure cross-check, as
specified in section 10.1.1, is conducted. The probe setup shall include
establishing a reference yaw-null position on the probe sheath to serve
as the location for installing the angle-measuring device. Physical
design features of the DA, DAT, and wedge probes are relied on to
determine the reference position. For the DA or DAT probe, this
reference position can be determined by setting a digital inclinometer
on the flat facet where the P1 pressure port is located and
then identifying the rotational position on the probe sheath where a
second angle-measuring device would give the same angle reading. The
reference position on a wedge probe shaft can be determined either
geometrically or by placing a digital inclinometer on each side of the
wedge and rotating the probe until equivalent readings are obtained.
With the latter approach, the reference position is the rotational
position on the probe sheath where an angle-measuring device would give
a reading of 0 deg.. After installing the angle-measuring device in the
reference yaw-null position on the probe sheath, determine the yaw angle
from the tested port. Repeat this measurement using the 90 deg. offset
port, which provides the pitch angle of flow. Determine the yaw and
pitch angles at all the point(s) in the test section where the velocity
pressure cross-check, as specified in section 10.1.1, is performed. This
includes all the points in the wind tunnel calibration location and the
point where the calibration pitot tube will be located. Perform this
check at the highest and lowest velocities at which the probes will be
calibrated. Record the values on a form similar to Table 2F-5. Each
measured yaw and pitch angle shall be within 3 deg. of
0 deg.. Exceeding the limits indicates unacceptable flow in the test
section. Until the problem is corrected and acceptable flow is verified
by repetition of this procedure, the wind tunnel shall not be used for
calibration of probes. Include the results in the probe calibration
report.
10.1.3 Wind tunnel audits.
10.1.3.1 Procedure. Upon the request of the Administrator, the
owner or operator of a wind tunnel shall calibrate a 3-D audit probe in
accordance with the procedures described in sections 10.3 through 10.6.
The calibration shall be performed at two velocities and over a pitch
angle range that encompasses the velocities and pitch angles typically
used for this method at the facility. The resulting calibration data and
curves shall be submitted to the Agency in an audit test report. These
results shall be compared by the Agency to reference calibrations of the
audit probe at the same velocity and pitch angle settings obtained at
two different wind tunnels.
10.1.3.2 Acceptance criteria. The audited tunnel's calibration is
acceptable if all of the following conditions are satisfied at each
velocity and pitch setting for the reference calibration obtained from
at least one of the wind tunnels. For pitch angle settings between
-15 deg. and +15 deg., no velocity calibration coefficient (i.e.,
F2) may differ from the corresponding reference value by more
than 3 percent. For pitch angle settings outside of this range (i.e.,
less than -15 deg. and greater than +15 deg.), no velocity calibration
coefficient may differ by more than 5 percent from the corresponding
reference value. If the acceptance criteria are not met, the audited
wind tunnel shall not be used to calibrate probes for use under this
method until the problems are resolved and acceptable results are
obtained upon completion of a subsequent audit.
10.2 Probe Inspection. Before each calibration of a 3-D probe,
carefully examine the physical condition of the probe head. Particular
attention shall be paid to the edges of the pressure ports and the
surfaces surrounding these ports. Any dents, scratches, or asymmetries
on the edges of the pressure ports and any scratches or indentations on

[[Page 61]]

the surfaces surrounding the pressure ports shall be noted because of
the potential effect on the probe's pressure readings. If the probe has
been previously calibrated, compare the current condition of the probe's
pressure ports and surfaces to the results of the inspection performed
during the probe's most recent wind tunnel calibration. Record the
results of this inspection on a form and in diagrams similar to Table
2F-1. The information in Table 2F-1 will be used as the basis for
comparison during the probe head inspections performed before each
subsequent field use.
10.3 Pre-Calibration Procedures. Prior to calibration, a scribe
line shall have been placed on the probe in accordance with section
10.4. The yaw angle and velocity calibration procedures shall not begin
until the pre-test requirements in sections 10.3.1 through 10.3.4 have
been met.
10.3.1 Perform the horizontal straightness check described in
section 8.2 on the probe assembly that will be calibrated in the wind
tunnel.
10.3.2 Perform a leak check in accordance with section 8.4.
10.3.3 Except as noted in section 10.3.3.3, calibrate all
differential pressure-measuring devices to be used in the probe
calibrations, using the following procedures. At a minimum, calibrate
these devices on each day that probe calibrations are performed.
10.3.3.1 Procedure. Before each wind tunnel use, all differential
pressure-measuring devices shall be calibrated against the reference
device specified in section 6.4.3 using a common pressure source.
Perform the calibration at three reference pressures representing 30,
60, and 90 percent of the full-scale range of the pressure-measuring
device being calibrated. For an inclined-vertical manometer, perform
separate calibrations on the inclined and vertical portions of the
measurement scale, considering each portion of the scale to be a
separate full-scale range. [For example, for a manometer with a 0- to
2.5-cm H2O (0- to 1-in. H2O) inclined scale and a
2.5- to 12.7-cm H2O (1- to 5-in. H2O) vertical
scale, calibrate the inclined portion at 7.6, 15.2, and 22.9 mm
H2O (0.3, 0.6, and 0.9 in. H2O), and calibrate the
vertical portion at 3.8, 7.6, and 11.4 cm H2O (1.5, 3.0, and
4.5 in. H2O).] Alternatively, for the vertical portion of the
scale, use three evenly spaced reference pressures, one of which is
equal to or higher than the highest differential pressure expected in
field applications.
10.3.3.2 Acceptance criteria. At each pressure setting, the two
pressure readings made using the reference device and the pressure-
measuring device being calibrated shall agree to within 2
percent of full scale of the device being calibrated or 0.5 mm
H2O (0.02 in. H2O), whichever is less restrictive.
For an inclined-vertical manometer, these requirements shall be met
separately using the respective full-scale upper limits of the inclined
and vertical portions of the scale. Differential pressure-measuring
devices not meeting the #2 percent of full scale or 0.5 mm
H2O (0.02 in. H2O) calibration requirement shall
not be used.
10.3.3.3 Exceptions. Any precision manometer that meets the
specifications for a reference device in section 6.4.3 and that is not
used for field testing does not require calibration, but must be leveled
and zeroed before each wind tunnel use. Any pressure device used
exclusively for yaw nulling does not require calibration, but shall be
checked for responsiveness to rotation of the probe prior to each wind
tunnel use.
10.3.4 Calibrate digital inclinometers on each day of wind tunnel
or field testing (prior to beginning testing) using the following
procedures. Calibrate the inclinometer according to the manufacturer's
calibration procedures. In addition, use a triangular block (illustrated
in Figure 2F-12) with a known angle, independently determined
using a protractor or equivalent device, between two adjacent sides to
verify the inclinometer readings.

Note: If other angle-measuring devices meeting the provisions of
section 6.2.3 are used in place of a digital inclinometer, comparable
calibration procedures shall be performed on such devices.)

Secure the triangular block in a fixed position. Place the inclinometer
on one side of the block (side A) to measure the angle of inclination
(R1). Repeat this measurement on the adjacent side of the
block (side B) using the inclinometer to obtain a second angle reading
(R2). The difference of the sum of the two readings from
180 deg. (i.e., 180 deg. -R1 -R2) shall be within
2 deg. of the known angle,
10.4 Placement of Reference Scribe Line. Prior to the first
calibration of a probe, a line shall be permanently inscribed on the
main probe sheath to serve as a reference mark for determining yaw
angles. Annex C in section 18 of this method gives a guideline for
placement of the reference scribe line.
10.4.1 This reference scribe line shall meet the specifications in
sections 6.1.6.1 and 6.1.6.3 of this method. To verify that the
alignment specification in section 6.1.6.3 is met, secure the probe in a
horizontal position and measure the rotational angle of each scribe line
and scribe line segment using an angle-measuring device that meets the
specifications in section 6.2.1 or 6.2.3. For any scribe line that is
longer than 30.5 cm (12 in.), check the line's rotational position at
30.5-cm (12-in.) intervals. For each line segment that is 30.5 cm (12
in.) or less in length, check the rotational position at the two
endpoints of the segment. To meet the alignment specification in section
6.1.6.3, the minimum and maximum of all of the rotational angles that
are measured along the full

[[Page 62]]

length of the main probe must not differ by more than 2 deg..

Note: A short reference scribe line segment [e.g., 15.2 cm (6 in.)
or less in length] meeting the alignment specifications in section
6.1.6.3 is fully acceptable under this method. See section 18.1.1.1 of
Annex A for an example of a probe marking procedure, suitable for use
with a short reference scribe line.

10.4.2 The scribe line should be placed on the probe first and then
its offset from the yaw-null position established (as specified in
section 10.5). The rotational position of the reference scribe line
relative to the yaw-null position of the probe, as determined by the yaw
angle calibration procedure in section 10.5, is defined as the reference
scribe line rotational offset, RSLO. The reference scribe
line rotational offset shall be recorded and retained as part of the
probe's calibration record.
10.4.3 Scribe line for automated probes. A scribe line may not be
necessary for an automated probe system if a reference rotational
position of the probe is built into the probe system design. For such
systems, a ``flat'' (or comparable, clearly identifiable physical
characteristic) should be provided on the probe casing or flange plate
to ensure that the reference position of the probe assembly remains in a
vertical or horizontal position. The rotational offset of the flat (or
comparable, clearly identifiable physical characteristic) needed to
orient the reference position of the probe assembly shall be recorded
and maintained as part of the automated probe system's specifications.
10.5 Yaw Angle Calibration Procedure. For each probe used to
measure yaw angles with this method, a calibration procedure shall be
performed in a wind tunnel meeting the specifications in section 10.1 to
determine the rotational position of the reference scribe line relative
to the probe's yaw-null position. This procedure shall be performed on
the main probe with all devices that will be attached to the main probe
in the field [such as thermocouples or resistance temperature detectors
(RTDs)] that may affect the flow around the probe head. Probe shaft
extensions that do not affect flow around the probe head need not be
attached during calibration. At a minimum, this procedure shall include
the following steps.
10.5.1 Align and lock the angle-measuring device on the reference
scribe line. If a marking procedure (such as that described in section
18.1.1.1) is used, align the angle-measuring device on a mark within
1 deg. of the rotational position of the reference scribe
line. Lock the angle-measuring device onto the probe sheath at this
position.
10.5.2 Zero the pressure-measuring device used for yaw nulling.
10.5.3 Insert the probe assembly into the wind tunnel through the
entry port, positioning the probe's impact port at the calibration
location. Check the responsiveness of the pressure-measurement device to
probe rotation, taking corrective action if the response is
unacceptable.
10.5.4 Ensure that the probe is in a horizontal position, using a
carpenter's level.
10.5.5 Rotate the probe either clockwise or counterclockwise until
a yaw null (P2 = P3) is obtained.
10.5.6 Use the reading displayed by the angle-measuring device at
the yaw-null position to determine the magnitude of the reference scribe
line rotational offset, RSLO, as defined in section 3.15.
Annex D in section 18 of this method provides a recommended procedure
for determining the magnitude of RSLO with a digital
inclinometer and a second procedure for determining the magnitude of
RSLO with a protractor wheel and pointer device. Table 2F-6
presents an example data form and Table 2F-7 is a look-up table with the
recommended procedure. Procedures other than those recommended in Annex
D in section 18 may be used, if they can determine RSLO to
within 1 deg. and are explained in detail in the field test
report. The algebraic sign of RSLO will either be positive,
if the rotational position of the reference scribe line (as viewed from
the ``tail'' end of the probe) is clockwise, or negative, if
counterclockwise with respect to the probe's yaw-null position. (This is
illustrated in Figure 2F-13.)
10.5.7 The steps in sections 10.5.3 through 10.5.6 shall be
performed twice at each of the velocities at which the probe will be
calibrated (in accordance with section 10.6). Record the values of
RSLO.
10.5.8 The average of all of the RSLO values shall be
documented as the reference scribe line rotational offset for the probe.
10.5.9 Use of reference scribe line offset. The reference scribe
line rotational offset shall be used to determine the yaw angle of flow
in accordance with section 8.9.4.
10.6 Pitch Angle and Velocity Pressure Calibrations. Use the
procedures in sections 10.6.1 through 10.6.16 to generate an appropriate
set (or sets) of pitch angle and velocity pressure calibration curves
for each probe. The calibration procedure shall be performed on the main
probe and all devices that will be attached to the main probe in the
field (e.g., thermocouple or RTDs) that may affect the flow around the
probe head. Probe shaft extensions that do not affect flow around the
probe head need not be attached during calibration. (Note: If a sampling
nozzle is part of the assembly, a wind tunnel demonstration shall be
performed that shows the probe's ability to measure velocity and yaw
null is not impaired when the nozzle is drawing a sample.) The
calibration

[[Page 63]]

procedure involves generating two calibration curves, F1
versus pitch angle and F2 versus pitch angle. To generate
these two curves, F1 and F2 shall be derived using
Equations 2F-1 and 2F-2, below. Table 2F-8 provides an example wind
tunnel calibration data sheet, used to log the measurements needed to
derive these two calibration curves.
10.6.1 Calibration velocities. The tester may calibrate the probe
at two nominal wind tunnel velocity settings of 18.3 m/sec and 27.4 m/
sec (60 ft/sec and 90 ft/sec) and average the results of these
calibrations, as described in section 10.6.16.1, in order to generate a
set of calibration curves. If this option is selected, this single set
of calibration curves may be used for all field applications over the
entire velocity range allowed by the method. Alternatively, the tester
may customize the probe calibration for a particular field test
application (or for a series of applications), based on the expected
average velocity(ies) at the test site(s). If this option is selected,
generate each set of calibration curves by calibrating the probe at two
nominal wind tunnel velocity settings, at least one of which is greater
than or equal to the expected average velocity(ies) for the field
application(s), and average the results as described in section
10.6.16.1. Whichever calibration option is selected, the probe
calibration coefficients (F2 values) obtained at the two
nominal calibration velocities shall, for the same pitch angle setting,
meet the conditions specified in section 10.6.16.
10.6.2 Pitch angle calibration curve (F1 versus pitch
angle). The pitch angle calibration involves generating a calibration
curve of calculated F1 values versus tested pitch angles,
where F1 is the ratio of the pitch pressure to the velocity
pressure, i.e.,
[GRAPHIC] [TIFF OMITTED] TR14MY99.049

See Figure 2F-14 for an example F1 versus pitch angle
calibration curve.
10.6.3 Velocity calibration curve (F2 versus pitch
angle). The velocity calibration involves generating a calibration curve
of the 3-D probe's F2 coefficient against the tested pitch
angles, where
[GRAPHIC] [TIFF OMITTED] TR14MY99.050

and

Cp = calibration pitot tube coefficient, and
Pstd = velocity pressure from the calibration pitot
tube.

See Figure 2F-15 for an example F2 versus pitch angle
calibration curve.
10.6.4 Connect the tested probe and calibration pitot probe to
their respective pressure-measuring devices. Zero the pressure-measuring
devices. Inspect and leak-check all pitot lines; repair or replace, if
necessary. Turn on the fan, and allow the wind tunnel air flow to
stabilize at the first of the two selected nominal velocity settings.
10.6.5 Position the calibration pitot tube at its measurement
location (determined as outlined in section 6.11.4.3), and align the
tube so that its tip is pointed directly into the flow. Ensure that the
entry port surrounding the tube is properly sealed. The calibration
pitot tube may either remain in the wind tunnel throughout the
calibration, or be removed from the wind tunnel while measurements are
taken with the probe being calibrated.
10.6.6 Set up the pitch protractor plate on the tested probe's
entry port to establish the pitch angle positions of the probe to within
2 deg..
10.6.7 Check the zero setting of each pressure-measuring device.
10.6.8 Insert the tested probe into the wind tunnel and align it so
that its P1 pressure port is pointed directly into the flow
and is positioned within the calibration location (as defined in section
3.20). Secure the probe at the 0 deg. pitch angle position. Ensure that
the entry port surrounding the probe is properly sealed.
10.6.9 Read the differential pressure from the calibration pitot
tube (Pstd), and record its value. Read the
barometric pressure to within 2.5 mm Hg (0.1 in.
Hg) and the temperature in the wind tunnel to within 0.6 deg.C
(1 deg.F). Record these values on a data form similar to Table 2F-8.
10.6.10 After the tested probe's differential pressure gauges have
had sufficient time to stabilize, yaw null the probe, then obtain
differential pressure readings for (P1-P2) and
(P4-P5). Record the yaw angle and differential
pressure readings. After taking these readings, ensure that the tested
probe has remained at the yaw-null position.
10.6.11 Either take paired differential pressure measurements with
both the calibration pitot tube and tested probe (according to sections
10.6.9 and 10.6.10) or take readings only with the tested probe
(according to section 10.6.10) in 5 deg. increments over the pitch-angle
range for which the probe is to be calibrated. The calibration pitch-
angle range shall be symmetric around 0 deg. and shall exceed the
largest pitch angle expected in the field by 5 deg.. At a minimum,
probes shall be calibrated over the range of -15 deg. to +15 deg.. If
paired calibration pitot tube and tested probe measurements are not
taken at each pitch angle setting, the differential pressure from the
calibration pitot tube shall be read, at a minimum, before taking the
tested probe's differential pressure reading at the first pitch angle
setting and after taking the

[[Page 64]]

tested probe's differential pressure readings at the last pitch angle
setting in each replicate.
10.6.12 Perform a second replicate of the procedures in sections
10.6.5 through 10.6.11 at the same nominal velocity setting.
10.6.13 For each replicate, calculate the F1 and
F2 values at each pitch angle. At each pitch angle, calculate
the percent difference between the two F2 values using
Equation 2F-3.
[GRAPHIC] [TIFF OMITTED] TR14MY99.051

If the percent difference is less than or equal to 2 percent,
calculate an average F1 value and an average F2
value at that pitch angle. If the percent difference is greater than 2
percent and less than or equal to 5 percent, perform a third repetition
at that angle and calculate an average F1 value and an
average F2 value using all three repetitions. If the percent
difference is greater than 5 percent, perform four additional
repetitions at that angle and calculate an average F1 value
and an average F2 value using all six repetitions. When
additional repetitions are required at any pitch angle, move the probe
by at least 5 deg. and then return to the specified pitch angle before
taking the next measurement. Record the average values on a form similar
to Table 2F-9.
10.6.14 Repeat the calibration procedures in sections 10.6.5
through 10.6.13 at the second selected nominal wind tunnel velocity
setting.
10.6.15 Velocity drift check. The following check shall be
performed, except when paired calibration pitot tube and tested probe
pressure measurements are taken at each pitch angle setting. At each
velocity setting, calculate the percent difference between consecutive
differential pressure measurements made with the calibration pitot tube.
If a measurement differs from the previous measurement by more than 2
percent or 0.25 mm H2O (0.01 in. H2O), whichever
is less restrictive, the calibration data collected between these
calibration pitot tube measurements may not be used, and the
measurements shall be repeated.
10.6.16 Compare the averaged F2 coefficients obtained
from the calibrations at the two selected nominal velocities, as
follows. At each pitch angle setting, use Equation 2F-3 to calculate the
difference between the corresponding average F2 values at the
two calibration velocities. At each pitch angle in the -15 deg. to
+15 deg. range, the percent difference between the average F2
values shall not exceed 3.0 percent. For pitch angles outside this range
(i.e., less than -15 deg.0 and greater than +15 deg.), the percent
difference shall not exceed 5.0 percent.
10.6.16.1 If the applicable specification in section 10.6.16 is met
at each pitch angle setting, average the results obtained at the two
nominal calibration velocities to produce a calibration record of
F1 and F2 at each pitch angle tested. Record these
values on a form similar to Table 2F-9. From these values, generate one
calibration curve representing F1 versus pitch angle and a
second curve representing F2 versus pitch angle. Computer
spreadsheet programs may be used to graph the calibration data and to
develop polynomial equations that can be used to calculate pitch angles
and axial velocities.
10.6.16.2 If the applicable specification in section 10.6.16 is
exceeded at any pitch angle setting, the probe shall not be used unless:
(1) the calibration is repeated at that pitch angle and acceptable
results are obtained or (2) values of F1 and F2
are obtained at two nominal velocities for which the specifications in
section 10.6.16 are met across the entire pitch angle range.
10.7 Recalibration. Recalibrate the probe using the procedures in
section 10 either within 12 months of its first field use after its most
recent calibration or after 10 field tests (as defined in section 3.4),
whichever occurs later. In addition, whenever there is visible damage to
the 3-D head, the probe shall be recalibrated before it is used again.
10.8 Calibration of pressure-measuring devices used in field tests.
Before its initial use in a field test, calibrate each pressure-
measuring device (except those used exclusively for yaw nulling) using
the three-point calibration procedure described in section 10.3.3. The
device shall be recalibrated according to the procedure in section
10.3.3 no later than 90 days after its first field use following its
most recent calibration. At the discretion of the tester, more frequent
calibrations (e.g., after a field test) may be performed. No
adjustments, other than adjustments to the zero setting, shall be made
to the device between calibrations.
10.8.1 Post-test calibration check. A single-point calibration
check shall be performed on each pressure-measuring device after
completion of each field test. At the discretion of the tester, more
frequent single-point calibration checks (e.g., after one or more field
test runs) may be performed. It is recommended that the post-test check
be performed before leaving the field test site. The check shall be
performed at a pressure between 50 and 90 percent of full scale by
taking a common pressure reading with the tested device and a reference
pressure-measuring device (as described in section 6.4.4) or by
challenging the tested device with a reference pressure source (as
described in section 6.4.4) or by performing an equivalent check using a
reference device approved by the Administrator.
10.8.2 Acceptance criterion. At the selected pressure setting, the
pressure readings

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made using the reference device and the tested device shall agree to
within 3 percent of full scale of the tested device or 0.8 mm
H2O (0.03 in. H2O), whichever is less restrictive.
If this specification is met, the test data collected during the field
test are valid. If the specification is not met, all test data collected
since the last successful calibration or calibration check are invalid
and shall be repeated using a pressure-measuring device with a current,
valid calibration. Any device that fails the calibration check shall not
be used in a field test until a successful recalibration is performed
according to the procedures in section 10.3.3.
10.9 Temperature Gauges. Same as Method 2, section 4.3. The
alternative thermocouple calibration procedures outlined in Emission
Measurement Center (EMC) Approved Alternative Method (ALT-011)
``Alternative Method 2 Thermocouple Calibration Procedure'' may be
performed. Temperature gauges shall be calibrated no more than 30 days
prior to the start of a field test or series of field tests and
recalibrated no more than 30 days after completion of a field test or
series of field tests.
10.10 Barometer. Same as Method 2, section 4.4. The barometer shall
be calibrated no more than 30 days prior to the start of a field test or
series of field tests.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

These calculations use the measured yaw angle, derived pitch angle,
and the differential pressure and temperature measurements at individual
traverse points to derive the axial flue gas velocity (va(i))
at each of those points. The axial velocity values at all traverse
points that comprise a full stack or duct traverse are then averaged to
obtain the average axial flue gas velocity (va (avg)). Round
off figures only in the final calculation of reported values.

12.1 Nomenclature

A = Cross-sectional area of stack or duct, m \2\ (ft \2\).
Bws = Water vapor in the gas stream (from Method 4 or
alternative), proportion by volume.
Kp Conversion factor (a constant),
[GRAPHIC] [TIFF OMITTED] TR14MY99.052

for the metric system, and
[GRAPHIC] [TIFF OMITTED] TR14MY99.053

for the English system.

Md = Molecular weight of stack or duct gas, dry basis (see
section 8.13), g/g-mole (lb/lb-mole).
Ms = Molecular weight of stack or duct gas, wet basis, g/g-
mole (lb/lb-mole).
[GRAPHIC] [TIFF OMITTED] TR14MY99.054

Pbar = Barometric pressure at measurement site, mm Hg (in.
Hg).
Pg = Stack or duct static pressure, mm H2O (in.
H2O).
Ps = Absolute stack or duct pressure, mm Hg (in. Hg),
[GRAPHIC] [TIFF OMITTED] TR14MY99.055

Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
13.6 = Conversion from mm H2O (in. H2O) to mm Hg
(in. Hg).
Qsd = Average dry-basis volumetric stack or duct gas flow
rate corrected to standard conditions, dscm/hr (dscf/hr).
Qsw = Average wet-basis volumetric stack or duct gas flow
rate corrected to standard conditions, wscm/hr (wscf/hr).
Ts(avg) = Average absolute stack or duct gas temperature
across all traverse points.
ts(i) = Stack or duct gas temperature, C (F), at traverse
point i.
Ts(i) = Absolute stack or duct gas temperature, K (R), at
traverse point i,
[GRAPHIC] [TIFF OMITTED] TR14MY99.056

for the metric system, and
[GRAPHIC] [TIFF OMITTED] TR14MY99.057

for the English system.
Tstd = Standard absolute temperature, 293 deg.K (528 deg.R).
F1(i) = Pitch angle ratio, applicable at traverse point i,
dimensionless.
F2(i) = 3-D probe velocity calibration coefficient,
applicable at traverse point i, dimensionless.
(P4-P5)i = Pitch differential pressure
of stack or duct gas flow, mm H2O (in.
H2O), at traverse point i.
(P1-P2)i = Velocity head (differential
pressure) of stack or duct gas flow, mm H2O (in.
H2O), at traverse point i.
va(i) = Reported stack or duct gas axial velocity, m/sec (ft/
sec), at traverse point i.
va(avg) = Average stack or duct gas axial velocity, m/sec
(ft/sec), across all traverse points.
3,600 = Conversion factor, sec/hr.

[[Page 66]]

18.0 = Molecular weight of water, g/g-mole (lb/lb-mole).
y(i) = Yaw angle, degrees, at traverse point i.
p(i) = Pitch angle, degrees, at traverse point i.
n = Number of traverse points.

12.2 Traverse Point Velocity Calculations. Perform the following
calculations from the measurements obtained at each traverse point.
12.2.1 Selection of calibration curves. Select calibration curves
as described in section 10.6.1.
12.2.2 Traverse point pitch angle ratio. Use Equation 2F-1, as
described in section 10.6.2, to calculate the pitch angle ratio,
F1(i), at each traverse point.
12.2.3 Pitch angle. Use the pitch angle ratio, F1(i), to
derive the pitch angle, p(i), at traverse point i
from the F1 versus pitch angle calibration curve generated
under section 10.6.16.1.
12.2.4 Velocity calibration coefficient. Use the pitch angle,
p(i), to obtain the probe velocity calibration
coefficient, F2(i), at traverse point i from the ``velocity
pressure calibration curve,'' i.e., the F2 versus pitch angle
calibration curve generated under section 10.6.16.1.
12.2.5 Axial velocity. Use the following equation to calculate the
axial velocity, va(i), from the differential pressure
(P1-P2)i and yaw angle,
y(i), measured at traverse point i and the
previously calculated values for the velocity calibration coefficient,
F2(i), absolute stack or duct standard temperature,
Ts(i), absolute stack or duct pressure, Ps,
molecular weight, Ms, and pitch angle,
``p(i).
[GRAPHIC] [TIFF OMITTED] TR14MY99.058

12.2.6 Handling multiple measurements at a traverse point. For
pressure or temperature devices that take multiple measurements at a
traverse point, the multiple measurements (or where applicable, their
square roots) may first be averaged and the resulting average values
used in the equations above. Alternatively, the individual measurements
may be used in the equations above and the resulting multiple calculated
values may then be averaged to obtain a single traverse point value.
With either approach, all of the individual measurements recorded at a
traverse point must be used in calculating the applicable traverse point
value.
12.3 Average Axial Velocity in Stack or Duct. Use the reported
traverse point axial velocity in the following equation.
[GRAPHIC] [TIFF OMITTED] TR14MY99.059

12.4 Acceptability of Results. The test results are acceptable and
the calculated value of va(avg) may be reported as the
average axial velocity for the test run if the conditions in either
section 12.4.1 or 12.4.2 are met.
12.4.1 The calibration curves were generated at nominal velocities
of 18.3 m/sec and 27.4 m/sec (60 ft/sec and 90 ft/sec).
12.4.2 The calibration curves were generated at nominal velocities
other than 18.3 m/sec and 27.4 m/sec (60 ft/sec and 90 ft/sec), and the
value of va(avg) obtained using Equation 2F-9 is less than or
equal to at least one of the nominal velocities used to derive the
F1 and F2 calibration curves.
12.4.3 If the conditions in neither section 12.4.1 nor section
12.4.2 are met, the test results obtained in Equation 2F-9 are not
acceptable, and the steps in sections 12.2 and 12.3 must be repeated
using a set of F1 and F2 calibration curves that
satisfies the conditions specified in section 12.4.1 or 12.4.2.
12.5 Average Gas Wet Volumetric Flow Rate in Stack or Duct. Use the
following equation to compute the average volumetric flow rate on a wet
basis.
[GRAPHIC] [TIFF OMITTED] TR14MY99.060

12.6 Average Gas Dry Volumetric Flow Rate in Stack or Duct. Use the
following equation to compute the average volumetric flow rate on a dry
basis.

[[Page 67]]

[GRAPHIC] [TIFF OMITTED] TR14MY99.061

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Reporting

16.1 Field Test Reports. Field test reports shall be submitted to
the Agency according to applicable regulatory requirements. Field test
reports should, at a minimum, include the following elements.
16.1.1 Description of the source. This should include the name and
location of the test site, descriptions of the process tested, a
description of the combustion source, an accurate diagram of stack or
duct cross-sectional area at the test site showing the dimensions of the
stack or duct, the location of the test ports, and traverse point
locations and identification numbers or codes. It should also include a
description and diagram of the stack or duct layout, showing the
distance of the test location from the nearest upstream and downstream
disturbances and all structural elements (including breachings, baffles,
fans, straighteners, etc.) affecting the flow pattern. If the source and
test location descriptions have been previously submitted to the Agency
in a document (e.g., a monitoring plan or test plan), referencing the
document in lieu of including this information in the field test report
is acceptable.
16.1.2 Field test procedures. These should include a description of
test equipment and test procedures. Testing conventions, such as
traverse point numbering and measurement sequence (e.g., sampling from
center to wall, or wall to center), should be clearly stated. Test port
identification and directional reference for each test port should be
included on the appropriate field test data sheets.
16.1.3 Field test data.
16.1.3.1 Summary of results. This summary should include the dates
and times of testing and the average axial gas velocity and the average
flue gas volumetric flow results for each run and tested condition.
16.1.3.2 Test data. The following values for each traverse point
should be recorded and reported:

(a) P1-P2 and P4-P5
differential pressures
(b) Stack or duct gas temperature at traverse point i
(ts(i))
(c) Absolute stack or duct gas temperature at traverse point i
(Ts(i))
(d) Yaw angle at each traverse point i (y(i))
(e) Pitch angle at each traverse point i (p(i))
(f) Stack or duct gas axial velocity at traverse point i
(va(i))

16.1.3.3 The following values should be reported once per run:

(a) Water vapor in the gas stream (from Method 4 or alternative),
proportion by volume (Bws), measured at the frequency
specified in the applicable regulation
(b) Molecular weight of stack or duct gas, dry basis (Md)
(c) Molecular weight of stack or duct gas, wet basis (Ms)
(d) Stack or duct static pressure (Pg)
(e) Absolute stack or duct pressure (Ps)
(f) Carbon dioxide concentration in the flue gas, dry basis (\0/
0\d CO2)
(g) Oxygen concentration in the flue gas, dry basis (\0/
0\d O2)
(h) Average axial stack or duct gas velocity (va(avg))
across all traverse points
(i) Gas volumetric flow rate corrected to standard conditions, dry
or wet basis as required by the applicable regulation (Qsd or
Qsw)

16.1.3.4 The following should be reported once per complete set of test
runs:

(a) Cross-sectional area of stack or duct at the test location (A)
(b) Measurement system response time (sec)
(c) Barometric pressure at measurement site (Pbar)

16.1.4 Calibration data. The field test report should include
calibration data for all probes and test equipment used in the field
test. At a minimum, the probe calibration data reported to the Agency
should include the following:

(a) Date of calibration
(b) Probe type
(c) Probe identification number(s) or code(s)
(d) Probe inspection sheets
(e) Pressure measurements and intermediate calculations of
F1 and F2 at each pitch angle used to obtain
calibration curves in accordance with section 10.6 of this method
(f) Calibration curves (in graphic or equation format) obtained in
accordance with sections 10.6.11 of this method
(g) Description and diagram of wind tunnel used for the calibration,
including dimensions of cross-sectional area and position and size of
the test section
(h) Documentation of wind tunnel qualification tests performed in
accordance with section 10.1 of this method

[[Page 68]]

16.1.5 Quality Assurance. Specific quality assurance and quality
control procedures used during the test should be described.

17.0 Bibliography

(1) 40 CFR Part 60, Appendix A, Method 1--Sample and velocity
traverses for stationary sources.
(2) 40 CFR Part 60, Appendix A, Method 2H--Determination of stack
gas velocity taking into account velocity decay near the stack wall.
(3) 40 CFR Part 60, Appendix A, Method 2--Determination of stack gas
velocity and volumetric flow rate (Type S pitot tube).
(4) 40 CFR Part 60, Appendix A, Method 3--Gas analysis for carbon
dioxide, oxygen, excess air, and dry molecular weight.
(5) 40 CFR Part 60, Appendix A, Method 3A--Determination of oxygen
and carbon dioxide concentrations in emissions from stationary sources
(instrumental analyzer procedure).
(6) 40 CFR Part 60, Appendix A, Method 4--Determination of moisture
content in stack gases.
(7) Emission Measurement Center (EMC) Approved Alternative Method
(ALT-011) ``Alternative Method 2 Thermocouple Calibration Procedure.''
(8) Electric Power Research Institute, Interim Report EPRI TR-
106698, ``Flue Gas Flow Rate Measurement Errors,'' June 1996.
(9) Electric Power Research Institute, Final Report EPRI TR-108110,
``Evaluation of Heat Rate Discrepancy from Continuous Emission
Monitoring Systems,'' August 1997.
(10) Fossil Energy Research Corporation, Final Report, ``Velocity
Probe Tests in Non-axial Flow Fields,'' November 1998, Prepared for the
U.S. Environmental Protection Agency.
(11) Fossil Energy Research Corporation, ``Additional Swirl Tunnel
Tests: E-DAT and T-DAT Probes,'' February 24, 1999, Technical Memorandum
Prepared for U.S. Environmental Protection Agency, P.O. No. 7W-1193-
NALX.
(12) Massachusetts Institute of Technology, Report WBWT-TR-1317,
``Calibration of Eight Wind Speed Probes Over a Reynolds Number Range of
46,000 to 725,000 Per Foot, Text and Summary Plots,'' Plus appendices,
October 15, 1998, Prepared for The Cadmus Group, Inc.
(13) National Institute of Standards and Technology, Special
Publication 250, ``NIST Calibration Services Users Guide 1991,'' Revised
October 1991, U.S. Department of Commerce, p. 2.
(14) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four Prandtl Probes, Four
S-Type Probes, Four French Probes, Four Modified Kiel Probes,'' Prepared
for the U.S. Environmental Protection Agency under IAG #DW13938432-01-0.
(15) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Five Autoprobes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(16) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Eight Spherical Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(17) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four DAT Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(18) Norfleet, S.K., ``An Evaluation of Wall Effects on Stack Flow
Velocities and Related Overestimation Bias in EPA's Stack Flow Reference
Methods,'' EPRI CEMS User's Group Meeting, New Orleans, Louisiana, May
13-15, 1998.
(19) Page, J.J., E.A. Potts, and R.T. Shigehara, ``3-D Pitot Tube
Calibration Study,'' EPA Contract No. 68-D1-0009, Work Assignment No. I-
121, March 11, 1993.
(20) Shigehara, R.T., W.F. Todd, and W.S. Smith, ``Significance of
Errors in Stack Sampling Measurements,'' Presented at the Annual Meeting
of the Air Pollution Control Association, St. Louis, Missouri, June 14-
19, 1970.
(21) The Cadmus Group, Inc., May 1999, ``EPA Flow Reference Method
Testing and Analysis: Findings Report,'' EPA/430-R-99-009.
(22) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, DeCordova Steam
Electric Station, Volume I: Test Description and Appendix A (Data
Distribution Package),'' EPA/430-R-98-015a.
(23) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, Lake Hubbard Steam
Electric Station, Volume I: Test Description and Appendix A (Data
Distribution Package),'' EPA/430-R-98-017a.
(24) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Pennsylvania Electric Co., G.P.U.
Genco Homer City Station: Unit 1, Volume I: Test Description and
Appendix A (Data Distribution Package),'' EPA/430-R-98-018a.
(25) The Cadmus Group, Inc., 1997, ``EPA Flow Reference Method
Testing and Analysis: Wind Tunnel Experimental Results,'' EPA/430-R-97-
013.

18.0 Annexes

Annex A, C, and D describe recommended procedures for meeting
certain provisions in sections 8.3, 10.4, and 10.5 of this method. Annex
B describes procedures to be followed

[[Page 69]]

when using the protractor wheel and pointer assembly to measure yaw
angles, as provided under section 8.9.1.
18.1 Annex A--Rotational Position Check. The following are
recommended procedures that may be used to satisfy the rotational
position check requirements of section 8.3 of this method and to
determine the angle-measuring device rotational offset RADO.
18.1.1 Rotational position check with probe outside stack. Where
physical constraints at the sampling location allow full assembly of the
probe outside the stack and insertion into the test port, the following
procedures should be performed before the start of testing. Two angle-
measuring devices that meet the specifications in section 6.2.1 or 6.2.3
are required for the rotational position check. An angle measuring
device whose position can be independently adjusted (e.g., by means of a
set screw) after being locked into position on the probe sheath shall
not be used for this check unless the independent adjustment is set so
that the device performs exactly like a device without the capability
for independent adjustment. That is, when aligned on the probe such a
device must give the same reading as a device that does not have the
capability of being independently adjusted. With the fully assembled
probe (including probe shaft extensions, if any) secured in a horizontal
position, affix one yaw angle-measuring device to the probe sheath and
lock it into position on the reference scribe line specified in section
6.1.6.1. Position the second angle-measuring device using the procedure
in section 18.1.1.1 or 18.1.1.2.
18.1.1.1 Marking procedure. The procedures in this section should
be performed at each location on the fully assembled probe where the yaw
angle-measuring device will be mounted during the velocity traverse.
Place the second yaw angle-measuring device on the main probe sheath (or
extension) at the position where a yaw angle will be measured during the
velocity traverse. Adjust the position of the second angle-measuring
device until it indicates the same angle (1 deg.) as the
reference device, and affix the second device to the probe sheath (or
extension). Record the angles indicated by the two angle-measuring
devices on a form similar to Table 2F-2. In this position, the second
angle-measuring device is considered to be properly positioned for yaw
angle measurement. Make a mark, no wider than 1.6 mm (1/16 in.), on the
probe sheath (or extension), such that the yaw angle-measuring device
can be re-affixed at this same properly aligned position during the
velocity traverse.
18.1.1.2 Procedure for probe extensions with scribe lines. If,
during a velocity traverse the angle-measuring device will be affixed to
a probe extension having a scribe line as specified in section 6.1.6.2,
the following procedure may be used to align the extension's scribe line
with the reference scribe line instead of marking the extension as
described in section 18.1.1.1. Attach the probe extension to the main
probe. Align and lock the second angle-measuring device on the probe
extension's scribe line. Then, rotate the extension until both measuring
devices indicate the same angle (1 deg.). Lock the extension
at this rotational position. Record the angles indicated by the two
angle-measuring devices on a form similar to Table 2F-2. An angle-
measuring device may be aligned at any position on this scribe line
during the velocity traverse, if the scribe line meets the alignment
specification in section 6.1.6.3.
18.1.1.3 Post-test rotational position check. If the fully
assembled probe includes one or more extensions, the following check
should be performed immediately after the completion of a velocity
traverse. At the discretion of the tester, additional checks may be
conducted after completion of testing at any sample port. Without
altering the alignment of any of the components of the probe assembly
used in the velocity traverse, secure the fully assembled probe in a
horizontal position. Affix an angle-measuring device at the reference
scribe line specified in section 6.1.6.1. Use the other angle-measuring
device to check the angle at each location where the device was checked
prior to testing. Record the readings from the two angle-measuring
devices.
18.1.2 Rotational position check with probe in stack. This section
applies only to probes that, due to physical constraints, cannot be
inserted into the test port as fully assembled with all necessary
extensions needed to reach the inner-most traverse point(s).
18.1.2.1 Perform the out-of-stack procedure in section 18.1.1 on
the main probe and any attached extensions that will be initially
inserted into the test port.
18.1.2.2 Use the following procedures to perform additional
rotational position check(s) with the probe in the stack, each time a
probe extension is added. Two angle-measuring devices are required. The
first of these is the device that was used to measure yaw angles at the
preceding traverse point, left in its properly aligned measurement
position. The second angle-measuring device is positioned on the added
probe extension. Use the applicable procedures in section 18.1.1.1 or
18.1.1.2 to align, adjust, lock, and mark (if necessary) the position of
the second angle-measuring device to within 1 deg. of the
first device. Record the readings of the two devices on a form similar
to Table 2F-2.
18.1.2.3 The procedure in section 18.1.2.2 should be performed at
the first port where measurements are taken. The procedure should be
repeated each time a probe extension is re-attached at a subsequent
port, unless the probe extensions are designed to be locked into a
mechanically fixed rotational

[[Page 70]]

position (e.g., through use of interlocking grooves), which can be
reproduced from port to port as specified in section 8.3.5.2.
18.2 Annex B--Angle Measurement Protocol for Protractor Wheel and
Pointer Device. The following procedure shall be used when a protractor
wheel and pointer assembly, such as the one described in section 6.2.2
and illustrated in Figure 2F-7 is used to measure the yaw angle of flow.
With each move to a new traverse point, unlock, re-align, and re-lock
the probe, angle-pointer collar, and protractor wheel to each other. At
each such move, particular attention is required to ensure that the
scribe line on the angle pointer collar is either aligned with the
reference scribe line on the main probe sheath or is at the rotational
offset position established under section 8.3.1. The procedure consists
of the following steps:
18.2.1 Affix a protractor wheel to the entry port for the test
probe in the stack or duct.
18.2.2 Orient the protractor wheel so that the 0 deg. mark
corresponds to the longitudinal axis of the stack or duct. For stacks,
vertical ducts, or ports on the side of horizontal ducts, use a digital
inclinometer meeting the specifications in section 6.2.1 to locate the
0 deg. orientation. For ports on the top or bottom of horizontal ducts,
identify the longitudinal axis at each test port and permanently mark
the duct to indicate the 0 deg. orientation. Once the protractor wheel
is properly aligned, lock it into position on the test port.
18.2.3 Move the pointer assembly along the probe sheath to the
position needed to take measurements at the first traverse point. Align
the scribe line on the pointer collar with the reference scribe line or
at the rotational offset position established under section 8.3.1.
Maintaining this rotational alignment, lock the pointer device onto the
probe sheath. Insert the probe into the entry port to the depth needed
to take measurements at the first traverse point.
18.2.4 Perform the yaw angle determination as specified in sections
8.9.3 and 8.9.4 and record the angle as shown by the pointer on the
protractor wheel. Then, take velocity pressure and temperature
measurements in accordance with the procedure in section 8.9.5. Perform
the alignment check described in section 8.9.6.
18.2.5 After taking velocity pressure measurements at that traverse
point, unlock the probe from the collar and slide the probe through the
collar to the depth needed to reach the next traverse point.
18.2.6 Align the scribe line on the pointer collar with the
reference scribe line on the main probe or at the rotational offset
position established under section 8.3.1. Lock the collar onto the
probe.
18.2.7 Repeat the steps in sections 18.2.4 through 18.2.6 at the
remaining traverse points accessed from the current stack or duct entry
port.
18.2.8 After completing the measurement at the last traverse point
accessed from a port, verify that the orientation of the protractor
wheel on the test port has not changed over the course of the traverse
at that port. For stacks, vertical ducts, or ports on the side of
horizontal ducts, use a digital inclinometer meeting the specifications
in section 6.2.1 to check the rotational position of the 0 deg. mark on
the protractor wheel. For ports on the top or bottom of horizontal
ducts, observe the alignment of the angle wheel 0 deg. mark relative to
the permanent 0 deg. mark on the duct at that test port. If these
observed comparisons exceed 2 deg. of 0 deg., all angle and
pressure measurements taken at that port since the protractor wheel was
last locked into position on the port shall be repeated.
18.2.9 Move to the next stack or duct entry port and repeat the
steps in sections 18.2.1 through 18.2.8.
18.3 Annex C--Guideline for Reference Scribe Line Placement. Use of
the following guideline is recommended to satisfy the requirements of
section 10.4 of this method. The rotational position of the reference
scribe line should be either 90 deg. or 180 deg. from the probe's impact
pressure port.
18.4 Annex D--Determination of Reference Scribe Line Rotational
Offset. The following procedures are recommended for determining the
magnitude and sign of a probe's reference scribe line rotational offset,
RSLO. Separate procedures are provided for two types of
angle-measuring devices: digital inclinometers and protractor wheel and
pointer assemblies.
18.4.1 Perform the following procedures on the main probe with all
devices that will be attached to the main probe in the field [such as
thermocouples or resistance temperature detectors (RTDs)] that may
affect the flow around the probe head. Probe shaft extensions that do
not affect flow around the probe head need not be attached during
calibration.
18.4.2 The procedures below assume that the wind tunnel duct used
for probe calibration is horizontal and that the flow in the calibration
wind tunnel is axial as determined by the axial flow verification check
described in section 10.1.2. Angle-measuring devices are assumed to
display angles in alternating 0 deg. to 90 deg. and 90 deg. to 0 deg.
intervals. If angle-measuring devices with other readout conventions are
used or if other calibration wind tunnel duct configurations are used,
make the appropriate calculational corrections.
18.4.2.1 Position the angle-measuring device in accordance with one
of the following procedures.
18.4.2.1.1 If using a digital inclinometer, affix the calibrated
digital inclinometer to

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the probe. If the digital inclinometer can be independently adjusted
after being locked into position on the probe sheath (e.g., by means of
a set screw), the independent adjustment must be set so that the device
performs exactly like a device without the capability for independent
adjustment. That is, when aligned on the probe the device must give the
same readings as a device that does not have the capability of being
independently adjusted. Either align it directly on the reference scribe
line or on a mark aligned with the scribe line determined according to
the procedures in section 18.1.1.1. Maintaining this rotational
alignment, lock the digital inclinometer onto the probe sheath.
18.4.2.1.2 If using a protractor wheel and pointer device, orient
the protractor wheel on the test port so that the 0 deg. mark is aligned
with the longitudinal axis of the wind tunnel duct. Maintaining this
alignment, lock the wheel into place on the wind tunnel test port. Align
the scribe line on the pointer collar with the reference scribe line or
with a mark aligned with the reference scribe line, as determined under
section 18.1.1.1. Maintaining this rotational alignment, lock the
pointer device onto the probe sheath.
18.4.2.2 Zero the pressure-measuring device used for yaw nulling.
18.4.2.3 Insert the probe assembly into the wind tunnel through the
entry port, positioning the probe's impact port at the calibration
location. Check the responsiveness of the pressure-measuring device to
probe rotation, taking corrective action if the response is
unacceptable.
18.4.2.4 Ensure that the probe is in a horizontal position using a
carpenter's level.
18.4.2.5 Rotate the probe either clockwise or counterclockwise
until a yaw null (P2=P3) is obtained.
18.4.2.6 Read and record the value of null,
the angle indicated by the angle-measuring device at the yaw-null
position. Record the angle reading on a form similar to Table 2F-6. Do
not associate an algebraic sign with this reading.
18.4.2.7 Determine the magnitude and algebraic sign of the
reference scribe line rotational offset, RSLO. The magnitude
of RSLO will be equal to either null or
(90 deg.-null), depending on the angle-measuring
device used. (See Table 2F-7 for a summary.) The algebraic sign of
RSLO will either be positive, if the rotational position of
the reference scribe line is clockwise, or negative, if counterclockwise
with respect to the probe's yaw-null position. Figure 2F-13 illustrates
how the magnitude and sign of RSLO are determined.
18.4.2.8 Perform the steps in sections 18.4.2.3 through 18.4.2.7
twice at each of the two calibration velocities selected for the probe
under section 10.6. Record the values of RSLO in a form
similar to Table 2F-6.
18.4.2.9 The average of all RSLO values is the reference
scribe line rotational offset for the probe.

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[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A see the List of CFR Sections Affected, which appears in the
Finding Aids section of the printed volume and on GPO Access.

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Appendix A-2 to Part 60--Test Methods 2G through 3C

Method 2G--Determination of Stack Gas Velocity and Volumetric Flow Rate
With Two-Dimensional Probes
Method 2H--Determination of Stack Gas Velocity Taking Into Account
Velocity Decay Near the Stack Wall
Method 3--Gas analysis for the determination of dry molecular weight
Method 3A--Determination of Oxygen and Carbon Dioxide Concentrations in
Emissions From Stationary Sources (Instrumental Analyzer
Procedure)
Method 3B--Gas analysis for the determination of emission rate
correction factor or excess air
Method 3C--Determination of carbon dioxide, methane, nitrogen, and
oxygen from stationary sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the the degree of detail should be similar to the detail contained
in the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 2G--Determination of Stack Gas Velocity and Volumetric Flow Rate
With Two-Dimensional Probes

[[Page 92]]

additional test methods: Methods 1, 2, 3 or 3A, and 4.

1.0 Scope and Application

1.1 This method is applicable for the determination of yaw angle,
near-axial velocity, and the volumetric flow rate of a gas stream in a
stack or duct using a two-dimensional (2-D) probe.

2.0 Summary of Method

2.1 A 2-D probe is used to measure the velocity pressure and the yaw
angle of the flow velocity vector in a stack or duct. Alternatively,
these measurements may be made by operating one of the three-dimensional
(3-D) probes described in Method 2F, in yaw determination mode only.
From these measurements and a determination of the stack gas density,
the average near-axial velocity of the stack gas is calculated. The
near-axial velocity accounts for the yaw, but not the pitch, component
of flow. The average gas volumetric flow rate in the stack or duct is
then determined from the average near-axial velocity.

3.0 Definitions

3.1. Angle-measuring Device Rotational Offset (RADO).
The rotational position of an angle-measuring device relative to the
reference scribe line, as determined during the pre-test rotational
position check described in section 8.3.
3.2 Calibration Pitot Tube. The standard (Prandtl type) pitot tube
used as a reference when calibrating a probe under this method.
3.3 Field Test. A set of measurements conducted at a specific unit
or exhaust stack/duct to satisfy the applicable regulation (e.g., a
three-run boiler performance test, a single-or multiple-load nine-run
relative accuracy test).
3.4 Full Scale of Pressure-measuring Device. Full scale refers to
the upper limit of the measurement range displayed by the device. For
bi-directional pressure gauges, full scale includes the entire pressure
range from the lowest negative value to the highest positive value on
the pressure scale.
3.5 Main probe. Refers to the probe head and that section of probe
sheath directly attached to the probe head. The main probe sheath is
distinguished from probe extensions, which are sections of sheath added
onto the main probe to extend its reach.
3.6 ``May,'' ``Must,'' ``Shall,'' ``Should,'' and the imperative
form of verbs.
3.6.1 ``May'' is used to indicate that a provision of this method is
optional.
3.6.2 ``Must,'' ``Shall,'' and the imperative form of verbs (such as
``record'' or ``enter'') are used to indicate that a provision of this
method is mandatory.
3.6.3 ``Should'' is used to indicate that a provision of this method
is not mandatory, but is highly recommended as good practice.
3.7 Method 1. Refers to 40 CFR part 60, appendix A, ``Method 1--
Sample and velocity traverses for stationary sources.''
3.8 Method 2. Refers to 40 CFR part 60, appendix A, ``Method 2--
Determination of stack gas velocity and volumetric flow rate (Type S
pitot tube).''
3.9 Method 2F. Refers to 40 CFR part 60, appendix A, ``Method 2F--
Determination of stack gas velocity and volumetric flow rate with three-
dimensional probes.''
3.10 Near-axial Velocity. The velocity vector parallel to the axis
of the stack or duct that accounts for the yaw angle component of gas
flow. The term ``near-axial'' is used herein to indicate that the
velocity and volumetric flow rate results account for the measured yaw
angle component of flow at each measurement point.
3.11 Nominal Velocity. Refers to a wind tunnel velocity setting that
approximates the actual wind tunnel velocity to within 1.5
m/sec (5 ft/sec).
3.12 Pitch Angle. The angle between the axis of the stack or duct
and the pitch component of flow, i.e., the component of the total
velocity vector in a plane defined by the traverse line and the axis of
the stack or duct. (Figure 2G-1 illustrates the ``pitch plane.'') From
the standpoint of a tester facing a test port in a vertical stack, the
pitch component of flow is the vector of flow moving from the center of
the stack toward or away from that test port. The pitch angle is the
angle described by this pitch component of flow and the vertical axis of
the stack.
3.13 Readability. For the purposes of this method, readability for
an analog measurement device is one half of the smallest scale division.
For a digital measurement device, it is the number of decimals displayed
by the device.
3.14 Reference Scribe Line. A line permanently inscribed on the
main probe sheath (in accordance with section 6.1.5.1) to serve as a
reference mark for determining yaw angles.
3.15 Reference Scribe Line Rotational Offset (RSLO). The
rotational position of a probe's reference scribe line relative to the
probe's yaw-null position, as determined during the yaw angle
calibration described in section 10.5.
3.16 Response Time. The time required for the measurement system to
fully respond to a change from zero differential pressure and ambient
temperature to the stable stack or duct pressure and temperature
readings at a traverse point.
3.17 Tested Probe. A probe that is being calibrated.
3.18 Three-dimensional (3-D) Probe. A directional probe used to
determine the velocity

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pressure and the yaw and pitch angles in a flowing gas stream.
3.19 Two-dimensional (2-D) Probe. A directional probe used to
measure velocity pressure and yaw angle in a flowing gas stream.
3.20 Traverse Line. A diameter or axis extending across a stack or
duct on which measurements of velocity pressure and flow angles are
made.
3.21 Wind Tunnel Calibration Location. A point, line, area, or
volume within the wind tunnel test section at, along, or within which
probes are calibrated. At a particular wind tunnel velocity setting, the
average velocity pressures at specified points at, along, or within the
calibration location shall vary by no more than 2 percent or 0.3 mm
H20 (0.01 in. H2O), whichever is less restrictive,
from the average velocity pressure at the calibration pitot tube
location. Air flow at this location shall be axial, i.e., yaw and pitch
angles within 3 deg. of 0 deg.. Compliance with these flow
criteria shall be demonstrated by performing the procedures prescribed
in sections 10.1.1 and 10.1.2. For circular tunnels, no part of the
calibration location may be closer to the tunnel wall than 10.2 cm (4
in.) or 25 percent of the tunnel diameter, whichever is farther from the
wall. For elliptical or rectangular tunnels, no part of the calibration
location may be closer to the tunnel wall than 10.2 cm (4 in.) or 25
percent of the applicable cross-sectional axis, whichever is farther
from the wall.
3.22 Wind Tunnel with Documented Axial Flow. A wind tunnel facility
documented as meeting the provisions of sections 10.1.1 (velocity
pressure cross-check) and 10.1.2 (axial flow verification) using the
procedures described in these sections or alternative procedures
determined to be technically equivalent.
3.23 Yaw Angle. The angle between the axis of the stack or duct and
the yaw component of flow, i.e., the component of the total velocity
vector in a plane perpendicular to the traverse line at a particular
traverse point. (Figure 2G-1 illustrates the ``yaw plane.'') From the
standpoint of a tester facing a test port in a vertical stack, the yaw
component of flow is the vector of flow moving to the left or right from
the center of the stack as viewed by the tester. (This is sometimes
referred to as ``vortex flow,'' i.e., flow around the centerline of a
stack or duct.) The yaw angle is the angle described by this yaw
component of flow and the vertical axis of the stack. The algebraic sign
convention is illustrated in Figure 2G-2.
3.24 Yaw Nulling. A procedure in which a Type-S pitot tube or a 3-D
probe is rotated about its axis in a stack or duct until a zero
differential pressure reading (``yaw null'') is obtained. When a Type S
probe is yaw-nulled, the rotational position of its impact port is
90 deg. from the direction of flow in the stack or duct and the
P reading is zero. When a 3-D probe is yaw-nulled, its impact
pressure port (P1) faces directly into the direction of flow
in the stack or duct and the differential pressure between pressure
ports P2 and P3 is zero.

4.0 Interferences. [Reserved]

5.0 Safety

5.1 This test method may involve hazardous operations and the use
of hazardous materials or equipment. This method does not purport to
address all of the safety problems associated with its use. It is the
responsibility of the user to establish and implement appropriate safety
and health practices and to determine the applicability of regulatory
limitations before using this test method.

6.0 Equipment and Supplies

6.1 Two-dimensional Probes. Probes that provide both the velocity
pressure and the yaw angle of the flow vector in a stack or duct, as
listed in sections 6.1.1 and 6.1.2, qualify for use based on
comprehensive wind tunnel and field studies involving both inter-and
intra-probe comparisons by multiple test teams. Each 2-D probe shall
have a unique identification number or code permanently marked on the
main probe sheath. Each probe shall be calibrated prior to use according
to the procedures in section 10. Manufacturer-supplied calibration data
shall be used as example information only, except when the manufacturer
calibrates the probe as specified in section 10 and provides complete
documentation.
6.1.1 Type S (Stausscheibe or reverse type) pitot tube. This is the
same as specified in Method 2, section 2.1, except for the following
additional specifications that enable the pitot tube to accurately
determine the yaw component of flow. For the purposes of this method,
the external diameter of the tubing used to construct the Type S pitot
tube (dimension Dt in Figure 2-2 of Method 2) shall be no
less than 9.5 mm (3/8 in.). The pitot tube shall also meet the following
alignment specifications. The angles 1,
2, 1, and 2,
as shown in Method 2, Figure 2-3, shall not exceed 2 deg..
The dimensions w and z, shown in Method 2, Figure 2-3 shall not exceed
0.5 mm (0.02 in.).
6.1.1.1 Manual Type S probe. This refers to a Type S probe that is
positioned at individual traverse points and yaw nulled manually by an
operator.
6.1.1.2 Automated Type S probe. This refers to a system that uses a
computer-controlled motorized mechanism to position the Type S pitot
head at individual traverse points and perform yaw angle determinations.
6.1.2 Three-dimensional probes used in 2-D mode. A 3-D probe, as
specified in sections 6.1.1 through 6.1.3 of Method 2F, may, for the

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purposes of this method, be used in a two-dimensional mode (i.e.,
measuring yaw angle, but not pitch angle). When the 3-D probe is used as
a 2-D probe, only the velocity pressure and yaw-null pressure are
obtained using the pressure taps referred to as P1,
P2, and P3. The differential pressure
P1-P2 is a function of total velocity and
corresponds to the P obtained using the Type S probe. The
differential pressure P2-P3 is used to yaw null
the probe and determine the yaw angle. The differential pressure
P4-P5, which is a function of pitch angle, is not
measured when the 3-D probe is used in 2-D mode.
6.1.3 Other probes. [Reserved]
6.1.4 Probe sheath. The probe shaft shall include an outer sheath
to: (1) provide a surface for inscribing a permanent reference scribe
line, (2) accommodate attachment of an angle-measuring device to the
probe shaft, and (3) facilitate precise rotational movement of the probe
for determining yaw angles. The sheath shall be rigidly attached to the
probe assembly and shall enclose all pressure lines from the probe head
to the farthest position away from the probe head where an angle-
measuring device may be attached during use in the field. The sheath of
the fully assembled probe shall be sufficiently rigid and straight at
all rotational positions such that, when one end of the probe shaft is
held in a horizontal position, the fully extended probe meets the
horizontal straightness specifications indicated in section 8.2 below.
6.1.5 Scribe lines.
6.1.5.1 Reference scribe line. A permanent line, no greater than
1.6 mm (1/16 in.) in width, shall be inscribed on each manual probe that
will be used to determine yaw angles of flow. This line shall be placed
on the main probe sheath in accordance with the procedures described in
section 10.4 and is used as a reference position for installation of the
yaw angle-measuring device on the probe. At the discretion of the
tester, the scribe line may be a single line segment placed at a
particular position on the probe sheath (e.g., near the probe head),
multiple line segments placed at various locations along the length of
the probe sheath (e.g., at every position where a yaw angle-measuring
device may be mounted), or a single continuous line extending along the
full length of the probe sheath.
6.1.5.2 Scribe line on probe extensions. A permanent line may also
be inscribed on any probe extension that will be attached to the main
probe in performing field testing. This allows a yaw angle-measuring
device mounted on the extension to be readily aligned with the reference
scribe line on the main probe sheath.
6.1.5.3 Alignment specifications. This specification shall be met
separately, using the procedures in section 10.4.1, on the main probe
and on each probe extension. The rotational position of the scribe line
or scribe line segments on the main probe or any probe extension must
not vary by more than 2 deg.. That is, the difference between the
minimum and maximum of all of the rotational angles that are measured
along the full length of the main probe or the probe extension must not
exceed 2 deg..
6.1.6 Probe and system characteristics to ensure horizontal
stability.
6.1.6.1 For manual probes, it is recommended that the effective
length of the probe (coupled with a probe extension, if necessary) be at
least 0.9 m (3 ft.) longer than the farthest traverse point mark on the
probe shaft away from the probe head. The operator should maintain the
probe's horizontal stability when it is fully inserted into the stack or
duct. If a shorter probe is used, the probe should be inserted through a
bushing sleeve, similar to the one shown in Figure 2G-3, that is
installed on the test port; such a bushing shall fit snugly around the
probe and be secured to the stack or duct entry port in such a manner as
to maintain the probe's horizontal stability when fully inserted into
the stack or duct.
6.1.6.2 An automated system that includes an external probe casing
with a transport system shall have a mechanism for maintaining
horizontal stability comparable to that obtained by manual probes
following the provisions of this method. The automated probe assembly
shall also be constructed to maintain the alignment and position of the
pressure ports during sampling at each traverse point. The design of the
probe casing and transport system shall allow the probe to be removed
from the stack or duct and checked through direct physical measurement
for angular position and insertion depth.
6.1.7 The tubing that is used to connect the probe and the
pressure-measuring device should have an inside diameter of at least 3.2
mm (\1/8\ in.), to reduce the time required for pressure equilibration,
and should be as short as practicable.
6.1.8 If a detachable probe head without a sheath [e.g., a pitot
tube, typically 15.2 to 30.5 cm (6 to 12 in.) in length] is coupled with
a probe sheath and calibrated in a wind tunnel in accordance with the
yaw angle calibration procedure in section 10.5, the probe head shall
remain attached to the probe sheath during field testing in the same
configuration and orientation as calibrated. Once the detachable probe
head is uncoupled or re-oriented, the yaw angle calibration of the probe
is no longer valid and must be repeated before using the probe in
subsequent field tests.
6.2 Yaw Angle-measuring Device. One of the following devices shall
be used for measurement of the yaw angle of flow.

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6.2.1 Digital inclinometer. This refers to a digital device capable
of measuring and displaying the rotational position of the probe to
within 1 deg.. The device shall be able to be locked into
position on the probe sheath or probe extension, so that it indicates
the probe's rotational position throughout the test. A rotational
position collar block that can be attached to the probe sheath (similar
to the collar shown in Figure 2G-4) may be required to lock the digital
inclinometer into position on the probe sheath.
6.2.2 Protractor wheel and pointer assembly. This apparatus,
similar to that shown in Figure 2G-5, consists of the following
components.
6.2.2.1 A protractor wheel that can be attached to a port opening
and set in a fixed rotational position to indicate the yaw angle
position of the probe's scribe line relative to the longitudinal axis of
the stack or duct. The protractor wheel must have a measurement ring on
its face that is no less than 17.8 cm (7 in.) in diameter, shall be able
to be rotated to any angle and then locked into position on the stack or
duct test port, and shall indicate angles to a resolution of 1 deg..
6.2.2.2 A pointer assembly that includes an indicator needle
mounted on a collar that can slide over the probe sheath and be locked
into a fixed rotational position on the probe sheath. The pointer needle
shall be of sufficient length, rigidity, and sharpness to allow the
tester to determine the probe's angular position to within 1 deg. from
the markings on the protractor wheel. Corresponding to the position of
the pointer, the collar must have a scribe line to be used in aligning
the pointer with the scribe line on the probe sheath.
6.2.3 Other yaw angle-measuring devices. Other angle-measuring
devices with a manufacturer's specified precision of 1 deg. or better
may be used, if approved by the Administrator.
6.3 Probe Supports and Stabilization Devices. When probes are used
for determining flow angles, the probe head should be kept in a stable
horizontal position. For probes longer than 3.0 m (10 ft.), the section
of the probe that extends outside the test port shall be secured. Three
alternative devices are suggested for maintaining the horizontal
position and stability of the probe shaft during flow angle
determinations and velocity pressure measurements: (1) monorails
installed above each port, (2) probe stands on which the probe shaft may
be rested, or (3) bushing sleeves of sufficient length secured to the
test ports to maintain probes in a horizontal position. Comparable
provisions shall be made to ensure that automated systems maintain the
horizontal position of the probe in the stack or duct. The physical
characteristics of each test platform may dictate the most suitable type
of stabilization device. Thus, the choice of a specific stabilization
device is left to the judgement of the testers.
6.4 Differential Pressure Gauges. The velocity pressure
(P) measuring devices used during wind tunnel calibrations and
field testing shall be either electronic manometers (e.g., pressure
transducers), fluid manometers, or mechanical pressure gauges (e.g.,
Magnehelic gauges). Use of electronic
manometers is recommended. Under low velocity conditions, use of
electronic manometers may be necessary to obtain acceptable
measurements.
6.4.1 Differential pressure-measuring device. This refers to a
device capable of measuring pressure differentials and having a
readability of 1 percent of full scale. The device shall be
capable of accurately measuring the maximum expected pressure
differential. Such devices are used to determine the following pressure
measurements: velocity pressure, static pressure, and yaw-null pressure.
For an inclined-vertical manometer, the readability specification of
1 percent shall be met separately using the respective full-
scale upper limits of the inclined anvertical portions of the scales. To
the extent practicable, the device shall be selected such that most of
the pressure readings are between 10 and 90 percent of the device's
full-scale measurement range (as defined in section 3.4). In addition,
pressure-measuring devices should be selected such that the zero does
not drift by more than 5 percent of the average expected pressure
readings to be encountered during the field test. This is particularly
important under low pressure conditions.
6.4.2 Gauge used for yaw nulling. The differential pressure-
measuring device chosen for yaw nulling the probe during the wind tunnel
calibrations and field testing shall be bi-directional, i.e., capable of
reading both positive and negative differential pressures. If a
mechanical, bi-directional pressure gauge is chosen, it shall have a
full-scale range no greater than 2.6 cm (i.e., -1.3 to +1.3 cm) [1 in.
H2O (i.e., -0.5 in. to +0.5 in.)].
6.4.3 Devices for calibrating differential pressure-measuring
devices. A precision manometer (e.g., a U-tube, inclined, or inclined-
vertical manometer, or micromanometer) or NIST (National Institute of
Standards and Technology) traceable pressure source shall be used for
calibrating differential pressure-measuring devices. The device shall be
maintained under laboratory conditions or in a similar protected
environment (e.g., a climate-controlled trailer). It shall not be used
in field tests. The precision manometer shall have a scale gradation of
0.3 mm H2O (0.01 in. H2O), or less, in the range
of 0 to 5.1 cm H2O (0 to 2 in. H2O) and 2.5 mm
H2O (0.1 in. H2O), or less, in the range of 5.1 to
25.4 cm H2O (2 to 10 in. H2O). The manometer shall
have manufacturer's documentation that it meets an accuracy
specification of at least 0.5 percent of full scale. The NIST-traceable
pressure source shall be recertified annually.

[[Page 96]]

6.4.4 Devices used for post-test calibration check. A precision
manometer meeting the specifications in section 6.4.3, a pressure-
measuring device or pressure source with a documented calibration
traceable to NIST, or an equivalent device approved by the Administrator
shall be used for the post-test calibration check. The pressure-
measuring device shall have a readability equivalent to or greater than
the tested device. The pressure source shall be capable of generating
pressures between 50 and 90 percent of the range of the tested device
and known to within 1 percent of the full scale of the
tested device. The pressure source shall be recertified annually.
6.5 Data Display and Capture Devices. Electronic manometers (if
used) shall be coupled with a data display device (such as a digital
panel meter, personal computer display, or strip chart) that allows the
tester to observe and validate the pressure measurements taken during
testing. They shall also be connected to a data recorder (such as a data
logger or a personal computer with data capture software) that has the
ability to compute and retain the appropriate average value at each
traverse point, identified by collection time and traverse point.
6.6 Temperature Gauges. For field tests, a thermocouple or
resistance temperature detector (RTD) capable of measuring temperature
to within 3 deg.C (5 deg.F) of the stack or duct
temperature shall be used. The thermocouple shall be attached to the
probe such that the sensor tip does not touch any metal. The position of
the thermocouple relative to the pressure port face openings shall be in
the same configuration as used for the probe calibrations in the wind
tunnel. Temperature gauges used for wind tunnel calibrations shall be
capable of measuring temperature to within 0.6 deg.C
(1 deg.F) of the temperature of the flowing gas stream in
the wind tunnel.
6.7 Stack or Duct Static Pressure Measurement. The pressure-
measuring device used with the probe shall be as specified in section
6.4 of this method. The static tap of a standard (Prandtl type) pitot
tube or one leg of a Type S pitot tube with the face opening planes
positioned parallel to the gas flow may be used for this measurement.
Also acceptable is the pressure differential reading of P1-
Pbar from a five-hole prism-shaped 3-D probe, as specified in
section 6.1.1 of Method 2F (such as the Type DA or DAT probe), with the
P1 pressure port face opening positioned parallel to the gas
flow in the same manner as the Type S probe. However, the 3-D spherical
probe, as specified in section 6.1.2 of Method 2F, is unable to provide
this measurement and shall not be used to take static pressure
measurements. Static pressure measurement is further described in
section 8.11.
6.8 Barometer. Same as Method 2, section 2.5.
6.9 Gas Density Determination Equipment. Method 3 or 3A shall be
used to determine the dry molecular weight of the stack or duct gas.
Method 4 shall be used for moisture content determination and
computation of stack or duct gas wet molecular weight. Other methods may
be used, if approved by the Administrator.
6.10 Calibration Pitot Tube. Same as Method 2, section 2.7.
6.11 Wind Tunnel for Probe Calibration. Wind tunnels used to
calibrate velocity probes must meet the following design specifications.
6.11.1 Test section cross-sectional area. The flowing gas stream
shall be confined within a circular, rectangular, or elliptical duct.
The cross-sectional area of the tunnel must be large enough to ensure
fully developed flow in the presence of both the calibration pitot tube
and the tested probe. The calibration site, or ``test section,'' of the
wind tunnel shall have a minimum diameter of 30.5 cm (12 in.) for
circular or elliptical duct cross-sections or a minimum width of 30.5 cm
(12 in.) on the shorter side for rectangular cross-sections. Wind
tunnels shall meet the probe blockage provisions of this section and the
qualification requirements prescribed in section 10.1. The projected
area of the portion of the probe head, shaft, and attached devices
inside the wind tunnel during calibration shall represent no more than 4
percent of the cross-sectional area of the tunnel. The projected area
shall include the combined area of the calibration pitot tube and the
tested probe if both probes are placed simultaneously in the same cross-
sectional plane in the wind tunnel, or the larger projected area of the
two probes if they are placed alternately in the wind tunnel.
6.11.2 Velocity range and stability. The wind tunnel should be
capable of maintaining velocities between 6.1 m/sec and 30.5 m/sec (20
ft/sec and 100 ft/sec). The wind tunnel shall produce fully developed
flow patterns that are stable and parallel to the axis of the duct in
the test section.
6.11.3 Flow profile at the calibration location. The wind tunnel
shall provide axial flow within the test section calibration location
(as defined in section 3.21). Yaw and pitch angles in the calibration
location shall be within 3 deg. of 0 deg.. The procedure for
determining that this requirement has been met is described in section
10.1.2.
6.11.4 Entry ports in the wind tunnel test section.
6.11.4.1 Port for tested probe. A port shall be constructed for the
tested probe. This port shall be located to allow the head of the tested
probe to be positioned within the wind tunnel calibration location (as
defined in section 3.21). The tested probe shall be able to be locked
into the 0 deg. pitch angle position. To facilitate alignment of the
probe during calibration, the test section should include a

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window constructed of a transparent material to allow the tested probe
to be viewed.
6.11.4.2 Port for verification of axial flow. Depending on the
equipment selected to conduct the axial flow verification prescribed in
section 10.1.2, a second port, located 90 deg. from the entry port for
the tested probe, may be needed to allow verification that the gas flow
is parallel to the central axis of the test section. This port should be
located and constructed so as to allow one of the probes described in
section 10.1.2.2 to access the same test point(s) that are accessible
from the port described in section 6.11.4.1.
6.11.4.3 Port for calibration pitot tube. The calibration pitot
tube shall be used in the port for the tested probe or in a separate
entry port. In either case, all measurements with the calibration pitot
tube shall be made at the same point within the wind tunnel over the
course of a probe calibration. The measurement point for the calibration
pitot tube shall meet the same specifications for distance from the wall
and for axial flow as described in section 3.21 for the wind tunnel
calibration location.

7.0 Reagents and Standards. [Reserved]

8.0 Sample Collection and Analysis

8.1 Equipment Inspection and Set Up

8.1.1 All 2-D and 3-D probes, differential pressure-measuring
devices, yaw angle-measuring devices, thermocouples, and barometers
shall have a current, valid calibration before being used in a field
test. (See sections 10.3.3, 10.3.4, and 10.5 through 10.10 for the
applicable calibration requirements.)
8.1.2 Before each field use of a Type S probe, perform a visual
inspection to verify the physical condition of the pitot tube. Record
the results of the inspection. If the face openings are noticeably
misaligned or there is visible damage to the face openings, the probe
shall not be used until repaired, the dimensional specifications
verified (according to the procedures in section 10.2.1), and the probe
recalibrated.
8.1.3 Before each field use of a 3-D probe, perform a visual
inspection to verify the physical condition of the probe head according
to the procedures in section 10.2 of Method 2F. Record the inspection
results on a form similar to Table 2F-1 presented in Method 2F. If there
is visible damage to the 3-D probe, the probe shall not be used until it
is recalibrated.
8.1.4 After verifying that the physical condition of the probe head
is acceptable, set up the apparatus using lengths of flexible tubing
that are as short as practicable. Surge tanks installed between the
probe and pressure-measuring device may be used to dampen pressure
fluctuations provided that an adequate measurement system response time
(see section 8.8) is maintained.
8.2 Horizontal Straightness Check. A horizontal straightness check
shall be performed before the start of each field test, except as
otherwise specified in this section. Secure the fully assembled probe
(including the probe head and all probe shaft extensions) in a
horizontal position using a stationary support at a point along the
probe shaft approximating the location of the stack or duct entry port
when the probe is sampling at the farthest traverse point from the stack
or duct wall. The probe shall be rotated to detect bends. Use an angle-
measuring device or trigonometry to determine the bend or sag between
the probe head and the secured end. (See Figure 2G-6.) Probes that are
bent or sag by more than 5 deg. shall not be used. Although this check
does not apply when the probe is used for a vertical traverse, care
should be taken to avoid the use of bent probes when conducting vertical
traverses. If the probe is constructed of a rigid steel material and
consists of a main probe without probe extensions, this check need only
be performed before the initial field use of the probe, when the probe
is recalibrated, when a change is made to the design or material of the
probe assembly, and when the probe becomes bent. With such probes, a
visual inspection shall be made of the fully assembled probe before each
field test to determine if a bend is visible. The probe shall be rotated
to detect bends. The inspection results shall be documented in the field
test report. If a bend in the probe is visible, the horizontal
straightness check shall be performed before the probe is used.
8.3 Rotational Position Check. Before each field test, and each
time an extension is added to the probe during a field test, a
rotational position check shall be performed on all manually operated
probes (except as noted in section 8.3.5 below) to ensure that,
throughout testing, the angle-measuring device is either: aligned to
within 1 deg. of the rotational position of the reference
scribe line; or is affixed to the probe such that the rotational offset
of the device from the reference scribe line is known to within
1 deg.. This check shall consist of direct measurements of
the rotational positions of the reference scribe line and angle-
measuring device sufficient to verify that these specifications are met.
Annex A in section 18 of this method gives recommended procedures for
performing the rotational position check, and Table 2G-2 gives an
example data form. Procedures other than those recommended in Annex A in
section 18 may be used, provided they demonstrate whether the alignment
specification is met and are explained in detail in the field test
report.
8.3.1 Angle-measuring device rotational offset. The tester shall
maintain a record of the angle-measuring device rotational offset,
RADO, as defined in section 3.1. Note that RADO is
assigned a value of 0 deg. when the angle-

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measuring device is aligned to within 1 deg. of the
rotational position of the reference scribe line. The RADO
shall be used to determine the yaw angle of flow in accordance with
section 8.9.4.
8.3.2 Sign of angle-measuring device rotational offset. The sign of
RADO is positive when the angle-measuring device (as viewed
from the ``tail'' end of the probe) is positioned in a clockwise
direction from the reference scribe line and negative when the device is
positioned in a counterclockwise direction from the reference scribe
line.
8.3.3 Angle-measuring devices that can be independently adjusted
(e.g., by means of a set screw), after being locked into position on the
probe sheath, may be used. However, the RADO must also take
into account this adjustment.
8.3.4 Post-test check. If probe extensions remain attached to the
main probe throughout the field test, the rotational position check
shall be repeated, at a minimum, at the completion of the field test to
ensure that the angle-measuring device has remained within
2 deg. of its rotational position established prior to
testing. At the discretion of the tester, additional checks may be
conducted after completion of testing at any sample port or after any
test run. If the 2 deg. specification is not met, all
measurements made since the last successful rotational position check
must be repeated. Section 18.1.1.3 of Annex A provides an example
procedure for performing the post-test check.
8.3.5 Exceptions.
8.3.5.1 A rotational position check need not be performed if, for
measurements taken at all velocity traverse points, the yaw angle-
measuring device is mounted and aligned directly on the reference scribe
line specified in sections 6.1.5.1 and 6.1.5.3 and no independent
adjustments, as described in section 8.3.3, are made to device's
rotational position.
8.3.5.2 If extensions are detached and re-attached to the probe
during a field test, a rotational position check need only be performed
the first time an extension is added to the probe, rather than each time
the extension is re-attached, if the probe extension is designed to be
locked into a mechanically fixed rotational position (e.g., through the
use of interlocking grooves), that can re-establish the initial
rotational position to within 1 deg..
8.4 Leak Checks. A pre-test leak check shall be conducted before
each field test. A post-test check shall be performed at the end of the
field test, but additional leak checks may be conducted after any test
run or group of test runs. The post-test check may also serve as the
pre-test check for the next group of test runs. If any leak check is
failed, all runs since the last passed leak check are invalid. While
performing the leak check procedures, also check each pressure device's
responsiveness to changes in pressure.
8.4.1 To perform the leak check on a Type S pitot tube, pressurize
the pitot impact opening until at least 7.6 cm H2O (3 in.
H2O) velocity pressure, or a pressure corresponding to
approximately 75 percent of the pressure device's measurement scale,
whichever is less, registers on the pressure device; then, close off the
impact opening. The pressure shall remain stable (2.5 mm
H2O, 0.10 in. H2O) for at least 15
seconds. Repeat this procedure for the static pressure side, except use
suction to obtain the required pressure. Other leak-check procedures may
be used, if approved by the Administrator.
8.4.2 To perform the leak check on a 3-D probe, pressurize the
probe's impact (P1) opening until at least 7.6 cm
H2O (3 in. H2O) velocity pressure, or a pressure
corresponding to approximately 75 percent of the pressure device's
measurement scale, whichever is less, registers on the pressure device;
then, close off the impact opening. The pressure shall remain stable
(2.5 mm H2O, 0.10 in. H2O)
for at least 15 seconds. Check the P2 and P3
pressure ports in the same fashion. Other leak-check procedures may be
used, if approved by the Administrator.
8.5 Zeroing the Differential Pressure-measuring Device. Zero each
differential pressure-measuring device, including the device used for
yaw nulling, before each field test. At a minimum, check the zero after
each field test. A zero check may also be performed after any test run
or group of test runs. For fluid manometers and mechanical pressure
gauges (e.g., Magnehelic gauges), the
zero reading shall not deviate from zero by more than 0.8 mm
H2O (0.03 in. H2O) or one minor scale
division, whichever is greater, between checks. For electronic
manometers, the zero reading shall not deviate from zero between checks
by more than: 0.3 mm H2O (0.01 in.
H2O), for full scales less than or equal to 5.1 cm
H2O (2.0 in. H2O); or 0.8 mm
H2O (0.03 in. H2O), for full scales
greater than 5.1 cm H2O (2.0 in. H2O). (Note: If
negative zero drift is not directly readable, estimate the reading based
on the position of the gauge oil in the manometer or of the needle on
the pressure gauge.) In addition, for all pressure-measuring devices
except those used exclusively for yaw nulling, the zero reading shall
not deviate from zero by more than 5 percent of the average measured
differential pressure at any distinct process condition or load level.
If any zero check is failed at a specific process condition or load
level, all runs conducted at that process condition or load level since
the last passed zero check are invalid.
8.6 Traverse Point Verification. The number and location of the
traverse points shall be selected based on Method 1 guidelines.

[[Page 99]]

The stack or duct diameter and port nipple lengths, including any
extension of the port nipples into the stack or duct, shall be verified
the first time the test is performed; retain and use this information
for subsequent field tests, updating it as required. Physically measure
the stack or duct dimensions or use a calibrated laser device; do not
use engineering drawings of the stack or duct. The probe length
necessary to reach each traverse point shall be recorded to within
6.4 mm (\1/4\ in.) and, for manual probes,
marked on the probe sheath. In determining these lengths, the tester
shall take into account both the distance that the port flange projects
outside of the stack and the depth that any port nipple extends into the
gas stream. The resulting point positions shall reflect the true
distances from the inside wall of the stack or duct, so that when the
tester aligns any of the markings with the outside face of the stack
port, the probe's impact port shall be located at the appropriate
distance from the inside wall for the respective Method 1 traverse
point. Before beginning testing at a particular location, an out-of-
stack or duct verification shall be performed on each probe that will be
used to ensure that these position markings are correct. The distances
measured during the verification must agree with the previously
calculated distances to within \1/4\ in. For manual probes,
the traverse point positions shall be verified by measuring the distance
of each mark from the probe's impact pressure port (the P1
port for a 3-D probe). A comparable out-of-stack test shall be performed
on automated probe systems. The probe shall be extended to each of the
prescribed traverse point positions. Then, the accuracy of the
positioning for each traverse point shall be verified by measuring the
distance between the port flange and the probe's impact pressure port.
8.7 Probe Installation. Insert the probe into the test port. A
solid material shall be used to seal the port.
8.8 System Response Time. Determine the response time of the probe
measurement system. Insert and position the ``cold'' probe (at ambient
temperature and pressure) at any Method 1 traverse point. Read and
record the probe differential pressure, temperature, and elapsed time at
15-second intervals until stable readings for both pressure and
temperature are achieved. The response time is the longer of these two
elapsed times. Record the response time.
8.9 Sampling.
8.9.1 Yaw angle measurement protocol. With manual probes, yaw angle
measurements may be obtained in two alternative ways during the field
test, either by using a yaw angle-measuring device (e.g., digital
inclinometer) affixed to the probe, or using a protractor wheel and
pointer assembly. For horizontal traversing, either approach may be
used. For vertical traversing, i.e., when measuring from on top or into
the bottom of a horizontal duct, only the protractor wheel and pointer
assembly may be used. With automated probes, curve-fitting protocols may
be used to obtain yaw-angle measurements.
8.9.1.1 If a yaw angle-measuring device affixed to the probe is to
be used, lock the device on the probe sheath, aligning it either on the
reference scribe line or in the rotational offset position established
under section 8.3.1.
8.9.1.2 If a protractor wheel and pointer assembly is to be used,
follow the procedures in Annex B of this method.
8.9.1.3 Curve-fitting procedures. Curve-fitting routines sweep
through a range of yaw angles to create curves correlating pressure to
yaw position. To find the zero yaw position and the yaw angle of flow,
the curve found in the stack is computationally compared to a similar
curve that was previously generated under controlled conditions in a
wind tunnel. A probe system that uses a curve-fitting routine for
determining the yaw-null position of the probe head may be used,
provided that it is verified in a wind tunnel to be able to determine
the yaw angle of flow to within 1 deg..
8.9.1.4 Other yaw angle determination procedures. If approved by
the Administrator, other procedures for determining yaw angle may be
used, provided that they are verified in a wind tunnel to be able to
perform the yaw angle calibration procedure as described in section
10.5.
8.9.2 Sampling strategy. At each traverse point, first yaw-null the
probe, as described in section 8.9.3, below. Then, with the probe
oriented into the direction of flow, measure and record the yaw angle,
the differential pressure and the temperature at the traverse point,
after stable readings are achieved, in accordance with sections 8.9.4
and 8.9.5. At the start of testing in each port (i.e., after a probe has
been inserted into the flue gas stream), allow at least the response
time to elapse before beginning to take measurements at the first
traverse point accessed from that port. Provided that the probe is not
removed from the flue gas stream, measurements may be taken at
subsequent traverse points accessed from the same test port without
waiting again for the response time to elapse.
8.9.3 Yaw-nulling procedure. In preparation for yaw angle
determination, the probe must first be yaw nulled. After positioning the
probe at the appropriate traverse point, perform the following
procedures.
8.9.3.1 For Type S probes, rotate the probe until a null
differential pressure reading is obtained. The direction of the probe
rotation shall be such that the thermocouple is located downstream of
the probe pressure ports at the yaw-null position. Rotate the

[[Page 100]]

probe 90 deg. back from the yaw-null position to orient the impact
pressure port into the direction of flow. Read and record the angle
displayed by the angle-measuring device.
8.9.3.2 For 3-D probes, rotate the probe until a null differential
pressure reading (the difference in pressures across the P2
and P3 pressure ports is zero, i.e., P2 =
P3) is indicated by the yaw angle pressure gauge. Read and
record the angle displayed by the angle-measuring device.
8.9.3.3 Sign of the measured angle. The angle displayed on the
angle-measuring device is considered positive when the probe's impact
pressure port (as viewed from the ``tail'' end of the probe) is oriented
in a clockwise rotational position relative to the stack or duct axis
and is considered negative when the probe's impact pressure port is
oriented in a counterclockwise rotational position (see Figure 2G-7).
8.9.4 Yaw angle determination. After performing the applicable yaw-
nulling procedure in section 8.9.3, determine the yaw angle of flow
according to one of the following procedures. Special care must be
observed to take into account the signs of the recorded angle reading
and all offsets.
8.9.4.1 Direct-reading. If all rotational offsets are zero or if
the angle-measuring device rotational offset (RADO)
determined in section 8.3 exactly compensates for the scribe line
rotational offset (RSLO) determined in section 10.5, then the
magnitude of the yaw angle is equal to the displayed angle-measuring
device reading from section 8.9.3.1 or 8.9.3.2. The algebraic sign of
the yaw angle is determined in accordance with section 8.9.3.3. [Note:
Under certain circumstances (e.g., testing of horizontal ducts) a
90 deg. adjustment to the angle-measuring device readings may be
necessary to obtain the correct yaw angles.]
8.9.4.2 Compensation for rotational offsets during data reduction.
When the angle-measuring device rotational offset does not compensate
for reference scribe line rotational offset, the following procedure
shall be used to determine the yaw angle:
(a) Enter the reading indicated by the angle-measuring device from
section 8.9.3.1 or 8.9.3.2.
(b) Associate the proper algebraic sign from section 8.9.3.3 with
the reading in step (a).
(c) Subtract the reference scribe line rotational offset,
RSLO, from the reading in step (b).
(d) Subtract the angle-measuring device rotational offset,
RADO, if any, from the result obtained in step (c).
(e) The final result obtained in step (d) is the yaw angle of flow.

[Note: It may be necessary to first apply a 90 deg. adjustment to the
reading in step (a), in order to obtain the correct yaw angle.]

8.9.4.3 Record the yaw angle measurements on a form similar to
Table 2G-3.
8.9.5 Impact velocity determination. Maintain the probe rotational
position established during the yaw angle determination. Then, begin
recording the pressure-measuring device readings. These pressure
measurements shall be taken over a sampling period of sufficiently long
duration to ensure representative readings at each traverse point. If
the pressure measurements are determined from visual readings of the
pressure device or display, allow sufficient time to observe the
pulsation in the readings to obtain a sight-weighted average, which is
then recorded manually. If an automated data acquisition system (e.g.,
data logger, computer-based data recorder, strip chart recorder) is used
to record the pressure measurements, obtain an integrated average of all
pressure readings at the traverse point. Stack or duct gas temperature
measurements shall be recorded, at a minimum, once at each traverse
point. Record all necessary data as shown in the example field data form
(Table 2G-3).
8.9.6 Alignment check. For manually operated probes, after the
required yaw angle and differential pressure and temperature
measurements have been made at each traverse point, verify (e.g., by
visual inspection) that the yaw angle-measuring device has remained in
proper alignment with the reference scribe line or with the rotational
offset position established in section 8.3. If, for a particular
traverse point, the angle-measuring device is found to be in proper
alignment, proceed to the next traverse point; otherwise, re-align the
device and repeat the angle and differential pressure measurements at
the traverse point. In the course of a traverse, if a mark used to
properly align the angle-measuring device (e.g., as described in section
18.1.1.1) cannot be located, re-establish the alignment mark before
proceeding with the traverse.
8.10 Probe Plugging. Periodically check for plugging of the
pressure ports by observing the responses on the pressure differential
readouts. Plugging causes erratic results or sluggish responses. Rotate
the probe to determine whether the readouts respond in the expected
direction. If plugging is detected, correct the problem and repeat the
affected measurements.
8.11 Static Pressure. Measure the static pressure in the stack or
duct using the equipment described in section 6.7.
8.11.1 If a Type S probe is used for this measurement, position the
probe at or between any traverse point(s) and rotate the probe until a
null differential pressure reading is obtained. Disconnect the tubing
from one of the pressure ports; read and record the P. For
pressure devices with one-directional scales, if a deflection in the
positive

[[Page 101]]

direction is noted with the negative side disconnected, then the static
pressure is positive. Likewise, if a deflection in the positive
direction is noted with the positive side disconnected, then the static
pressure is negative.
8.11.2 If a 3-D probe is used for this measurement, position the
probe at or between any traverse point(s) and rotate the probe until a
null differential pressure reading is obtained at P2-
P3. Rotate the probe 90 deg.. Disconnect the P2
pressure side of the probe and read the pressure P1-
Pbar and record as the static pressure. (Note: The spherical
probe, specified in section 6.1.2 of Method 2F, is unable to provide
this measurement and shall not be used to take static pressure
measurements.)
8.12 Atmospheric Pressure. Determine the atmospheric pressure at
the sampling elevation during each test run following the procedure
described in section 2.5 of Method 2.
8.13 Molecular Weight. Determine the stack or duct gas dry
molecular weight. For combustion processes or processes that emit
essentially CO2, O2, CO, and N2, use
Method 3 or 3A. For processes emitting essentially air, an analysis need
not be conducted; use a dry molecular weight of 29.0. Other methods may
be used, if approved by the Administrator.
8.14 Moisture. Determine the moisture content of the stack gas
using Method 4 or equivalent.
8.15 Data Recording and Calculations. Record all required data on a
form similar to Table 2G-3.
8.15.1 2-D probe calibration coefficient. When a Type S pitot tube
is used in the field, the appropriate calibration coefficient as
determined in section 10.6 shall be used to perform velocity
calculations. For calibrated Type S pitot tubes, the A-side coefficient
shall be used when the A-side of the tube faces the flow, and the B-side
coefficient shall be used when the B-side faces the flow.
8.15.2 3-D calibration coefficient. When a 3-D probe is used to
collect data with this method, follow the provisions for the calibration
of 3-D probes in section 10.6 of Method 2F to obtain the appropriate
velocity calibration coefficient (F2 as derived using
Equation 2F-2 in Method 2F) corresponding to a pitch angle position of
0 deg..
8.15.3 Calculations. Calculate the yaw-adjusted velocity at each
traverse point using the equations presented in section 12.2. Calculate
the test run average stack gas velocity by finding the arithmetic
average of the point velocity results in accordance with sections 12.3
and 12.4, and calculate the stack gas volumetric flow rate in accordance
with section 12.5 or 12.6, as applicable.

9.0 Quality Control

10.0 Calibration

[[Page 102]]

At each velocity setting, the average velocity pressure obtained at the
wind tunnel calibration location shall be within 2 percent
or 2.5 mm H2O (0.01 in. H2O), whichever is less
restrictive, of the average velocity pressure obtained at the fixed
calibration pitot tube location. This comparative check shall be
performed at 2.5-cm (1-in.), or smaller, intervals across the full
length, width, and depth (if applicable) of the wind tunnel calibration
location. If the criteria are not met at every tested point, the wind
tunnel calibration location must be redefined, so that acceptable
results are obtained at every point. Include the results of the velocity
pressure cross-check in the calibration data section of the field test
report. (See section 16.1.4.)
10.1.2 Axial flow verification. The following procedures shall be
performed to demonstrate that there is fully developed axial flow within
the wind tunnel calibration location and at the calibration pitot tube
location. Two options are available to conduct this check.
10.1.2.1 Using a calibrated 3-D probe. A probe that has been
previously calibrated in a wind tunnel with documented axial flow (as
defined in section 3.22) may be used to conduct this check. Insert the
calibrated 3-D probe into the wind tunnel test section using the tested
probe port. Following the procedures in sections 8.9 and 12.2 of Method
2F, determine the yaw and pitch angles at all the point(s) in the test
section where the velocity pressure cross-check, as specified in section
10.1.1, is performed. This includes all the points in the calibration
location and the point where the calibration pitot tube will be located.
Determine the yaw and pitch angles at each point. Repeat these
measurements at the highest and lowest velocities at which the probes
will be calibrated. Record the values on a form similar to Table 2G-5.
Each measured yaw and pitch angle shall be within 3 deg. of
0 deg.. Exceeding the limits indicates unacceptable flow in the test
section. Until the problem is corrected and acceptable flow is verified
by repetition of this procedure, the wind tunnel shall not be used for
calibration of probes. Include the results of the axial flow
verification in the calibration data section of the field test report.
(See section 16.1.4.)
10.1.2.2 Using alternative probes. Axial flow verification may be
performed using an uncalibrated prism-shaped 3-D probe (e.g., DA or DAT
probe) or an uncalibrated wedge probe. (Figure 2G-8 illustrates a
typical wedge probe.) This approach requires use of two ports: the
tested probe port and a second port located 90 deg. from the tested
probe port. Each port shall provide access to all the points within the
wind tunnel test section where the velocity pressure cross-check, as
specified in section 10.1.1, is conducted. The probe setup shall include
establishing a reference yaw-null position on the probe sheath to serve
as the location for installing the angle-measuring device. Physical
design features of the DA, DAT, and wedge probes are relied on to
determine the reference position. For the DA or DAT probe, this
reference position can be determined by setting a digital inclinometer
on the flat facet where the P1 pressure port is located and
then identifying the rotational position on the probe sheath where a
second angle-measuring device would give the same angle reading. The
reference position on a wedge probe shaft can be determined either
geometrically or by placing a digital inclinometer on each side of the
wedge and rotating the probe until equivalent readings are obtained.
With the latter approach, the reference position is the rotational
position on the probe sheath where an angle-measuring device would give
a reading of 0 deg.. After installation of the angle-measuring device in
the reference yaw-null position on the probe sheath, determine the yaw
angle from the tested port. Repeat this measurement using the 90 deg.
offset port, which provides the pitch angle of flow. Determine the yaw
and pitch angles at all the point(s) in the test section where the
velocity pressure cross-check, as specified in section 10.1.1, is
performed. This includes all the points in the wind tunnel calibration
location and the point where the calibration pitot tube will be located.
Perform this check at the highest and lowest velocities at which the
probes will be calibrated. Record the values on a form similar to Table
2G-5. Each measured yaw and pitch angle shall be within
3 deg. of 0 deg.. Exceeding the limits indicates
unacceptable flow in the test section. Until the problem is corrected
and acceptable flow is verified by repetition of this procedure, the
wind tunnel shall not be used for calibration of probes. Include the
results in the probe calibration report.
10.1.3 Wind tunnel audits.
10.1.3.1 Procedure. Upon the request of the Administrator, the
owner or operator of a wind tunnel shall calibrate a 2-D audit probe in
accordance with the procedures described in sections 10.3 through 10.6.
The calibration shall be performed at two velocities that encompass the
velocities typically used for this method at the facility. The resulting
calibration data shall be submitted to the Agency in an audit test
report. These results shall be compared by the Agency to reference
calibrations of the audit probe at the same velocity settings obtained
at two different wind tunnels.
10.1.3.2 Acceptance criterion. The audited tunnel's calibration
coefficient is acceptable if it is within 3 percent of the
reference calibrations obtained at each velocity setting by one (or
both) of the wind tunnels. If the acceptance criterion is not met at
each calibration velocity setting, the audited wind tunnel shall not be
used to calibrate probes

[[Page 103]]

for use under this method until the problems are resolved and acceptable
results are obtained upon completion of a subsequent audit.
10.2 Probe Inspection.
10.2.1 Type S probe. Before each calibration of a Type S probe,
verify that one leg of the tube is permanently marked A, and the other,
B. Carefully examine the pitot tube from the top, side, and ends.
Measure the angles (1, 2,
1, and 2) and the dimensions (w
and z) illustrated in Figures 2-2 and 2-3 in Method 2. Also measure the
dimension A, as shown in the diagram in Table 2G-1, and the external
tubing diameter (dimension Dt, Figure 2-2b in Method 2). For
the purposes of this method, Dt shall be no less than 9.5 mm
(\3/8\ in.). The base-to-opening plane distances PA and
PB in Figure 2-3 of Method 2 shall be equal, and the
dimension A in Table 2G-1 should be between 2.10Dt and
3.00Dt. Record the inspection findings and probe measurements
on a form similar to Table CD2-1 of the ``Quality Assurance Handbook for
Air Pollution Measurement Systems: Volume III, Stationary Source-
Specific Methods' (EPA/600/R-94/038c, September 1994). For reference,
this form is reproduced herein as Table 2G-1. The pitot tube shall not
be used under this method if it fails to meet the specifications in this
section and the alignment specifications in section 6.1.1. All Type S
probes used to collect data with this method shall be calibrated
according to the procedures outlined in sections 10.3 through 10.6
below. During calibration, each Type S pitot tube shall be configured in
the same manner as used, or planned to be used, during the field test,
including all components in the probe assembly (e.g., thermocouple,
probe sheath, sampling nozzle). Probe shaft extensions that do not
affect flow around the probe head need not be attached during
calibration.
10.2.2 3-D probe. If a 3-D probe is used to collect data with this
method, perform the pre-calibration inspection according to procedures
in Method 2F, section 10.2.
10.3 Pre-Calibration Procedures. Prior to calibration, a scribe
line shall have been placed on the probe in accordance with section
10.4. The yaw angle and velocity calibration procedures shall not begin
until the pre-test requirements in sections 10.3.1 through 10.3.4 have
been met.
10.3.1 Perform the horizontal straightness check described in
section 8.2 on the probe assembly that will be calibrated in the wind
tunnel.
10.3.2 Perform a leak check in accordance with section 8.4.
10.3.3 Except as noted in section 10.3.3.3, calibrate all
differential pressure-measuring devices to be used in the probe
calibrations, using the following procedures. At a minimum, calibrate
these devices on each day that probe calibrations are performed.
10.3.3.1 Procedure. Before each wind tunnel use, all differential
pressure-measuring devices shall be calibrated against the reference
device specified in section 6.4.3 using a common pressure source.
Perform the calibration at three reference pressures representing 30,
60, and 90 percent of the full-scale range of the pressure-measuring
device being calibrated. For an inclined-vertical manometer, perform
separate calibrations on the inclined and vertical portions of the
measurement scale, considering each portion of the scale to be a
separate full-scale range. [For example, for a manometer with a 0-to
2.5-cm H2O (0-to 1-in. H2O) inclined scale and a
2.5-to 12.7-cm H2O (1-to 5-in. H2O) vertical
scale, calibrate the inclined portion at 7.6, 15.2, and 22.9 mm
H2O (0.3, 0.6, and 0.9 in. H2O), and calibrate the
vertical portion at 3.8, 7.6, and 11.4 cm H2O (1.5, 3.0, and
4.5 in. H2O).] Alternatively, for the vertical portion of the
scale, use three evenly spaced reference pressures, one of which is
equal to or higher than the highest differential pressure expected in
field applications.
10.3.3.2 Acceptance criteria. At each pressure setting, the two
pressure readings made using the reference device and the pressure-
measuring device being calibrated shall agree to within 2
percent of full scale of the device being calibrated or 0.5 mm
H2O (0.02 in. H2O), whichever is less restrictive.
For an inclined-vertical manometer, these requirements shall be met
separately using the respective full-scale upper limits of the inclined
and vertical portions of the scale. Differential pressure-measuring
devices not meeting the 2 percent of full scale or 0.5 mm
H2O (0.02 in. H2O) calibration requirement shall
not be used.
10.3.3.3 Exceptions. Any precision manometer that meets the
specifications for a reference device in section 6.4.3 and that is not
used for field testing does not require calibration, but must be leveled
and zeroed before each wind tunnel use. Any pressure device used
exclusively for yaw nulling does not require calibration, but shall be
checked for responsiveness to rotation of the probe prior to each wind
tunnel use.
10.3.4 Calibrate digital inclinometers on each day of wind tunnel
or field testing (prior to beginning testing) using the following
procedures. Calibrate the inclinometer according to the manufacturer's
calibration procedures. In addition, use a triangular block (illustrated
in Figure 2G-9) with a known angle , independently determined
using a protractor or equivalent device, between two adjacent sides to
verify the inclinometer readings. (Note: If other angle-measuring
devices meeting the provisions of section 6.2.3 are used in place of a
digital inclinometer, comparable calibration procedures shall be
performed on such devices.) Secure the triangular block in a fixed
position. Place the inclinometer on one side of

[[Page 104]]

the block (side A) to measure the angle of inclination (R1).
Repeat this measurement on the adjacent side of the block (side B) using
the inclinometer to obtain a second angle reading (R2). The
difference of the sum of the two readings from 180 deg. (i.e., 180 deg.-
R1-R2) shall be within 2 deg. of the
known angle, .
10.4 Placement of Reference Scribe Line. Prior to the first
calibration of a probe, a line shall be permanently inscribed on the
main probe sheath to serve as a reference mark for determining yaw
angles. Annex C in section 18 of this method gives a guideline for
placement of the reference scribe line.
10.4.1 This reference scribe line shall meet the specifications in
sections 6.1.5.1 and 6.1.5.3 of this method. To verify that the
alignment specification in section 6.1.5.3 is met, secure the probe in a
horizontal position and measure the rotational angle of each scribe line
and scribe line segment using an angle-measuring device that meets the
specifications in section 6.2.1 or 6.2.3. For any scribe line that is
longer than 30.5 cm (12 in.), check the line's rotational position at
30.5-cm (12-in.) intervals. For each line segment that is 12 in. or less
in length, check the rotational position at the two endpoints of the
segment. To meet the alignment specification in section 6.1.5.3, the
minimum and maximum of all of the rotational angles that are measured
along the full length of main probe must not differ by more than 2 deg..
(Note: A short reference scribe line segment [e.g., 15.2 cm (6 in.) or
less in length] meeting the alignment specifications in section 6.1.5.3
is fully acceptable under this method. See section 18.1.1.1 of Annex A
for an example of a probe marking procedure, suitable for use with a
short reference scribe line.)
10.4.2 The scribe line should be placed on the probe first and then
its offset from the yaw-null position established (as specified in
section 10.5). The rotational position of the reference scribe line
relative to the yaw-null position of the probe, as determined by the yaw
angle calibration procedure in section 10.5, is the reference scribe
line rotational offset, RSLO. The reference scribe line
rotational offset shall be recorded and retained as part of the probe's
calibration record.
10.4.3 Scribe line for automated probes. A scribe line may not be
necessary for an automated probe system if a reference rotational
position of the probe is built into the probe system design. For such
systems, a ``flat'' (or comparable, clearly identifiable physical
characteristic) should be provided on the probe casing or flange plate
to ensure that the reference position of the probe assembly remains in a
vertical or horizontal position. The rotational offset of the flat (or
comparable, clearly identifiable physical characteristic) needed to
orient the reference position of the probe assembly shall be recorded
and maintained as part of the automated probe system's specifications.
10.5 Yaw Angle Calibration Procedure. For each probe used to
measure yaw angles with this method, a calibration procedure shall be
performed in a wind tunnel meeting the specifications in section 10.1 to
determine the rotational position of the reference scribe line relative
to the probe's yaw-null position. This procedure shall be performed on
the main probe with all devices that will be attached to the main probe
in the field [such as thermocouples, resistance temperature detectors
(RTDs), or sampling nozzles] that may affect the flow around the probe
head. Probe shaft extensions that do not affect flow around the probe
head need not be attached during calibration. At a minimum, this
procedure shall include the following steps.
10.5.1 Align and lock the angle-measuring device on the reference
scribe line. If a marking procedure (such as described in section
18.1.1.1) is used, align the angle-measuring device on a mark within
1 deg. of the rotational position of the reference scribe
line. Lock the angle-measuring device onto the probe sheath at this
position.
10.5.2 Zero the pressure-measuring device used for yaw nulling.
10.5.3 Insert the probe assembly into the wind tunnel through the
entry port, positioning the probe's impact port at the calibration
location. Check the responsiveness of the pressure-measurement device to
probe rotation, taking corrective action if the response is
unacceptable.
10.5.4 Ensure that the probe is in a horizontal position, using a
carpenter's level.
10.5.5 Rotate the probe either clockwise or counterclockwise until
a yaw null [zero P for a Type S probe or zero (P2-
P3) for a 3-D probe] is obtained. If using a Type S probe
with an attached thermocouple, the direction of the probe rotation shall
be such that the thermocouple is located downstream of the probe
pressure ports at the yaw-null position.
10.5.6 Use the reading displayed by the angle-measuring device at
the yaw-null position to determine the magnitude of the reference scribe
line rotational offset, RSLO, as defined in section 3.15.
Annex D in section 18 of this method gives a recommended procedure for
determining the magnitude of RSLO with a digital inclinometer
and a second procedure for determining the magnitude of RSLO
with a protractor wheel and pointer device. Table 2G-6 gives an example
data form and Table 2G-7 is a look-up table with the recommended
procedure. Procedures other than those recommended in Annex D in section
18 may be used, if they can determine RSLO to within 1 deg.
and are explained in detail in the field test report. The algebraic sign
of RSLO will either be positive if the rotational position of
the reference scribe line (as viewed from the ``tail'' end of the probe)
is clockwise, or negative, if counterclockwise

[[Page 105]]

with respect to the probe's yaw-null position. (This is illustrated in
Figure 2G-10.)
10.5.7 The steps in sections 10.5.3 through 10.5.6 shall be
performed twice at each of the velocities at which the probe will be
calibrated (in accordance with section 10.6). Record the values of
RSLO.
10.5.8 The average of all of the RSLO values shall be
documented as the reference scribe line rotational offset for the probe.
10.5.9 Use of reference scribe line offset. The reference scribe
line rotational offset shall be used to determine the yaw angle of flow
in accordance with section 8.9.4.
10.6 Velocity Calibration Procedure. When a 3-D probe is used under
this method, follow the provisions for the calibration of 3-D probes in
section 10.6 of Method 2F to obtain the necessary velocity calibration
coefficients (F2 as derived using Equation 2F-2 in Method 2F)
corresponding to a pitch angle position of 0 deg.. The following
procedure applies to Type S probes. This procedure shall be performed on
the main probe and all devices that will be attached to the main probe
in the field (e.g., thermocouples, RTDs, sampling nozzles) that may
affect the flow around the probe head. Probe shaft extensions that do
not affect flow around the probe head need not be attached during
calibration. (Note: If a sampling nozzle is part of the assembly, two
additional requirements must be satisfied before proceeding. The
distance between the nozzle and the pitot tube shall meet the minimum
spacing requirement prescribed in Method 2, and a wind tunnel
demonstration shall be performed that shows the probe's ability to yaw
null is not impaired when the nozzle is drawing sample.) To obtain
velocity calibration coefficient(s) for the tested probe, proceed as
follows.
10.6.1 Calibration velocities. The tester may calibrate the probe
at two nominal wind tunnel velocity settings of 18.3 m/sec and 27.4 m/
sec (60 ft/sec and 90 ft/sec) and average the results of these
calibrations, as described in sections 10.6.12 through 10.6.14, in order
to generate the calibration coefficient, Cp. If this option
is selected, this calibration coefficient may be used for all field
applications where the velocities are 9.1 m/sec (30 ft/sec) or greater.
Alternatively, the tester may customize the probe calibration for a
particular field test application (or for a series of applications),
based on the expected average velocity(ies) at the test site(s). If this
option is selected, generate the calibration coefficients by calibrating
the probe at two nominal wind tunnel velocity settings, one of which is
less than or equal to and the other greater than or equal to the
expected average velocity(ies) for the field application(s), and average
the results as described in sections 10.6.12 through 10.6.14. Whichever
calibration option is selected, the probe calibration coefficient(s)
obtained at the two nominal calibration velocities shall meet the
conditions specified in sections 10.6.12 through 10.6.14.
10.6.2 Connect the tested probe and calibration pitot tube to their
respective pressure-measuring devices. Zero the pressure-measuring
devices. Inspect and leak-check all pitot lines; repair or replace them,
if necessary. Turn on the fan, and allow the wind tunnel air flow to
stabilize at the first of the selected nominal velocity settings.
10.6.3 Position the calibration pitot tube at its measurement
location (determined as outlined in section 6.11.4.3), and align the
tube so that its tip is pointed directly into the flow. Ensure that the
entry port surrounding the tube is properly sealed. The calibration
pitot tube may either remain in the wind tunnel throughout the
calibration, or be removed from the wind tunnel while measurements are
taken with the probe being calibrated.
10.6.4 Check the zero setting of each pressure-measuring device.
10.6.5 Insert the tested probe into the wind tunnel and align it so
that the designated pressure port (e.g., either the A-side or B-side of
a Type S probe) is pointed directly into the flow and is positioned
within the wind tunnel calibration location (as defined in section
3.21). Secure the probe at the 0 deg. pitch angle position. Ensure that
the entry port surrounding the probe is properly sealed.
10.6.6 Read the differential pressure from the calibration pitot
tube (Pstd), and record its value. Read the
barometric pressure to within 2.5 mm Hg (0.1 in.
Hg) and the temperature in the wind tunnel to within 0.6 deg.C
(1 deg.F). Record these values on a data form similar to Table 2G-8.
10.6.7 After the tested probe's differential pressure gauges have
had sufficient time to stabilize, yaw null the probe (and then rotate it
back 90 deg. for Type S probes), then obtain the differential pressure
reading (P). Record the yaw angle and differential pressure
readings.
10.6.8 Take paired differential pressure measurements with the
calibration pitot tube and tested probe (according to sections 10.6.6
and 10.6.7). The paired measurements in each replicate can be made
either simultaneously (i.e., with both probes in the wind tunnel) or by
alternating the measurements of the two probes (i.e., with only one
probe at a time in the wind tunnel).
10.6.9 Repeat the steps in sections 10.6.6 through 10.6.8 at the
same nominal velocity setting until three pairs of P readings
have been obtained from the calibration pitot tube and the tested probe.
10.6.10 Repeat the steps in sections 10.6.6 through 10.6.9 above
for the A-side and B-side of the Type S pitot tube. For a probe assembly
constructed such that its pitot tube is always used in the same
orientation, only one side of the pitot tube need be calibrated (the

[[Page 106]]

side that will face the flow). However, the pitot tube must still meet
the alignment and dimension specifications in section 6.1.1 and must
have an average deviation () value of 0.01 or less as provided
in section 10.6.12.4.
10.6.11 Repeat the calibration procedures in sections 10.6.6
through 10.6.10 at the second selected nominal wind tunnel velocity
setting.
10.6.12 Perform the following calculations separately on the A-side
and B-side values.
10.6.12.1 Calculate a Cp value for each of the three
replicates performed at the lower velocity setting where the
calibrations were performed using Equation 2-2 in section 4.1.4 of
Method 2.
10.6.12.2 Calculate the arithmetic average, Cp(avg-low),
of the three Cp values.
10.6.12.3 Calculate the deviation of each of the three individual
values of Cp from the A-side average Cp(avg-low)
value using Equation 2-3 in Method 2.
10.6.12.4 Calculate the average deviation () of the three
individual Cp values from Cp(avg-low) using
Equation 2-4 in Method 2. Use the Type S pitot tube only if the values
of (side A) and (side B) are less than or equal to
0.01. If both A-side and B-side calibration coefficients are calculated,
the absolute value of the difference between Cp(avg-low)
(side A) and Cp(avg-low) (side B) must not exceed 0.01.
10.6.13 Repeat the calculations in section 10.6.12 using the data
obtained at the higher velocity setting to derive the arithmetic
Cp values at the higher velocity setting,
Cp(avg-high), and to determine whether the conditions in
10.6.12.4 are met by both the A-side and B-side calibrations at this
velocity setting.
10.6.14 Use equation 2G-1 to calculate the percent difference of
the averaged Cp values at the two calibration velocities.
[GRAPHIC] [TIFF OMITTED] TR14MY99.062

The percent difference between the averaged Cp values shall
not exceed 3 percent. If the specification is met, average
the A-side values of Cp(avg-low) and Cp(avg-high)
to produce a single A-side calibration coefficient, Cp.
Repeat for the B-side values if calibrations were performed on that side
of the pitot. If the specification is not met, make necessary
adjustments in the selected velocity settings and repeat the calibration
procedure until acceptable results are obtained.
10.6.15 If the two nominal velocities used in the calibration were
18.3 and 27.4 m/sec (60 and 90 ft/sec), the average Cp from
section 10.6.14 is applicable to all velocities 9.1 m/sec (30 ft/sec) or
greater. If two other nominal velocities were used in the calibration,
the resulting average Cp value shall be applicable only in
situations where the velocity calculated using the calibration
coefficient is neither less than the lower nominal velocity nor greater
than the higher nominal velocity.
10.7 Recalibration. Recalibrate the probe using the procedures in
section 10 either within 12 months of its first field use after its most
recent calibration or after 10 field tests (as defined in section 3.3),
whichever occurs later. In addition, whenever there is visible damage to
the probe head, the probe shall be recalibrated before it is used again.
10.8 Calibration of pressure-measuring devices used in the field.
Before its initial use in a field test, calibrate each pressure-
measuring device (except those used exclusively for yaw nulling) using
the three-point calibration procedure described in section 10.3.3. The
device shall be recalibrated according to the procedure in section
10.3.3 no later than 90 days after its first field use following its
most recent calibration. At the discretion of the tester, more frequent
calibrations (e.g., after a field test) may be performed. No
adjustments, other than adjustments to the zero setting, shall be made
to the device between calibrations.
10.8.1 Post-test calibration check. A single-point calibration
check shall be performed on each pressure-measuring device after
completion of each field test. At the discretion of the tester, more
frequent single-point calibration checks (e.g., after one or more field
test runs) may be performed. It is recommended that the post-test check
be performed before leaving the field test site. The check shall be
performed at a pressure between 50 and 90 percent of full scale by
taking a common pressure reading with the tested probe and a reference
pressure-measuring device (as described in section 6.4.4) or by
challenging the tested device with a reference pressure source (as
described in section 6.4.4) or by performing an equivalent check using a
reference device approved by the Administrator.
10.8.2 Acceptance criterion. At the selected pressure setting, the
pressure readings made using the reference device and the tested device
shall agree to within 3 percent of full scale of the tested
device or 0.8 mm H2O

[[Page 107]]

(0.03 in. H2O), whichever is less restrictive. If this
specification is met, the test data collected during the field test are
valid. If the specification is not met, all test data collected since
the last successful calibration or calibration check are invalid and
shall be repeated using a pressure-measuring device with a current,
valid calibration. Any device that fails the calibration check shall not
be used in a field test until a successful recalibration is performed
according to the procedures in section 10.3.3.
10.9 Temperature Gauges. Same as Method 2, section 4.3. The
alternative thermocouple calibration procedures outlined in Emission
Measurement Center (EMC) Approved Alternative Method (ALT-011)
``Alternative Method 2 Thermocouple Calibration Procedure'' may be
performed. Temperature gauges shall be calibrated no more than 30 days
prior to the start of a field test or series of field tests and
recalibrated no more than 30 days after completion of a field test or
series of field tests.
10.10 Barometer. Same as Method 2, section 4.4. The barometer shall
be calibrated no more than 30 days prior to the start of a field test or
series of field tests.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
section 8.0).

12.0 Data Analysis and Calculations

These calculations use the measured yaw angle and the differential
pressure and temperature measurements at individual traverse points to
derive the near-axial flue gas velocity (va(i)) at each of
those points. The near-axial velocity values at all traverse points that
comprise a full stack or duct traverse are then averaged to obtain the
average near-axial stack or duct gas velocity (va(avg)).

12.1 Nomenclature

A = Cross-sectional area of stack or duct at the test port location, m
\2\ (ft \2\).
Bws = Water vapor in the gas stream (from Method 4 or
alternative), proportion by volume.
Cp = Pitot tube calibration coefficient, dimensionless.
F2(i) = 3-D probe velocity coefficient at 0 pitch, applicable
at traverse point i.
Kp = Pitot tube constant,
[GRAPHIC] [TIFF OMITTED] TR14MY99.063

for the metric system, and
[GRAPHIC] [TIFF OMITTED] TR14MY99.064

for the English system.

Pbar = Barometric pressure at velocity measurement site, mm
Hg (in. Hg).
Pg = Stack or duct static pressure, mm H2O (in.
H2O).
Ps = Absolute stack or duct pressure, mm Hg (in. Hg),
[GRAPHIC] [TIFF OMITTED] TR14MY99.066

Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
13.6 = Conversion from mm H2O (in. H2O) to mm Hg
(in. Hg).
Qsd = Average dry-basis volumetric stack or duct gas flow
rate corrected to standard conditions, dscm/hr (dscf/hr).
Qsw = Average wet-basis volumetric stack or duct gas flow
rate corrected to standard conditions, wscm/hr (wscf/hr).
ts(i) = Stack or duct temperature, deg.C ( deg.F), at
traverse point i.
Ts(i) = Absolute stack or duct temperature, deg.K ( deg.R),
at traverse point i.
[GRAPHIC] [TIFF OMITTED] TR14MY99.067

for the metric system, and
[GRAPHIC] [TIFF OMITTED] TR14MY99.068

for the English system.

Ts(avg)=Average absolute stack or duct gas temperature across
all traverse points.
Tstd=Standard absolute temperature, 293 deg.K (528 deg.R).
va(i)=Measured stack or duct gas impact velocity, m/sec (ft/
sec), at traverse point i.
va(avg)=Average near-axial stack or duct gas velocity, m/sec
(ft/sec) across all traverse points.
Pi=Velocity head (differential pressure) of stack or
duct gas, mm H2O (in. H2O), applicable
at traverse point i.
(P1-P2)=Velocity head (differential pressure) of
stack or duct gas measured by a 3-D probe, mm H2O
(in. H2O), applicable at traverse point i.
3,600=Conversion factor, sec/hr.
18.0=Molecular weight of water, g/g-mole (lb/lb-mole).
y(i)=Yaw angle of the flow velocity vector, at
traverse point i.

[[Page 108]]

n=Number of traverse points.

12.2 Traverse Point Velocity Calculations. Perform the following
calculations from the measurements obtained at each traverse point.
12.2.1 Selection of calibration coefficient. Select the calibration
coefficient as described in section 10.6.1.
12.2.2 Near-axial traverse point velocity. When using a Type S
probe, use the following equation to calculate the traverse point near-
axial velocity (va(i)) from the differential pressure
(Pi), yaw angle (y(i)),
absolute stack or duct standard temperature (Ts(i)) measured
at traverse point i, the absolute stack or duct pressure
(Ps), and molecular weight (Ms).
[GRAPHIC] [TIFF OMITTED] TR14MY99.069

Use the following equation when using a 3-D probe.
[GRAPHIC] [TIFF OMITTED] TR14MY99.070

12.2.3 Handling multiple measurements at a traverse point. For
pressure or temperature devices that take multiple measurements at a
traverse point, the multiple measurements (or where applicable, their
square roots) may first be averaged and the resulting average values
used in the equations above. Alternatively, the individual measurements
may be used in the equations above and the resulting calculated values
may then be averaged to obtain a single traverse point value. With
either approach, all of the individual measurements recorded at a
traverse point must be used in calculating the applicable traverse point
value.
12.3 Average Near-Axial Velocity in Stack or Duct. Use the reported
traverse point near-axial velocity in the following equation.
[GRAPHIC] [TIFF OMITTED] TR14MY99.071

12.4 Acceptability of Results. The acceptability provisions in
section 12.4 of Method 2F apply to 3-D probes used under Method 2G. The
following provisions apply to Type S probes. For Type S probes, the test
results are acceptable and the calculated value of va(avg)
may be reported as the average near-axial velocity for the test run if
the conditions in either section 12.4.1 or 12.4.2 are met.
12.4.1 The average calibration coefficient Cp used in
Equation 2G-6 was generated at nominal velocities of 18.3 and 27.4 m/sec
(60 and 90 ft/sec) and the value of va(avg) calculated using
Equation 2G-8 is greater than or equal to 9.1 m/sec (30 ft/sec).
12.4.2 The average calibration coefficient Cp used in
Equation 2G-6 was generated at nominal velocities other than 18.3 or
27.4 m/sec (60 or 90 ft/sec) and the value of va(avg)
calculated using Equation 2G-8 is greater than or equal to the lower
nominal velocity and less than or equal to the higher nominal velocity
used to derive the average Cp.
12.4.3 If the conditions in neither section 12.4.1 nor section
12.4.2 are met, the test results obtained from Equation 2G-8 are not
acceptable, and the steps in sections 12.2 and 12.3 must be repeated
using an average calibration coefficient Cp that satisfies
the conditions in section 12.4.1 or 12.4.2.
12.5 Average Gas Volumetric Flow Rate in Stack or Duct (Wet Basis).
Use the following equation to compute the average volumetric flow rate
on a wet basis.

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[GRAPHIC] [TIFF OMITTED] TR14MY99.072

12.6 Average Gas Volumetric Flow Rate in Stack or Duct (Dry Basis).
Use the following equation to compute the average volumetric flow rate
on a dry basis.
[GRAPHIC] [TIFF OMITTED] TR14MY99.073

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Reporting.

16.1 Field Test Reports. Field test reports shall be submitted to
the Agency according to applicable regulatory requirements. Field test
reports should, at a minimum, include the following elements.
16.1.1 Description of the source. This should include the name and
location of the test site, descriptions of the process tested, a
description of the combustion source, an accurate diagram of stack or
duct cross-sectional area at the test site showing the dimensions of the
stack or duct, the location of the test ports, and traverse point
locations and identification numbers or codes. It should also include a
description and diagram of the stack or duct layout, showing the
distance of the test location from the nearest upstream and downstream
disturbances and all structural elements (including breachings, baffles,
fans, straighteners, etc.) affecting the flow pattern. If the source and
test location descriptions have been previously submitted to the Agency
in a document (e.g., a monitoring plan or test plan), referencing the
document in lieu of including this information in the field test report
is acceptable.
16.1.2 Field test procedures. These should include a description of
test equipment and test procedures. Testing conventions, such as
traverse point numbering and measurement sequence (e.g., sampling from
center to wall, or wall to center), should be clearly stated. Test port
identification and directional reference for each test port should be
included on the appropriate field test data sheets.
16.1.3 Field test data.
16.1.3.1 Summary of results. This summary should include the dates
and times of testing, and the average near-axial gas velocity and the
average flue gas volumetric flow results for each run and tested
condition.
16.1.3.2 Test data. The following values for each traverse point
should be recorded and reported:

(a) Differential pressure at traverse point i
(Pi)
(b) Stack or duct temperature at traverse point i (ts(i))
(c) Absolute stack or duct temperature at traverse point i
(Ts(i))
(d) Yaw angle at traverse point i (y(i))
(e) Stack gas near-axial velocity at traverse point i
(va(i))

16.1.3.3 The following values should be reported once per run:

(a) Water vapor in the gas stream (from Method 4 or alternative),
proportion by volume (Bws), measured at the frequency
specified in the applicable regulation
(b) Molecular weight of stack or duct gas, dry basis (Md)
(c) Molecular weight of stack or duct gas, wet basis (Ms)
(d) Stack or duct static pressure (Pg)
(e) Absolute stack or duct pressure (Ps)
(f) Carbon dioxide concentration in the flue gas, dry basis
(%d CO2)
(g) Oxygen concentration in the flue gas, dry basis (%d
O2)
(h) Average near-axial stack or duct gas velocity
(va(avg)) across all traverse points
(i) Gas volumetric flow rate corrected to standard conditions, dry
or wet basis as required by the applicable regulation (Qsd or
Qsw)

16.1.3.4 The following should be reported once per complete set of
test runs:

(a) Cross-sectional area of stack or duct at the test location (A)
(b) Pitot tube calibration coefficient (Cp)
(c) Measurement system response time (sec)
(d) Barometric pressure at measurement site (Pbar)

16.1.4 Calibration data. The field test report should include
calibration data for all

[[Page 110]]

probes and test equipment used in the field test. At a minimum, the
probe calibration data reported to the Agency should include the
following:

(a) Date of calibration
(b) Probe type
(c) Probe identification number(s) or code(s)
(d) Probe inspection sheets
(e) Pressure measurements and calculations used to obtain
calibration coefficients in accordance with section 10.6 of this method
(f) Description and diagram of wind tunnel used for the calibration,
including dimensions of cross-sectional area and position and size of
the test section
(g) Documentation of wind tunnel qualification tests performed in
accordance with section 10.1 of this method

16.1.5 Quality assurance. Specific quality assurance and quality
control procedures used during the test should be described.

17.0 Bibliography.

(1) 40 CFR Part 60, Appendix A, Method 1--Sample and velocity
traverses for stationary sources.
(2) 40 CFR Part 60, Appendix A, Method 2--Determination of stack gas
velocity and volumetric flow rate (Type S pitot tube) .
(3) 40 CFR Part 60, Appendix A, Method 2F--Determination of stack
gas velocity and volumetric flow rate with three-dimensional probes.
(4) 40 CFR Part 60, Appendix A, Method 2H--Determination of stack
gas velocity taking into account velocity decay near the stack wall.
(5) 40 CFR Part 60, Appendix A, Method 3--Gas analysis for carbon
dioxide, oxygen, excess air, and dry molecular weight.
(6) 40 CFR Part 60, Appendix A, Method 3A--Determination of oxygen
and carbon dioxide concentrations in emissions from stationary sources
(instrumental analyzer procedure).
(7) 40 CFR Part 60, Appendix A, Method 4--Determination of moisture
content in stack gases.
(8) Emission Measurement Center (EMC) Approved Alternative Method
(ALT-011) ``Alternative Method 2 Thermocouple Calibration Procedure.''
(9) Electric Power Research Institute, Interim Report EPRI TR-
106698, ``Flue Gas Flow Rate Measurement Errors,'' June 1996.
(10) Electric Power Research Institute, Final Report EPRI TR-108110,
``Evaluation of Heat Rate Discrepancy from Continuous Emission
Monitoring Systems,'' August 1997.
(11) Fossil Energy Research Corporation, Final Report, ``Velocity
Probe Tests in Non-axial Flow Fields,'' November 1998, Prepared for the
U.S. Environmental Protection Agency.
(12) Fossil Energy Research Corporation, ``Additional Swirl Tunnel
Tests: E-DAT and T-DAT Probes,'' February 24, 1999, Technical Memorandum
Prepared for U.S. Environmental Protection Agency, P.O. No. 7W-1193-
NALX.
(13) Massachusetts Institute of Technology, Report WBWT-TR-1317,
``Calibration of Eight Wind Speed Probes Over a Reynolds Number Range of
46,000 to 725,000 Per Foot, Text and Summary Plots,'' Plus appendices,
October 15, 1998, Prepared for The Cadmus Group, Inc.
(14) National Institute of Standards and Technology, Special
Publication 250, ``NIST Calibration Services Users Guide 1991,'' Revised
October 1991, U.S. Department of Commerce, p. 2.
(15) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four Prandtl Probes, Four
S-Type Probes, Four French Probes, Four Modified Kiel Probes,'' Prepared
for the U.S. Environmental Protection Agency under IAG #DW13938432-01-0.
(16) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed In-strumentation, Five Autoprobes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(17) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Eight Spherical Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(18) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four DAT Probes, ``
Prepared for the U.S. Environmental Protection Agency under IAG
#DW13938432-01-0.
(19) Norfleet, S.K., ``An Evaluation of Wall Effects on Stack Flow
Velocities and Related Overestimation Bias in EPA's Stack Flow Reference
Methods,'' EPRI CEMS User's Group Meeting, New Orleans, Louisiana, May
13-15, 1998.
(20) Page, J.J., E.A. Potts, and R.T. Shigehara, ``3-D Pitot Tube
Calibration Study,'' EPA Contract No. 68D10009, Work Assignment No. I-
121, March 11, 1993.
(21) Shigehara, R.T., W.F. Todd, and W.S. Smith, ``Significance of
Errors in Stack Sampling Measurements,'' Presented at the Annual Meeting
of the Air Pollution Control Association, St. Louis, Missouri, June
1419, 1970.
(22) The Cadmus Group, Inc., May 1999, ``EPA Flow Reference Method
Testing and Analysis: Findings Report,'' EPA/430-R-99-009.
(23) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, DeCordova Steam
Electric Station, Volume

[[Page 111]]

I: Test Description and Appendix A (Data Distribution Package),'' EPA/
430-R-98-015a.
(24) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, Lake Hubbard Steam
Electric Station, Volume I: Test Description and Appendix A (Data
Distribution Package),'' EPA/430-R-98-017a.
(25) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Pennsylvania Electric Co., G.P.U.
Genco Homer City Station: Unit 1, Volume I: Test Description and
Appendix A (Data Distribution Package),'' EPA/430-R-98-018a.
(26) The Cadmus Group, Inc., 1997, ``EPA Flow Reference Method
Testing and Analysis: Wind Tunnel Experimental Results,'' EPA/430-R-97-
013.

18.0 Annexes

Annex A, C, and D describe recommended procedures for meeting
certain provisions in sections 8.3, 10.4, and 10.5 of this method. Annex
B describes procedures to be followed when using the protractor wheel
and pointer assembly to measure yaw angles, as provided under section
8.9.1.
18.1 Annex A--Rotational Position Check. The following are
recommended procedures that may be used to satisfy the rotational
position check requirements of section 8.3 of this method and to
determine the angle-measuring device rotational offset
(RADO).
18.1.1 Rotational position check with probe outside stack. Where
physical constraints at the sampling location allow full assembly of the
probe outside the stack and insertion into the test port, the following
procedures should be performed before the start of testing. Two angle-
measuring devices that meet the specifications in section 6.2.1 or 6.2.3
are required for the rotational position check. An angle measuring
device whose position can be independently adjusted (e.g., by means of a
set screw) after being locked into position on the probe sheath shall
not be used for this check unless the independent adjustment is set so
that the device performs exactly like a device without the capability
for independent adjustment. That is, when aligned on the probe such a
device must give the same reading as a device that does not have the
capability of being independently adjusted. With the fully assembled
probe (including probe shaft extensions, if any) secured in a horizontal
position, affix one yaw angle-measuring device to the probe sheath and
lock it into position on the reference scribe line specified in section
6.1.5.1. Position the second angle-measuring device using the procedure
in section 18.1.1.1 or 18.1.1.2.
18.1.1.1 Marking procedure. The procedures in this section should
be performed at each location on the fully assembled probe where the yaw
angle-measuring device will be mounted during the velocity traverse.
Place the second yaw angle-measuring device on the main probe sheath (or
extension) at the position where a yaw angle will be measured during the
velocity traverse. Adjust the position of the second angle-measuring
device until it indicates the same angle (1 deg.) as the
reference device, and affix the second device to the probe sheath (or
extension). Record the angles indicated by the two angle-measuring
devices on a form similar to table 2G-2. In this position, the second
angle-measuring device is considered to be properly positioned for yaw
angle measurement. Make a mark, no wider than 1.6 mm (\1/16\ in.), on
the probe sheath (or extension), such that the yaw angle-measuring
device can be re-affixed at this same properly aligned position during
the velocity traverse.
18.1.1.2 Procedure for probe extensions with scribe lines. If,
during a velocity traverse the angle-measuring device will be affixed to
a probe extension having a scribe line as specified in section 6.1.5.2,
the following procedure may be used to align the extension's scribe line
with the reference scribe line instead of marking the extension as
described in section 18.1.1.1. Attach the probe extension to the main
probe. Align and lock the second angle-measuring device on the probe
extension's scribe line. Then, rotate the extension until both measuring
devices indicate the same angle (1 deg.). Lock the extension
at this rotational position. Record the angles indicated by the two
angle-measuring devices on a form similar to table 2G-2. An angle-
measuring device may be aligned at any position on this scribe line
during the velocity traverse, if the scribe line meets the alignment
specification in section 6.1.5.3.
18.1.1.3 Post-test rotational position check. If the fully
assembled probe includes one or more extensions, the following check
should be performed immediately after the completion of a velocity
traverse. At the discretion of the tester, additional checks may be
conducted after completion of testing at any sample port. Without
altering the alignment of any of the components of the probe assembly
used in the velocity traverse, secure the fully assembled probe in a
horizontal position. Affix an angle-measuring device at the reference
scribe line specified in section 6.1.5.1. Use the other angle-measuring
device to check the angle at each location where the device was checked
prior to testing. Record the readings from the two angle-measuring
devices.
18.1.2 Rotational position check with probe in stack. This section
applies only to probes that, due to physical constraints, cannot be
inserted into the test port as fully assembled with all necessary
extensions needed to reach the inner-most traverse point(s).
18.1.2.1 Perform the out-of-stack procedure in section 18.1.1 on
the main probe and

[[Page 112]]

any attached extensions that will be initially inserted into the test
port.
18.1.2.2 Use the following procedures to perform additional
rotational position check(s) with the probe in the stack, each time a
probe extension is added. Two angle-measuring devices are required. The
first of these is the device that was used to measure yaw angles at the
preceding traverse point, left in its properly aligned measurement
position. The second angle-measuring device is positioned on the added
probe extension. Use the applicable procedures in section 18.1.1.1 or
18.1.1.2 to align, adjust, lock, and mark (if necessary) the position of
the second angle-measuring device to within 1 deg. of the
first device. Record the readings of the two devices on a form similar
to Table 2G-2.
18.1.2.3 The procedure in section 18.1.2.2 should be performed at
the first port where measurements are taken. The procedure should be
repeated each time a probe extension is re-attached at a subsequent
port, unless the probe extensions are designed to be locked into a
mechanically fixed rotational position (e.g., through use of
interlocking grooves), which can be reproduced from port to port as
specified in section 8.3.5.2.
18.2 Annex B--Angle Measurement Protocol for Protractor Wheel and
Pointer Device. The following procedure shall be used when a protractor
wheel and pointer assembly, such as the one described in section 6.2.2
and illustrated in Figure 2G-5 is used to measure the yaw angle of flow.
With each move to a new traverse point, unlock, re-align, and re-lock
the probe, angle-pointer collar, and protractor wheel to each other. At
each such move, particular attention is required to ensure that the
scribe line on the angle pointer collar is either aligned with the
reference scribe line on the main probe sheath or is at the rotational
offset position established under section 8.3.1. The procedure consists
of the following steps:
18.2.1 Affix a protractor wheel to the entry port for the test
probe in the stack or duct.
18.2.2 Orient the protractor wheel so that the 0 deg. mark
corresponds to the longitudinal axis of the stack or duct. For stacks,
vertical ducts, or ports on the side of horizontal ducts, use a digital
inclinometer meeting the specifications in section 6.2.1 to locate the
0 deg. orientation. For ports on the top or bottom of horizontal ducts,
identify the longitudinal axis at each test port and permanently mark
the duct to indicate the 0 deg. orientation. Once the protractor wheel
is properly aligned, lock it into position on the test port.
18.2.3 Move the pointer assembly along the probe sheath to the
position needed to take measurements at the first traverse point. Align
the scribe line on the pointer collar with the reference scribe line or
at the rotational offset position established under section 8.3.1.
Maintaining this rotational alignment, lock the pointer device onto the
probe sheath. Insert the probe into the entry port to the depth needed
to take measurements at the first traverse point.
18.2.4 Perform the yaw angle determination as specified in sections
8.9.3 and 8.9.4 and record the angle as shown by the pointer on the
protractor wheel. Then, take velocity pressure and temperature
measurements in accordance with the procedure in section 8.9.5. Perform
the alignment check described in section 8.9.6.
18.2.5 After taking velocity pressure measurements at that traverse
point, unlock the probe from the collar and slide the probe through the
collar to the depth needed to reach the next traverse point.
18.2.6 Align the scribe line on the pointer collar with the
reference scribe line on the main probe or at the rotational offset
position established under section 8.3.1. Lock the collar onto the
probe.
18.2.7 Repeat the steps in sections 18.2.4 through 18.2.6 at the
remaining traverse points accessed from the current stack or duct entry
port.
18.2.8 After completing the measurement at the last traverse point
accessed from a port, verify that the orientation of the protractor
wheel on the test port has not changed over the course of the traverse
at that port. For stacks, vertical ducts, or ports on the side of
horizontal ducts, use a digital inclinometer meeting the specifications
in section 6.2.1 to check the rotational position of the 0 deg. mark on
the protractor wheel. For ports on the top or bottom of horizontal
ducts, observe the alignment of the angle wheel 0 deg. mark relative to
the permanent 0 deg. mark on the duct at that test port. If these
observed comparisons exceed 2 deg. of 0 deg., all angle and
pressure measurements taken at that port since the protractor wheel was
last locked into position on the port shall be repeated.
18.2.9 Move to the next stack or duct entry port and repeat the
steps in sections 18.2.1 through 18.2.8.
18.3 Annex C--Guideline for Reference Scribe Line Placement. Use of
the following guideline is recommended to satisfy the requirements of
section 10.4 of this method. The rotational position of the reference
scribe line should be either 90 deg. or 180 deg. from the probe's impact
pressure port. For Type-S probes, place separate scribe lines, on
opposite sides of the probe sheath, if both the A and B sides of the
pitot tube are to be used for yaw angle measurements.
18.4 Annex D--Determination of Reference Scribe Line Rotational
Offset. The following procedures are recommended for determining the
magnitude and sign of a probe's reference scribe line rotational offset,
RSLO. Separate procedures are provided for two types of
angle-measuring devices:

[[Page 113]]

digital inclinometers and protractor wheel and pointer assemblies.
18.4.1 Perform the following procedures on the main probe with all
devices that will be attached to the main probe in the field [such as
thermocouples, resistance temperature detectors (RTDs), or sampling
nozzles] that may affect the flow around the probe head. Probe shaft
extensions that do not affect flow around the probe head need not be
attached during calibration.
18.4.2 The procedures below assume that the wind tunnel duct used
for probe calibration is horizontal and that the flow in the calibration
wind tunnel is axial as determined by the axial flow verification check
described in section 10.1.2. Angle-measuring devices are assumed to
display angles in alternating 0 deg. to 90 deg. and 90 deg. to 0 deg.
intervals. If angle-measuring devices with other readout conventions are
used or if other calibration wind tunnel duct configurations are used,
make the appropriate calculational corrections. For Type-S probes,
calibrate the A-side and B-sides separately, using the appropriate
scribe line (see section 18.3, above), if both the A and B sides of the
pitot tube are to be used for yaw angle determinations.
18.4.2.1 Position the angle-measuring device in accordance with one
of the following procedures.
18.4.2.1.1 If using a digital inclinometer, affix the calibrated
digital inclinometer to the probe. If the digital inclinometer can be
independently adjusted after being locked into position on the probe
sheath (e.g., by means of a set screw), the independent adjustment must
be set so that the device performs exactly like a device without the
capability for independent adjustment. That is, when aligned on the
probe the device must give the same readings as a device that does not
have the capability of being independently adjusted. Either align it
directly on the reference scribe line or on a mark aligned with the
scribe line determined according to the procedures in section 18.1.1.1.
Maintaining this rotational alignment, lock the digital inclinometer
onto the probe sheath.
18.4.2.1.2 If using a protractor wheel and pointer device, orient
the protractor wheel on the test port so that the 0 deg. mark is aligned
with the longitudinal axis of the wind tunnel duct. Maintaining this
alignment, lock the wheel into place on the wind tunnel test port. Align
the scribe line on the pointer collar with the reference scribe line or
with a mark aligned with the reference scribe line, as determined under
section 18.1.1.1. Maintaining this rotational alignment, lock the
pointer device onto the probe sheath.
18.4.2.2 Zero the pressure-measuring device used for yaw nulling.
18.4.2.3 Insert the probe assembly into the wind tunnel through the
entry port, positioning the probe's impact port at the calibration
location. Check the responsiveness of the pressure-measuring device to
probe rotation, taking corrective action if the response is
unacceptable.
18.4.2.4 Ensure that the probe is in a horizontal position using a
carpenter's level.
18.4.2.5 Rotate the probe either clockwise or counterclockwise
until a yaw null [zero P for a Type S probe or zero
(P2-P3) for a 3-D probe] is obtained. If using a
Type S probe with an attached thermocouple, the direction of the probe
rotation shall be such that the thermocouple is located downstream of
the probe pressure ports at the yaw-null position.
18.4.2.6 Read and record the value of null,
the angle indicated by the angle-measuring device at the yaw-null
position. Record the angle reading on a form similar to Table 2G-6. Do
not associate an algebraic sign with this reading.
18.4.2.7 Determine the magnitude and algebraic sign of the
reference scribe line rotational offset, RSLO. The magnitude
of RSLO will be equal to either null or
(90 deg.-null), depending on the type of probe
being calibrated and the type of angle-measuring device used. (See Table
2G-7 for a summary.) The algebraic sign of RSLO will either
be positive if the rotational position of the reference scribe line is
clockwise or negative if counterclockwise with respect to the probe's
yaw-null position. Figure 2G-10 illustrates how the magnitude and sign
of RSLO are determined.
18.4.2.8 Perform the steps in sections 18.3.2.3 through 18.3.2.7
twice at each of the two calibration velocities selected for the probe
under section 10.6. Record the values of RSLO in a form
similar to Table 2G-6.
18.4.2.9 The average of all RSLO values is the reference
scribe line rotational offset for the probe.

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Method 2H--Determination of Stack Gas Velocity Taking Into Account
Velocity Decay Near the Stack Wall

1.0 Scope and Application

1.1 This method is applicable in conjunction with Methods 2, 2F,
and 2G (40 CFR Part 60, Appendix A) to account for velocity decay near
the wall in circular stacks and ducts.
1.2 This method is not applicable for testing stacks and ducts less
than 3.3 ft (1.0 m) in diameter.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A wall effects adjustment factor is determined. It is used to
adjust the average stack gas velocity obtained under Method 2, 2F, or 2G
of this appendix to take into account velocity decay near the stack or
duct wall.
2.2 The method contains two possible procedures: a calculational
approach which derives an adjustment factor from velocity measurements
and a default procedure which assigns a generic adjustment factor based
on the construction of the stack or duct.
2.2.1 The calculational procedure derives a wall effects adjustment
factor from velocity measurements taken using Method 2, 2F, or 2G at 16
(or more) traverse points specified under Method 1 of this appendix and
a total of eight (or more) wall effects traverse points specified under
this method. The calculational procedure based on velocity measurements
is not applicable for horizontal circular ducts where build-up of
particulate matter or other material in the bottom of the duct is
present.
2.2.2 A default wall effects adjustment factor of 0.9900 for brick
and mortar stacks and 0.9950 for all other types of stacks and ducts may
be used without taking wall effects measurements in a stack or duct.
2.3 When the calculational procedure is conducted as part of a
relative accuracy test audit (RATA) or other multiple-run test
procedure, the wall effects adjustment factor derived from a single
traverse (i.e., single RATA run) may be applied to all runs of the same
RATA without repeating the wall effects measurements. Alternatively,
wall effects adjustment factors may be derived for several traverses and
an average wall effects adjustment factor applied to all runs of the
same RATA.
3.0 Definitions.
3.1 Complete wall effects traverse means a traverse in which
measurements are taken at drem (see section 3.3) and at 1-in.
intervals in each of the four Method 1 equal-area sectors closest to the
wall, beginning not farther than 4 in. (10.2 cm) from the wall and
extending either (1) across the entire width of the Method 1 equal-area
sector or (2) for stacks or ducts where this width exceeds 12 in. (30.5
cm) (i.e., stacks or ducts greater than or equal to 15.6 ft [4.8 m] in
diameter), to a distance of not less than 12 in. (30.5 cm) from the
wall. Note: Because this method specifies that measurements must be
taken at whole number multiples of 1 in. from a stack or duct wall, for
clarity numerical quantities in this method are expressed in English
units followed by metric units in parentheses. To enhance readability,
hyphenated terms such as ``1-in. intervals'' or ``1-in. incremented,''
are expressed in English units only.
3.2 dlast Depending on context, dlast means
either (1) the distance from the wall of the last 1-in. incremented wall
effects traverse point or (2) the traverse point located at that
distance (see Figure 2H-2).
3.3 drem Depending on context, drem means
either (1) the distance from the wall of the centroid of the area
between dlast and the interior edge of the Method 1 equal-
area sector closest to the wall or (2) the traverse point located at
that distance (see Figure 2H-2).
3.4 ``May,'' ``Must,'' ``Shall,'' ``Should,'' and the imperative
form of verbs.
3.4.1 ``May'' is used to indicate that a provision of this method
is optional.
3.4.2 ``Must,'' ``Shall,'' and the imperative form of verbs (such
as ``record'' or ``enter'') are used to indicate that a provision of
this method is mandatory.
3.4.3 ``Should'' is used to indicate that a provision of this
method is not mandatory but is highly recommended as good practice.
3.5 Method 1 refers to 40 CFR part 60, appendix A, ``Method 1--
Sample and velocity traverses for stationary sources.''
3.6 Method 1 exterior equal-area sector and Method 1 equal-area
sector closest to the wall mean any one of the four equal-area sectors
that are closest to the wall for a circular stack or duct laid out in
accordance with section 2.3.1 of Method 1 (see Figure 2H-1).
3.7 Method 1 interior equal-area sector means any of the equal-area
sectors other than the Method 1 exterior equal-area sectors (as defined
in section 3.6) for a circular stack or duct laid out in accordance with
section 2.3.1 of Method 1 (see Figure 2H-1).
3.8 Method 1 traverse point and Method 1 equal-area traverse point
mean a traverse point located at the centroid of an equal-area sector of
a circular stack laid out in accordance with section 2.3.1 of Method 1.
3.9 Method 2 refers to 40 CFR part 60, appendix A, ``Method 2--
Determination of stack gas velocity and volumetric flow rate (Type S
pitot tube).''
3.10 Method 2F refers to 40 CFR part 60, appendix A, ``Method 2F--
Determination of stack gas velocity and volumetric flow rate with three-
dimensional probes.''

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3.11 Method 2G refers to 40 CFR part 60, appendix A, ``Method 2G--
Determination of stack gas velocity and volumetric flow rate with two-
dimensional probes.''
3.12 1-in. incremented wall effects traverse point means any of the
wall effects traverse points that are located at 1-in. intervals, i.e.,
traverse points d1 through dlast (see Figure 2H-
2).
3.13 Partial wall effects traverse means a traverse in which
measurements are taken at fewer than the number of traverse points
required for a ``complete wall effects traverse'' (as defined in section
3.1), but are taken at a minimum of two traverse points in each Method 1
equal-area sector closest to the wall, as specified in section 8.2.2.
3.14 Relative accuracy test audit (RATA) is a field test procedure
performed in a stack or duct in which a series of concurrent
measurements of the same stack gas stream is taken by a reference method
and an installed monitoring system. A RATA usually consists of series of
9 to 12 sets of such concurrent measurements, each of which is referred
to as a RATA run. In a volumetric flow RATA, each reference method run
consists of a complete traverse of the stack or duct.
3.15 Wall effects-unadjusted average velocity means the average
stack gas velocity, not accounting for velocity decay near the wall, as
determined in accordance with Method 2, 2F, or 2G for a Method 1
traverse consisting of 16 or more points.
3.16 Wall effects-adjusted average velocity means the average stack
gas velocity, taking into account velocity decay near the wall, as
calculated from measurements at 16 or more Method 1 traverse points and
at the additional wall effects traverse points specified in this method.
3.17 Wall effects traverse point means a traverse point located in
accordance with sections 8.2.2 or 8.2.3 of this method.

4.0 Interferences. [Reserved]

5.0 Safety

5.1 This method may involve hazardous materials, operations, and
equipment. This method does not purport to address all of the health and
safety considerations associated with its use. It is the responsibility
of the user of this method to establish appropriate health and safety
practices and to determine the applicability of occupational health and
safety regulatory requirements prior to performing this method.

6.0 Equipment and Supplies

6.1 The provisions pertaining to equipment and supplies in the
method that is used to take the traverse point measurements (i.e.,
Method 2, 2F, or 2G) are applicable under this method.

7.0 Reagents and Standards. [Reserved]

8.0 Sample Collection and Analysis

8.1 Default Wall Effects Adjustment Factors. A default wall effects
adjustment factor of 0.9900 for brick and mortar stacks and 0.9950 for
all other types of stacks and ducts may be used without conducting the
following procedures.
8.2 Traverse Point Locations. Determine the location of the Method
1 traverse points in accordance with section 8.2.1 and the location of
the traverse points for either a partial wall effects traverse in
accordance with section 8.2.2 or a complete wall effects traverse in
accordance with section 8.2.3.
8.2.1 Method 1 equal-area traverse point locations. Determine the
location of the Method 1 equal-area traverse points for a traverse
consisting of 16 or more points using Table 1-2 (Location of Traverse
Points in Circular Stacks) of Method 1.
8.2.2 Partial wall effects traverse. For a partial wall effects
traverse, measurements must be taken at a minimum of the following two
wall effects traverse point locations in all four Method 1 equal-area
sectors closest to the wall: (1) 1 in. (2.5 cm) from the wall (except as
provided in section 8.2.2.1) and (2) drem, as determined
using Equation 2H-1 or 2H-2 (see section 8.2.2.2).
8.2.2.1 If the probe cannot be positioned at 1 in. (2.5 cm) from
the wall (e.g., because of insufficient room to withdraw the probe
shaft) or if velocity pressure cannot be detected at 1 in. (2.5 cm) from
the wall (for any reason other than build-up of particulate matter in
the bottom of a duct), take measurements at the 1-in. incremented wall
effects traverse point closest to the wall where the probe can be
positioned and velocity pressure can be detected.
8.2.2.2 Calculate the distance of drem from the wall to
within \1/4\ in. (6.4 mm) using Equation 2H-1 or Equation
2H-2 (for a 16-point traverse).
[GRAPHIC] [TIFF OMITTED] TR14MY99.074

Where:

r = the stack or duct radius determined from direct measurement of the
stack or duct diameter in accordance with section 8.6 of
Method 2F or Method 2G, in. (cm);
p = the number of Method 1 equal-area traverse points on a diameter, p
8 (e.g., for a 16-point traverse, p = 8);
dlast and drem are defined in sections
3.2 and 3.3 respectively, in. (cm).

For a 16-point Method 1 traverse, Equation 2H-1 becomes:

[[Page 131]]

[GRAPHIC] [TIFF OMITTED] TR14MY99.075

8.2.2.3 Measurements may be taken at any number of additional wall
effects traverse points, with the following provisions.
(a) dlast must not be closer to the center of the stack
or duct than the distance of the interior edge (boundary),
db, of the Method 1 equal-area sector closest to the wall
(see Figure 2H-2 or 2H-3). That is,

Where:
[GRAPHIC] [TIFF OMITTED] TR14MY99.076

Table 2H-1 shows db as a function of the stack or duct
radius, r, for traverses ranging from 16 to 48 points (i.e., for values
of p ranging from 8 to 24).
(b) Each point must be located at a distance that is a whole number
(e.g., 1, 2, 3) multiple of 1 in. (2.5 cm).
(c) Points do not have to be located at consecutive 1-in. intervals.
That is, one or more 1-in. incremented points may be skipped. For
example, it would be acceptable for points to be located at 1 in. (2.5
cm), 3 in. (7.6 cm), 5 in. (12.7 cm), dlast, and
drem; or at 1 in. (2.5 cm), 2 in. (5.1 cm), 4 in. (10.2 cm),
7 in. (17.8 cm), dlast, and drem. Follow the
instructions in section 8.7.1.2 of this method for recording results for
wall effects traverse points that are skipped. It should be noted that
the full extent of velocity decay may not be accounted for if
measurements are not taken at all 1-in. incremented points close to the
wall.
8.2.3 Complete wall effects traverse. For a complete wall effects
traverse, measurements must be taken at the following points in all four
Method 1 equal-area sectors closest to the wall.
(a) The 1-in. incremented wall effects traverse point closest to the
wall where the probe can be positioned and velocity can be detected, but
no farther than 4 in. (10.2 cm) from the wall.
(b) Every subsequent 1-in. incremented wall effects traverse point
out to the interior edge of the Method 1 equal-area sector or to 12 in.
(30.5 cm) from the wall, whichever comes first. Note: In stacks or ducts
with diameters greater than 15.6 ft (4.8 m) the interior edge of the
Method 1 equal-area sector is farther from the wall than 12 in. (30.5
cm).
(c) drem, as determined using Equation 2H-1 or 2H-2 (as
applicable). Note: For a complete traverse of a stack or duct with a
diameter less than 16.5 ft (5.0 m), the distance between
drem and dlast is less than or equal to \1/2\ in.
(12.7 mm). As discussed in section 8.2.4.2, when the distance between
drem and dlast is less than or equal to \1/2\ in.
(12.7 mm), the velocity measured at dlast may be used for
drem. Thus, it is not necessary to calculate the distance of
drem or to take measurements at drem when
conducting a complete traverse of a stack or duct with a diameter less
than 16.5 ft (5.0 m).
8.2.4 Special considerations. The following special considerations
apply when the distance between traverse points is less than or equal to
\1/2\ in. (12.7 mm).
8.2.4.1 A wall effects traverse point and the Method 1 traverse
point. If the distance between a wall effects traverse point and the
Method 1 traverse point is less than or equal to \1/2\ in. (12.7 mm),
taking measurements at both points is allowed but not required or
recommended; if measurements are taken at only one point, take the
measurements at the point that is farther from the wall and use the
velocity obtained at that point as the value for both points (see
sections 8.2.3 and 9.2 for related requirements).
8.2.4.2 drem and dlast. If the distance
between drem and dlast is less than or equal to
\1/2\ in. (12.7 mm), taking measurements at drem is allowed
but not required or recommended; if measurements are not taken at
drem, the measured velocity value at dlast must be
used as the value for both dlast and drem.
8.3 Traverse Point Sampling Order and Probe Selection. Determine
the sampling order of the Method 1 and wall effects traverse points and
select the appropriate probe for the measurements, taking into account
the following considerations.
8.3.1 Traverse points on any radius may be sampled in either
direction (i.e., from the wall toward the center of the stack or duct,
or vice versa).
8.3.2 To reduce the likelihood of velocity variations during the
time of the traverse and the attendant potential impact on the wall
effects-adjusted and unadjusted average velocities, the following
provisions of this method shall be met.
8.3.2.1 Each complete set of Method 1 and wall effects traverse
points accessed from the same port shall be sampled without
interruption. Unless traverses are performed simultaneously in all ports
using separate probes at each port, this provision disallows first
sampling all Method 1 points at all ports and then sampling all the wall
effects points.
8.3.2.2 The entire integrated Method 1 and wall effects traverse
across all test ports shall be as short as practicable, consistent with
the measurement system response time

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(see section 8.4.1.1) and sampling (see section 8.4.1.2) provisions of
this method.
8.3.3 It is recommended but not required that in each Method 1
equal-area sector closest to the wall, the Method 1 equal-area traverse
point should be sampled in sequence between the adjacent wall effects
traverse points. For example, for the traverse point configuration shown
in Figure 2H-2, it is recommended that the Method 1 equal-area traverse
point be sampled between dlast and drem. In this
example, if the traverse is conducted from the wall toward the center of
the stack or duct, it is recommended that measurements be taken at
points in the following order: d1, d2,
dlast, the Method 1 traverse point, drem, and then
at the traverse points in the three Method 1 interior equal-area
sectors.
8.3.4 The same type of probe must be used to take measurements at
all Method 1 and wall effects traverse points. However, different copies
of the same type of probe may be used at different ports (e.g., Type S
probe 1 at port A, Type S probe 2 at port B) or at different traverse
points accessed from a particular port (e.g., Type S probe 1 for Method
1 interior traverse points accessed from port A, Type S probe 2 for wall
effects traverse points and the Method 1 exterior traverse point
accessed from port A). The identification number of the probe used to
obtain measurements at each traverse point must be recorded.
8.4 Measurements at Method 1 and Wall Effects Traverse Points.
Conduct measurements at Method 1 and wall effects traverse points in
accordance with Method 2, 2F, or 2G and in accordance with the
provisions of the following subsections (some of which are included in
Methods 2F and 2G but not in Method 2), which are particularly important
for wall effects testing.
8.4.1 Probe residence time at wall effects traverse points. Due to
the steep temperature and pressure gradients that can occur close to the
wall, it is very important for the probe residence time (i.e., the total
time spent at a traverse point) to be long enough to ensure collection
of representative temperature and pressure measurements. The provisions
of Methods 2F and 2G in the following subsections shall be observed.
8.4.1.1 System response time. Determine the response time of each
probe measurement system by inserting and positioning the ``cold'' probe
(at ambient temperature and pressure) at any Method 1 traverse point.
Read and record the probe differential pressure, temperature, and
elapsed time at 15-second intervals until stable readings for both
pressure and temperature are achieved. The response time is the longer
of these two elapsed times. Record the response time.
8.4.1.2 Sampling. At the start of testing in each port (i.e., after
a probe has been inserted into the stack gas stream), allow at least the
response time to elapse before beginning to take measurements at the
first traverse point accessed from that port. Provided that the probe is
not removed from the stack gas stream, measurements may be taken at
subsequent traverse points accessed from the same test port without
waiting again for the response time to elapse.
8.4.2 Temperature measurement for wall effects traverse points.
Either (1) take temperature measurements at each wall effects traverse
point in accordance with the applicable provisions of Method 2, 2F, or
2G; or (2) use the temperature measurement at the Method 1 traverse
point closest to the wall as the temperature measurement for all the
wall effects traverse points in the corresponding equal-area sector.
8.4.3 Non-detectable velocity pressure at wall effects traverse
points. If the probe cannot be positioned at a wall effects traverse
point or if no velocity pressure can be detected at a wall effects
point, measurements shall be taken at the first subsequent wall effects
traverse point farther from the wall where velocity can be detected.
Follow the instructions in section 8.7.1.2 of this method for recording
results for wall effects traverse points where velocity pressure cannot
be detected. It should be noted that the full extent of velocity decay
may not be accounted for if measurements are not taken at the 1-in.
incremented wall effects traverse points closest to the wall.
8.5 Data Recording. For each wall effects and Method 1 traverse
point where measurements are taken, record all pressure, temperature,
and attendant measurements prescribed in section 3 of Method 2 or
section 8.0 of Method 2F or 2G, as applicable.
8.6 Point Velocity Calculation. For each wall effects and Method 1
traverse point, calculate the point velocity value (vi) in
accordance with sections 12.1 and 12.2 of Method 2F for tests using
Method 2F and in accordance with sections 12.1 and 12.2 of Method 2G for
tests using Method 2 and Method 2G. (Note that the term (vi)
in this method corresponds to the term (va(i)) in Methods 2F
and 2G.) When the equations in the indicated sections of Method 2G are
used in deriving point velocity values for Method 2 tests, set the value
of the yaw angles appearing in the equations to 0 deg..
8.7 Tabulating Calculated Point Velocity Values for Wall Effects
Traverse Points. Enter the following values in a hardcopy or electronic
form similar to Form 2H-1 (for 16-point Method 1 traverses) or Form 2H-2
(for Method 1 traverses consisting of more than 16 points). A separate
form must be completed for each of the four Method 1 equal-area sectors
that are closest to the wall.
(a) Port ID (e.g., A, B, C, or D)
(b) Probe type
(c) Probe ID

[[Page 133]]

(d) Stack or duct diameter in ft (m) (determined in accordance with
section 8.6 of Method 2F or Method 2G)
(e) Stack or duct radius in in. (cm)
(f) Distance from the wall of wall effects traverse points at 1-in.
intervals, in ascending order starting with 1 in. (2.5 cm) (column A of
Form 2H-1 or 2H-2)
(g) Point velocity values (vd) for 1-in. incremented
traverse points (see section 8.7.1), including dlast (see
section 8.7.2)
(h) Point velocity value (vdrem) at drem (see
section 8.7.3).

8.7.1 Point velocity values at wall effects traverse points other
than dlast. For every 1-in. incremented wall effects traverse
point other than dlast, enter in column B of Form 2H-1 or 2H-
2 either the velocity measured at the point (see section 8.7.1.1) or the
velocity measured at the first subsequent traverse point farther from
the wall (see section 8.7.1.2). A velocity value must be entered in
column B of Form 2H-1 or 2H-2 for every 1-in. incremented traverse point
from d1 (representing the wall effects traverse point 1 in.
[2.5 cm] from the wall) to dlast.
8.7.1.1 For wall effects traverse points where the probe can be
positioned and velocity pressure can be detected, enter the value
obtained in accordance with section 8.6.
8.7.1.2 For wall effects traverse points that were skipped [see
section 8.2.2.3(c)] and for points where the probe cannot be positioned
or where no velocity pressure can be detected, enter the value obtained
at the first subsequent traverse point farther from the wall where
velocity pressure was detected and measured and follow the entered value
with a ``flag,'' such as the notation ``NM,'' to indicate that ``no
measurements'' were actually taken at this point.
8.7.2 Point velocity value at dlast. For
dlast, enter in column B of Form 2H-1 or 2H-2 the measured
value obtained in accordance with section 8.6.
8.7.3 Point velocity value (vdrem) at drem.
Enter the point velocity value obtained at drem in column G
of row 4a in Form 2H-1 or 2H-2. If the distance between drem
and dlast is less than or equal to \1/2\ in. (12.7 mm), the
measured velocity value at dlast may be used as the value at
drem (see section 8.2.4.2).
9.0 Quality Control.
9.1 Particulate Matter Build-up in Horizontal Ducts. Wall effects
testing of horizontal circular ducts should be conducted only if build-
up of particulate matter or other material in the bottom of the duct is
not present.
9.2 Verifying Traverse Point Distances. In taking measurements at
wall effects traverse points, it is very important for the probe impact
pressure port to be positioned as close as practicable to the traverse
point locations in the gas stream. For this reason, before beginning
wall effects testing, it is important to calculate and record the
traverse point positions that will be marked on each probe for each
port, taking into account the distance that each port nipple (or probe
mounting flange for automated probes) extends out of the stack and any
extension of the port nipple (or mounting flange) into the gas stream.
To ensure that traverse point positions are properly identified, the
following procedures should be performed on each probe used.
9.2.1 Manual probes. Mark the probe insertion distance of the wall
effects and Method 1 traverse points on the probe sheath so that when a
mark is aligned with the outside face of the stack port, the probe
impact port is located at the calculated distance of the traverse point
from the stack inside wall. The use of different colored marks is
recommended for designating the wall effects and Method 1 traverse
points. Before the first use of each probe, check to ensure that the
distance of each mark from the center of the probe impact pressure port
agrees with the previously calculated traverse point positions to within
\1/4\ in. (6.4 mm).
9.2.2 Automated probe systems. For automated probe systems that
mechanically position the probe head at prescribed traverse point
positions, activate the system with the probe assemblies removed from
the test ports and sequentially extend the probes to the programmed
location of each wall effects traverse point and the Method 1 traverse
points. Measure the distance between the center of the probe impact
pressure port and the inside of the probe assembly mounting flange for
each traverse point. The measured distances must agree with the
previously calculated traverse point positions to within \1/
4\ in. (6.4 mm).
9.3 Probe Installation. Properly sealing the port area is
particularly important in taking measurements at wall effects traverse
points. For testing involving manual probes, the area between the probe
sheath and the port should be sealed with a tightly fitting flexible
seal made of an appropriate material such as heavy cloth so that leakage
is minimized. For automated probe systems, the probe assembly mounting
flange area should be checked to verify that there is no leakage.
9.4 Velocity Stability. This method should be performed only when
the average gas velocity in the stack or duct is relatively constant
over the duration of the test. If the average gas velocity changes
significantly during the course of a wall effects test, the test results
should be discarded.

10.0 Calibration

10.1 The calibration coefficient(s) or curves obtained under Method
2, 2F, or 2G and used to perform the Method 1 traverse are applicable
under this method.

[[Page 134]]

11.0 Analytical Procedure

11.1 Sample collection and analysis are concurrent for this method
(see section 8).

12.0 Data Analysis and Calculations

12.1 The following calculations shall be performed to obtain a wall
effects adjustment factor (WAF) from (1) the wall effects-unadjusted
average velocity (T4avg), (2) the replacement velocity (vej)
for each of the four Method 1 sectors closest to the wall, and (3) the
average stack gas velocity that accounts for velocity decay near the
wall (vavg).
12.2 Nomenclature. The following terms are listed in the order in
which they appear in Equations 2H-5 through 2H-21.

vavg=the average stack gas velocity, unadjusted for wall
effects, actual ft/sec (m/sec);
vii=stack gas point velocity value at Method 1 interior
equal-area sectors, actual ft/sec (m/sec);
vej=stack gas point velocity value, unadjusted for wall
effects, at Method 1 exterior equal-area sectors, actual ft/sec (m/sec);
i=index of Method 1 interior equal-area traverse points;
j=index of Method 1 exterior equal-area traverse points;
n=total number of traverse points in the Method 1 traverse;
vdecd=the wall effects decay velocity for a sub-sector
located between the traverse points at distances d-1 (in metric units,
d-2.5) and d from the wall, actual ft/sec (m/sec);
vd=the measured stack gas velocity at distance d from the
wall, actual ft/sec (m/sec); Note: v0=0;
d=the distance of a 1-in. incremented wall effects traverse point from
the wall, for traverse points d1 through dlast,
in. (cm);
Ad=the cross-sectional area of a sub-sector located between
the traverse points at distances d-1 (in metric units, d-2.5) and d from
the wall, in.\2\ (cm \2\) ( e.g., sub-sector A2 shown in
Figures 2H-3 and 2H-4);
r=the stack or duct radius, in. (cm);
Qd=the stack gas volumetric flow rate for a sub-sector
located between the traverse points at distances d-1 (in metric units,
d-2.5) and d from the wall, actual ft-in.\2\/sec (m-cm \2\/sec);
Qd1dlast= the total stack gas volumetric
flow rate for all sub-sectors located between the wall and dlast,
actual ft-in.\2\/sec (m-cm \2\/sec);
dlast=the distance from the wall of the last 1-in.
incremented wall effects traverse point, in. (cm);
Adrem=the cross-sectional area of the sub-sector located
between dlast and the interior edge of the Method 1 equal-
area sector closest to the wall, in.\2\ (cm \2\) (see Figure 2H-4);
p=the number of Method 1 traverse points per diameter, p8
(e.g., for a 16-point traverse, p=8);
drem=the distance from the wall of the centroid of the area
between dlast and the interior edge of the Method 1 equal-
area sector closest to the wall, in. (cm);
Qdrem=the total stack gas volumetric flow rate for the sub-
sector located between dlast and the interior edge of the
Method 1 equal-area sector closest to the wall, actual ft-in.\2\/sec (m-
cm \2\/sec);
vdrem=the measured stack gas velocity at distance drem
from the wall, actual ft/sec (m/sec);
QT=the total stack gas volumetric flow rate for the Method 1
equal-area sector closest to the wall, actual ft-in.\2\/sec (m-cm \2\/
sec);
vej=the replacement stack gas velocity for the Method 1
equal-area sector closest to the wall, i.e., the stack gas point
velocity value, adjusted for wall effects, for the j^thMethod
1 equal-area sector closest to the wall, actual ft/sec (m/sec);
vavg=the average stack gas velocity that accounts for
velocity decay near the wall, actual ft/sec (m/sec);
WAF=the wall effects adjustment factor derived from vavg and
vavg for a single traverse, dimensionless;
vfinal=the final wall effects-adjusted average stack gas
velocity that replaces the unadjusted average stack gas velocity
obtained using Method 2, 2F, or 2G for a field test consisting of a
single traverse, actual ft/sec (m/sec);
WAF=the wall effects adjustment factor that is applied to the average
velocity, unadjusted for wall effects, in order to obtain the final wall
effects-adjusted stack gas velocity, vfinal or,
vfinal(k), dimensionless;
vfinal(k)=the final wall effects-adjusted average stack gas
velocity that replaces the unadjusted average stack gas velocity
obtained using Method 2, 2F, or 2G on run k of a RATA or other multiple-
run field test procedure, actual ft/sec (m/sec);
vavg(k)=the average stack gas velocity, obtained on run k of
a RATA or other multiple-run procedure, unadjusted for velocity decay
near the wall, actual ft/sec (m/sec);
k=index of runs in a RATA or other multiple-run procedure.

12.3 Calculate the average stack gas velocity that does not account
for velocity decay near the wall (vavg) using Equation 2H-5.
[GRAPHIC] [TIFF OMITTED] TR14MY99.077

[[Page 135]]

(Note that vavg in Equation 2H-5 is the same as v(a)avg
in Equations 2F-9 and 2G-8 in Methods 2F and 2G, respectively.)
For a 16-point traverse, Equation 2H-5 may be written as follows:
[GRAPHIC] [TIFF OMITTED] TR14MY99.078

12.4 Calculate the replacement velocity, vej, for each
of the four Method 1 equal-area sectors closest to the wall using the
procedures described in sections 12.4.1 through 12.4.8. Forms 2H-1 and
2H-2 provide sample tables that may be used in either hardcopy or
spreadsheet format to perform the calculations described in sections
12.4.1 through 12.4.8. Forms 2H-3 and 2H-4 provide examples of Form 2H-1
filled in for partial and complete wall effects traverses.
12.4.1 Calculate the average velocity (designated the ``decay
velocity,'' vdecd) for each sub-sector located between the
wall and dlast (see Figure 2H-3) using Equation 2H-7.
[GRAPHIC] [TIFF OMITTED] TR14MY99.079

For each line in column A of Form 2H-1 or 2H-2 that contains a value of
d, enter the corresponding calculated value of vdecd in
column C.
12.4.2 Calculate the cross-sectional area between the wall and the
first 1-in. incremented wall effects traverse point and between
successive 1-in. incremented wall effects traverse points, from the wall
to dlast (see Figure 2H-3), using Equation 2H-8.
[GRAPHIC] [TIFF OMITTED] TR14MY99.080

For each line in column A of Form 2H-1 or 2H-2 that contains a value of
d, enter the value of the expression \1/4\ (r-d+1)²
in column D, the value of the expression \1/4\
(r-d)² in column E, and the value of Ad
in column F. Note that Equation 2H-8 is designed for use only with
English units (in.). If metric units (cm) are used, the first term, \1/
4\ (r-d+1)², must be changed to \1/4\
(r-d+2.5)². This change must also be made in column
D of Form 2H-1 or 2H-2.
12.4.3 Calculate the volumetric flow through each cross-sectional
area derived in section 12.4.2 by multiplying the values of
vdecd, derived according to section 12.4.1, by the cross-
sectional areas derived in section 12.4.2 using Equation 2H-9.
[GRAPHIC] [TIFF OMITTED] TR14MY99.081

For each line in column A of Form 2H-1 or 2H-2 that contains a value of
d, enter the corresponding calculated value of Qd in column
G.
12.4.4 Calculate the total volumetric flow through all sub-sectors
located between the wall and dlast, using Equation 2H-10.
[GRAPHIC] [TIFF OMITTED] TN09JY99.003

Enter the calculated value of Qd1dlast in
line 3 of column G of Form 2H-1 or 2H-2.
12.4.5 Calculate the cross-sectional area of the sub-sector located
between dlast and the interior edge of the Method 1 equal-
area sector (e.g., sub-sector Adrem shown in Figures 2H-3 and
2H-4) using Equation 2H-11.
[GRAPHIC] [TIFF OMITTED] TR14MY99.083

[[Page 136]]

For a 16-point traverse (eight points per diameter), Equation 2H-11 may
be written as follows:
[GRAPHIC] [TIFF OMITTED] TR14MY99.084

Enter the calculated value of Adrem in line 4b of column G of
Form 2H-1 or 2H-2.
12.4.6 Calculate the volumetric flow for the sub-sector located
between dlast and the interior edge of the Method 1 equal-
area sector, using Equation 2H-13.
[GRAPHIC] [TIFF OMITTED] TR14MY99.085

In Equation 2H-13, vdrem is either (1) the measured velocity
value at drem or (2) the measured velocity at
dlast, if the distance between drem and
dlast is less than or equal to \1/2\ in. (12.7 mm) and no
velocity measurement is taken at drem (see section 8.2.4.2).
Enter the calculated value of Qdrem in line 4c of column G of
Form 2H-1 or 2H-2.
12.4.7 Calculate the total volumetric flow for the Method 1 equal-
area sector closest to the wall, using Equation 2H-14.
[GRAPHIC] [TIFF OMITTED] TR14MY99.086

Enter the calculated value of QT in line 5a of column G of
Form 2H-1 or 2H-2.
12.4.8 Calculate the wall effects-adjusted replacement velocity
value for the Method 1 equal-area sector closest to the wall, using
Equation 2H-15.
[GRAPHIC] [TIFF OMITTED] TR14MY99.087

For a 16-point traverse (eight points per diameter), Equation 2H-15 may
be written as follows:
[GRAPHIC] [TIFF OMITTED] TR14MY99.088

Enter the calculated value of vej in line 5B of column G of
Form 2H-1 or 2H-2.
12.5 Calculate the wall effects-adjusted average velocity,
vavg, by replacing the four values of vej shown in
Equation 2H-5 with the four wall effects-adjusted replacement velocity
values,vej, calculated according to section 12.4.8, using
Equation 2H-17.
[GRAPHIC] [TIFF OMITTED] TR14MY99.089

For a 16-point traverse, Equation 2H-17 may be written as follows:
[GRAPHIC] [TIFF OMITTED] TR14MY99.090

12.6 Calculate the wall effects adjustment factor, WAF, using
Equation 2H-19.
[GRAPHIC] [TIFF OMITTED] TR14MY99.091

12.6.1 Partial wall effects traverse. If a partial wall effects
traverse (see section 8.2.2) is conducted, the value obtained from
Equation 2H-19 is acceptable and may be reported as the wall effects
adjustment factor provided that the value is greater than or equal to
0.9800. If the value is less than 0.9800, it shall not be used and a
wall effects adjustment factor of 0.9800 may be used instead.
12.6.2 Complete wall effects traverse. If a complete wall effects
traverse (see section 8.2.3) is conducted, the value obtained from
Equation 2H-19 is acceptable and may be reported as the wall effects
adjustment factor provided that the value is greater than or equal to
0.9700. If the value is less than 0.9700, it shall not be used and a
wall effects adjustment factor of 0.9700 may be used instead. If the
wall effects adjustment factor for a particular stack or duct is less
than 0.9700, the tester may (1) repeat the wall effects test, taking
measurements at more Method 1 traverse points and (2) recalculate the
wall effects adjustment factor from these measurements, in an attempt to
obtain a wall effects adjustment factor that meets the 0.9700
specification and completely characterizes the wall effects.
12.7 Applying a Wall Effects Adjustment Factor. A default wall
effects adjustment

[[Page 137]]

factor, as specified in section 8.1, or a calculated wall effects
adjustment factor meeting the requirements of section 12.6.1 or 12.6.2
may be used to adjust the average stack gas velocity obtained using
Methods 2, 2F, or 2G to take into account velocity decay near the wall
of circular stacks or ducts. Default wall effects adjustment factors
specified in section 8.1 and calculated wall effects adjustment factors
that meet the requirements of section 12.6.1 and 12.6.2 are summarized
in Table 2H-2.
12.7.1 Single-run tests. Calculate the final wall effects-adjusted
average stack gas velocity for field tests consisting of a single
traverse using Equation 2H-20.
[GRAPHIC] [TIFF OMITTED] TR14MY99.092

The wall effects adjustment factor, WAF, shown in Equation 2H-20, may be
(1) a default wall effects adjustment factor, as specified in section
8.1, or (2) a calculated adjustment factor that meets the specifications
in sections 12.6.1 or 12.6.2. If a calculated adjustment factor is used
in Equation 2H-20, the factor must have been obtained during the same
traverse in which vavg was obtained.
12.7.2 RATA or other multiple run test procedure. Calculate the
final wall effects-adjusted average stack gas velocity for any run k of
a RATA or other multiple-run procedure using Equation 2H-21.
[GRAPHIC] [TIFF OMITTED] TR14MY99.093

The wall effects adjustment factor, WAF, shown in Equation 2H-21 may be
(1) a default wall effects adjustment factor, as specified in section
8.1; (2) a calculated adjustment factor (meeting the specifications in
sections 12.6.1 or 12.6.2) obtained from any single run of the RATA that
includes run k; or (3) the arithmetic average of more than one WAF (each
meeting the specifications in sections 12.6.1 or 12.6.2) obtained
through wall effects testing conducted during several runs of the RATA
that includes run k. If wall effects adjustment factors (meeting the
specifications in sections 12.6.1 or 12.6.2) are determined for more
than one RATA run, the arithmetic average of all of the resulting
calculated wall effects adjustment factors must be used as the value of
WAF and applied to all runs of that RATA. If a calculated, not a
default, wall effects adjustment factor is used in Equation 2H-21, the
average velocity unadjusted for wall effects, vavg(k) must be
obtained from runs in which the number of Method 1 traverse points
sampled does not exceed the number of Method 1 traverse points in the
runs used to derive the wall effects adjustment factor, WAF, shown in
Equation 2H-21.
12.8 Calculating Volumetric Flow Using Final Wall Effects-Adjusted
Average Velocity Value. To obtain a stack gas flow rate that accounts
for velocity decay near the wall of circular stacks or ducts, replace
vs in Equation 2-10 in Method 2, or va(avg) in
Equations 2F-10 and 2F-11 in Method 2F, or va(avg) in
Equations 2G-9 and 2G-10 in Method 2G with one of the following.
12.8.1 For single-run test procedures, use the final wall effects-
adjusted average stack gas velocity, vfinal, calculated
according to Equation 2H-20.
12.8.2 For RATA and other multiple run test procedures, use the
final wall effects-adjusted average stack gas velocity,
vfinal(k), calculated according to Equation 2H-21.

13.0 Method Performance. [Reserved]

414.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Reporting

16.1 Field Test Reports. Field test reports shall be submitted to
the Agency according to the applicable regulatory requirements. When
Method 2H is performed in conjunction with Method 2, 2F, or 2G to derive
a wall effects adjustment factor, a single consolidated Method 2H/2F (or
2H/2G) field test report should be prepared. At a minimum, the
consolidated field test report should contain (1) all of the general
information, and data for Method 1 points, specified in section 16.0 of
Method 2F (when Method 2H is used in conjunction with Method 2F) or
section 16.0 of Method 2G (when Method 2H is used in conjunction with
Method 2 or 2G) and (2) the additional general information, and data for
Method 1 points and wall effects points, specified in this section (some
of which are included in section 16.0 of Methods 2F and 2G and are
repeated in this section to ensure complete reporting for wall effects
testing).
16.1.1 Description of the source and site. The field test report
should include the descriptive information specified in section 16.1.1
of Method 2F (when using Method 2F) or 2G (when using either Method 2 or
2G). It should also include a description of the stack or duct's
construction material along with the diagram showing the dimensions of
the stack or duct at the test port elevation prescribed in Methods 2F
and 2G. The diagram should indicate the location of all wall effects
traverse points where measurements were taken as well as the Method 1
traverse points. The diagram should provide a unique identification
number for each wall effects and Method 1 traverse point, its distance
from the wall, and its location relative to the probe entry ports.
16.1.2 Field test forms. The field test report should include a
copy of Form 2H-1, 2H-2, or an equivalent for each Method 1 exterior
equal-area sector.

[[Page 138]]

16.1.3 Field test data. The field test report should include the
following data for the Method 1 and wall effects traverse.
16.1.3.1 Data for each traverse point. The field test report should
include the values specified in section 16.1.3.2 of Method 2F (when
using Method 2F) or 2G (when using either Method 2 or 2G) for each
Method 1 and wall effects traverse point. The provisions of section
8.4.2 of Method 2H apply to the temperature measurements reported for
wall effects traverse points. For each wall effects and Method 1
traverse point, the following values should also be included in the
field test report.
(a) Traverse point identification number for each Method 1 and wall
effects traverse point.
(b) Probe type.
(c) Probe identification number.
(d) Probe velocity calibration coefficient (i.e., Cp when
Method 2 or 2G is used; F2 when Method 2F is used).

For each Method 1 traverse point in an exterior equal-area sector,
the following additional value should be included.
(e) Calculated replacement velocity, vej, accounting for
wall effects.
16.1.3.2 Data for each run. The values specified in section
16.1.3.3 of Method 2F (when using Method 2F) or 2G (when using either
Method 2 or 2G) should be included in the field test report once for
each run. The provisions of section 12.8 of Method 2H apply for
calculating the reported gas volumetric flow rate. In addition, the
following Method 2H run values should also be included in the field test
report.
(a) Average velocity for run, accounting for wall effects,
vavg.
(b) Wall effects adjustment factor derived from a test run, WAF.
16.1.3.3 Data for a complete set of runs. The values specified in
section 16.1.3.4 of Method 2F (when using Method 2F) or 2G (when using
either Method 2 or 2G) should be included in the field test report once
for each complete set of runs. In addition, the field test report should
include the wall effects adjustment factor, WAF, that is applied in
accordance with section 12.7.1 or 12.7.2 to obtain the final wall
effects-adjusted average stack gas velocity vfinal or
vfinal(k).
16.1.4 Quality assurance and control. Quality assurance and control
procedures, specifically tailored to wall effects testing, should be
described.
16.2 Reporting a Default Wall Effects Adjustment Factor. When a
default wall effects adjustment factor is used in accordance with
section 8.1 of this method, its value and a description of the stack or
duct's construction material should be reported in lieu of submitting a
test report.
17.0 References.
(1) 40 CFR Part 60, Appendix A, Method 1'Sample and velocity
traverses for stationary sources.
(2) 40 CFR Part 60, Appendix A, Method 2'Determination of stack gas
velocity and volumetric flow rate (Type S pitot tube).
(3) 40 CFR Part 60, Appendix A, Method 2F'Determination of stack gas
velocity and volumetric flow rate with three-dimensional probes.
(4) 40 CFR Part 60, Appendix A, Method 2G'Determination of stack gas
velocity and volumetric flow rate with two-dimensional probes.
(5) 40 CFR Part 60, Appendix A, Method 3'Gas analysis for carbon
dioxide, oxygen, excess air, and dry molecular weight.
(6) 40 CFR Part 60, Appendix A, Method 3A--Determination of oxygen
and carbon dioxide concentrations in emissions from stationary sources
(instrumental analyzer procedure).
(7) 40 CFR Part 60, Appendix A, Method 4--Determination of moisture
content in stack gases.
(8) Emission Measurement Center (EMC) Approved Alternative Method
(ALT-011) ``Alternative Method 2 Thermocouple Calibration Procedure.''
(9) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, DeCordova Steam
Electric Station, Volume I: Test Description and Appendix A (Data
Distribution Package),'' EPA/430-R-98-015a.
(10) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Texas Utilities, Lake Hubbard Steam
Electric Station, Volume I: Test Description and Appendix A (Data
Distribution Package),'' EPA/430-R-98-017a.
(11) The Cadmus Group, Inc., 1998, ``EPA Flow Reference Method
Testing and Analysis: Data Report, Pennsylvania Electric Co., G.P.U.
Genco Homer City Station: Unit 1, Volume I: Test Description and
Appendix A (Data Distribution Package),'' EPA/430-R-98-018a.
(12) The Cadmus Group, Inc., May 1999, ``EPA Flow Reference Method
Testing and Analysis: Findings Report,'' EPA/430-R-99-009.
(13) The Cadmus Group, Inc., 1997, ``EPA Flow Reference Method
Testing and Analysis: Wind Tunnel Experimental Results,'' EPA/430-R-97-
013.
(14) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four Prandtl Probes, Four
S-Type Probes, Four French Probes, Four Modified Kiel Probes,'' Prepared
for the U.S. Environmental Protection Agency under IAG No. DW13938432-
01-0.
(15) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Five

[[Page 139]]

Autoprobes,'' Prepared for the U.S. Environmental Protection Agency
under IAG No. DW13938432-01-0.
(16) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Eight Spherical Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG No.
DW13938432-01-0.
(17) National Institute of Standards and Technology, 1998, ``Report
of Special Test of Air Speed Instrumentation, Four DAT Probes,''
Prepared for the U.S. Environmental Protection Agency under IAG No.
DW13938432-01-0.
(18) Massachusetts Institute of Technology (MIT), 1998,
``Calibration of Eight Wind Speed Probes Over a Reynolds Number Range of
46,000 to 725,000 per Foot, Text and Summary Plots,'' Plus Appendices,
WBWT-TR-1317, Prepared for The Cadmus Group, Inc., under EPA Contract
68-W6-0050, Work Assignment 0007AA-3.
(19) Fossil Energy Research Corporation, Final Report, ``Velocity
Probe Tests in Non-axial Flow Fields,'' November 1998, Prepared for the
U.S. Environmental Protection Agency.
(20) Fossil Energy Research Corporation, ``Additional Swirl Tunnel
Tests: E-DAT and T-DAT Probes,'' February 24, 1999, Technical Memorandum
Prepared for U.S. Environmental Protection Agency, P.O. No. 7W-1193-
NALX.

[GRAPHIC] [TIFF OMITTED] TR14MY99.036

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[GRAPHIC] [TIFF OMITTED] TR14MY99.044

Method 3--Gas Analysis for the Determination of Dry Molecular Weight

1.0 Scope and Application

1.1 Analytes.

[[Page 148]]

------------------------------------------------------------------------
Analytes CAS No. Sensitivity
------------------------------------------------------------------------
Oxygen (O2)....................... 7782-44-7 2,000 ppmv.
Nitrogen (N2)..................... 7727-37-9 N/A.
Carbon dioxide (CO2).............. 124-38-9 2,000 ppmv.
Carbon monoxide (CO).............. 630-08-0 N/A.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of CO2 and O2 concentrations and dry molecular
weight of a sample from an effluent gas stream of a fossil-fuel
combustion process or other process.
1.3 Other methods, as well as modifications to the procedure
described herein, are also applicable for all of the above
determinations. Examples of specific methods and modifications include:
(1) A multi-point grab sampling method using an Orsat analyzer to
analyze the individual grab sample obtained at each point; (2) a method
for measuring either CO2 or O2 and using
stoichiometric calculations to determine dry molecular weight; and (3)
assigning a value of 30.0 for dry molecular weight, in lieu of actual
measurements, for processes burning natural gas, coal, or oil. These
methods and modifications may be used, but are subject to the approval
of the Administrator. The method may also be applicable to other
processes where it has been determined that compounds other than
CO2, O2, carbon monoxide (CO), and nitrogen
(N2) are not present in concentrations sufficient to affect
the results.
1.4 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from a stack by one of the following
methods: (1) single-point, grab sampling; (2) single-point, integrated
sampling; or (3) multi-point, integrated sampling. The gas sample is
analyzed for percent CO2 and percent O2. For dry
molecular weight determination, either an Orsat or a Fyrite analyzer may
be used for the analysis.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Several compounds can interfere, to varying degrees, with the
results of Orsat or Fyrite analyses. Compounds that interfere with
CO2 concentration measurement include acid gases (e.g.,
sulfur dioxide, hydrogen chloride); compounds that interfere with
O2 concentration measurement include unsaturated hydrocarbons
(e.g., acetone, acetylene), nitrous oxide, and ammonia. Ammonia reacts
chemically with the O2 absorbing solution, and when present
in the effluent gas stream must be removed before analysis.

5.0 Safety

6.0 Equipment and Supplies

Note: As an alternative to the sampling apparatus and systems
described herein, other sampling systems (e.g., liquid displacement) may
be used, provided such systems are capable of obtaining a representative
sample and maintaining a constant sampling rate, and are, otherwise,
capable of yielding acceptable results. Use of such systems is subject
to the approval of the Administrator.
6.1 Grab Sampling (See Figure 3-1).
6.1.1 Probe. Stainless steel or borosilicate glass tubing equipped
with an in-stack or out-of-stack filter to remove particulate matter (a
plug of glass wool is satisfactory for this purpose). Any other
materials, resistant to temperature at sampling conditions and inert to
all components of the gas stream, may be used for the probe. Examples of
such materials may include aluminum, copper, quartz glass, and Teflon.
6.1.2 Pump. A one-way squeeze bulb, or equivalent, to transport the
gas sample to the analyzer.
6.2 Integrated Sampling (Figure 3-2).
6.2.1 Probe. Same as in Section 6.1.1.

[[Page 149]]

6.2.2 Condenser. An air-cooled or water-cooled condenser, or other
condenser no greater than 250 ml that will not remove O2,
CO2, CO, and N2, to remove excess moisture which
would interfere with the operation of the pump and flowmeter.
6.2.3 Valve. A needle valve, to adjust sample gas flow rate.
6.2.4 Pump. A leak-free, diaphragm-type pump, or equivalent, to
transport sample gas to the flexible bag. Install a small surge tank
between the pump and rate meter to eliminate the pulsation effect of the
diaphragm pump on the rate meter.
6.2.5 Rate Meter. A rotameter, or equivalent, capable of measuring
flow rate to 2 percent of the selected flow rate. A flow
rate range of 500 to 1000 ml/min is suggested.
6.2.6 Flexible Bag. Any leak-free plastic (e.g., Tedlar, Mylar,
Teflon) or plastic-coated aluminum (e.g., aluminized Mylar) bag, or
equivalent, having a capacity consistent with the selected flow rate and
duration of the test run. A capacity in the range of 55 to 90 liters
(1.9 to 3.2 ft³) is suggested. To leak-check the bag, connect
it to a water manometer, and pressurize the bag to 5 to 10 cm
H2O (2 to 4 in. H2O). Allow to stand for 10
minutes. Any displacement in the water manometer indicates a leak. An
alternative leak-check method is to pressurize the bag to 5 to 10 cm (2
to 4 in.) H2O and allow to stand overnight. A deflated bag
indicates a leak.
6.2.7 Pressure Gauge. A water-filled U-tube manometer, or
equivalent, of about 30 cm (12 in.), for the flexible bag leak-check.
6.2.8 Vacuum Gauge. A mercury manometer, or equivalent, of at least
760 mm (30 in.) Hg, for the sampling train leak-check.
6.3 Analysis. An Orsat or Fyrite type combustion gas analyzer.

7.0 Reagents and Standards

7.1 Reagents. As specified by the Orsat or Fyrite-type combustion
analyzer manufacturer.
7.2 Standards. Two standard gas mixtures, traceable to National
Institute of Standards and Technology (NIST) standards, to be used in
auditing the accuracy of the analyzer and the analyzer operator
technique:
7.2.1. Gas cylinder containing 2 to 4 percent O2 and 14
to 18 percent CO2.
7.2.2. Gas cylinder containing 2 to 4 percent CO2 and
about 15 percent O2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Single Point, Grab Sampling Procedure.
8.1.1 The sampling point in the duct shall either be at the
centroid of the cross section or at a point no closer to the walls than
1.0 m (3.3 ft), unless otherwise specified by the Administrator.
8.1.2 Set up the equipment as shown in Figure 3-1, making sure all
connections ahead of the analyzer are tight. If an Orsat analyzer is
used, it is recommended that the analyzer be leak-checked by following
the procedure in Section 11.5; however, the leak-check is optional.
8.1.3 Place the probe in the stack, with the tip of the probe
positioned at the sampling point. Purge the sampling line long enough to
allow at least five exchanges. Draw a sample into the analyzer, and
immediately analyze it for percent CO2 and percent
O2 according to Section 11.2.
8.2 Single-Point, Integrated Sampling Procedure.
8.2.1 The sampling point in the duct shall be located as specified
in Section 8.1.1.
8.2.2 Leak-check (optional) the flexible bag as in Section 6.2.6.
Set up the equipment as shown in Figure 3-2. Just before sampling, leak-
check (optional) the train by placing a vacuum gauge at the condenser
inlet, pulling a vacuum of at least 250 mm Hg (10 in. Hg), plugging the
outlet at the quick disconnect, and then turning off the pump. The
vacuum should remain stable for at least 0.5 minute. Evacuate the
flexible bag. Connect the probe, and place it in the stack, with the tip
of the probe positioned at the sampling point. Purge the sampling line.
Next, connect the bag, and make sure that all connections are tight.
8.2.3 Sample Collection. Sample at a constant rate (10
percent). The sampling run should be simultaneous with, and for the same
total length of time as, the pollutant emission rate determination.
Collection of at least 28 liters (1.0 ft³) of sample gas is
recommended; however, smaller volumes may be collected, if desired.
8.2.4 Obtain one integrated flue gas sample during each pollutant
emission rate determination. Within 8 hours after the sample is taken,
analyze it for percent CO2 and percent O2 using
either an Orsat analyzer or a Fyrite type combustion gas analyzer
according to Section 11.3.
Note: When using an Orsat analyzer, periodic Fyrite readings may be
taken to verify/confirm the results obtained from the Orsat.
8.3 Multi-Point, Integrated Sampling Procedure.
8.3.1 Unless otherwise specified in an applicable regulation, or by
the Administrator, a minimum of eight traverse points shall be used for
circular stacks having diameters less than 0.61 m (24 in.), a minimum of
nine shall be used for rectangular stacks having equivalent diameters
less than 0.61 m (24 in.), and a minimum of 12 traverse points shall be
used for all other cases. The traverse points shall be located according
to Method 1.
8.3.2 Follow the procedures outlined in Sections 8.2.2 through
8.2.4, except for the following: Traverse all sampling points, and
sample at each point for an equal length of

[[Page 150]]

time. Record sampling data as shown in Figure 3-3.

9.0 Quality Control

10.0 Calibration and Standardization

10.1 Analyzer. The analyzer and analyzer operator's technique
should be audited periodically as follows: take a sample from a manifold
containing a known mixture of CO2 and O2, and
analyze according to the procedure in Section 11.3. Repeat this
procedure until the measured concentration of three consecutive samples
agrees with the stated value 0.5 percent. If necessary,
take corrective action, as specified in the analyzer users manual.
10.2 Rotameter. The rotameter need not be calibrated, but should be
cleaned and maintained according to the manufacturer's instruction.

11.0 Analytical Procedure

11.1 Maintenance. The Orsat or Fyrite-type analyzer should be
maintained and operated according to the manufacturers specifications.
11.2 Grab Sample Analysis. Use either an Orsat analyzer or a
Fyrite-type combustion gas analyzer to measure O2 and
CO2 concentration for dry molecular weight determination,
using procedures as specified in the analyzer user's manual. If an Orsat
analyzer is used, it is recommended that the Orsat leak-check, described
in Section 11.5, be performed before this determination; however, the
check is optional. Calculate the dry molecular weight as indicated in
Section 12.0. Repeat the sampling, analysis, and calculation procedures
until the dry molecular weights of any three grab samples differ from
their mean by no more than 0.3 g/g-mole (0.3 lb/lb-mole). Average these
three molecular weights, and report the results to the nearest 0.1 g/g-
mole (0.1 lb/lb-mole).
11.3 Integrated Sample Analysis. Use either an Orsat analyzer or a
Fyrite-type combustion gas analyzer to measure O2 and
CO2 concentration for dry molecular weight determination,
using procedures as specified in the analyzer user's manual. If an Orsat
analyzer is used, it is recommended that the Orsat leak-check, described
in Section 11.5, be performed before this determination; however, the
check is optional. Calculate the dry molecular weight as indicated in
Section 12.0. Repeat the analysis and calculation procedures until the
individual dry molecular weights for any three analyses differ from
their mean by no more than 0.3 g/g-mole (0.3 lb/lb-mole). Average these
three molecular weights, and report the results to the nearest 0.1 g/g-
mole (0.1 lb/lb-mole).
11.4 Standardization. A periodic check of the reagents and of
operator technique should be conducted at least once every three series
of test runs as outlined in Section 10.1.
11.5 Leak-Check Procedure for Orsat Analyzer. Moving an Orsat
analyzer frequently causes it to leak. Therefore, an Orsat analyzer
should be thoroughly leak-checked on site before the flue gas sample is
introduced into it. The procedure for leak-checking an Orsat analyzer is
as follows:
11.5.1 Bring the liquid level in each pipette up to the reference
mark on the capillary tubing, and then close the pipette stopcock.
11.5.2 Raise the leveling bulb sufficiently to bring the confining
liquid meniscus onto the graduated portion of the burette, and then
close the manifold stopcock.
11.5.3 Record the meniscus position.
11.5.4 Observe the meniscus in the burette and the liquid level in
the pipette for movement over the next 4 minutes.
11.5.5 For the Orsat analyzer to pass the leak-check, two
conditions must be met:
11.5.5.1 The liquid level in each pipette must not fall below the
bottom of the capillary tubing during this 4-minute interval.
11.5.5.2 The meniscus in the burette must not change by more than
0.2 ml during this 4-minute interval.
11.5.6 If the analyzer fails the leak-check procedure, check all
rubber connections and stopcocks to determine whether they might be the
cause of the leak. Disassemble, clean, and regrease any leaking
stopcocks. Replace leaking rubber connections. After the analyzer is
reassembled, repeat the leak-check procedure.

12.0 Calculations and Data Analysis

12.1 Nomenclature.

Md = Dry molecular weight, g/g-mole (lb/lb-mole).
%CO2 = Percent CO2 by volume, dry basis.
%O2 = Percent O2 by volume, dry basis.
%CO = Percent CO by volume, dry basis.
%N2 = Percent N2 by volume, dry basis.

[[Page 151]]

0.280 = Molecular weight of N2 or CO, divided by 100.
0.320 = Molecular weight of O2 divided by 100.
0.440 = Molecular weight of CO2 divided by 100.
12.2 Nitrogen, Carbon Monoxide Concentration. Determine the
percentage of the gas that is N2 and CO by subtracting the
sum of the percent CO2 and percent O2 from 100
percent.
12.3 Dry Molecular Weight. Use Equation 3-1 to calculate the dry
molecular weight of the stack gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.090

Note: The above Equation 3-1 does not consider the effect on
calculated dry molecular weight of argon in the effluent gas. The
concentration of argon, with a molecular weight of 39.9, in ambient air
is about 0.9 percent. A negative error of approximately 0.4 percent is
introduced. The tester may choose to include argon in the analysis using
procedures subject to approval of the Administrator.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Altshuller, A.P. Storage of Gases and Vapors in Plastic Bags.
International Journal of Air and Water Pollution. 6:75-81. 1963.
2. Conner, William D. and J.S. Nader. Air Sampling with Plastic
Bags. Journal of the American Industrial Hygiene Association. 25:291-
297. 1964.
3. Burrell Manual for Gas Analysts, Seventh edition. Burrell
Corporation, 2223 Fifth Avenue, Pittsburgh, PA. 15219. 1951.
4. Mitchell, W.J. and M.R. Midgett. Field Reliability of the Orsat
Analyzer. Journal of Air Pollution Control Association. 26:491-495. May
1976.
5. Shigehara, R.T., R.M. Neulicht, and W.S. Smith. Validating Orsat
Analysis Data from Fossil Fuel-Fired Units. Stack Sampling News.
4(2):21-26. August 1976.

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.091

[[Page 152]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.092

----------------------------------------------------------------------------------------------------------------
Time Traverse point Q (liter/min) % Deviation ^a
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

Figure 3-3. Sampling Rate Data

Method 3A--Determination of Oxygen and Carbon Dioxide Concentrations in
Emissions From Stationary Sources (Instrumental Analyzer Procedure)

1. Applicability and Principle

1.1 Applicability. This method is applicable to the determination
of oxygen (O2) and carbon dioxide (CO2)
concentrations in emissions from stationary sources only when specified
within the regulations.
1.2 Principle. A sample is continuously extracted from the effluent
stream: a portion of the sample stream is conveyed to an instrumental
analyzer(s) for determination of O2 and CO2
concentration(s). Performance specifications and test procedures are
provided to ensure reliable data.

2. Range and Sensitivity

[[Page 153]]

Same as Method 6C, Sections 2.1 and 2.2, except that the span of the
monitoring system shall be selected such that the average O2
or CO2 concentration is not less than 20 percent of the span.

3. Definitions

3.1 Measurement System. The total equipment required for the
determination of the O2 or CO2 concentration. The
measurement system consists of the same major subsystems as defined in
Method 6C, Sections 3.1.1, 3.1.2, and 3.1.3.
3.2 Span, Calibration Gas, Analyzer Calibration Error, Sampling
System Bias, Zero Drift, Calibration Drift, Response Time, and
Calibration Curve. Same as Method 6C, Sections 3.2 through 3.8, and
3.10.
3.3 Interference Response. The output response of the measurement
system to a component in the sample gas, other than the gas component
being measured.

4. Measurement System Performance Specifications

Same as Method 6C, Sections 4.1 through 4.4.

5. Apparatus and Reagents

5.1 Measurement System. Any measurement system for O2 or
CO2 that meets the specifications of this method. A schematic
of an acceptable measurement system is shown in Figure 6C-1 of Method
6C. The essential components of the measurement system are described
below:
5.1.1 Sample Probe. A leak-free probe, of sufficient length to
traverse the sample points.
5.1.2 Sample Line. Tubing, to transport the sample gas from the
probe to the moisture removal system. A heated sample line is not
required for systems that measure the O2 or CO2
concentration on a dry basis, or transport dry gases.
5.1.3 Sample Transport Line, Calibration Value Assembly, Moisture
Removal System, Particulate Filter, Sample Pump, Sample Flow Rate
Control, Sample Gas Manifold, and Data Recorder. Same as Method 6C,
Sections 5.1.3 through 5.1.9, and 5.1.11, except that the requirements
to use stainless steel, Teflon, and nonreactive glass filters do not
apply.
5.1.4 Gas Analyzer. An analyzer to determine continuously the
O2 or CO2 concentration in the sample gas stream.
The analyzer shall meet the applicable performance specifications of
Section 4. A means of controlling the analyzer flow rate and a device
for determining proper sample flow rate (e.g., precision rotameter,
pressure gauge downstream of all flow controls, etc.) shall be provided
at the analyzer. The requirements for measuring and controlling the
analyzer flow rate are not applicable if data are presented that
demonstrate the analyzer is insensitive to flow variations over the
range encountered during the test.
5.2 Calibration Gases. The calibration gases for CO2
analyzers shall be CO2 in N2 or CO2 in
air. Alternatively, CO2/SO2, O2/
SO2 , or O2/CO2/SO2 gas
mixtures in N2 may be used. Three calibration gases, as
specified Section 5.3.1 through 5.3.3 of Method 6C, shall be used. For
O2 monitors that cannot analyze zero gas, a calibration gas
concentration equivalent to less than 10 percent of the span may be used
in place of zero gas.

6. Measurement System Performance Test Procedures

Perform the following procedures before measurement of emissions
(Section 7).
6.1 Calibration Concentration Verification. Follow Section 6.1 of
Method 6C, except if calibration gas analysis is required, use Method 3
and change the acceptance criteria for agreement among Method 3 results
to 5 percent (or 0.2 percent by volume, whichever is greater).
6.2 Interference Response. Conduct an interference response test of
the analyzer prior to its initial use in the field. Thereafter, recheck
the measurement system if changes are made in the instrumentation that
could alter the interference response (e.g., changes in the type of gas
detector). Conduct the interference response in accordance with Section
5.4 of Method 20.
6.3 Measurement System Preparation, Analyzer Calibration Error, and
Sampling System Bias Check. Follow Sections 6.2 through 6.4 of Method
6C.

7. Emission Test Procedure

7.1 Selection of Sampling Site and Sampling Points. Select a
measurement site and sampling points using the same criteria that are
applicable to tests performed using Method 3.
7.2 Sample Collection. Position the sampling probe at the first
measurement point, and begin sampling at the same rate as used during
the sampling system bias check. Maintain constant rate sampling (i.e.,
10 percent) during the entire run. The sampling time per run
shall be the same as for tests conducted using Method 3 plus twice the
system response time. For each run, use only those measurements obtained
after twice the response time of the measurement system has elapsed to
determine the average effluent concentration.
7.3 Zero and Calibration Drift Test. Follow Section 7.4 of Method
6C.

8. Quality Control Procedures

The following quality control procedures are recommended when the
results of this method are used for an emission rate correction factor,
or excess air determination. The tester should select one of the
following options for validating measurement results:

[[Page 154]]

8.1 If both O2 and CO2 are measured using
Method 3A, the procedures described in Section 4.4 of Method 3 should be
followed to validate the O2 and CO2 measurement
results.
8.2 If only O2 is measured using Method 3A, measurements
of the sample stream CO2 concentration should be obtained at
the sample by-pass vent discharge using an Orsat or Fyrite analyzer, or
equivalent. Duplicate samples should be obtained concurrent with at
least one run. Average the duplicate Orsat or Fyrite analysis results
for each run. Use the average CO2 values for comparison with
the O2 measurements in accordance with the procedures
described in Section 4.4 of Method 3.
8.3 If only CO2 is measured using Method 3A, concurrent
measurements of the sample stream CO2 concentration should be
obtained using an Orsat or Fyrite analyzer as described in Section 8.2.
For each run, differences greater than 0.5 percent between the Method 3A
results and the average of the duplicate Fyrite analysis should be
investigated.

9. Emission Calculation

For all CO2 analyzers, and for O2 analyzers
that can be calibrated with zero gas, follow Section 8 of Method 6C,
except express all concentrations as percent, rather than ppm.
For O2 analyzers that use a low-level calibration gas in
place of a zero gas, calculate the effluent gas concentration using
Equation 3A-1.
[GRAPHIC] [TIFF OMITTED] TC16NO91.116

Where:

Cgas=Effluent gas concentration, dry basis, percent.
Cma=Actual concentration of the upscale calibration gas,
percent.
Coa=Actual concentration of the low-level calibration gas,
percent.
Cm=Average of initial and final system calibration bias check
responses for the upscale calibration gas, percent.
Co=Average of initial and final system calibration bias check
responses for the low-level gas, percent.
C=Average gas concentration indicated by the gas analyzer, dry basis,
percent.

10. Bibliography

Same as bibliography of Method 6C.

Method 3B--Gas Analysis for the Determination of Emission Rate
Correction Factor or Excess Air

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Oxygen (O2)....................... 7782-44-7 2,000 ppmv.
Carbon Dioxide (CO2).............. 124-38-9 2,000 ppmv.
Carbon Monoxide (CO).............. 630-08-0 N/A.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of O2, CO2, and CO concentrations in the effluent
from fossil-fuel combustion processes for use in excess air or emission
rate correction factor calculations. Where compounds other than
CO2, O2, CO, and nitrogen (N2) are
present in concentrations sufficient to affect the results, the
calculation procedures presented in this method must be modified,
subject to the approval of the Administrator.
1.3 Other methods, as well as modifications to the procedure
described herein, are also applicable for all of the above
determinations. Examples of specific methods and modifications include:
(1) A multi-point sampling method using an Orsat analyzer to analyze
individual grab samples obtained at each point, and (2) a method using
CO2 or O2 and stoichiometric calculations to
determine excess air. These methods and modifications may be used, but
are subject to the approval of the Administrator.

[[Page 155]]

1.4 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from a stack by one of the following
methods: (1) Single-point, grab sampling; (2) single-point, integrated
sampling; or (3) multi-point, integrated sampling. The gas sample is
analyzed for percent CO2, percent O2, and, if
necessary, percent CO using an Orsat combustion gas analyzer.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Several compounds can interfere, to varying degrees, with the
results of Orsat analyses. Compounds that interfere with CO2
concentration measurement include acid gases (e.g., sulfur dioxide,
hydrogen chloride); compounds that interfere with O2
concentration measurement include unsaturated hydrocarbons (e.g.,
acetone, acetylene), nitrous oxide, and ammonia. Ammonia reacts
chemically with the O2 absorbing solution, and when present
in the effluent gas stream must be removed before analysis.

5.0 Safety

6.0 Equipment and Supplies

Note: As an alternative to the sampling apparatus and systems
described herein, other sampling systems (e.g., liquid displacement) may
be used, provided such systems are capable of obtaining a representative
sample and maintaining a constant sampling rate, and are, otherwise,
capable of yielding acceptable results. Use of such systems is subject
to the approval of the Administrator.
6.1 Grab Sampling and Integrated Sampling. Same as in Sections 6.1
and 6.2, respectively for Method 3.
6.2 Analysis. An Orsat analyzer only. For low CO2 (less
than 4.0 percent) or high O2 (greater than 15.0 percent)
concentrations, the measuring burette of the Orsat must have at least
0.1 percent subdivisions. For Orsat maintenance and operation
procedures, follow the instructions recommended by the manufacturer,
unless otherwise specified herein.

7.0 Reagents and Standards

7.1 Reagents. Same as in Method 3, Section 7.1.
7.2 Standards. Same as in Method 3, Section 7.2.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: Each of the three procedures below shall be used only when
specified in an applicable subpart of the standards. The use of these
procedures for other purposes must have specific prior approval of the
Administrator. A Fyrite-type combustion gas analyzer is not acceptable
for excess air or emission rate correction factor determinations, unless
approved by the Administrator. If both percent CO2 and
percent O2 are measured, the analytical results of any of the
three procedures given below may also be used for calculating the dry
molecular weight (see Method 3).

8.1 Single-Point, Grab Sampling and Analytical Procedure.

8.1.1 The sampling point in the duct shall either be at the
centroid of the cross section or at a point no closer to the walls than
1.0 m (3.3 ft), unless otherwise specified by the Administrator.
8.1.2 Set up the equipment as shown in Figure 3-1 of Method 3,
making sure all connections ahead of the analyzer are tight. Leak-check
the Orsat analyzer according to the procedure described in Section 11.5
of Method 3. This leak-check is mandatory.
8.1.3 Place the probe in the stack, with the tip of the probe
positioned at the sampling point; purge the sampling line long enough to
allow at least five exchanges. Draw a sample into the analyzer. For
emission rate correction factor determinations, immediately analyze the
sample for percent CO2 or percent O2, as outlined
in Section 11.2. For excess air determination, immediately analyze the
sample for percent CO2, O2, and CO, as outlined in
Section 11.2, and calculate excess air as outlined in Section 12.2.
8.1.4 After the analysis is completed, leak-check (mandatory) the
Orsat analyzer once again, as described in Section 11.5 of Method 3. For
the results of the analysis to be valid, the Orsat analyzer must pass
this leak-test before and after the analysis.

[[Page 156]]

8.2 Single-Point, Integrated Sampling and Analytical Procedure.

8.2.1 The sampling point in the duct shall be located as specified
in Section 8.1.1.
8.2.2 Leak-check (mandatory) the flexible bag as in Section 6.2.6
of Method 3. Set up the equipment as shown in Figure 3-2 of Method 3.
Just before sampling, leak-check (mandatory) the train by placing a
vacuum gauge at the condenser inlet, pulling a vacuum of at least 250 mm
Hg (10 in. Hg), plugging the outlet at the quick disconnect, and then
turning off the pump. The vacuum should remain stable for at least 0.5
minute. Evacuate the flexible bag. Connect the probe, and place it in
the stack, with the tip of the probe positioned at the sampling point;
purge the sampling line. Next, connect the bag, and make sure that all
connections are tight.
8.2.3 Sample at a constant rate, or as specified by the
Administrator. The sampling run must be simultaneous with, and for the
same total length of time as, the pollutant emission rate determination.
Collect at least 28 liters (1.0 ft\3\) of sample gas. Smaller volumes
may be collected, subject to approval of the Administrator.
8.2.4 Obtain one integrated flue gas sample during each pollutant
emission rate determination. For emission rate correction factor
determination, analyze the sample within 4 hours after it is taken for
percent CO2 or percent O2 (as outlined in Section
11.2).

8.3 Multi-Point, Integrated Sampling and Analytical Procedure.

8.3.1 Unless otherwise specified in an applicable regulation, or by
the Administrator, a minimum of eight traverse points shall be used for
circular stacks having diameters less than 0.61 m (24 in.), a minimum of
nine shall be used for rectangular stacks having equivalent diameters
less than 0.61 m (24 in.), and a minimum of 12 traverse points shall be
used for all other cases. The traverse points shall be located according
to Method 1.
8.3.2 Follow the procedures outlined in Sections 8.2.2 through
8.2.4, except for the following: Traverse all sampling points, and
sample at each point for an equal length of time. Record sampling data
as shown in Figure 3-3 of Method 3.

9.0 Quality Control

9.1 Data Validation Using Fuel Factor. Although in most instances,
only CO2 or O2 measurement is required, it is
recommended that both CO2 and O2 be measured to
provide a check on the quality of the data. The data validation
procedure of Section 12.3 is suggested.

Note: Since this method for validating the CO2 and
O2 analyses is based on combustion of organic and fossil
fuels and dilution of the gas stream with air, this method does not
apply to sources that (1) remove CO2 or O2 through
processes other than combustion, (2) add O2 (e.g., oxygen
enrichment) and N2 in proportions different from that of air,
(3) add CO2 (e.g., cement or lime kilns), or (4) have no fuel
factor, FO, values obtainable (e.g., extremely variable waste
mixtures). This method validates the measured proportions of
CO2 and O2 for fuel type, but the method does not
detect sample dilution resulting from leaks during or after sample
collection. The method is applicable for samples collected downstream of
most lime or limestone flue-gas desulfurization units as the
CO2 added or removed from the gas stream is not significant
in relation to the total CO2 concentration. The
CO2 concentrations from other types of scrubbers using only
water or basic slurry can be significantly affected and would render the
fuel factor check minimally useful.

10.0 Calibration and Standardization

10.1 Analyzer. The analyzer and analyzer operator technique should
be audited periodically as follows: take a sample from a manifold
containing a known mixture of CO2 and O2, and
analyze according to the procedure in Section 11.3. Repeat this
procedure until the measured concentration of three consecutive samples
agrees with the stated value 0.5 percent. If necessary, take
corrective action, as specified in the analyzer users manual.
10.2 Rotameter. The rotameter need not be calibrated, but should be
cleaned and maintained according to the manufacturer's instruction.

11.0 Analytical Procedure

11.1 Maintenance. The Orsat analyzer should be maintained according
to the manufacturers specifications.
11.2 Grab Sample Analysis. To ensure complete absorption of the
CO2, O2, or if applicable, CO, make repeated
passes through each absorbing solution until two consecutive readings
are the same. Several passes (three or four) should be made between
readings. (If constant readings cannot be obtained after three
consecutive readings, replace the absorbing solution.) Although in most
cases, only CO2 or O2 concentration is required,
it is recommended that both CO2 and O2 be
measured, and that the procedure in Section 12.3 be used to validate the
analytical data.

Note: Since this single-point, grab sampling and analytical
procedure is normally conducted in conjunction with a single-point, grab
sampling and analytical procedure for a pollutant, only one analysis is
ordinarily conducted. Therefore, great care must be taken to obtain a
valid sample and analysis.

[[Page 157]]

11.3 Integrated Sample Analysis. The Orsat analyzer must be leak-
checked (see Section 11.5 of Method 3) before the analysis. If excess
air is desired, proceed as follows: (1) within 4 hours after the sample
is taken, analyze it (as in Sections 11.3.1 through 11.3.3) for percent
CO2, O2, and CO; (2) determine the percentage of
the gas that is N2 by subtracting the sum of the percent
CO2, percent O2, and percent CO from 100 percent;
and (3) calculate percent excess air, as outlined in Section 12.2.
11.3.1 To ensure complete absorption of the CO2,
O2, or if applicable, CO, follow the procedure described in
Section 11.2.

Note: Although in most instances only CO2 or
O2 is required, it is recommended that both CO2
and O2 be measured, and that the procedures in Section 12.3
be used to validate the analytical data.

11.3.2 Repeat the analysis until the following criteria are met:
11.3.2.1 For percent CO2, repeat the analytical
procedure until the results of any three analyses differ by no more than
(a) 0.3 percent by volume when CO2 is greater than 4.0
percent or (b) 0.2 percent by volume when CO2 is less than or
equal to 4.0 percent. Average three acceptable values of percent
CO2, and report the results to the nearest 0.2 percent.
11.3.2.2 For percent O2, repeat the analytical procedure
until the results of any three analyses differ by no more than (a) 0.3
percent by volume when O2 is less than 15.0 percent or (b)
0.2 percent by volume when O2 is greater than or equal to
15.0 percent. Average the three acceptable values of percent
O2, and report the results to the nearest 0.1 percent.
11.3.2.3 For percent CO, repeat the analytical procedure until the
results of any three analyses differ by no more than 0.3 percent.
Average the three acceptable values of percent CO, and report the
results to the nearest 0.1 percent.
11.3.3 After the analysis is completed, leak-check (mandatory) the
Orsat analyzer once again, as described in Section 11.5 of Method 3. For
the results of the analysis to be valid, the Orsat analyzer must pass
this leak-test before and after the analysis.
11.4 Standardization. A periodic check of the reagents and of
operator technique should be conducted at least once every three series
of test runs as indicated in Section 10.1.

12.0 Calculations and Data Analysis

12.1 Nomenclature. Same as Section 12.1 of Method 3 with the
addition of the following:
%EA = Percent excess air.
0.264 = Ratio of O2 to N2 in air, v/v.

12.2 Percent Excess Air. Determine the percentage of the gas that
is N2 by subtracting the sum of the percent CO2,
percent CO, and percent O2 from 100 percent. Calculate the
percent excess air (if applicable) by substituting the appropriate
values of percent O2, CO, and N2 into Equation 3B-
1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.093

Note: The equation above assumes that ambient air is used as the
source of O2 and that the fuel does not contain appreciable
amounts of N2 (as do coke oven or blast furnace gases). For
those cases when appreciable amounts of N2 are present (coal,
oil, and natural gas do not contain appreciable amounts of
N2) or when oxygen enrichment is used, alternative methods,
subject to approval of the Administrator, are required.
12.3 Data Validation When Both CO2 and O2 Are
Measured.
12.3.1 Fuel Factor, Fo. Calculate the fuel factor (if
applicable) using Equation 3B-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.094

Where:

%O2 = Percent O2 by volume, dry basis.
%CO2 = Percent CO2 by volume, dry basis.
20.9 = Percent O2 by volume in ambient air.

If CO is present in quantities measurable by this method, adjust the
O2 and CO2 values using Equations 3B-3 and 3B-4
before performing the calculation for Fo:
[GRAPHIC] [TIFF OMITTED] TR17OC00.095

[GRAPHIC] [TIFF OMITTED] TR17OC00.096

Where:
%CO = Percent CO by volume, dry basis.

12.3.2 Compare the calculated Fo factor with the
expected Fo values. Table 3B-1 in Section 17.0 may be used in
establishing acceptable ranges for the expected Fo if the
fuel being burned is known. When fuels are burned in combinations,
calculate the combined fuel Fd and Fc factors (as
defined in Method 19, Section 12.2) according to the procedure in Method
19, Sections 12.2 and 12.3.

[[Page 158]]

Then calculate the Fo factor according to Equation 3B-5.
[GRAPHIC] [TIFF OMITTED] TR17OC00.097

12.3.3 Calculated Fo values, beyond the acceptable
ranges shown in this table, should be investigated before accepting the
test results. For example, the strength of the solutions in the gas
analyzer and the analyzing technique should be checked by sampling and
analyzing a known concentration, such as air; the fuel factor should be
reviewed and verified. An acceptability range of 12 percent
is appropriate for the Fo factor of mixed fuels with variable
fuel ratios. The level of the emission rate relative to the compliance
level should be considered in determining if a retest is appropriate;
i.e., if the measured emissions are much lower or much greater than the
compliance limit, repetition of the test would not significantly change
the compliance status of the source and would be unnecessarily time
consuming and costly.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Method 3, Section 16.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 3B-1.--Fo Factors for Selected Fuels
------------------------------------------------------------------------
Fuel type Fo range
------------------------------------------------------------------------
Coal:
Anthracite and lignite.............................. 1.016-1.130
Bituminous.......................................... 1.083-1.230
Oil:
Distillate.......................................... 1.260-1.413
Residual............................................ 1.210-1.370
Gas:
Natural............................................. 1.600-1.836
Propane............................................. 1.434-1.586
Butane.............................................. 1.405-1.553
Wood.................................................... 1.000-1.120
Wood bark............................................... 1.003-1.130
------------------------------------------------------------------------

Method 3C--Determination of Carbon Dioxide, Methane, Nitrogen, and
Oxygen From Stationary Sources

1. Applicability and Principle

1.1 Applicability. This method applies to the analysis of carbon
dioxide (CO2), methane (CH4), nitrogen
(N2), and oxygen (O2) in samples from municipal
solid waste landfills and other sources when specified in an applicable
subpart.
1.2 Principle. A portion of the sample is injected into a gas
chromatograph (GC) and the CO2, CH4,
N2, and O2 concentrations are determined by using
a thermal conductivity detector (TCD) and integrator.

2. Range and Sensitivity

2.1 Range. The range of this method depends upon the concentration
of samples. The analytical range of TCD's is generally between
approximately 10 ppmv and the upper percent range.
2.2 Sensitivity. The sensitivity limit for a compound is defined as
the minimum detectable concentration of that compound, or the
concentration that produces a signal-to-noise ratio of three to one. For
CO2, CH4, N2, and O2, the
sensitivity limit is in the low ppmv range.

3. Interferences

Since the TCD exhibits universal response and detects all gas
components except the carrier, interferences may occur. Choosing the
appropriate GC or shifting the retention times by changing the column
flow rate may help to eliminate resolution interferences.
To assure consistent detector response, helium is used to prepare
calibration gases. Frequent exposure to samples or carrier gas
containing oxygen may gradually destroy filaments.

4. Apparatus

4.1 Gas Chromatograph. GC having at least the following components:
4.1.1 Separation Column. Appropriate column(s) to resolve
CO2, CH4, N2, O2, and other
gas components that may be present in the sample.
4.1.2 Sample Loop. Teflon or stainless steel tubing of the
appropriate diameter. Note: Mention of trade names or specific products
does not constitute endorsement or recommendation by the U. S.
Environmental Protection Agency.
4.1.3 Conditioning System. To maintain the column and sample loop
at constant temperature.
4.1.4 Thermal Conductivity Detector.
4.2 Recorder. Recorder with linear strip chart. Electronic
integrator (optional) is recommended.
4.3 Teflon Tubing. Diameter and length determined by connection
requirements of cylinder regulators and the GC.
4.4 Regulators. To control gas cylinder pressures and flow rates.
4.5 Adsorption Tubes. Applicable traps to remove any O2
from the carrier gas.

5. Reagents

5.1 Calibration and Linearity Gases. Standard cylinder gas mixtures
for each

[[Page 159]]

compound of interest with at least three concentration levels spanning
the range of suspected sample concentrations. The calibration gases
shall be prepared in helium.
5.2 Carrier Gas. Helium, high-purity.

6. Analysis

6.1 Sample Collection. Use the sample collection procedures
described in Methods 3 or 25C to collect a sample of landfill gas (LFG).
6.2 Preparation of GC. Before putting the GC analyzer into routine
operation, optimize the operational conditions according to the
manufacturer's specifications to provide good resolution and minimum
analysis time. Establish the appropriate carrier gas flow and set the
detector sample and reference cell flow rates at exactly the same
levels. Adjust the column and detector temperatures to the recommended
levels. Allow sufficient time for temperature stabilization. This may
typically require 1 hour for each change in temperature.
6.3 Analyzer Linearity Check and Calibration. Perform this test
before sample analysis. Using the gas mixtures in section 5.1, verify
the detector linearity over the range of suspected sample concentrations
with at least three points per compound of interest. This initial check
may also serve as the initial instrument calibration. All subsequent
calibrations may be performed using a single-point standard gas provided
the calibration point is within 20 percent of the sample component
concentration. For each instrument calibration, record the carrier and
detector flow rates, detector filament and block temperatures,
attenuation factor, injection time, chart speed, sample loop volume, and
component concentrations. Plot a linear regression of the standard
concentrations versus area values to obtain the response factor of each
compound. Alternatively, response factors of uncorrected component
concentrations (wet basis) may be generated using instrumental
integration. Note: Peak height may be used instead of peak area
throughout this method.
6.4 Sample Analysis. Purge the sample loop with sample, and allow
to come to atmospheric pressure before each injection. Analyze each
sample in duplicate, and calculate the average sample area (A). The
results are acceptable when the peak areas for two consecutive
injections agree within 5 percent of their average. If they do not
agree, run additional samples until consistent area data are obtained.
Determine the tank sample concentrations according to section 7.2.

7. Calculations

Carry out calculations retaining at least one extra decimal figure
beyond that of the acquired data. Round off results only after the final
calculation.
7.1 Nomenclature.

A = average sample area
Bw = moisture content in the sample, fraction
C = component concentration in the sample, dry basis, ppmv
Ct = calculated NMOC concentration, ppmv C equivalent
Ctm = measured NMOC concentration, ppmv C equivalent
Pbar = barometric pressure, mm Hg
Pti = gas sample tank pressure after evacuation, mm Hg
absolute
Pt = gas sample tank pressure after sampling, but before
pressurizing, mm Hg absolute
Ptf = final gas sample tank pressure after pressurizing, mm
Hg absolute
Pw = vapor pressure of H2O (from table 3C-1), mm
Hg
Tti = sample tank temperature before sampling, deg.K
Tt = sample tank temperature at completion of sampling,
deg.K
Ttf = sample tank temperature after pressurizing, deg.K
r = total number of analyzer injections of sample tank during analysis
(where j = injection number, 1 . . . r)
R = Mean calibration response factor for specific sample component,
area/ppmv

Table 3C-1.--Moisture Correction
------------------------------------------------------------------------
Vapor
Temperature deg.C Pressure of
H2O, mm Hg
------------------------------------------------------------------------
4.......................................................... 6.1
6.......................................................... 7.0
8.......................................................... 8.0
10......................................................... 9.2
12......................................................... 10.5
14......................................................... 12.0
16......................................................... 13.6
18......................................................... 15.5
20......................................................... 17.5
22......................................................... 19.8
24......................................................... 22.4
26......................................................... 25.2
28......................................................... 28.3
30......................................................... 31.8
------------------------------------------------------------------------

7.2 Concentration of Sample Components. Calculate C for each
compound using Equations 3C-1 and 3C-2. Use the temperature and
barometric pressure at the sampling site to calculate Bw. If the sample
was diluted with helium using the procedures in Method 25C, use Equation
3C-3 to calculate the concentration.

[[Page 160]]

[GRAPHIC] [TIFF OMITTED] TR12MR96.031

8. Bibliography

1. McNair, H.M., and E.J. Bonnelli. Basic Gas Chromatography.
Consolidated Printers, Berkeley, CA. 1969.

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A see the List of CFR Sections Affected, which appears in the
Finding Aids section of the printed volume and on GPO Access.

Appendix A-3 to Part 60--Test Methods 4 through 5I

Method 4--Determination of moisture content in stack gases
Method 5--Determination of particulate matter emissions from stationary
sources
Method 5A--Determination of particulate matter emissions from the
asphalt processing and asphalt roofing industry
Method 5B--Determination of nonsulfuric acid particulate matter
emissions from stationary sources
Method 5C [Reserved]
Method 5D--Determination of particulate matter emissions from positive
pressure fabric filters
Method 5E--Determination of particulate matter emissions from the wool
fiberglass insulation manufacturing industry
Method 5F--Determination of nonsulfate particulate matter emissions from
stationary sources
Method 5G--Determination of particulate matter emissions from wood
heaters (dilution tunnel sampling location)
Method 5H--Determination of particulate emissions from wood heaters from
a stack location
Method 5I--Determination of Low Level Particulate Matter Emissions From
Stationary Sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but

[[Page 161]]

must be identified in the test report. The potentially approvable
options are cited as ``subject to the approval of the Administrator'' or
as ``or equivalent.'' Such potentially approvable techniques or
alternatives may be used at the discretion of the owner without prior
approval. However, detailed descriptions for applying these potentially
approvable techniques or alternatives are not provided in the test
methods. Also, the potentially approvable options are not necessarily
acceptable in all applications. Therefore, an owner electing to use such
potentially approvable techniques or alternatives is responsible for:
(1) assuring that the techniques or alternatives are in fact applicable
and are properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the the degree of detail should be similar to the detail contained
in the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 4--Determination of Moisture Content in Stack Gases

Note: This method does not include all the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling) essential to its
performance. Some material is incorporated by reference from other
methods in this part. Therefore, to obtain reliable results, persons
using this method should have a thorough knowledge of at least the
following additional test methods: Method 1, Method 5, and Method 6.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Water vapor (H2O)................. 7732-18-5 N/A
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the moisture content of stack gas.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted at a constant rate from the source;
moisture is removed from the sample stream and determined either
volumetrically or gravimetrically.
2.2 The method contains two possible procedures: a reference method
and an approximation method.
2.2.1 The reference method is used for accurate determinations of
moisture content (such as are needed to calculate emission data). The
approximation method, provides estimates of percent moisture to aid in
setting isokinetic sampling rates prior to a pollutant emission
measurement run. The approximation method described herein is only a
suggested approach; alternative means for approximating the moisture
content (e.g., drying tubes, wet bulb-dry bulb techniques, condensation
techniques, stoichiometric calculations, previous experience, etc.) are
also acceptable.
2.2.2 The reference method is often conducted simultaneously with a
pollutant emission measurement run. When it is, calculation of percent
isokinetic, pollutant emission rate, etc., for the run shall be based
upon the results of the reference method or its equivalent. These
calculations shall not be based upon the results of the approximation
method, unless the approximation method is shown, to the satisfaction of
the Administrator, to be capable of yielding results within one percent
H2O of the reference method.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 The moisture content of saturated gas streams or streams that
contain water droplets, as measured by the reference method, may be
positively biased. Therefore, when these conditions exist or are
suspected, a second determination of the moisture content shall be made
simultaneously with the reference method, as follows: Assume that the
gas stream is saturated. Attach a temperature sensor [capable of
measuring to 1 deg.C (2 deg.F)] to the reference method
probe. Measure the stack gas temperature at each traverse point (see
Section 8.1.1.1) during the reference method traverse, and calculate the
average stack gas temperature. Next, determine the moisture percentage,
either by: (1) Using a psychrometric chart and making appropriate
corrections if the stack pressure is different from that of the chart,
or (2) using saturation vapor pressure tables. In cases where the
psychrometric chart or the saturation vapor pressure tables are not
applicable (based on evaluation of the process), alternative methods,
subject to the approval of the Administrator, shall be used.

5.0 Safety

[[Page 162]]

and health practices and determine the applicability of regulatory
limitations prior to performing this test method.

6.0 Equipment and Supplies

6.1 Reference Method. A schematic of the sampling train used in
this reference method is shown in Figure 4-1.
6.1.1 Probe. Stainless steel or glass tubing, sufficiently heated
to prevent water condensation, and equipped with a filter, either in-
stack (e.g., a plug of glass wool inserted into the end of the probe) or
heated out-of-stack (e.g., as described in Method 5), to remove
particulate matter. When stack conditions permit, other metals or
plastic tubing may be used for the probe, subject to the approval of the
Administrator.
6.1.2 Condenser. Same as Method 5, Section 6.1.1.8.
6.1.3 Cooling System. An ice bath container, crushed ice, and water
(or equivalent), to aid in condensing moisture.
6.1.4 Metering System. Same as in Method 5, Section 6.1.1.9, except
do not use sampling systems designed for flow rates higher than 0.0283
m\3\/min (1.0 cfm). Other metering systems, capable of maintaining a
constant sampling rate to within 10 percent and determining sample gas
volume to within 2 percent, may be used, subject to the approval of the
Administrator.
6.1.5 Barometer and Graduated Cylinder and/or Balance. Same as
Method 5, Sections 6.1.2 and 6.2.5, respectively.
6.2. Approximation Method. A schematic of the sampling train used
in this approximation method is shown in Figure 4-2.
6.2.1 Probe. Same as Section 6.1.1.
6.2.2 Condenser. Two midget impingers, each with 30-ml capacity, or
equivalent.
6.2.3 Cooling System. Ice bath container, crushed ice, and water,
to aid in condensing moisture in impingers.
6.2.4 Drying Tube. Tube packed with new or regenerated 6- to 16-
mesh indicating-type silica gel (or equivalent desiccant), to dry the
sample gas and to protect the meter and pump.
6.2.5 Valve. Needle valve, to regulate the sample gas flow rate.
6.2.6 Pump. Leak-free, diaphragm type, or equivalent, to pull the
gas sample through the train.
6.2.7 Volume Meter. Dry gas meter, sufficiently accurate to measure
the sample volume to within 2 percent, and calibrated over the range of
flow rates and conditions actually encountered during sampling.
6.2.8 Rate Meter. Rotameter, or equivalent, to measure the flow
range from 0 to 3 liters/min (0 to 0.11 cfm).
6.2.9 Graduated Cylinder. 25-ml.
6.2.10 Barometer. Same as Method 5, Section 6.1.2.
6.2.11 Vacuum Gauge. At least 760-mm (30-in.) Hg gauge, to be used
for the sampling leak check.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Reference Method. The following procedure is intended for a
condenser system (such as the impinger system described in Section
6.1.1.8 of Method 5) incorporating volumetric analysis to measure the
condensed moisture, and silica gel and gravimetric analysis to measure
the moisture leaving the condenser.
8.1.1 Preliminary Determinations.
8.1.1.1 Unless otherwise specified by the Administrator, a minimum
of eight traverse points shall be used for circular stacks having
diameters less than 0.61 m (24 in.), a minimum of nine points shall be
used for rectangular stacks having equivalent diameters less than 0.61 m
(24 in.), and a minimum of twelve traverse points shall be used in all
other cases. The traverse points shall be located according to Method 1.
The use of fewer points is subject to the approval of the Administrator.
Select a suitable probe and probe length such that all traverse points
can be sampled. Consider sampling from opposite sides of the stack (four
total sampling ports) for large stacks, to permit use of shorter probe
lengths. Mark the probe with heat resistant tape or by some other method
to denote the proper distance into the stack or duct for each sampling
point.
8.1.1.2 Select a total sampling time such that a minimum total gas
volume of 0.60 scm (21 scf) will be collected, at a rate no greater than
0.021 m\3\/min (0.75 cfm). When both moisture content and pollutant
emission rate are to be determined, the moisture determination shall be
simultaneous with, and for the same total length of time as, the
pollutant emission rate run, unless otherwise specified in an applicable
subpart of the standards.
8.1.2 Preparation of Sampling Train.
8.1.2.1 Place known volumes of water in the first two impingers;
alternatively, transfer water into the first two impingers and record
the weight of each impinger (plus water) to the nearest 0.5 g. Weigh and
record the weight of the silica gel to the nearest 0.5 g, and transfer
the silica gel to the fourth impinger; alternatively, the silica gel may
first be transferred to the impinger, and the weight of the silica gel
plus impinger recorded.
8.1.2.2 Set up the sampling train as shown in Figure 4-1. Turn on
the probe heater and (if applicable) the filter heating system to
temperatures of approximately 120 deg.C (248 deg.F), to prevent water
condensation ahead of the condenser. Allow time for the temperatures to
stabilize. Place crushed ice and water in the ice bath container.

[[Page 163]]

8.1.3 Leak Check Procedures. It is recommended, but not required,
that the volume metering system and sampling train be leak-checked as
follows:
8.1.3.1 Metering System. Same as Method 5, Section 8.4.1.
8.1.3.2 Sampling Train. Disconnect the probe from the first
impinger or (if applicable) from the filter holder. Plug the inlet to
the first impinger (or filter holder), and pull a 380 mm (15 in.) Hg
vacuum. A lower vacuum may be used, provided that it is not exceeded
during the test. A leakage rate in excess of 4 percent of the average
sampling rate or 0.00057 m\3\/min (0.020 cfm), whichever is less, is
unacceptable. Following the leak check, reconnect the probe to the
sampling train.
8.1.4 Sampling Train Operation. During the sampling run, maintain a
sampling rate within 10 percent of constant rate, or as specified by the
Administrator. For each run, record the data required on a data sheet
similar to that shown in Figure 4-3. Be sure to record the dry gas meter
reading at the beginning and end of each sampling time increment and
whenever sampling is halted. Take other appropriate readings at each
sample point at least once during each time increment.

Note: When Method 4 is used concurrently with an isokinetic method
(e.g., Method 5) the sampling rate should be maintained at isokinetic
conditions rather than 10 percent of constant rate.

8.1.4.1 To begin sampling, position the probe tip at the first
traverse point. Immediately start the pump, and adjust the flow to the
desired rate. Traverse the cross section, sampling at each traverse
point for an equal length of time. Add more ice and, if necessary, salt
to maintain a temperature of less than 20 deg.C (68 deg.F) at the
silica gel outlet.
8.1.4.2 After collecting the sample, disconnect the probe from the
first impinger (or from the filter holder), and conduct a leak check
(mandatory) of the sampling train as described in Section 8.1.3.2.
Record the leak rate. If the leakage rate exceeds the allowable rate,
either reject the test results or correct the sample volume as in
Section 12.3 of Method 5.
8.2 Approximation Method.
Note: The approximation method described below is presented only as
a suggested method (see Section 2.0).

8.2.1 Place exactly 5 ml water in each impinger. Leak check the
sampling train as follows: Temporarily insert a vacuum gauge at or near
the probe inlet. Then, plug the probe inlet and pull a vacuum of at
least 250 mm (10 in.) Hg. Note the time rate of change of the dry gas
meter dial; alternatively, a rotameter (0 to 40 ml/min) may be
temporarily attached to the dry gas meter outlet to determine the
leakage rate. A leak rate not in excess of 2 percent of the average
sampling rate is acceptable.
Note: Release the probe inlet plug slowly before turning off the
pump.

8.2.2 Connect the probe, insert it into the stack, and sample at a
constant rate of 2 liters/min (0.071 cfm). Continue sampling until the
dry gas meter registers about 30 liters (1.1 ft\3\) or until visible
liquid droplets are carried over from the first impinger to the second.
Record temperature, pressure, and dry gas meter readings as indicated by
Figure 4-4.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
Section 8.1.1.4............... Leak rate of the Ensures the accuracy
sampling system of the volume of gas
cannot exceed sampled. (Reference
four percent of Method)
the average
sampling rate or
0.00057 m\3\/min
(0.20 cfm).
Section 8.2.1................. Leak rate of the Ensures the accuracy
sampling system of the volume of gas
cannot exceed sampled.
two percent of (Approximation
the average Method)
sampling rate.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.
10.1 Reference Method. Calibrate the metering system, temperature
sensors, and barometer according to Method 5, Sections 10.3, 10.5, and
10.6, respectively.
10.2 Approximation Method. Calibrate the metering system and the
barometer according to Method 6, Section 10.1 and Method 5, Section
10.6, respectively.

11.0 Analytical Procedure

11.1 Reference Method. Measure the volume of the moisture condensed
in each of the impingers to the nearest ml. Alternatively, if the
impingers were weighed prior to sampling, weigh the impingers after
sampling and record the difference in weight to the nearest 0.5 g.
Determine the increase in

[[Page 164]]

weight of the silica gel (or silica gel plus impinger) to the nearest
0.5 g. Record this information (see example data sheet, Figure 4-5), and
calculate the moisture content, as described in Section 12.0.
11.2 Approximation Method. Combine the contents of the two
impingers, and measure the volume to the nearest 0.5 ml.

12.0 Data Analysis and Calculations

Carry out the following calculations, retaining at least one extra
significant figure beyond that of the acquired data. Round off figures
after final calculation.
12.1 Reference Method.
12.1.1 Nomenclature.
Bws = Proportion of water vapor, by volume, in the gas
stream.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pm = Absolute pressure (for this method, same as barometric
pressure) at the dry gas meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 (mm Hg)(m\3\)/(g-mole)( deg.K) for
metric units and 21.85 (in. Hg)(ft\3\)/(lb-mole)( deg.R) for
English units.
Tm = Absolute temperature at meter, deg.K ( deg.R).
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Vf = Final volume of condenser water, ml.
Vi = Initial volume, if any, of condenser water, ml.
Vm = Dry gas volume measured by dry gas meter, dcm (dcf).
Vm(std) = Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vwc(std) = Volume of water vapor condensed, corrected to
standard conditions, scm (scf).
Vwsg(std) = Volume of water vapor collected in silica gel,
corrected to standard conditions, scm (scf).
Wf = Final weight of silica gel or silica gel plus impinger,
g.
Wi = Initial weight of silica gel or silica gel plus
impinger, g.
Y = Dry gas meter calibration factor.
Vm = Incremental dry gas volume measured by dry gas
meter at each traverse point, dcm (dcf).
w = Density of water, 0.9982 g/ml (0.002201 lb/ml).

12.1.2 Volume of Water Vapor Condensed.
[GRAPHIC] [TIFF OMITTED] TR17OC00.098

Where:

K1 = 0.001333 m\3\/ml for metric units,
= 0.04706 ft\3\/ml for English units.

12.1.3 Volume of Water Collected in Silica Gel.
[GRAPHIC] [TIFF OMITTED] TR17OC00.099

Where:

K2 = 1.0 g/g for metric units,
= 453.6 g/lb for English units.
K3 = 0.001335 m\3\/g for metric units,
= 0.04715 ft\3\/g for English units.

12.1.4 Sample Gas Volume.
[GRAPHIC] [TIFF OMITTED] TR17OC00.100

Where:

K4 = 0.3855 deg.K/mm Hg for metric units,
= 17.64 deg.R/in. Hg for English units.
Note: If the post-test leak rate (Section 8.1.4.2) exceeds the
allowable rate, correct the value of Vm in Equation 4-3, as described in
Section 12.3 of Method 5.
12.1.5 Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.101

12.1.6 Verification of Constant Sampling Rate. For each time
increment, determine the Vm. Calculate the average.
If the value for any time increment differs from the average by more
than 10 percent, reject the results, and repeat the run.
12.1.7 In saturated or moisture droplet-laden gas streams, two
calculations of the moisture content of the stack gas shall be made, one
using a value based upon the saturated conditions (see Section 4.1), and
another based upon the results of the impinger analysis. The lower of
these two values of Bws shall be considered correct.

[[Page 165]]

12.2 Approximation Method. The approximation method presented is
designed to estimate the moisture in the stack gas; therefore, other
data, which are only necessary for accurate moisture determinations, are
not collected. The following equations adequately estimate the moisture
content for the purpose of determining isokinetic sampling rate
settings.
12.2.1 Nomenclature.
Bwm = Approximate proportion by volume of water vapor in the
gas stream leaving the second impinger, 0.025.
Bws = Water vapor in the gas stream, proportion by volume.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pm = Absolute pressure (for this method, same as barometric
pressure) at the dry gas meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 [(mm Hg)(m\3\)]/[(g-mole)(K)] for metric
units and 21.85 [(in. Hg)(ft\3\)]/[(lb-mole)( deg.R)] for
English units.
Tm = Absolute temperature at meter, deg.K ( deg.R).
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Vf = Final volume of impinger contents, ml.
Vi = Initial volume of impinger contents, ml.
Vm = Dry gas volume measured by dry gas meter, dcm (dcf).
Vm(std) = Dry gas volume measured by dry gas meter, corrected
to standard conditions, dscm (dscf).
Vwc(std) = Volume of water vapor condensed, corrected to
standard conditions, scm (scf).
Y = Dry gas meter calibration factor.
w = Density of water, 0.09982 g/ml (0.002201 lb/ml).

12.2.2 Volume of Water Vapor Collected.
[GRAPHIC] [TIFF OMITTED] TR17OC00.102

Where:

K5 = 0.001333 m\3\/ml for metric units,
= 0.04706 ft\3\/ml for English units.

12.2.3 Sample Gas Volume.
[GRAPHIC] [TIFF OMITTED] TR17OC00.103

Where:

K6 = 0.3855 deg.K/mm Hg for metric units,
= 17.64 deg.R/in. Hg for English units.

12.2.4 Approximate Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.104

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

The procedure described in Method 5 for determining moisture content
is acceptable as a reference method.

17.0 References

1. Air Pollution Engineering Manual (Second Edition). Danielson,
J.A. (ed.). U.S. Environmental Protection Agency, Office of Air Quality
Planning and Standards. Research Triangle Park, NC. Publication No. AP-
40. 1973.
2. Devorkin, Howard, et al. Air Pollution Source Testing Manual. Air
Pollution Control District, Los Angeles, CA. November 1963.
3. Methods for Determination of Velocity, Volume, Dust and Mist
Content of Gases. Western Precipitation Division of Joy Manufacturing
Co. Los Angeles, CA. Bulletin WP-50. 1968.

[[Page 166]]

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.105

[[Page 167]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.106

[[Page 168]]

Plant

Location

Operator

Date

Run No.

Ambient temperature

Barometric pressure

Probe Length

------------------------------------------------------------------------

-------------------------------------------------------------------------

------------------------------------------------------------------------

SCHEMATIC OF STACK CROSS SECTION

[[Page 169]]

--------------------------------------------------------------------------------------------------------------------------------------------------------
Gas sample temperature Temperature
Pressure Meter at dry gas meter of gas
Sampling Stack differential reading gas -------------------------- leaving
time temperature across sample Vm condenser
Traverse Pt. No. (), deg.C ( orifice volume m\3\ Inlet Tmin Outlet or last
min deg.F) meter out impinger
D>H mm (ft\3\) deg.F) deg.C ( deg.C (
(in.) H2O deg.F) deg.F)
--------------------------------------------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------
Average
--------------------------------------------------------------------------------------------------------------------------------------------------------

[[Page 170]]

Location

Test

Date

Operator

Barometric pressure

Comments:

Figure 4-3. Moisture Determination--Reference Method

----------------------------------------------------------------------------------------------------------------
Gas Volume through Rate meter setting m³/ Meter temperature
Clock time meter, (Vm), m³ (ft³) min (ft³/min) deg.C ( deg.F)
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

Figure 4-4. Example Moisture Determination Field Data Sheet--
Approximation Method

------------------------------------------------------------------------
Impinger volume, Silica gel weight,
ml g
------------------------------------------------------------------------
Final
Initial
Difference
------------------------------------------------------------------------

Figure 4-5. Analytical Data--Reference Method

Method 5--Determination of Particulate Matter Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the determination
of PM emissions from stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
collected on a glass fiber filter maintained at a temperature of 120
14 deg.C (248 25 deg.F) or such other
temperature as specified by an applicable subpart of the standards or
approved by the Administrator for a particular application. The PM mass,
which includes any material that condenses at or above the filtration
temperature, is determined gravimetrically after the removal of
uncombined water.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

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6.0 Equipment and Supplies

6.1 Sample Collection. The following items are required for sample
collection:
6.1.1 Sampling Train. A schematic of the sampling train used in
this method is shown in Figure 5-1 in Section 18.0. Complete
construction details are given in APTD-0581 (Reference 2 in Section
17.0); commercial models of this train are also available. For changes
from APTD-0581 and for allowable modifications of the train shown in
Figure 5-1, see the following subsections.
Note: The operating and maintenance procedures for the sampling
train are described in APTD-0576 (Reference 3 in Section 17.0). Since
correct usage is important in obtaining valid results, all users should
read APTD-0576 and adopt the operating and maintenance procedures
outlined in it, unless otherwise specified herein.
6.1.1.1 Probe Nozzle. Stainless steel (316) or glass with a sharp,
tapered leading edge. The angle of taper shall be 30 deg.,
and the taper shall be on the outside to preserve a constant internal
diameter. The probe nozzle shall be of the button-hook or elbow design,
unless otherwise specified by the Administrator. If made of stainless
steel, the nozzle shall be constructed from seamless tubing. Other
materials of construction may be used, subject to the approval of the
Administrator. A range of nozzle sizes suitable for isokinetic sampling
should be available. Typical nozzle sizes range from 0.32 to 1.27 cm
(\1/8\ to \1/2\ in) inside diameter (ID) in increments of 0.16 cm (\1/
16\ in). Larger nozzles sizes are also available if higher volume
sampling trains are used. Each nozzle shall be calibrated, according to
the procedures outlined in Section 10.1.
6.1.1.2 Probe Liner. Borosilicate or quartz glass tubing with a
heating system capable of maintaining a probe gas temperature during
sampling of 120 14 deg.C (248 25 deg.F), or
such other temperature as specified by an applicable subpart of the
standards or as approved by the Administrator for a particular
application. Since the actual temperature at the outlet of the probe is
not usually monitored during sampling, probes constructed according to
APTD-0581 and utilizing the calibration curves of APTD-0576 (or
calibrated according to the procedure outlined in APTD-0576) will be
considered acceptable. Either borosilicate or quartz glass probe liners
may be used for stack temperatures up to about 480 deg.C (900 deg.F);
quartz glass liners shall be used for temperatures between 480 and 900
deg.C (900 and 1,650 deg.F). Both types of liners may be used at higher
temperatures than specified for short periods of time, subject to the
approval of the Administrator. The softening temperature for
borosilicate glass is 820 deg.C (1500 deg.F), and for quartz glass it
is 1500 deg.C (2700 deg.F). Whenever practical, every effort should be
made to use borosilicate or quartz glass probe liners. Alternatively,
metal liners (e.g., 316 stainless steel, Incoloy 825 or other corrosion
resistant metals) made of seamless tubing may be used, subject to the
approval of the Administrator.
6.1.1.3 Pitot Tube. Type S, as described in Section 6.1 of Method
2, or other device approved by the Administrator. The pitot tube shall
be attached to the probe (as shown in Figure 5-1) to allow constant
monitoring of the stack gas velocity. The impact (high pressure) opening
plane of the pitot tube shall be even with or above the nozzle entry
plane (see Method 2, Figure 2-7) during sampling. The Type S pitot tube
assembly shall have a known coefficient, determined as outlined in
Section 10.0 of Method 2.
6.1.1.4 Differential Pressure Gauge. Inclined manometer or
equivalent device (two), as described in Section 6.2 of Method 2. One
manometer shall be used for velocity head (p) readings, and the
other, for orifice differential pressure readings.
6.1.1.5 Filter Holder. Borosilicate glass, with a glass frit filter
support and a silicone rubber gasket. Other materials of construction
(e.g., stainless steel, Teflon, or Viton) may be used, subject to the
approval of the Administrator. The holder design shall provide a
positive seal against leakage from the outside or around the filter. The
holder shall be attached immediately at the outlet of the probe (or
cyclone, if used).
6.1.1.6 Filter Heating System. Any heating system capable of
maintaining a temperature around the filter holder of 120 14
deg.C (248 25 deg.F) during sampling, or such other
temperature as specified by an applicable subpart of the standards or
approved by the Administrator for a particular application.
6.1.1.7 Temperature Sensor. A temperature sensor capable of
measuring temperature to within 3 deg.C (5.4 deg.F) shall
be installed so that the sensing tip of the temperature sensor is in
direct contact with the sample gas, and the temperature around the
filter holder can be regulated and monitored during sampling.
6.1.1.8 Condenser. The following system shall be used to determine
the stack gas moisture content: Four impingers connected in series with
leak-free ground glass fittings or any similar leak-free
noncontaminating fittings. The first, third, and fourth impingers shall
be of the Greenburg-Smith design, modified by replacing the tip with a
1.3 cm (\1/2\ in.) ID glass tube extending to about 1.3 cm (\1/2\ in.)
from the bottom of the flask. The second impinger shall be of the
Greenburg-Smith design with the standard tip. Modifications (e.g., using
flexible connections between the impingers, using materials other than
glass, or using flexible vacuum lines to connect the filter holder to
the condenser) may be used, subject to the approval of the
Administrator. The first and

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second impingers shall contain known quantities of water (Section
8.3.1), the third shall be empty, and the fourth shall contain a known
weight of silica gel, or equivalent desiccant. A temperature sensor,
capable of measuring temperature to within 1 deg.C (2 deg.F) shall be
placed at the outlet of the fourth impinger for monitoring purposes.
Alternatively, any system that cools the sample gas stream and allows
measurement of the water condensed and moisture leaving the condenser,
each to within 1 ml or 1 g may be used, subject to the approval of the
Administrator. An acceptable technique involves the measurement of
condensed water either gravimetrically or volumetrically and the
determination of the moisture leaving the condenser by: (1) monitoring
the temperature and pressure at the exit of the condenser and using
Dalton's law of partial pressures; or (2) passing the sample gas stream
through a tared silica gel (or equivalent desiccant) trap with exit
gases kept below 20 deg.C (68 deg.F) and determining the weight gain.
If means other than silica gel are used to determine the amount of
moisture leaving the condenser, it is recommended that silica gel (or
equivalent) still be used between the condenser system and pump to
prevent moisture condensation in the pump and metering devices and to
avoid the need to make corrections for moisture in the metered volume.

Note: If a determination of the PM collected in the impingers is
desired in addition to moisture content, the impinger system described
above shall be used, without modification. Individual States or control
agencies requiring this information shall be contacted as to the sample
recovery and analysis of the impinger contents.

6.1.1.9 Metering System. Vacuum gauge, leak-free pump, temperature
sensors capable of measuring temperature to within 3 deg.C (5.4
deg.F), dry gas meter (DGM) capable of measuring volume to within 2
percent, and related equipment, as shown in Figure 5-1. Other metering
systems capable of maintaining sampling rates within 10 percent of
isokinetic and of determining sample volumes to within 2 percent may be
used, subject to the approval of the Administrator. When the metering
system is used in conjunction with a pitot tube, the system shall allow
periodic checks of isokinetic rates.
6.1.1.10 Sampling trains utilizing metering systems designed for
higher flow rates than that described in APTD-0581 or APTD-0576 may be
used provided that the specifications of this method are met.
6.1.2 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in.).
Note: The barometric pressure reading may be obtained from a nearby
National Weather Service station. In this case, the station value (which
is the absolute barometric pressure) shall be requested and an
adjustment for elevation differences between the weather station and
sampling point shall be made at a rate of minus 2.5 mm Hg (0.1 in.) per
30 m (100 ft) elevation increase or plus 2.5 mm Hg (0.1 in) per 30 m
(100 ft) elevation decrease.

6.1.3 Gas Density Determination Equipment. Temperature sensor and
pressure gauge, as described in Sections 6.3 and 6.4 of Method 2, and
gas analyzer, if necessary, as described in Method 3. The temperature
sensor shall, preferably, be permanently attached to the pitot tube or
sampling probe in a fixed configuration, such that the tip of the sensor
extends beyond the leading edge of the probe sheath and does not touch
any metal. Alternatively, the sensor may be attached just prior to use
in the field. Note, however, that if the temperature sensor is attached
in the field, the sensor must be placed in an interference-free
arrangement with respect to the Type S pitot tube openings (see Method
2, Figure 2-4). As a second alternative, if a difference of not more
than 1 percent in the average velocity measurement is to be introduced,
the temperature sensor need not be attached to the probe or pitot tube.
(This alternative is subject to the approval of the Administrator.)
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Probe-Liner and Probe-Nozzle Brushes. Nylon bristle brushes
with stainless steel wire handles. The probe brush shall have extensions
(at least as long as the probe) constructed of stainless steel, Nylon,
Teflon, or similarly inert material. The brushes shall be properly sized
and shaped to brush out the probe liner and nozzle.
6.2.2 Wash Bottles. Two Glass wash bottles are recommended.
Alternatively, polyethylene wash bottles may be used. It is recommended
that acetone not be stored in polyethylene bottles for longer than a
month.
6.2.3 Glass Sample Storage Containers. Chemically resistant,
borosilicate glass bottles, for acetone washes, 500 ml or 1000 ml. Screw
cap liners shall either be rubber-backed Teflon or shall be constructed
so as to be leak-free and resistant to chemical attack by acetone.
(Narrow mouth glass bottles have been found to be less prone to
leakage.) Alternatively, polyethylene bottles may be used.
6.2.4 Petri Dishes. For filter samples; glass or polyethylene,
unless otherwise specified by the Administrator.
6.2.5 Graduated Cylinder and/or Balance. To measure condensed water
to within 1 ml or 0.5 g. Graduated cylinders shall have subdivisions no
greater than 2 ml.
6.2.6 Plastic Storage Containers. Air-tight containers to store
silica gel.

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6.2.7 Funnel and Rubber Policeman. To aid in transfer of silica gel
to container; not necessary if silica gel is weighed in the field.
6.2.8 Funnel. Glass or polyethylene, to aid in sample recovery.
6.3 Sample Analysis. The following equipment is required for sample
analysis:
6.3.1 Glass Weighing Dishes.
6.3.2 Desiccator.
6.3.3 Analytical Balance. To measure to within 0.1 mg.
6.3.4 Balance. To measure to within 0.5 g.
6.3.5 Beakers. 250 ml.
6.3.6 Hygrometer. To measure the relative humidity of the
laboratory environment.
6.3.7 Temperature Sensor. To measure the temperature of the
laboratory environment.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Filters. Glass fiber filters, without organic binder,
exhibiting at least 99.95 percent efficiency (0.05 percent penetration)
on 0.3 micron dioctyl phthalate smoke particles. The filter efficiency
test shall be conducted in accordance with ASTM Method D 2986-71, 78, or
95a (incorporated by reference--see Sec. 60.17). Test data from the
supplier's quality control program are sufficient for this purpose. In
sources containing SO2 or SO3, the filter material
must be of a type that is unreactive to SO2 or
SO3. Reference 10 in Section 17.0 may be used to select the
appropriate filter.
7.1.2 Silica Gel. Indicating type, 6 to 16 mesh. If previously
used, dry at 175 deg.C (350 deg.F) for 2 hours. New silica gel may be
used as received. Alternatively, other types of desiccants (equivalent
or better) may be used, subject to the approval of the Administrator.
7.1.3 Water. When analysis of the material caught in the impingers
is required, deionized distilled water (to conform to ASTM D 1193-77 or
91 Type 3 (incorporated by reference--see Sec. 60.17)) shall be used.
Run blanks prior to field use to eliminate a high blank on test samples.
7.1.4 Crushed Ice.
7.1.5 Stopcock Grease. Acetone-insoluble, heat-stable silicone
grease. This is not necessary if screw-on connectors with Teflon
sleeves, or similar, are used. Alternatively, other types of stopcock
grease may be used, subject to the approval of the Administrator.
7.2 Sample Recovery. Acetone, reagent grade, 0.001
percent residue, in glass bottles, is required. Acetone from metal
containers generally has a high residue blank and should not be used.
Sometimes, suppliers transfer acetone to glass bottles from metal
containers; thus, acetone blanks shall be run prior to field use and
only acetone with low blank values (0.001 percent) shall be
used. In no case shall a blank value of greater than 0.001 percent of
the weight of acetone used be subtracted from the sample weight.
7.3 Sample Analysis. The following reagents are required for sample
analysis:
7.3.1 Acetone. Same as in Section 7.2.
7.3.2 Desiccant. Anhydrous calcium sulfate, indicating type.
Alternatively, other types of desiccants may be used, subject to the
approval of the Administrator.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. It is suggested that sampling equipment be
maintained according to the procedures described in APTD-0576.
8.1.1 Place 200 to 300 g of silica gel in each of several air-tight
containers. Weigh each container, including silica gel, to the nearest
0.5 g, and record this weight. As an alternative, the silica gel need
not be preweighed, but may be weighed directly in its impinger or
sampling holder just prior to train assembly.
8.1.2 Check filters visually against light for irregularities,
flaws, or pinhole leaks. Label filters of the proper diameter on the
back side near the edge using numbering machine ink. As an alternative,
label the shipping containers (glass or polyethylene petri dishes), and
keep each filter in its identified container at all times except during
sampling.
8.1.3 Desiccate the filters at 20 5.6 deg.C (68
10 deg.F) and ambient pressure for at least 24 hours.
Weigh each filter (or filter and shipping container) at intervals of at
least 6 hours to a constant weight (i.e., 0.5 mg change from
previous weighing). Record results to the nearest 0.1 mg. During each
weighing, the period for which the filter is exposed to the laboratory
atmosphere shall be less than 2 minutes. Alternatively (unless otherwise
specified by the Administrator), the filters may be oven dried at 105
deg.C (220 deg.F) for 2 to 3 hours, desiccated for 2 hours, and
weighed. Procedures other than those described, which account for
relative humidity effects, may be used, subject to the approval of the
Administrator.
8.2 Preliminary Determinations.
8.2.1 Select the sampling site and the minimum number of sampling
points according to Method 1 or as specified by the Administrator.
Determine the stack pressure, temperature, and the range of velocity
heads using Method 2; it is recommended that a leak check of the pitot
lines (see Method 2, Section 8.1) be performed. Determine the moisture
content using Approximation Method 4 or its alternatives for the purpose
of making isokinetic sampling rate settings. Determine the stack gas dry
molecular weight, as described in Method 2, Section 8.6; if integrated
Method 3 sampling is used for

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molecular weight determination, the integrated bag sample shall be taken
simultaneously with, and for the same total length of time as, the
particulate sample run.
8.2.2 Select a nozzle size based on the range of velocity heads,
such that it is not necessary to change the nozzle size in order to
maintain isokinetic sampling rates. During the run, do not change the
nozzle size. Ensure that the proper differential pressure gauge is
chosen for the range of velocity heads encountered (see Section 8.3 of
Method 2).
8.2.3 Select a suitable probe liner and probe length such that all
traverse points can be sampled. For large stacks, consider sampling from
opposite sides of the stack to reduce the required probe length.
8.2.4 Select a total sampling time greater than or equal to the
minimum total sampling time specified in the test procedures for the
specific industry such that (l) the sampling time per point is not less
than 2 minutes (or some greater time interval as specified by the
Administrator), and (2) the sample volume taken (corrected to standard
conditions) will exceed the required minimum total gas sample volume.
The latter is based on an approximate average sampling rate.
8.2.5 The sampling time at each point shall be the same. It is
recommended that the number of minutes sampled at each point be an
integer or an integer plus one-half minute, in order to avoid
timekeeping errors.
8.2.6 In some circumstances (e.g., batch cycles) it may be
necessary to sample for shorter times at the traverse points and to
obtain smaller gas sample volumes. In these cases, the Administrator's
approval must first be obtained.
8.3 Preparation of Sampling Train.
8.3.1 During preparation and assembly of the sampling train, keep
all openings where contamination can occur covered until just prior to
assembly or until sampling is about to begin. Place 100 ml of water in
each of the first two impingers, leave the third impinger empty, and
transfer approximately 200 to 300 g of preweighed silica gel from its
container to the fourth impinger. More silica gel may be used, but care
should be taken to ensure that it is not entrained and carried out from
the impinger during sampling. Place the container in a clean place for
later use in the sample recovery. Alternatively, the weight of the
silica gel plus impinger may be determined to the nearest 0.5 g and
recorded.
8.3.2 Using a tweezer or clean disposable surgical gloves, place a
labeled (identified) and weighed filter in the filter holder. Be sure
that the filter is properly centered and the gasket properly placed so
as to prevent the sample gas stream from circumventing the filter. Check
the filter for tears after assembly is completed.
8.3.3 When glass probe liners are used, install the selected nozzle
using a Viton A O-ring when stack temperatures are less than 260 deg.C
(500 deg.F) or a heat-resistant string gasket when temperatures are
higher. See APTD-0576 for details. Other connecting systems using either
316 stainless steel or Teflon ferrules may be used. When metal liners
are used, install the nozzle as discussed above or by a leak-free direct
mechanical connection. Mark the probe with heat resistant tape or by
some other method to denote the proper distance into the stack or duct
for each sampling point.
8.3.4 Set up the train as shown in Figure 5-1, using (if necessary)
a very light coat of silicone grease on all ground glass joints,
greasing only the outer portion (see APTD-0576) to avoid the possibility
of contamination by the silicone grease. Subject to the approval of the
Administrator, a glass cyclone may be used between the probe and filter
holder when the total particulate catch is expected to exceed 100 mg or
when water droplets are present in the stack gas.
8.3.5 Place crushed ice around the impingers.
8.4 Leak-Check Procedures.
8.4.1 Leak Check of Metering System Shown in Figure 5-1. That
portion of the sampling train from the pump to the orifice meter should
be leak-checked prior to initial use and after each shipment. Leakage
after the pump will result in less volume being recorded than is
actually sampled. The following procedure is suggested (see Figure 5-2):
Close the main valve on the meter box. Insert a one-hole rubber stopper
with rubber tubing attached into the orifice exhaust pipe. Disconnect
and vent the low side of the orifice manometer. Close off the low side
orifice tap. Pressurize the system to 13 to 18 cm (5 to 7 in.) water
column by blowing into the rubber tubing. Pinch off the tubing, and
observe the manometer for one minute. A loss of pressure on the
manometer indicates a leak in the meter box; leaks, if present, must be
corrected.
8.4.2 Pretest Leak Check. A pretest leak check of the sampling
train is recommended, but not required. If the pretest leak check is
conducted, the following procedure should be used.
8.4.2.1 After the sampling train has been assembled, turn on and
set the filter and probe heating systems to the desired operating
temperatures. Allow time for the temperatures to stabilize. If a Viton A
O-ring or other leak-free connection is used in assembling the probe
nozzle to the probe liner, leak-check the train at the sampling site by
plugging the nozzle and pulling a 380 mm (15 in.) Hg vacuum.

Note: A lower vacuum may be used, provided that it is not exceeded
during the test.

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8.4.2.2 If a heat-resistant string is used, do not connect the
probe to the train during the leak check. Instead, leak-check the train
by first plugging the inlet to the filter holder (cyclone, if
applicable) and pulling a 380 mm (15 in.) Hg vacuum (see Note in Section
8.4.2.1). Then connect the probe to the train, and leak-check at
approximately 25 mm (1 in.) Hg vacuum; alternatively, the probe may be
leak-checked with the rest of the sampling train, in one step, at 380 mm
(15 in.) Hg vacuum. Leakage rates in excess of 4 percent of the average
sampling rate or 0.00057 m\3\/min (0.020 cfm), whichever is less, are
unacceptable.
8.4.2.3 The following leak-check instructions for the sampling
train described in APTD-0576 and APTD-0581 may be helpful. Start the
pump with the bypass valve fully open and the coarse adjust valve
completely closed. Partially open the coarse adjust valve, and slowly
close the bypass valve until the desired vacuum is reached. Do not
reverse the direction of the bypass valve, as this will cause water to
back up into the filter holder. If the desired vacuum is exceeded,
either leak-check at this higher vacuum, or end the leak check and start
over.
8.4.2.4 When the leak check is completed, first slowly remove the
plug from the inlet to the probe, filter holder, or cyclone (if
applicable), and immediately turn off the vacuum pump. This prevents the
water in the impingers from being forced backward into the filter holder
and the silica gel from being entrained backward into the third
impinger.
8.4.3 Leak Checks During Sample Run. If, during the sampling run, a
component (e.g., filter assembly or impinger) change becomes necessary,
a leak check shall be conducted immediately before the change is made.
The leak check shall be done according to the procedure outlined in
Section 8.4.2 above, except that it shall be done at a vacuum equal to
or greater than the maximum value recorded up to that point in the test.
If the leakage rate is found to be no greater than 0.00057
m³/min (0.020 cfm) or 4 percent of the average sampling rate
(whichever is less), the results are acceptable, and no correction will
need to be applied to the total volume of dry gas metered; if, however,
a higher leakage rate is obtained, either record the leakage rate and
plan to correct the sample volume as shown in Section 12.3 of this
method, or void the sample run.

Note: Immediately after component changes, leak checks are optional.
If such leak checks are done, the procedure outlined in Section 8.4.2
above should be used.

8.4.4 Post-Test Leak Check. A leak check of the sampling train is
mandatory at the conclusion of each sampling run. The leak check shall
be performed in accordance with the procedures outlined in Section
8.4.2, except that it shall be conducted at a vacuum equal to or greater
than the maximum value reached during the sampling run. If the leakage
rate is found to be no greater than 0.00057 m³ min (0.020
cfm) or 4 percent of the average sampling rate (whichever is less), the
results are acceptable, and no correction need be applied to the total
volume of dry gas metered. If, however, a higher leakage rate is
obtained, either record the leakage rate and correct the sample volume
as shown in Section 12.3 of this method, or void the sampling run.
8.5 Sampling Train Operation. During the sampling run, maintain an
isokinetic sampling rate (within 10 percent of true isokinetic unless
otherwise specified by the Administrator) and a temperature around the
filter of 120 14 deg.C (248 25 deg.F), or
such other temperature as specified by an applicable subpart of the
standards or approved by the Administrator.
8.5.1 For each run, record the data required on a data sheet such
as the one shown in Figure 5-3. Be sure to record the initial DGM
reading. Record the DGM readings at the beginning and end of each
sampling time increment, when changes in flow rates are made, before and
after each leak check, and when sampling is halted. Take other readings
indicated by Figure 5-3 at least once at each sample point during each
time increment and additional readings when significant changes (20
percent variation in velocity head readings) necessitate additional
adjustments in flow rate. Level and zero the manometer. Because the
manometer level and zero may drift due to vibrations and temperature
changes, make periodic checks during the traverse.
8.5.2 Clean the portholes prior to the test run to minimize the
chance of collecting deposited material. To begin sampling, verify that
the filter and probe heating systems are up to temperature, remove the
nozzle cap, verify that the pitot tube and probe are properly
positioned. Position the nozzle at the first traverse point with the tip
pointing directly into the gas stream. Immediately start the pump, and
adjust the flow to isokinetic conditions. Nomographs are available which
aid in the rapid adjustment of the isokinetic sampling rate without
excessive computations. These nomographs are designed for use when the
Type S pitot tube coefficient (Cp) is 0.85 0.02,
and the stack gas equivalent density [dry molecular weight
(Md)] is equal to 29 4. APTD-0576 details the
procedure for using the nomographs. If Cp and Md
are outside the above stated ranges, do not use the nomographs unless
appropriate steps (see Reference 7 in Section 17.0) are taken to
compensate for the deviations.
8.5.3 When the stack is under significant negative pressure (i.e.,
height of impinger stem), take care to close the coarse adjust valve
before inserting the probe into the stack to prevent water from backing
into the

[[Page 176]]

filter holder. If necessary, the pump may be turned on with the coarse
adjust valve closed.
8.5.4 When the probe is in position, block off the openings around
the probe and porthole to prevent unrepresentative dilution of the gas
stream.
8.5.5 Traverse the stack cross-section, as required by Method 1 or
as specified by the Administrator, being careful not to bump the probe
nozzle into the stack walls when sampling near the walls or when
removing or inserting the probe through the portholes; this minimizes
the chance of extracting deposited material.
8.5.6 During the test run, make periodic adjustments to keep the
temperature around the filter holder at the proper level; add more ice
and, if necessary, salt to maintain a temperature of less than 20 deg.C
(68 deg.F) at the condenser/silica gel outlet. Also, periodically check
the level and zero of the manometer.
8.5.7 If the pressure drop across the filter becomes too high,
making isokinetic sampling difficult to maintain, the filter may be
replaced in the midst of the sample run. It is recommended that another
complete filter assembly be used rather than attempting to change the
filter itself. Before a new filter assembly is installed, conduct a leak
check (see Section 8.4.3). The total PM weight shall include the
summation of the filter assembly catches.
8.5.8 A single train shall be used for the entire sample run,
except in cases where simultaneous sampling is required in two or more
separate ducts or at two or more different locations within the same
duct, or in cases where equipment failure necessitates a change of
trains. In all other situations, the use of two or more trains will be
subject to the approval of the Administrator.

Note: When two or more trains are used, separate analyses of the
front-half and (if applicable) impinger catches from each train shall be
performed, unless identical nozzle sizes were used on all trains, in
which case, the front-half catches from the individual trains may be
combined (as may the impinger catches) and one analysis of front-half
catch and one analysis of impinger catch may be performed. Consult with
the Administrator for details concerning the calculation of results when
two or more trains are used.

8.5.9 At the end of the sample run, close the coarse adjust valve,
remove the probe and nozzle from the stack, turn off the pump, record
the final DGM meter reading, and conduct a post-test leak check, as
outlined in Section 8.4.4. Also, leak-check the pitot lines as described
in Method 2, Section 8.1. The lines must pass this leak check, in order
to validate the velocity head data.
8.6 Calculation of Percent Isokinetic. Calculate percent isokinetic
(see Calculations, Section 12.11) to determine whether the run was valid
or another test run should be made. If there was difficulty in
maintaining isokinetic rates because of source conditions, consult with
the Administrator for possible variance on the isokinetic rates.
8.7 Sample Recovery.
8.7.1 Proper cleanup procedure begins as soon as the probe is
removed from the stack at the end of the sampling period. Allow the
probe to cool.
8.7.2 When the probe can be safely handled, wipe off all external
PM near the tip of the probe nozzle, and place a cap over it to prevent
losing or gaining PM. Do not cap off the probe tip tightly while the
sampling train is cooling down. This would create a vacuum in the filter
holder, thereby drawing water from the impingers into the filter holder.
8.7.3 Before moving the sample train to the cleanup site, remove
the probe from the sample train, wipe off the silicone grease, and cap
the open outlet of the probe. Be careful not to lose any condensate that
might be present. Wipe off the silicone grease from the filter inlet
where the probe was fastened, and cap it. Remove the umbilical cord from
the last impinger, and cap the impinger. If a flexible line is used
between the first impinger or condenser and the filter holder,
disconnect the line at the filter holder, and let any condensed water or
liquid drain into the impingers or condenser. After wiping off the
silicone grease, cap off the filter holder outlet and impinger inlet.
Either ground-glass stoppers, plastic caps, or serum caps may be used to
close these openings.
8.7.4 Transfer the probe and filter-impinger assembly to the
cleanup area. This area should be clean and protected from the wind so
that the chances of contaminating or losing the sample will be
minimized.
8.7.5 Save a portion of the acetone used for cleanup as a blank.
Take 200 ml of this acetone directly from the wash bottle being used,
and place it in a glass sample container labeled ``acetone blank.''
8.7.6 Inspect the train prior to and during disassembly, and note
any abnormal conditions. Treat the samples as follows:
8.7.6.1 Container No. 1. Carefully remove the filter from the
filter holder, and place it in its identified petri dish container. Use
a pair of tweezers and/or clean disposable surgical gloves to handle the
filter. If it is necessary to fold the filter, do so such that the PM
cake is inside the fold. Using a dry Nylon bristle brush and/or a sharp-
edged blade, carefully transfer to the petri dish any PM and/or filter
fibers that adhere to the filter holder gasket. Seal the container.
8.7.6.2 Container No. 2. Taking care to see that dust on the
outside of the probe or other exterior surfaces does not get into the
sample, quantitatively recover PM or any condensate from the probe
nozzle, probe fitting,

[[Page 177]]

probe liner, and front half of the filter holder by washing these
components with acetone and placing the wash in a glass container.
Deionized distilled water may be used instead of acetone when approved
by the Administrator and shall be used when specified by the
Administrator. In these cases, save a water blank, and follow the
Administrator's directions on analysis. Perform the acetone rinse as
follows:
8.7.6.2.1 Carefully remove the probe nozzle. Clean the inside
surface by rinsing with acetone from a wash bottle and brushing with a
Nylon bristle brush. Brush until the acetone rinse shows no visible
particles, after which make a final rinse of the inside surface with
acetone.
8.7.6.2.2 Brush and rinse the inside parts of the fitting with
acetone in a similar way until no visible particles remain.
8.7.6.2.3 Rinse the probe liner with acetone by tilting and
rotating the probe while squirting acetone into its upper end so that
all inside surfaces will be wetted with acetone. Let the acetone drain
from the lower end into the sample container. A funnel (glass or
polyethylene) may be used to aid in transferring liquid washes to the
container. Follow the acetone rinse with a probe brush. Hold the probe
in an inclined position, squirt acetone into the upper end as the probe
brush is being pushed with a twisting action through the probe; hold a
sample container underneath the lower end of the probe, and catch any
acetone and particulate matter that is brushed from the probe. Run the
brush through the probe three times or more until no visible PM is
carried out with the acetone or until none remains in the probe liner on
visual inspection. With stainless steel or other metal probes, run the
brush through in the above prescribed manner at least six times since
metal probes have small crevices in which particulate matter can be
entrapped. Rinse the brush with acetone, and quantitatively collect
these washings in the sample container. After the brushing, make a final
acetone rinse of the probe.
8.7.6.2.4 It is recommended that two people clean the probe to
minimize sample losses. Between sampling runs, keep brushes clean and
protected from contamination.
8.7.6.2.5 After ensuring that all joints have been wiped clean of
silicone grease, clean the inside of the front half of the filter holder
by rubbing the surfaces with a Nylon bristle brush and rinsing with
acetone. Rinse each surface three times or more if needed to remove
visible particulate. Make a final rinse of the brush and filter holder.
Carefully rinse out the glass cyclone, also (if applicable). After all
acetone washings and particulate matter have been collected in the
sample container, tighten the lid on the sample container so that
acetone will not leak out when it is shipped to the laboratory. Mark the
height of the fluid level to allow determination of whether leakage
occurred during transport. Label the container to identify clearly its
contents.
8.7.6.3 Container No. 3. Note the color of the indicating silica
gel to determine whether it has been completely spent, and make a
notation of its condition. Transfer the silica gel from the fourth
impinger to its original container, and seal. A funnel may make it
easier to pour the silica gel without spilling. A rubber policeman may
be used as an aid in removing the silica gel from the impinger. It is
not necessary to remove the small amount of dust particles that may
adhere to the impinger wall and are difficult to remove. Since the gain
in weight is to be used for moisture calculations, do not use any water
or other liquids to transfer the silica gel. If a balance is available
in the field, follow the procedure for Container No. 3 in Section
11.2.3.
8.7.6.4 Impinger Water. Treat the impingers as follows: Make a
notation of any color or film in the liquid catch. Measure the liquid
that is in the first three impingers to within 1 ml by using a graduated
cylinder or by weighing it to within 0.5 g by using a balance. Record
the volume or weight of liquid present. This information is required to
calculate the moisture content of the effluent gas. Discard the liquid
after measuring and recording the volume or weight, unless analysis of
the impinger catch is required (see NOTE, Section 6.1.1.8). If a
different type of condenser is used, measure the amount of moisture
condensed either volumetrically or gravimetrically.
8.8 Sample Transport. Whenever possible, containers should be
shipped in such a way that they remain upright at all times.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.4, 10.1-10.6................ Sampling Ensures accurate
equipment leak measurement of stack
check and gas flow rate,
calibration. sample volume.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. The following procedures are
suggested to check the volume metering system calibration values at the
field test site prior to sample collection. These procedures are
optional.

[[Page 178]]

9.2.1 Meter Orifice Check. Using the calibration data obtained
during the calibration procedure described in Section 10.3, determine
the H@ for the metering system orifice. The H@ is the
orifice pressure differential in units of in. H2O that
correlates to 0.75 cfm of air at 528 deg.R and 29.92 in. Hg. The
H@ is calculated as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.107

Where:

H = Average pressure differential across the orifice meter, in.
H2O.
Tm = Absolute average DGM temperature, deg.R.
Pbar = Barometric pressure, in. Hg.
= Total sampling time, min.
Y = DGM calibration factor, dimensionless.
Vm = Volume of gas sample as measured by DGM, dcf.
0.0319 = (0.0567 in. Hg/ deg.R) (0.75 cfm)\2\

9.2.1.1 Before beginning the field test (a set of three runs
usually constitutes a field test), operate the metering system (i.e.,
pump, volume meter, and orifice) at the H@ pressure
differential for 10 minutes. Record the volume collected, the DGM
temperature, and the barometric pressure. Calculate a DGM calibration
check value, Yc, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.108

where:

Yc = DGM calibration check value, dimensionless.
10 = Run time, min.
9.2.1.2 Compare the Yc value with the dry gas meter
calibration factor Y to determine that: 0.97Y Yc 1.03Y. If
the Yc value is not within this range, the volume metering
system should be investigated before beginning the test.
9.2.2 Calibrated Critical Orifice. A critical orifice, calibrated
against a wet test meter or spirometer and designed to be inserted at
the inlet of the sampling meter box, may be used as a check by following
the procedure of Section 16.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.
10.1 Probe Nozzle. Probe nozzles shall be calibrated before their
initial use in the field. Using a micrometer, measure the ID of the
nozzle to the nearest 0.025 mm (0.001 in.). Make three separate
measurements using different diameters each time, and obtain the average
of the measurements. The difference between the high and low numbers
shall not exceed 0.1 mm (0.004 in.). When nozzles become nicked, dented,
or corroded, they shall be reshaped, sharpened, and recalibrated before
use. Each nozzle shall be permanently and uniquely identified.
10.2 Pitot Tube Assembly. The Type S pitot tube assembly shall be
calibrated according to the procedure outlined in Section 10.1 of Method
2.
10.3 Metering System.
10.3.1 Calibration Prior to Use. Before its initial use in the
field, the metering system shall be calibrated as follows: Connect the
metering system inlet to the outlet of a wet test meter that is accurate
to within 1 percent. Refer to Figure 5-4. The wet test meter should have
a capacity of 30 liters/rev (1 ft³/rev). A spirometer of 400
liters (14 ft³) or more capacity, or equivalent, may be used
for this calibration, although a wet test meter is usually more
practical. The wet test meter should be periodically calibrated with a
spirometer or a liquid displacement meter to ensure the accuracy of the
wet test meter. Spirometers or wet test meters of other sizes may be
used, provided that the specified accuracies of the procedure are
maintained. Run the metering system pump for about 15 minutes with the
orifice manometer indicating a median reading as expected in field use
to allow the pump to warm up and to permit the interior surface of the
wet test meter to be thoroughly wetted. Then, at each of a minimum of
three orifice manometer settings, pass an exact quantity of gas through
the wet test meter and note the gas volume indicated by the DGM. Also
note the barometric pressure and the temperatures of the wet test meter,
the inlet of the DGM, and the outlet of the DGM. Select the highest and
lowest orifice settings to bracket the expected field operating range of
the orifice. Use a minimum volume of 0.14 m³ (5
ft³) at all orifice settings. Record all the data on a form
similar to Figure 5-5 and calculate Y, the DGM calibration factor, and
H@, the orifice calibration factor, at each orifice
setting as shown on Figure 5-5. Allowable tolerances for individual Y
and H@ values are given in Figure 5-5. Use the
average of the Y values in the calculations in Section 12.0.
10.3.1.1 Before calibrating the metering system, it is suggested
that a leak check be conducted. For metering systems having diaphragm
pumps, the normal leak-check procedure will not detect leakages within
the pump. For these cases the following leak-check procedure is
suggested: make a 10-minute calibration run at 0.00057 m³/min
(0.020 cfm). At the end of the run, take the difference of the measured
wet test meter and DGM volumes. Divide the difference by 10 to get the
leak rate. The leak rate should not exceed 0.00057 m³/min
(0.020 cfm).
10.3.2 Calibration After Use. After each field use, the calibration
of the metering system shall be checked by performing three calibration
runs at a single, intermediate

[[Page 179]]

orifice setting (based on the previous field test), with the vacuum set
at the maximum value reached during the test series. To adjust the
vacuum, insert a valve between the wet test meter and the inlet of the
metering system. Calculate the average value of the DGM calibration
factor. If the value has changed by more than 5 percent, recalibrate the
meter over the full range of orifice settings, as detailed in Section
10.3.1.

Note: Alternative procedures (e.g., rechecking the orifice meter
coefficient) may be used, subject to the approval of the Administrator.

10.3.3 Acceptable Variation in Calibration. If the DGM coefficient
values obtained before and after a test series differ by more than 5
percent, the test series shall either be voided, or calculations for the
test series shall be performed using whichever meter coefficient value
(i.e., before or after) gives the lower value of total sample volume.
10.4 Probe Heater Calibration. Use a heat source to generate air
heated to selected temperatures that approximate those expected to occur
in the sources to be sampled. Pass this air through the probe at a
typical sample flow rate while measuring the probe inlet and outlet
temperatures at various probe heater settings. For each air temperature
generated, construct a graph of probe heating system setting versus
probe outlet temperature. The procedure outlined in APTD-0576 can also
be used. Probes constructed according to APTD-0581 need not be
calibrated if the calibration curves in APTD-0576 are used. Also, probes
with outlet temperature monitoring capabilities do not require
calibration.
Note: The probe heating system shall be calibrated before its
initial use in the field.

10.5 Temperature Sensors. Use the procedure in Section 10.3 of
Method 2 to calibrate in-stack temperature sensors. Dial thermometers,
such as are used for the DGM and condenser outlet, shall be calibrated
against mercury-in-glass thermometers.
10.6 Barometer. Calibrate against a mercury barometer.

11.0 Analytical Procedure

11.1 Record the data required on a sheet such as the one shown in
Figure 5-6.
11.2 Handle each sample container as follows:
11.2.1 Container No. 1. Leave the contents in the shipping
container or transfer the filter and any loose PM from the sample
container to a tared glass weighing dish. Desiccate for 24 hours in a
desiccator containing anhydrous calcium sulfate. Weigh to a constant
weight, and report the results to the nearest 0.1 mg. For the purposes
of this section, the term ``constant weight'' means a difference of no
more than 0.5 mg or 1 percent of total weight less tare weight,
whichever is greater, between two consecutive weighings, with no less
than 6 hours of desiccation time between weighings. Alternatively, the
sample may be oven dried at 104 deg.C (220 deg.F) for 2 to 3 hours,
cooled in the desiccator, and weighed to a constant weight, unless
otherwise specified by the Administrator. The sample may be oven dried
at 104 deg.C (220 deg.F) for 2 to 3 hours. Once the sample has cooled,
weigh the sample, and use this weight as a final weight.
11.2.2 Container No. 2. Note the level of liquid in the container,
and confirm on the analysis sheet whether leakage occurred during
transport. If a noticeable amount of leakage has occurred, either void
the sample or use methods, subject to the approval of the Administrator,
to correct the final results. Measure the liquid in this container
either volumetrically to 1 ml or gravimetrically to
0.5 g. Transfer the contents to a tared 250 ml beaker, and
evaporate to dryness at ambient temperature and pressure. Desiccate for
24 hours, and weigh to a constant weight. Report the results to the
nearest 0.1 mg.
11.2.3 Container No. 3. Weigh the spent silica gel (or silica gel
plus impinger) to the nearest 0.5 g using a balance. This step may be
conducted in the field.
11.2.4 Acetone Blank Container. Measure the acetone in this
container either volumetrically or gravimetrically. Transfer the acetone
to a tared 250 ml beaker, and evaporate to dryness at ambient
temperature and pressure. Desiccate for 24 hours, and weigh to a
constant weight. Report the results to the nearest 0.1 mg.

Note: The contents of Container No. 2 as well as the acetone blank
container may be evaporated at temperatures higher than ambient. If
evaporation is done at an elevated temperature, the temperature must be
below the boiling point of the solvent; also, to prevent ``bumping,''
the evaporation process must be closely supervised, and the contents of
the beaker must be swirled occasionally to maintain an even temperature.
Use extreme care, as acetone is highly flammable and has a low flash
point.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after the
final calculation. Other forms of the equations may be used, provided
that they give equivalent results.
12.1 Nomenclature.
An = Cross-sectional area of nozzle, m²
(ft²).
Bws = Water vapor in the gas stream, proportion by volume.
Ca = Acetone blank residue concentration, mg/mg.

[[Page 180]]

cs = Concentration of particulate matter in stack gas, dry
basis, corrected to standard conditions, g/dscm (gr/dscf).
I = Percent of isokinetic sampling.
L1 = Individual leakage rate observed during the leak-check
conducted prior to the first component change, m³/
min (ft³/min)
La = Maximum acceptable leakage rate for either a pretest
leak-check or for a leak-check following a component change;
equal to 0.00057 m³/min (0.020 cfm) or 4 percent of
the average sampling rate, whichever is less.
Li = Individual leakage rate observed during the leak-check
conducted prior to the ``i\th\'' component change (i = 1, 2, 3
. . . n), m³/min (cfm).
Lp = Leakage rate observed during the post-test leak-check,
m³/min (cfm).
ma = Mass of residue of acetone after evaporation, mg.
mn = Total amount of particulate matter collected, mg.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in.
Hg).
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 ((mm Hg)(m \3\))/((K)(g-mole)) {21.85
((in. Hg) (ft \3\))/(( deg.R) (lb-mole))}.
Tm = Absolute average DGM temperature (see Figure 5-3), K
( deg.R).
Ts = Absolute average stack gas temperature (see Figure 5-3),
K ( deg.R).
Tstd = Standard absolute temperature, 293 K (528 deg.R).
Va = Volume of acetone blank, ml.
Vaw = Volume of acetone used in wash, ml.
V1c = Total volume of liquid collected in impingers and
silica gel (see Figure 5-6), ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm
(dcf).
Vm(std) = Volume of gas sample measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vw(std) = Volume of water vapor in the gas sample, corrected
to standard conditions, scm (scf).
Vs = Stack gas velocity, calculated by Method 2, Equation 2-
7, using data obtained from Method 5, m/sec (ft/sec).
Wa = Weight of residue in acetone wash, mg.
Y = Dry gas meter calibration factor.
H = Average pressure differential across the orifice meter (see
Figure 5-4), mm H2O (in. H2O).
a = Density of acetone, mg/ml (see label on bottle).
w = Density of water, 0.9982 g/ml.(0.002201 lb/ml).
= Total sampling time, min.
1 = Sampling time interval, from the beginning of a
run until the first component change, min.
i = Sampling time interval, between two successive
component changes, beginning with the interval between the
first and second changes, min.
p = Sampling time interval, from the final (n \th\)
component change until the end of the sampling run, min.
13.6 = Specific gravity of mercury.
60 = Sec/min.
100 = Conversion to percent.

12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 5-3).
12.3 Dry Gas Volume. Correct the sample volume measured by the dry
gas meter to standard conditions (20 deg.C, 760 mm Hg or 68 deg.F,
29.92 in. Hg) by using Equation 5-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.109

Where:

K1 = 0.3858 deg.K/mm Hg for metric units, = 17.64 deg.R/in.
Hg for English units.

Note: Equation 5-1 can be used as written unless the leakage rate
observed during any of the mandatory leak checks (i.e., the post-test
leak check or leak checks conducted prior to component changes) exceeds
La. If Lp or Li exceeds La,
Equation 5-1 must be modified as follows:

[[Page 181]]

(a) Case I. No component changes made during sampling run. In this case,
replace Vm in Equation 5-1 with the expression:
[GRAPHIC] [TIFF OMITTED] TR17OC00.110

(b) Case II. One or more component changes made during the sampling run.
In this case, replace Vm in Equation 5-1 by the expression:
[GRAPHIC] [TIFF OMITTED] TR17OC00.111

and substitute only for those leakage rates (Li or
Lp) which exceed La.
12.4 Volume of Water Vapor Condensed.
[GRAPHIC] [TIFF OMITTED] TR17OC00.112

Where:

K2 = 0.001333 m \3\/ml for metric units, = 0.04706 ft \3\/ml
for English units.
12.5 Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.113

Note: In saturated or water droplet-laden gas streams, two
calculations of the moisture content of the stack gas shall be made, one
from the impinger analysis (Equation 5-3), and a second from the
assumption of saturated conditions. The lower of the two values of
Bws shall be considered correct. The procedure for
determining the moisture content based upon the assumption of saturated
conditions is given in Section 4.0 of Method 4. For the purposes of this
method, the average stack gas temperature from Figure 5-3 may be used to
make this determination, provided that the accuracy of the in-stack
temperature sensor is 1 deg.C (2 deg.F).

12.6 Acetone Blank Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.114

12.7 Acetone Wash Blank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.115

12.8 Total Particulate Weight. Determine the total particulate
matter catch from the sum of the weights obtained from Containers 1 and
2 less the acetone blank (see Figure 5-6).

Note: In no case shall a blank value of greater than 0.001 percent
of the weight of acetone used be subtracted from the sample weight.
Refer to Section 8.5.8 to assist in calculation of results involving two
or more filter assemblies or two or more sampling trains.
12.9 Particulate Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.116

Where:

K3 = 0.001 g/mg for metric units.
= 0.0154 gr/mg for English units.
12.10 Conversion Factors:

------------------------------------------------------------------------
From To Multiply by
------------------------------------------------------------------------
ft\3\............................... m\3\ 0.02832
gr.................................. mg 64.80004
gr/ft\3\............................ mg/m\3\ 2288.4
mg.................................. g 0.001
gr.................................. lb 1.429 x 10^-\4\
------------------------------------------------------------------------

12.11 Isokinetic Variation.
12.11.1 Calculation from Raw Data.

[[Page 182]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.117

Where:
K4 = 0.003454 ((mm Hg)(m\3\))/((ml)( deg.K)) for metric
units,
= 0.002669 ((in. Hg)(ft\3\))/((ml)( deg.R)) for English units.

12.11.2 Calculation from Intermediate Values.
[GRAPHIC] [TIFF OMITTED] TR17OC00.118

Where:

K5 = 4.320 for metric units,
= 0.09450 for English units.

12.11.3 Acceptable Results. If 90 percent I
110 percent, the results are acceptable. If the PM results are low in
comparison to the standard, and ``I'' is over 110 percent or less than
90 percent, the Administrator may opt to accept the results. Reference 4
in Section 17.0 may be used to make acceptability judgments. If ``I'' is
judged to be unacceptable, reject the results, and repeat the sampling
run.
12.12 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate, if needed, using
data obtained in this method and the equations in Sections 12.3 and 12.4
of Method 2.
13.0 Method Performance. [Reserved]
14.0 Pollution Prevention. [Reserved]
15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 Dry Gas Meter as a Calibration Standard. A DGM may be used as
a calibration standard for volume measurements in place of the wet test
meter specified in Section 10.3, provided that it is calibrated
initially and recalibrated periodically as follows:
16.1.1 Standard Dry Gas Meter Calibration.
16.1.1.1. The DGM to be calibrated and used as a secondary
reference meter should be of high quality and have an appropriately
sized capacity (e.g., 3 liters/rev (0.1 ft\3\/rev)). A spirometer (400
liters (14 ft\3\) or more capacity), or equivalent, may be used for this
calibration, although a wet test meter is usually more practical. The
wet test meter should have a capacity of 30 liters/rev (1 ft\3\/rev) and
capable of measuring volume to within 1.0 percent. Wet test meters
should be checked against a spirometer or a liquid displacement meter to
ensure the accuracy of the wet test meter. Spirometers or wet test
meters of other sizes may be used, provided that the specified
accuracies of the procedure are maintained.
16.1.1.2 Set up the components as shown in Figure 5-7. A
spirometer, or equivalent, may be used in place of the wet test meter in
the system. Run the pump for at least 5 minutes at a flow rate of about
10 liters/min (0.35 cfm) to condition the interior surface of the wet
test meter. The pressure drop indicated by the manometer at the inlet
side of the DGM should be minimized (no greater than 100 mm
H2O (4 in. H2O) at a flow rate of 30 liters/min (1
cfm)). This can be accomplished by using large diameter tubing
connections and straight pipe fittings.
16.1.1.3 Collect the data as shown in the example data sheet (see
Figure 5-8). Make triplicate runs at each of the flow rates and at no
less than five different flow rates. The range of flow rates should be
between 10 and 34 liters/min (0.35 and 1.2 cfm) or over the expected
operating range.
16.1.1.4 Calculate flow rate, Q, for each run using the wet test
meter volume, VW, and the run time, . Calculate the
DGM coefficient, Yds, for each run. These calculations are as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.119

[[Page 183]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.120

Where:

K1 = 0.3858 deg.C/mm Hg for metric units=17.64 deg.F/in. Hg
for English units.
VW = Wet test meter volume, liter (ft\3\).
Vds = Dry gas meter volume, liter (ft\3\).
Tds = Average dry gas meter temperature, deg.C ( deg.F).
Tadj = 273 deg.C for metric units = 460 deg.F for English
units.
TW = Average wet test meter temperature, deg.C ( deg.F)
Pbar = Barometric pressure, mm Hg (in. Hg).
p = Dry gas meter inlet differential pressure, mm
H2O (in. H2O).
= Run time, min.

16.1.1.5 Compare the three Yds values at each of the
flow rates and determine the maximum and minimum values. The difference
between the maximum and minimum values at each flow rate should be no
greater than 0.030. Extra sets of triplicate runs may be made in order
to complete this requirement. In addition, the meter coefficients should
be between 0.95 and 1.05. If these specifications cannot be met in three
sets of successive triplicate runs, the meter is not suitable as a
calibration standard and should not be used as such. If these
specifications are met, average the three Yds values at each
flow rate resulting in no less than five average meter coefficients,
Yds.
16.1.1.6 Prepare a curve of meter coefficient, Yds,
versus flow rate, Q, for the DGM. This curve shall be used as a
reference when the meter is used to calibrate other DGMs and to
determine whether recalibration is required.
16.1.2 Standard Dry Gas Meter Recalibration.
16.1.2.1 Recalibrate the standard DGM against a wet test meter or
spirometer annually or after every 200 hours of operation, whichever
comes first. This requirement is valid provided the standard DGM is kept
in a laboratory and, if transported, cared for as any other laboratory
instrument. Abuse to the standard meter may cause a change in the
calibration and will require more frequent recalibrations.
16.1.2.2 As an alternative to full recalibration, a two-point
calibration check may be made. Follow the same procedure and equipment
arrangement as for a full recalibration, but run the meter at only two
flow rates [suggested rates are 14 and 30 liters/min (0.5 and 1.0 cfm)].
Calculate the meter coefficients for these two points, and compare the
values with the meter calibration curve. If the two coefficients are
within 1.5 percent of the calibration curve values at the same flow
rates, the meter need not be recalibrated until the next date for a
recalibration check.
16.2 Critical Orifices As Calibration Standards. Critical orifices
may be used as calibration standards in place of the wet test meter
specified in Section 16.1, provided that they are selected, calibrated,
and used as follows:
16.2.1 Selection of Critical Orifices.
16.2.1.1 The procedure that follows describes the use of hypodermic
needles or stainless steel needle tubings which have been found suitable
for use as critical orifices. Other materials and critical orifice
designs may be used provided the orifices act as true critical orifices
(i.e., a critical vacuum can be obtained, as described in Section
16.2.2.2.3). Select five critical orifices that are appropriately sized
to cover the range of flow rates between 10 and 34 liters/min (0.35 and
1.2 cfm) or the expected operating range. Two of the critical orifices
should bracket the expected operating range. A minimum of three critical
orifices will be needed to calibrate a Method 5 DGM; the other two
critical orifices can serve as spares and provide better selection for
bracketing the range of operating flow rates. The needle sizes and
tubing lengths shown in Table 5-1 in Section 18.0 give the approximate
flow rates.
16.2.1.2 These needles can be adapted to a Method 5 type sampling
train as follows: Insert a serum bottle stopper, 13 by 20 mm sleeve
type, into a \1/2\-inch Swagelok (or equivalent) quick connect. Insert
the needle into the stopper as shown in Figure 5-9.
16.2.2 Critical Orifice Calibration. The procedure described in
this section uses the Method 5 meter box configuration with a DGM as
described in Section 6.1.1.9 to calibrate the critical orifices. Other
schemes may be used, subject to the approval of the Administrator.
16.2.2.1 Calibration of Meter Box. The critical orifices must be
calibrated in the same configuration as they will be used (i.e., there
should be no connections to the inlet of the orifice).
16.2.2.1.1 Before calibrating the meter box, leak check the system
as follows: Fully open the coarse adjust valve, and completely close the
by-pass valve. Plug the inlet. Then turn on the pump, and determine
whether there is any leakage. The leakage rate shall be zero (i.e., no
detectable movement of the DGM dial shall be seen for 1 minute).

[[Page 184]]

16.2.2.1.2 Check also for leakages in that portion of the sampling
train between the pump and the orifice meter. See Section 8.4.1 for the
procedure; make any corrections, if necessary. If leakage is detected,
check for cracked gaskets, loose fittings, worn O-rings, etc., and make
the necessary repairs.
16.2.2.1.3 After determining that the meter box is leakless,
calibrate the meter box according to the procedure given in Section
10.3. Make sure that the wet test meter meets the requirements stated in
Section 16.1.1.1. Check the water level in the wet test meter. Record
the DGM calibration factor, Y.
16.2.2.2 Calibration of Critical Orifices. Set up the apparatus as
shown in Figure 5-10.
16.2.2.2.1 Allow a warm-up time of 15 minutes. This step is
important to equilibrate the temperature conditions through the DGM.
16.2.2.2.2 Leak check the system as in Section 16.2.2.1.1. The
leakage rate shall be zero.
16.2.2.2.3 Before calibrating the critical orifice, determine its
suitability and the appropriate operating vacuum as follows: Turn on the
pump, fully open the coarse adjust valve, and adjust the by-pass valve
to give a vacuum reading corresponding to about half of atmospheric
pressure. Observe the meter box orifice manometer reading, H.
Slowly increase the vacuum reading until a stable reading is obtained on
the meter box orifice manometer. Record the critical vacuum for each
orifice. Orifices that do not reach a critical value shall not be used.
16.2.2.2.4 Obtain the barometric pressure using a barometer as
described in Section 6.1.2. Record the barometric pressure,
Pbar, in mm Hg (in. Hg).
16.2.2.2.5 Conduct duplicate runs at a vacuum of 25 to 50 mm Hg (1
to 2 in. Hg) above the critical vacuum. The runs shall be at least 5
minutes each. The DGM volume readings shall be in increments of complete
revolutions of the DGM. As a guideline, the times should not differ by
more than 3.0 seconds (this includes allowance for changes in the DGM
temperatures) to achieve 0.5 percent in K' (see Eq. 5-11).
Record the information listed in Figure 5-11.
16.2.2.2.6 Calculate K' using Equation 5-11.
[GRAPHIC] [TIFF OMITTED] TR17OC00.121

Where:

K' = Critical orifice coefficient,
[m \3\)( deg.K)\1/2\]/
[(mm Hg)(min)] {[(ft \3\)( deg.R)\1/2\)] [(in. Hg)(min)].
Tamb = Absolute ambient temperature, deg.K ( deg.R).
Calculate the arithmetic mean of the K' values. The individual K' values
should not differ by more than 0.5 percent from the mean
value.
16.2.3 Using the Critical Orifices as Calibration Standards.
16.2.3.1 Record the barometric pressure.
16.2.3.2 Calibrate the metering system according to the procedure
outlined in Section 16.2.2. Record the information listed in Figure 5-
12.
16.2.3.3 Calculate the standard volumes of air passed through the DGM
and the critical orifices, and calculate the DGM calibration factor, Y,
using the equations below:
[GRAPHIC] [TIFF OMITTED] TR17OC00.122

[GRAPHIC] [TIFF OMITTED] TR17OC00.123

[GRAPHIC] [TIFF OMITTED] TR17OC00.124

[[Page 185]]

Where:

Vcr(std) = Volume of gas sample passed through the critical
orifice, corrected to standard conditions, dscm (dscf).
K1 = 0.3858 K/mm Hg for metric units
= 17.64 deg.R/in. Hg for English units.

16.2.3.4 Average the DGM calibration values for each of the flow rates.
The calibration factor, Y, at each of the flow rates should not differ
by more than 2 percent from the average.
16.2.3.5 To determine the need for recalibrating the critical orifices,
compare the DGM Y factors obtained from two adjacent orifices each time
a DGM is calibrated; for example, when checking orifice 13/2.5, use
orifices 12/10.2 and 13/5.1. If any critical orifice yields a DGM Y
factor differing by more than 2 percent from the others, recalibrate the
critical orifice according to Section 16.2.2.

17.0 References.

1. Addendum to Specifications for Incinerator Testing at Federal
Facilities. PHS, NCAPC. December 6, 1967.
2. Martin, Robert M. Construction Details of Isokinetic Source-
Sampling Equipment. Environmental Protection Agency. Research Triangle
Park, NC. APTD-0581. April 1971.
3. Rom, Jerome J. Maintenance, Calibration, and Operation of
Isokinetic Source Sampling Equipment. Environmental Protection Agency.
Research Triangle Park, NC. APTD-0576. March 1972.
4. Smith, W.S., R.T. Shigehara, and W.F. Todd. A Method of
Interpreting Stack Sampling Data. Paper Presented at the 63rd Annual
Meeting of the Air Pollution Control Association, St. Louis, MO. June
14-19, 1970.
5. Smith, W.S., et al. Stack Gas Sampling Improved and Simplified
With New Equipment. APCA Paper No. 67-119. 1967.
6. Specifications for Incinerator Testing at Federal Facilities.
PHS, NCAPC. 1967.
7. Shigehara, R.T. Adjustment in the EPA Nomograph for Different
Pitot Tube Coefficients and Dry Molecular Weights. Stack Sampling News
2:4-11. October 1974.
8. Vollaro, R.F. A Survey of Commercially Available Instrumentation
for the Measurement of Low-Range Gas Velocities. U.S. Environmental
Protection Agency, Emission Measurement Branch. Research Triangle Park,
NC. November 1976 (unpublished paper).
9. Annual Book of ASTM Standards. Part 26. Gaseous Fuels; Coal and
Coke; Atmospheric Analysis. American Society for Testing and Materials.
Philadelphia, PA. 1974. pp. 617-622.
10. Felix, L.G., G.I. Clinard, G.E. Lacy, and J.D. McCain. Inertial
Cascade Impactor Substrate Media for Flue Gas Sampling. U.S.
Environmental Protection Agency. Research Triangle Park, NC 27711.
Publication No. EPA-600/7-77-060. June 1977. 83 pp.
11. Westlin, P.R. and R.T. Shigehara. Procedure for Calibrating and
Using Dry Gas Volume Meters as Calibration Standards. Source Evaluation
Society Newsletter. 3(1):17-30. February 1978.
12. Lodge, J.P., Jr., J.B. Pate, B.E. Ammons, and G.A. Swanson. The
Use of Hypodermic Needles as Critical Orifices in Air Sampling. J. Air
Pollution Control Association. 16:197-200. 1966.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

----------------------------------------------------------------------------------------------------------------
Flow rate Flow rate
Gauge/cm liters/min. Gauge/cm liters/min.
----------------------------------------------------------------------------------------------------------------
12/7.6.......................................................... 32.56 14/2.5 19.54
12/10.2......................................................... 30.02 14/5.1 17.27
13/2.5.......................................................... 25.77 14/7.6 16.14
13/5.1.......................................................... 23.50 15/3.2 14.16
13/7.6.......................................................... 22.37 15/7.6 11.61
13/10.2......................................................... 20.67 15/10.2 10.48
----------------------------------------------------------------------------------------------------------------

[[Page 186]]

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[[Page 187]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.126

[[Page 188]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.127

[[Page 189]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.128

[[Page 190]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.129

[[Page 191]]

Plant

Date

Run No.

Filter No.

Amount liquid lost during transport

Acetone blank volume, m1

Acetone blank concentration, mg/mg (Equation 5-4)

Acetone wash blank, mg (Equation 5-5)

----------------------------------------------------------------------------------------------------------------
Weight of particulate collected, mg
Container number --------------------------------------------------------------------------
Final weight Tare weight Weight gain
----------------------------------------------------------------------------------------------------------------
1.
----------------------------------------------------------------------------------------------------------------
2.
----------------------------------------------------------------------------------------------------------------
Total:
Less acetone blank...........
Weight of particulate matter.
----------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------
Volume of liquid water collected
---------------------------------------
Impinger volume, Silica gel weight,
ml g
------------------------------------------------------------------------
Final
Initial
Liquid collected
Total volume collected.... .................. g* ml
------------------------------------------------------------------------
* Convert weight of water to volume by dividing total weight increase by
density of water (1 g/ml).

Figure 5-6. Analytical Data Sheet
[GRAPHIC] [TIFF OMITTED] TR17OC00.147

[[Page 192]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.130

[[Page 193]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.131

[[Page 194]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.132

[[Page 195]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.133

[[Page 196]]

Date

Train ID

DGM cal. factor

Critical orifice ID

------------------------------------------------------------------------
Run No.
Dry gas meter -------------------------
1 2
------------------------------------------------------------------------
Final reading................ m³ (ft³)....... ........... ...........
Initial reading.............. m³ (ft³)....... ........... ...........
Difference, V^m............... m ³ (ft ³)..... ........... ...........
Inlet/Outlet................. ............... ........... ...........
Temperatures:............ deg.C ( / /
deg.F).
Initial.................. deg.C ( / /
deg.F).
Final.................... min/sec........ / /
Av. Temeperature, t m.... min............ ........... ...........
Time, ............. ............... ........... ...........
Orifice man. rdg., H mm (in.) H 2... ........... ...........
Bar. pressure, P ^bar......... mm (in.) Hg.... ........... ...........
Ambient temperature, tamb.... mm (in.) Hg.... ........... ...........
Pump vacuum.................. ............... ........... ...........
K' factor.................... ............... ........... ...........
Average.................. ............... ........... ...........
------------------------------------------------------------------------

Figure 5-11. Data sheet of determining K' factor.

Date

Train ID

Critical orifice ID

Critical orifice K' factor

------------------------------------------------------------------------
Run No.
Dry gas meter -------------------------
1 2
------------------------------------------------------------------------
Final reading................ m\3\ (ft\3\)... ........... ...........
Initial reading.............. m\3\ (ft\3\)... ........... ...........
Difference, Vm............... m\3\ (ft\3\)... ........... ...........
Inlet/outlet temperatures.... deg.C ( / /
deg.F).
Initial.................. deg.C ( / /
deg.F).
Final.................... deg.C ( ........... ...........
deg.F).
Avg. Temperature, tm..... min/sec........ / /
Time, ............. min............ ........... ...........
Orifice man. rdg., H min............ ........... ...........
Bar. pressure, Pbar.......... mm (in.) H2O... ........... ...........
Ambient temperature, tamb.... mm (in.) Hg.... ........... ...........
Pump vacuum.................. deg.C ( ........... ...........
deg.F).
Vm(std)...................... mm (in.) Hg.... ........... ...........
Vcr(std)..................... m\3\ (ft\3\)... ........... ...........
DGM cal. factor, Y........... m\3\ (ft\3\)... ........... ...........
------------------------------------------------------------------------

Figure 5-12. Data Sheet for Determining DGM Y Factor

Method 5A--Determination of Particulate Matter Emissions From the
Asphalt Processing and Asphalt Roofing Industry

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Applications

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the determination
of PM emissions from asphalt roofing industry process saturators,
blowing stills, and other sources as specified in the regulations.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

[[Page 197]]

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
collected on a glass fiber filter maintained at a temperature of 42
10 deg.C (108 18 deg.F). The PM mass, which
includes any material that condenses at or above the filtration
temperature, is determined gravimetrically after the removal of
uncombined water.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 5, Section 6.1, with the
following exceptions and additions:
6.1.1 Probe Liner. Same as Method 5, Section 6.1.1.2, with the note
that at high stack gas temperatures greater than 250 deg.C (480
deg.F), water-cooled probes may be required to control the probe exit
temperature to 42 10 deg.C (108 18 deg.F).
6.1.2 Precollector Cyclone. Borosilicate glass following the
construction details shown in Air Pollution Technical Document (APTD)-
0581, ``Construction Details of Isokinetic Source-Sampling Equipment''
(Reference 2 in Method 5, Section 17.0).

Note: The cyclone shall be used when the stack gas moisture is
greater than 10 percent, and shall not be used otherwise.

6.1.3 Filter Heating System. Any heating (or cooling) system
capable of maintaining a sample gas temperature at the exit end of the
filter holder during sampling at 42 10 deg.C (108
18 deg.F).
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Probe-Liner and Probe-Nozzle Brushes, Graduated Cylinder and/
or Balance, Plastic Storage Containers, and Funnel and Rubber Policeman.
Same as in Method 5, Sections 6.2.1, 6.2.5, 6.2.6, and 6.2.7,
respectively.
6.2.2 Wash Bottles. Glass.
6.2.3 Sample Storage Containers. Chemically resistant 500-ml or
1,000-ml borosilicate glass bottles, with rubber-backed Teflon screw cap
liners or caps that are constructed so as to be leak-free, and resistant
to chemical attack by 1,1,1-trichloroethane (TCE). (Narrow-mouth glass
bottles have been found to be less prone to leakage.)
6.2.4 Petri Dishes. Glass, unless otherwise specified by the
Administrator.
6.2.5 Funnel. Glass.
6.3 Sample Analysis. Same as Method 5, Section 6.3, with the
following additions:
6.3.1 Beakers. Glass, 250-ml and 500-ml.
6.3.2 Separatory Funnel. 100-ml or greater.

7.0. Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Filters, Silica Gel, Water, and Crushed Ice. Same as in
Method 5, Sections 7.1.1, 7.1.2, 7.1.3, and 7.1.4, respectively.
7.1.2 Stopcock Grease. TCE-insoluble, heat-stable grease (if
needed). This is not necessary if screw-on connectors with Teflon
sleeves, or similar, are used.
7.2 Sample Recovery. Reagent grade TCE, 0.001 percent
residue and stored in glass bottles. Run TCE blanks before field use,
and use only TCE with low blank values (0.001 percent). In no
case shall a blank value of greater than 0.001 percent of the weight of
TCE used be subtracted from the sample weight.
7.3 Analysis. Two reagents are required for the analysis:
7.3.1 TCE. Same as in Section 7.2.
7.3.2 Desiccant. Same as in Method 5, Section 7.3.2.

8.0. Sample Collection, Preservation, Storage, and Transport

8.1. Pretest Preparation. Unless otherwise specified, maintain and
calibrate all components according to the procedure described in APTD-
0576, ``Maintenance, Calibration, and Operation of Isokinetic Source-
Sampling Equipment'' (Reference 3 in Method 5, Section 17.0).
8.1.1 Prepare probe liners and sampling nozzles as needed for use.
Thoroughly clean each component with soap and water followed by a
minimum of three TCE rinses. Use the probe and nozzle brushes during at
least one of the TCE rinses (refer to Section 8.7 for rinsing
techniques). Cap or seal the open ends of the probe liners and nozzles
to prevent contamination during shipping.
8.1.2 Prepare silica gel portions and glass filters as specified in
Method 5, Section 8.1.
8.2 Preliminary Determinations. Select the sampling site, probe
nozzle, and probe length as specified in Method 5, Section 8.2. Select a
total sampling time greater than or equal to the minimum total sampling
time specified in the ``Test Methods and Procedures'' section of the
applicable subpart of the regulations. Follow the guidelines outlined in
Method 5, Section 8.2 for sampling time per point and total sample
volume collected.

[[Page 198]]

8.3 Preparation of Sampling Train. Prepare the sampling train as
specified in Method 5, Section 8.3, with the addition of the
precollector cyclone, if used, between the probe and filter holder. The
temperature of the precollector cyclone, if used, should be maintained
in the same range as that of the filter, i.e., 42 10 deg.C
(108 18 deg.F). Use no stopcock grease on ground glass
joints unless grease is insoluble in TCE.
8.4 Leak-Check Procedures. Same as Method 5, Section 8.4.
8.5 Sampling Train Operation. Operate the sampling train as
described in Method 5, Section 8.5, except maintain the temperature of
the gas exiting the filter holder at 42 10 deg.C (108
18 deg.F).
8.6 Calculation of Percent Isokinetic. Same as Method 5, Section
8.6.
8.7 Sample Recovery. Same as Method 5, Section 8.7.1 through
8.7.6.1, with the addition of the following:
8.7.1 Container No. 2 (Probe to Filter Holder).
8.7.1.1 Taking care to see that material on the outside of the
probe or other exterior surfaces does not get into the sample,
quantitatively recover PM or any condensate from the probe nozzle, probe
fitting, probe liner, precollector cyclone and collector flask (if
used), and front half of the filter holder by washing these components
with TCE and placing the wash in a glass container. Carefully measure
the total amount of TCE used in the rinses. Perform the TCE rinses as
described in Method 5, Section 8.7.6.2, using TCE instead of acetone.
8.7.1.2 Brush and rinse the inside of the cyclone, cyclone
collection flask, and the front half of the filter holder. Brush and
rinse each surface three times or more, if necessary, to remove visible
PM.
8.7.2 Container No. 3 (Silica Gel). Same as in Method 5, Section
8.7.6.3.
8.7.3 Impinger Water. Same as Method 5, Section 8.7.6.4.
8.8 Blank. Save a portion of the TCE used for cleanup as a blank.
Take 200 ml of this TCE directly from the wash bottle being used, and
place it in a glass sample container labeled ``TCE Blank.''

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 A quality control (QC) check of the volume metering system at
the field site is suggested before collecting the sample. Use the
procedure outlined in Method 5, Section 9.2.

10.0 Calibration and Standardization

Same as Method 5, Section 10.0.

11.0 Analytical Procedures

11.1 Analysis. Record the data required on a sheet such as the one
shown in Figure 5A-1. Handle each sample container as follows:
11.1.1 Container No. 1 (Filter). Transfer the filter from the
sample container to a tared glass weighing dish, and desiccate for 24
hours in a desiccator containing anhydrous calcium sulfate. Rinse
Container No. 1 with a measured amount of TCE, and analyze this rinse
with the contents of Container No. 2. Weigh the filter to a constant
weight. For the purpose of this analysis, the term ``constant weight''
means a difference of no more than 10 percent of the net filter weight
or 2 mg (whichever is greater) between two consecutive weighings made 24
hours apart. Report the ``final weight'' to the nearest 0.1 mg as the
average of these two values.
11.1.2 Container No. 2 (Probe to Filter Holder).
11.1.2.1 Before adding the rinse from Container No. 1 to Container
No. 2, note the level of liquid in Container No. 2, and confirm on the
analysis sheet whether leakage occurred during transport. If noticeable
leakage occurred, either void the sample or take steps, subject to the
approval of the Administrator, to correct the final results.
11.1.2.2 Add the rinse from Container No. 1 to Container No. 2 and
measure the liquid in this container either volumetrically to
1 ml or gravimetrically to 0.5 g. Check to see
whether there is any appreciable quantity of condensed water present in
the TCE rinse (look for a boundary layer or phase separation). If the
volume of condensed water appears larger than 5 ml, separate the oil-TCE
fraction from the water fraction using a separatory funnel. Measure the
volume of the water phase to the nearest ml; adjust the stack gas
moisture content, if necessary (see Sections 12.3 and 12.4). Next,
extract the water phase with several 25-ml portions of TCE until, by
visual observation, the TCE does not remove any additional organic
material. Transfer the remaining water fraction to a tared beaker and
evaporate to dryness at 93 deg.C (200 deg.F), desiccate for 24 hours,
and weigh to the nearest 0.1 mg.
11.1.2.3 Treat the total TCE fraction (including TCE from the
filter container rinse and water phase extractions) as follows:

[[Page 199]]

Transfer the TCE and oil to a tared beaker, and evaporate at ambient
temperature and pressure. The evaporation of TCE from the solution may
take several days. Do not desiccate the sample until the solution
reaches an apparent constant volume or until the odor of TCE is not
detected. When it appears that the TCE has evaporated, desiccate the
sample, and weigh it at 24-hour intervals to obtain a ``constant
weight'' (as defined for Container No. 1 above). The ``total weight''
for Container No. 2 is the sum of the evaporated PM weight of the TCE-
oil and water phase fractions. Report the results to the nearest 0.1 mg.
11.1.3 Container No. 3 (Silica Gel). This step may be conducted in
the field. Weigh the spent silica gel (or silica gel plus impinger) to
the nearest 0.5 g using a balance.
11.1.4 ``TCE Blank'' Container. Measure TCE in this container
either volumetrically or gravimetrically. Transfer the TCE to a tared
250-ml beaker, and evaporate to dryness at ambient temperature and
pressure. Desiccate for 24 hours, and weigh to a constant weight. Report
the results to the nearest 0.1 mg.

Note: In order to facilitate the evaporation of TCE liquid samples,
these samples may be dried in a controlled temperature oven at
temperatures up to 38 deg.C (100 deg.F) until the liquid is
evaporated.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after the
final calculation. Other forms of the equations may be used as long as
they give equivalent results.
12.1 Nomenclature. Same as Method 5, Section 12.1, with the
following additions:

Ct = TCE blank residue concentration, mg/g.
mt = Mass of residue of TCE blank after evaporation, mg.
Vpc = Volume of water collected in precollector, ml.
Vt = Volume of TCE blank, ml.
Vtw = Volume of TCE used in wash, ml.
Wt = Weight of residue in TCE wash, mg.
t = Density of TCE (see label on bottle), g/ml.

12.2 Dry Gas Meter Temperature, Orifice Pressure Drop, and Dry Gas
Volume. Same as Method 5, Sections 12.2 and 12.3, except use data
obtained in performing this test.
12.3 Volume of Water Vapor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.134

Where:

K2 = 0.001333 m\3\/ml for metric units.
= 0.04706 ft\3\/ml for English units.

12.4 Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.135

Note: In saturated or water droplet-laden gas streams, two
calculations of the moisture content of the stack gas shall be made, one
from the impinger and precollector analysis (Equations 5A-1 and 5A-2)
and a second from the assumption of saturated conditions. The lower of
the two values of moisture content shall be considered correct. The
procedure for determining the moisture content based upon assumption of
saturated conditions is given in Section 4.0 of Method 4. For the
purpose of this method, the average stack gas temperature from Figure 5-
3 of Method 5 may be used to make this determination, provided that the
accuracy of the in-stack temperature sensor is within 1 deg.C (2
deg.F).

12.5 TCE Blank Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.136

Note: In no case shall a blank value of greater than 0.001 percent
of the weight of TCE used be subtracted from the sample weight.

12.6 TCE Wash Blank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.137

12.7 Total PM Weight. Determine the total PM catch from the sum of
the weights obtained from Containers 1 and 2, less the TCE blank.
12.8 PM Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.138

Where:

K3 = 0.001 g/mg for metric units
= 0.0154 gr/mg for English units

12.9 Isokinetic Variation. Same as in Method 5, Section 12.11.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 5, Section 17.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 200]]

Plant

Date

Run No.

Filter No.

Amount liquid lost during transport

Acetone blank volume, m1

Acetone blank concentration, mg/mg (Equation 5-4)

Acetone wash blank, mg (Equation 5-5)

[GRAPHIC] [TIFF OMITTED] TR17OC00.139

Method 5B--Determination of Nonsulfuric Acid Particulate Matter
Emissions From Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5.

1.0 Scope and Application

1.1 Analyte. Nonsulfuric acid particulate matter. No CAS number
assigned.
1.2 Applicability. This method is determining applicable for the
determination of nonsulfuric acid particulate matter from stationary
sources, only where specified by an applicable subpart of the
regulations or where approved by the Administrator for a particular
application.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
collected on a glass fiber filter maintained at a temperature of 160
14 deg.C (320 25 deg.F). The collected
sample is then heated in an oven at 160 deg.C (320 deg.F) for 6 hours
to volatilize any condensed sulfuric acid that may have been collected,
and the nonsulfuric acid particulate mass is determined gravimetrically.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Method 5, Section 6.0, with the following addition and
exceptions:
6.1 Sample Collection. The probe liner heating system and filter
heating system must be capable of maintaining a sample gas temperature
of 160 14 deg.C (320 25 deg.F).

[[Page 201]]

6.2 Sample Preparation. An oven is required for drying the sample.

7.0 Reagents and Standards

Same as Method 5, Section 7.0.

8.0 Sample Collection, Preservation, Storage, and Transport.

Same as Method 5, with the exception of the following:
8.1 Initial Filter Tare. Oven dry the filter at 160 5
deg.C (320 10 deg.F) for 2 to 3 hours, cool in a
desiccator for 2 hours, and weigh. Desiccate to constant weight to
obtain the initial tare weight. Use the applicable specifications and
techniques of Section 8.1.3 of Method 5 for this determination.
8.2 Probe and Filter Temperatures. Maintain the probe outlet and
filter temperatures at 160 14 deg.C (320 25
deg.F).

9.0 Quality Control

Same as Method 5, Section 9.0.

10.0 Calibration and Standardization

Same as Method 5, Section 10.0.

11.0 Analytical Procedure

Same as Method 5, Section 11.0, except replace Section
11.2.2 With the following:
11.1 Container No. 2. Note the level of liquid in the container,
and confirm on the analysis sheet whether leakage occurred during
transport. If a noticeable amount of leakage has occurred, either void
the sample or use methods, subject to the approval of the Administrator,
to correct the final results. Measure the liquid in this container
either volumetrically to 1 ml or gravimetrically to
0.5 g. Transfer the contents to a tared 250 ml beaker, and
evaporate to dryness at ambient temperature and pressure. Then oven dry
the probe and filter samples at a temperature of 160 5
deg.C (320 10 deg.F) for 6 hours. Cool in a desiccator for
2 hours, and weigh to constant weight. Report the results to the nearest
0.1 mg.

12.0 Data Analysis and Calculations

Same as in Method 5, Section 12.0.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 5, Section 17.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 5C--[Reserved]

Method 5D--Determination of Particulate Matter Emissions from Positive
Pressure Fabric Filters

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, Method 17.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability.
1.2.1 This method is applicable for the determination of PM
emissions from positive pressure fabric filters. Emissions are
determined in terms of concentration (mg/m³ or gr/
ft³) and emission rate (kg/hr or lb/hr).
1.2.2 The General Provisions of 40 CFR part 60, Sec. 60.8(e),
require that the owner or operator of an affected facility shall provide
performance testing facilities. Such performance testing facilities
include sampling ports, safe sampling platforms, safe access to sampling
sites, and utilities for testing. It is intended that affected
facilities also provide sampling locations that meet the specification
for adequate stack length and minimal flow disturbances as described in
Method 1. Provisions for testing are often overlooked factors in
designing fabric filters or are extremely costly. The purpose of this
procedure is to identify appropriate alternative locations and
procedures for sampling the emissions from positive pressure fabric
filters. The requirements that the affected facility owner or operator
provide adequate access to performance testing facilities remain in
effect.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter is withdrawn isokinetically from the source
and collected on a glass fiber filter maintained at a temperature at or
above the exhaust gas temperature up to a nominal 120 deg.C (248
25 deg.F). The particulate mass, which includes any

[[Page 202]]

material that condenses at or above the filtration temperature, is
determined gravimetrically after the removal of uncombined water.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Section 6.0 of either Method 5 or Method 17.

7.0 Reagents and Standards

Same as Section 7.0 of either Method 5 or Method 17.

8.0 Sample Collection, Preservation, Storage, and Transport

Same Section 8.0 of either Method 5 or Method 17, except replace
Section 8.2.1 of Method 5 with the following:
8.1 Determination of Measurement Site. The configuration of
positive pressure fabric filter structures frequently are not amenable
to emission testing according to the requirements of Method 1. Following
are several alternatives for determining measurement sites for positive
pressure fabric filters.
8.1.1 Stacks Meeting Method 1 Criteria. Use a measurement site as
specified in Method 1, Section 11.1.
8.1.2 Short Stacks Not Meeting Method 1 Criteria. Use stack
extensions and the procedures in Method 1. Alternatively, use flow
straightening vanes of the ``egg-crate'' type (see Figure 5D-1). Locate
the measurement site downstream of the straightening vanes at a distance
equal to or greater than two times the average equivalent diameter of
the vane openings and at least one-half of the overall stack diameter
upstream of the stack outlet.
8.1.3 Roof Monitor or Monovent. (See Figure 5D-2). For a positive
pressure fabric filter equipped with a peaked roof monitor, ridge vent,
or other type of monovent, use a measurement site at the base of the
monovent. Examples of such locations are shown in Figure 5D-2. The
measurement site must be upstream of any exhaust point (e.g., louvered
vent).
8.1.4 Compartment Housing. Sample immediately downstream of the
filter bags directly above the tops of the bags as shown in the examples
in Figure 5D-2. Depending on the housing design, use sampling ports in
the housing walls or locate the sampling equipment within the
compartment housing.
8.2 Determination of Number and Location of Traverse Points. Locate
the traverse points according to Method 1, Section 11.3. Because a
performance test consists of at least three test runs and because of the
varied configurations of positive pressure fabric filters, there are
several schemes by which the number of traverse points can be determined
and the three test runs can be conducted.
8.2.1 Single Stacks Meeting Method 1 Criteria. Select the number of
traverse points according to Method 1. Sample all traverse points for
each test run.
8.2.2 Other Single Measurement Sites. For a roof monitor or
monovent, single compartment housing, or other stack not meeting Method
1 criteria, use at least 24 traverse points. For example, for a
rectangular measurement site, such as a monovent, use a balanced 5 x 5
traverse point matrix. Sample all traverse points for each test run.
8.2.3 Multiple Measurement Sites. Sampling from two or more stacks
or measurement sites may be combined for a test run, provided the
following guidelines are met:
8.2.3.1 All measurement sites up to 12 must be sampled. For more
than 12 measurement sites, conduct sampling on at least 12 sites or 50
percent of the sites, whichever is greater. The measurement sites
sampled should be evenly, or nearly evenly, distributed among the
available sites; if not, all sites are to be sampled.
8.2.3.2 The same number of measurement sites must be sampled for
each test run.
8.2.3.3 The minimum number of traverse points per test run is 24.
An exception to the 24-point minimum would be a test combining the
sampling from two stacks meeting Method 1 criteria for acceptable stack
length, and Method 1 specifies fewer than 12 points per site.
8.2.3.4 As long as the 24 traverse points per test run criterion is
met, the number of traverse points per measurement site may be reduced
to eight.
8.2.3.5 Alternatively, conduct a test run for each measurement site
individually using the criteria in Section 8.2.1 or 8.2.2 to determine
the number of traverse points. Each test run shall count toward the
total of three required for a performance test. If more than three
measurement sites are sampled, the number of traverse points per
measurement site may be reduced to eight as long as at least 72 traverse
points are sampled for all the tests.
8.2.3.6 The following examples demonstrate the procedures for
sampling multiple measurement sites.
8.2.3.6.1 Example 1: A source with nine circular measurement sites
of equal areas

[[Page 203]]

may be tested as follows: For each test run, traverse three measurement
sites using four points per diameter (eight points per measurement
site). In this manner, test run number 1 will include sampling from
sites 1,2, and 3; run 2 will include samples from sites 4, 5, and 6; and
run 3 will include sites 7, 8, and 9. Each test area may consist of a
separate test of each measurement site using eight points. Use the
results from all nine tests in determining the emission average.
8.2.3.6.2 Example 2: A source with 30 rectangular measurement sites
of equal areas may be tested as follows: For each of the three test
runs, traverse five measurement sites using a 3 x 3 matrix of traverse
points for each site. In order to distribute the sampling evenly over
all the available measurement sites while sampling only 50 percent of
the sites, number the sites consecutively from 1 to 30 and sample all
the even numbered (or odd numbered) sites. Alternatively, conduct a
separate test of each of 15 measurement sites using Section 8.2.1 or
8.2.2 to determine the number and location of traverse points, as
appropriate.
8.2.3.6.3 Example 3: A source with two measurement sites of equal
areas may be tested as follows: For each test of three test runs,
traverse both measurement sites, using Section 8.2.3 in determining the
number of traverse points. Alternatively, conduct two full emission test
runs for each measurement site using the criteria in Section 8.2.1 or
8.2.2 to determine the number of traverse points.
8.2.3.7 Other test schemes, such as random determination of
traverse points for a large number of measurement sites, may be used
with prior approval from the Administrator.
8.3 Velocity Determination.
8.3.1 The velocities of exhaust gases from positive pressure
baghouses are often too low to measure accurately with the type S pitot
tube specified in Method 2 (i.e., velocity head 1.3 mm H2O
(0.05 in. H2O)). For these conditions, measure the gas flow
rate at the fabric filter inlet following the procedures outlined in
Method 2. Calculate the average gas velocity at the measurement site as
shown in Section 12.2 and use this average velocity in determining and
maintaining isokinetic sampling rates.
8.3.2 Velocity determinations to determine and maintain isokinetic
rates at measurement sites with gas velocities within the range
measurable with the type S pitot tube (i.e., velocity head greater than
1.3 mm H2O (0.05 in. H2O)) shall be conducted
according to the procedures outlined in Method 2.
8.4 Sampling. Follow the procedures specified in Sections 8.1
through 8.6 of Method 5 or Sections 8.1 through 8.25 in Method 17 with
the exceptions as noted above.
8.5 Sample Recovery. Follow the procedures specified in Section 8.7
of Method 5 or Section 8.2 of Method 17.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Same as Section 10.0 of either Method 5 or Method 17.

11.0 Analytical Procedure

Same as Section 11.0 of either Method 5 or Method 17.

12.0 Data Analysis and Calculations

Same as Section 12.0 of either Method 5 or Method 17 with the
following exceptions:
12.1 Nomenclature.
Ao = Measurement site(s) total cross-sectional area, m\2\
(ft\2\).
C or Cavg = Average concentration of PM for all n runs, mg/
scm (gr/scf).
Qi = Inlet gas volume flow rate, m\3\/sec (ft\3\/sec).
mi = Mass collected for run i of n, mg (gr).
To = Average temperature of gas at measurement site, deg.K
( deg.R).
Ti = Average temperature of gas at inlet, deg.K ( deg.R).
Voli = Sample volume collected for run i of n, scm (scf).
v = Average gas velocity at the measurement site(s), m/s (ft/s)
Qo = Total baghouse exhaust volumetric flow rate, m\3\/sec
(ft\3\/sec).
Qd = Dilution air flow rate, m\3\/sec (ft\3\/sec).
Tamb = Ambient Temperature, ( deg.K).

12.2 Average Gas Velocity. When following Section 8.3.1, calculate
the average gas velocity at the measurement site as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.140

12.3 Volumetric Flow Rate. Total volumetric flow rate may be
determined as follows:

[[Page 204]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.141

12.4 Dilution Air Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.142

12.5 Average PM Concentration. For multiple measurement sites,
calculate the average PM concentration as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.143

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Method 5, Section 17.0.

[[Page 205]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.144

[[Page 206]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.145

Method 5E--Determination of Particulate Matter Emissions From the Wool
Fiberglass Insulation Manufacturing Industry

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Applications

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

[[Page 207]]

1.2 Applicability. This method is applicable for the determination
of PM emissions from wool fiberglass insulation manufacturing sources.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
is collected either on a glass fiber filter maintained at a temperature
in the range of 120 14 deg.C (248 25 deg.F)
and in impingers in solutions of 0.1 N sodium hydroxide (NaOH). The
filtered particulate mass, which includes any material that condenses at
or above the filtration temperature, is determined gravimetrically after
the removal of uncombined water. The condensed PM collected in the
impinger solutions is determined as total organic carbon (TOC) using a
nondispersive infrared type of analyzer. The sum of the filtered PM mass
and the condensed PM is reported as the total PM mass.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 5, Section 6.1, with the
exception of the following:
6.1.1 Probe Liner. Same as described in Section 6.1.1.2 of Method 5
except use only borosilicate or quartz glass liners.
6.1.2 Filter Holder. Same as described in Section 6.1.1.5 of Method
5 with the addition of a leak-tight connection in the rear half of the
filter holder designed for insertion of a temperature sensor used for
measuring the sample gas exit temperature.
6.2 Sample Recovery. Same as Method 5, Section 6.2, except three
wash bottles are needed instead of two and only glass storage bottles
and funnels may be used.
6.3 Sample Analysis. Same as Method 5, Section 6.3, with the
additional equipment for TOC analysis as described below:
6.3.1 Sample Blender or Homogenizer. Waring type or ultrasonic.
6.3.2 Magnetic Stirrer.
6.3.3 Hypodermic Syringe. 0- to 100-l capacity.
6.3.4 Total Organic Carbon Analyzer. Rosemount Model 2100A analyzer
or equivalent and a recorder.
6.3.5 Beaker. 30-ml.
6.3.6 Water Bath. Temperature controlled.
6.3.7 Volumetric Flasks. 1000-ml and 500-ml.

7.0 Reagents and Standards

[[Page 208]]

(Na2CO3.) in about 500 ml of CO2-free
water in a 1-liter volumetric flask. Add 3.497 g anhydrous sodium
bicarbonate (NaHCO3) to the flask, and dilute to 1 liter with
CO2 -free water. This solution contains 1000 mg/L inorganic
carbon.
7.3.5 Oxygen Gas. CO2 -free.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation and Preliminary Determinations. Same as
Method 5, Sections 8.1 and 8.2, respectively.
8.2 Preparation of Sampling Train. Same as Method 5, Section 8.3,
except that 0.1 N NaOH is used in place of water in the impingers. The
volumes of the solutions are the same as in Method 5.
8.3 Leak-Check Procedures, Sampling Train Operation, Calculation of
Percent Isokinetic. Same as Method 5, Sections 8.4 through 8.6,
respectively.
8.4 Sample Recovery. Same as Method 5, Sections 8.7.1 through
8.7.4, with the addition of the following:
8.4.1 Save portions of the water, acetone, and 0.1 N NaOH used for
cleanup as blanks. Take 200 ml of each liquid directly from the wash
bottles being used, and place in glass sample containers labeled ``water
blank,'' ``acetone blank,'' and ``NaOH blank,'' respectively.
8.4.2 Inspect the train prior to and during disassembly, and note
any abnormal conditions. Treat the samples as follows:
8.4.2.1 Container No. 1. Same as Method 5, Section 8.7.6.1.
8.4.2.2 Container No. 2. Use water to rinse the sample nozzle,
probe, and front half of the filter holder three times in the manner
described in Section 8.7.6.2 of Method 5 except that no brushing is
done. Put all the water wash in one container, seal, and label.
8.4.2.3 Container No. 3. Rinse and brush the sample nozzle, probe,
and front half of the filter holder with acetone as described for
Container No. 2 in Section 8.7.6.2 of Method 5.
8.4.2.4 Container No. 4. Place the contents of the silica gel
impinger in its original container as described for Container No. 3 in
Section 8.7.6.3 of Method 5.
8.4.2.5 Container No. 5. Measure the liquid in the first three
impingers and record the volume or weight as described for the Impinger
Water in Section 8.7.6.4 of Method 5. Do not discard this liquid, but
place it in a sample container using a glass funnel to aid in the
transfer from the impingers or graduated cylinder (if used) to the
sample container. Rinse each impinger thoroughly with 0.1 N NaOH three
times, as well as the graduated cylinder (if used) and the funnel, and
put these rinsings in the same sample container. Seal the container and
label to clearly identify its contents.
8.5 Sample Transport. Whenever possible, containers should be
shipped in such a way that they remain upright at all times.

9.0 Quality Control.

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Same as Method 5, Section 10.0, with the addition of the following
procedures for calibrating the total organic carbon analyzer:
10.1 Preparation of Organic Carbon Standard Curve.
10.1.1 Add 10 ml, 20 ml, 30 ml, 40 ml, and 50 ml of the organic
carbon stock solution to a series of five 1000-ml volumetric flasks. Add
30 ml, 40 ml, and 50 ml of the same solution to a series of three 500-ml
volumetric flasks. Dilute the contents of each flask to the mark using
CO2-free water. These flasks contain 10, 20, 30, 40, 50, 60,
80, and 100 mg/L organic carbon, respectively.
10.1.2 Use a hypodermic syringe to withdraw a 20- to 50-l
aliquot from the 10 mg/L standard solution and inject it into the total
carbon port of the analyzer. Measure the peak height. Repeat the
injections until three consecutive peaks are obtained within 10 percent
of their arithmetic mean. Repeat this procedure for the remaining
organic carbon standard solutions.
10.1.3 Calculate the corrected peak height for each standard by
deducting the blank correction (see Section 11.2.5.3) as follows:

[[Page 209]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.146

Where:

A = Peak height of standard or sample, mm or other appropriate unit.
B = Peak height of blank, mm or other appropriate unit.

10.1.4 Prepare a linear regression plot of the arithmetic mean of
the three consecutive peak heights obtained for each standard solution
against the concentration of that solution. Calculate the calibration
factor as the inverse of the slope of this curve. If the product of the
arithmetic mean peak height for any standard solution and the
calibration factor differs from the actual concentration by more than 5
percent, remake and reanalyze that standard.
10.2 Preparation of Inorganic Carbon Standard Curve. Repeat the
procedures outlined in Sections 10.1.1 through 10.1.4, substituting the
inorganic carbon stock solution for the organic carbon stock solution,
and the inorganic carbon port of the analyzer for the total carbon port.

11.0 Analytical Procedure

11.1 Record the data required on a sheet such as the one shown in
Figure 5-6 of Method 5.
11.2 Handle each sample container as follows:
11.2.1 Container No. 1. Same as Method 5, Section 11.2.1, except
that the filters must be dried at 20 6 deg.C (68
10 deg.F) and ambient pressure.
11.2.2 Containers No. 2 and No. 3. Same as Method 5, Section
11.2.2, except that evaporation of the samples must be at 20
6 deg.C (68 10 deg.F) and ambient pressure.
11.2.3 Container No. 4. Same as Method 5, Section 11.2.3.
11.2.4 ``Water Blank'' and ``Acetone Blank'' Containers. Determine
the water and acetone blank values following the procedures for the
``Acetone Blank'' container in Section 11.2.4 of Method 5. Evaporate the
samples at ambient temperature (20 6 deg.C (68
10 deg.F)) and pressure.
11.2.5 Container No. 5. For the determination of total organic
carbon, perform two analyses on successive identical samples, i.e.,
total carbon and inorganic carbon. The desired quantity is the
difference between the two values obtained. Both analyses are based on
conversion of sample carbon into carbon dioxide for measurement by a
nondispersive infrared analyzer. Results of analyses register as peaks
on a strip chart recorder.
11.2.5.1 The principal differences between the operating parameters
for the two channels involve the combustion tube packing material and
temperature. In the total carbon channel, a high temperature (950 deg.C
(1740 deg.F)) furnace heats a Hastelloy combustion tube packed with
cobalt oxide-impregnated asbestos fiber. The oxygen in the carrier gas,
the elevated temperature, and the catalytic effect of the packing result
in oxidation of both organic and inorganic carbonaceous material to
CO2, and steam. In the inorganic carbon channel, a low
temperature (150 deg.C (300 deg.F)) furnace heats a glass tube
containing quartz chips wetted with 85 percent phosphoric acid. The acid
liberates CO2 and steam from inorganic carbonates. The
operating temperature is below that required to oxidize organic matter.
Follow the manufacturer's instructions for assembly, testing,
calibration, and operation of the analyzer.
11.2.5.2 As samples collected in 0.1 N NaOH often contain a high
measure of inorganic carbon that inhibits repeatable determinations of
TOC, sample pretreatment is necessary. Measure and record the liquid
volume of each sample (or impinger contents). If the sample contains
solids or immiscible liquid matter, homogenize the sample with a blender
or ultrasonics until satisfactory repeatability is obtained. Transfer a
representative portion of 10 to 15 ml to a 30-ml beaker, and acidify
with about 2 drops of concentrated HCl to a pH of 2 or less. Warm the
acidified sample at 50 deg.C (120 deg.F) in a water bath for 15
minutes.
11.2.5.3 While stirring the sample with a magnetic stirrer, use a
hypodermic syringe to withdraw a 20-to 50-1 aliquot from the
beaker. Analyze the sample for total carbon and calculate its corrected
mean peak height according to the procedures outlined in Sections 10.1.2
and 10.1.3. Similarly analyze an aliquot of the sample for inorganic
carbon. Repeat the analyses for all the samples and for the 0.1 N NaOH
blank.
11.2.5.4 Ascertain the total carbon and inorganic carbon
concentrations (CTC and CIC, respectively) of each
sample and blank by comparing the corrected mean peak heights for each
sample and blank to the appropriate standard curve.

Note: If samples must be diluted for analysis, apply an appropriate
dilution factor.

12.0 Data Analysis and Calculations

Same as Method 5, Section 12.0, with the addition of the following:
12.1 Nomenclature.

Cc = Concentration of condensed particulate matter in stack
gas, gas dry basis, corrected to standard conditions, g/dscm
(gr/dscf).
CIC = Concentration of condensed TOC in the liquid sample,
from Section 11.2.5, mg/L.

[[Page 210]]

Ct = Total particulate concentration, dry basis, corrected to
standard conditions, g/dscm (gr/dscf).
CTC = Concentration of condensed TOC in the liquid sample,
from Section 11.2.5, mg/L.
CTOC = Concentration of condensed TOC in the liquid sample,
mg/L.
mTOC = Mass of condensed TOC collected in the impingers, mg.
Vm(std) = Volume of gas sample measured by the dry gas meter,
corrected to standard conditions, from Section 12.3 of Method
5, dscm (dscf).
Vs = Total volume of liquid sample, ml.

12.2 Concentration of Condensed TOC in Liquid Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.148

12.3 Mass of Condensed TOC Collected.
[GRAPHIC] [TIFF OMITTED] TR17OC00.149

Where:

0.001 = Liters per milliliter.

12.4 Concentration of Condensed Particulate Material.
[GRAPHIC] [TIFF OMITTED] TR17OC00.150

Where:

K4 = 0.001 g/mg for metric units.
= 0.0154 gr/mg for English units.

12.5 Total Particulate Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.151

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References.

Same as Section 17.0 of Method 5, with the addition of the
following:

1. American Public Health Association, American Water Works
Association, Water Pollution Control Federation. Standard Methods for
the Examination of Water and Wastewater. Fifteenth Edition. Washington,
D.C. 1980.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 5F--Determination of Nonsulfate Particulate Matter Emissions From
Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Applications

1.1 Analyte. Nonsulfate particulate matter (PM). No CAS number
assigned.
1.2 Applicability. This method is applicable for the determination
of nonsulfate PM emissions from stationary sources. Use of this method
must be specified by an applicable subpart of the standards, or approved
by the Administrator for a particular application.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

Particulate matter is withdrawn isokinetically from the source and
collected on a filter maintained at a temperature in the range 160
14 deg.C (320 25 deg.F). The collected
sample is extracted with water. A portion of the extract is analyzed for
sulfate content by ion chromatography. The remainder is neutralized with
ammonium hydroxide (NH4OH), dried, and weighed. The weight of
sulfate in the sample is calculated as ammonium sulfate
((NH4)2SO4), and is subtracted from the
total particulate weight; the result is reported as nonsulfate
particulate matter.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection and Recovery. Same as Method 5, Sections 6.1
and 6.2, respectively.
6.2 Sample Analysis. Same as Method 5, Section 6.3, with the
addition of the following:
6.2.1 Erlenmeyer Flasks. 125-ml, with ground glass joints.
6.2.2 Air Condenser. With ground glass joint compatible with the
Erlenmeyer flasks.
6.2.3 Beakers. 600-ml.
6.2.4 Volumetric Flasks. 1-liter, 500-ml (one for each sample),
200-ml, and 50-ml (one for each sample and standard).

[[Page 211]]

6.2.5 Pipet. 5-ml (one for each sample and standard).
6.2.6 Ion Chromatograph. The ion chromatograph should have at least
the following components.
6.2.6.1 Columns. An anion separation column or other column capable
of resolving the sulfate ion from other species present and a standard
anion suppressor column. Suppressor columns are produced as proprietary
items; however, one can be produced in the laboratory using the resin
available from BioRad Company, 32nd and Griffin Streets, Richmond,
California. Other systems which do not use suppressor columns may also
be used.
6.2.6.2 Pump. Capable of maintaining a steady flow as required by
the system.
6.2.6.3 Flow Gauges. Capable of measuring the specified system flow
rate.
6.2.6.4 Conductivity Detector.
6.2.6.5 Recorder. Compatible with the output voltage range of the
detector.

7.0 Reagents and Standards

Unless otherwise indicated, it is intended that all reagents conform
to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available; otherwise, use the best available grade.
7.1 Sample Collection. Same as Method 5, Section 7.1.
7.2 Sample Recovery. Same as Method 5, Section 7.2, with the
addition of the following:
7.2.1 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91 Type 3 (incorporated by reference--see Sec. 60.17). The potassium
permanganate (KMnO4) test for oxidizable organic matter may
be omitted when high concentrations of organic matter are not expected
to be present.
7.3 Analysis. Same as Method 5, Section 7.3, with the addition of
the following:
7.3.1 Water. Same as in Section 7.2.1.
7.3.2 Stock Standard Solution, 1 mg
(NH4)2SO4/ml. Dry an adequate amount of
primary standard grade ammonium sulfate
((NH4)2SO4) at 105 to 110 deg.C (220
to 230 deg.F) for a minimum of 2 hours before preparing the standard
solution. Then dissolve exactly 1.000 g of dried
(NH4)2SO4 in water in a 1-liter
volumetric flask, and dilute to 1 liter. Mix well.
7.3.3 Working Standard Solution, 25 g
(NH4)2SO4/ml. Pipet 5 ml of the stock
standard solution into a 200-ml volumetric flask. Dilute to 200 ml with
water.
7.3.4 Eluent Solution. Weigh 1.018 g of sodium carbonate
(Na2CO3) and 1.008 g of sodium bicarbonate
(NaHCO3), and dissolve in 4 liters of water. This solution is
0.0024 M Na2CO3/0.003 M NaHCO3. Other
eluents appropriate to the column type and capable of resolving sulfate
ion from other species present may be used.
7.3.5 Ammonium Hydroxide. Concentrated, 14.8 M.
7.3.6 Phenolphthalein Indicator. 3,3-Bis(4-hydroxyphenyl)-1-(3H)-
isobenzo-furanone. Dissolve 0.05 g in 50 ml of ethanol and 50 ml of
water.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 5, Section 8.0, with the exception of the following:
8.1 Sampling Train Operation. Same as Method 5, Section 8.5, except
that the probe outlet and filter temperatures shall be maintained at 160
14 deg.C (320 25 deg.F).
8.2 Sample Recovery. Same as Method 5, Section 8.7, except that the
recovery solvent shall be water instead of acetone, and a clean filter
from the same lot as those used during testing shall be saved for
analysis as a blank.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Same as Method 5, Section 10.0, with the addition of the following:
10.1 Determination of Ion Chromatograph Calibration Factor S.
Prepare a series of five standards by adding 1.0, 2.0, 4.0, 6.0, and
10.0 ml of working standard solution (25 g/ml) to a series of
five 50-ml volumetric flasks. (The standard masses will equal 25, 50,
100, 150, and 250 g.) Dilute each flask to the mark with water,
and mix well. Analyze each standard according to the chromatograph
manufacturer's instructions. Take peak height measurements with
symmetrical peaks; in all other cases, calculate peak areas. Prepare or
calculate a linear regression plot of the standard masses in g
(x-axis) versus their responses (y-axis). From

[[Page 212]]

this line, or equation, determine the slope and calculate its reciprocal
which is the calibration factor, S. If any point deviates from the line
by more than 7 percent of the concentration at that point, remake and
reanalyze that standard. This deviation can be determined by multiplying
S times the response for each standard. The resultant concentrations
must not differ by more than 7 percent from each known standard mass
(i.e., 25, 50, 100, 150, and 250 g).
10.2 Conductivity Detector. Calibrate according to manufacturer's
specifications prior to initial use.

11.0 Analytical Procedure

11.1 Sample Extraction.
11.1.1 Note on the analytical data sheet, the level of the liquid
in the container, and whether any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the
final results.
11.1.2 Cut the filter into small pieces, and place it in a 125-ml
Erlenmeyer flask with a ground glass joint equipped with an air
condenser. Rinse the shipping container with water, and pour the rinse
into the flask. Add additional water to the flask until it contains
about 75 ml, and place the flask on a hot plate. Gently reflux the
contents for 6 to 8 hours. Cool the solution, and transfer it to a 500-
ml volumetric flask. Rinse the Erlenmeyer flask with water, and transfer
the rinsings to the volumetric flask including the pieces of filter.
11.1.3 Transfer the probe rinse to the same 500-ml volumetric flask
with the filter sample. Rinse the sample bottle with water, and add the
rinsings to the volumetric flask. Dilute the contents of the flask to
the mark with water.
11.1.4 Allow the contents of the flask to settle until all solid
material is at the bottom of the flask. If necessary, remove and
centrifuge a portion of the sample.
11.1.5 Repeat the procedures outlined in Sections 11.1.1 through
11.1.4 for each sample and for the filter blank.
11.2 Sulfate (SO4) Analysis.
11.2.1 Prepare a standard calibration curve according to the
procedures outlined in Section 10.1.
11.2.2 Pipet 5 ml of the sample into a 50-ml volumetric flask, and
dilute to 50 ml with water. (Alternatively, eluent solution may be used
instead of water in all sample, standard, and blank dilutions.) Analyze
the set of standards followed by the set of samples, including the
filter blank, using the same injection volume used for the standards.
11.2.3 Repeat the analyses of the standards and the samples, with
the standard set being done last. The two peak height or peak area
responses for each sample must agree within 5 percent of their
arithmetic mean for the analysis to be valid. Perform this analysis
sequence on the same day. Dilute any sample and the blank with equal
volumes of water if the concentration exceeds that of the highest
standard.
11.2.4 Document each sample chromatogram by listing the following
analytical parameters: injection point, injection volume, sulfate
retention time, flow rate, detector sensitivity setting, and recorder
chart speed.
11.3 Sample Residue.
11.3.1 Transfer the remaining contents of the volumetric flask to a
tared 600-ml beaker or similar container. Rinse the volumetric flask
with water, and add the rinsings to the tared beaker. Make certain that
all particulate matter is transferred to the beaker. Evaporate the water
in an oven at 105 deg.C (220 deg.F) until only about 100 ml of water
remains. Remove the beakers from the oven, and allow them to cool.
11.3.2 After the beakers have cooled, add five drops of
phenolphthalein indicator, and then add concentrated ammonium hydroxide
until the solution turns pink. Return the samples to the oven at 105
deg.C (220 deg.F), and evaporate the samples to dryness. Cool the
samples in a desiccator, and weigh the samples to constant weight.

12.0 Data Analysis and Calculations

Same as Method 5, Section 12.0, with the addition of the following:
12.1 Nomenclature.

CW = Water blank residue concentration, mg/ml.
F = Dilution factor (required only if sample dilution was needed to
reduce the concentration into the range of calibration).
HS = Arithmetic mean response of duplicate sample analyses,
mm for height or mm2 for area.
Hb = Arithmetic mean response of duplicate filter blank
analyses, mm for height or mm2 for area.
mb = Mass of beaker used to dry sample, mg.
mf = Mass of sample filter, mg.
mn = Mass of nonsulfate particulate matter in the sample as
collected, mg.
ms = Mass of ammonium sulfate in the sample as collected, mg.
mt = Mass of beaker, filter, and dried sample, mg.
mw = Mass of residue after evaporation of water blank, mg.
S = Calibration factor, g/mm.
Vb = Volume of water blank, ml.
VS = Volume of sample collected, 500 ml.

12.2 Water Blank Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.152

12.3 Mass of Ammonium Sulfate.

[[Page 213]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.153

Where:

100 = Aliquot factor, 495 ml/5 ml
1000 = Constant, g/mg

12.4 Mass of Nonsulfate Particulate Matter.
[GRAPHIC] [TIFF OMITTED] TR17OC00.154

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 The following procedure may be used as an alternative to the
procedure in Section 11.0
16.1.1 Apparatus. Same as for Method 6, Sections 6.3.3 to 6.3.6
with the following additions.
16.1.1.1 Beakers. 250-ml, one for each sample, and 600-ml.
16.1.1.2 Oven. Capable of maintaining temperatures of 75
5 deg.C (167 9 deg.F) and 105 5
deg.C (221 9 deg.F).
16.1.1.3 Buchner Funnel.
16.1.1.4 Glass Columns. 25-mm x 305-mm (1-in. x 12-in.) with Teflon
stopcock.
16.1.1.5 Volumetric Flasks. 50-ml and 500-ml, one set for each
sample, and 100-ml, 200-ml, and 1000-ml.
16.1.1.6 Pipettes. Two 20-ml and one 200-ml, one set for each
sample, and 5-ml.
16.1.1.7 Filter Flasks. 500-ml.
16.1.1.8 Polyethylene Bottle. 500-ml, one for each sample.
16.1.2 Reagents. Same as Method 6, Sections 7.3.2 to 7.3.5 with the
following additions:
16.1.2.1 Water, Ammonium Hydroxide, and Phenolphthalein. Same as
Sections 7.2.1, 7.3.5, and 7.3.6 of this method, respectively.
16.1.2.2 Filter. Glass fiber to fit Buchner funnel.
16.1.2.3 Hydrochloric Acid (HCl), 1 m. Add 8.3 ml of concentrated
HCl (12 M) to 50 ml of water in a 100-ml volumetric flask. Dilute to 100
ml with water.
16.1.2.4 Glass Wool.
16.1.2.5 Ion Exchange Resin. Strong cation exchange resin, hydrogen
form, analytical grade.
16.1.2.6 pH Paper. Range of 1 to 7.
16.1.3 Analysis.
16.1.3.1 Ion Exchange Column Preparation. Slurry the resin with 1 M
HCl in a 250-ml beaker, and allow to stand overnight. Place 2.5 cm (1
in.) of glass wool in the bottom of the glass column. Rinse the slurried
resin twice with water. Resuspend the resin in water, and pour
sufficient resin into the column to make a bed 5.1 cm (2 in.) deep. Do
not allow air bubbles to become entrapped in the resin or glass wool to
avoid channeling, which may produce erratic results. If necessary, stir
the resin with a glass rod to remove air bubbles, after the column has
been prepared, never let the liquid level fall below the top of the
upper glass wool plug. Place a 2.5-cm (1-in.) plug of glass wool on top
of the resin. Rinse the column with water until the eluate gives a pH of
5 or greater as measured with pH paper.
16.1.3.2 Sample Extraction. Followup the procedure given in Section
11.1.3 except do not dilute the sample to 500 ml.
16.1.3.3 Sample Residue.
16.1.3.3.1 Place at least one clean glass filter for each sample in
a Buchner funnel, and rinse the filters with water. Remove the filters
from the funnel, and dry them in an oven at 105 5 deg.C
(221 9 deg.F); then cool in a desiccator. Weigh each
filter to constant weight according to the procedure in Method 5,
Section 11.0. Record the weight of each filter to the nearest 0.1 mg.
16.1.3.3.2 Assemble the vacuum filter apparatus, and place one of
the clean, tared glass fiber filters in the Buchner funnel. Decant the
liquid portion of the extracted sample (Section 16.1.3.2) through the
tared glass fiber filter into a clean, dry, 500-ml filter flask. Rinse
all the particulate matter remaining in the volumetric flask onto the
glass fiber filter with water. Rinse the particulate matter with
additional water. Transfer the filtrate to a 500-ml volumetric flask,
and dilute to 500 ml with water. Dry the filter overnight at 105
5 deg.C (221 9 deg.F), cool in a desiccator,
and weigh to the nearest 0.1 mg.
16.1.3.3.3 Dry a 250-ml beaker at 75 5 deg.C (167
9 deg.F), and cool in a desiccator; then weigh to constant
weight to the nearest 0.1 mg. Pipette 200 ml of the filtrate that was
saved into a tared 250-ml beaker; add five drops of phenolphthalein
indicator and sufficient concentrated ammonium hydroxide to turn the
solution pink. Carefully evaporate the contents of the beaker to dryness
at 75 5 deg.C (167 9 deg.F). Check for
dryness every 30 minutes. Do not continue to bake the sample once it has
dried. Cool the sample in a desiccator, and weigh to constant weight to
the nearest 0.1 mg.

[[Page 214]]

16.1.3.4 Sulfate Analysis. Adjust the flow rate through the ion
exchange column to 3 ml/min. Pipette a 20-ml aliquot of the filtrate
onto the top of the ion exchange column, and collect the eluate in a 50-
ml volumetric flask. Rinse the column with two 15-ml portions of water.
Stop collection of the eluate when the volume in the flask reaches 50-
ml. Pipette a 20-ml aliquot of the eluate into a 250-ml Erlenmeyer
flask, add 80 ml of 100 percent isopropanol and two to four drops of
thorin indicator, and titrate to a pink end point using 0.0100 N barium
perchlorate. Repeat and average the titration volumes. Run a blank with
each series of samples. Replicate titrations must agree within 1 percent
or 0.2 ml, whichever is larger. Perform the ion exchange and titration
procedures on duplicate portions of the filtrate. Results should agree
within 5 percent. Regenerate or replace the ion exchange resin after 20
sample aliquots have been analyzed or if the end point of the titration
becomes unclear.

Note: Protect the 0.0100 N barium perchlorate solution from
evaporation at all times.

16.1.3.5 Blank Determination. Begin with a sample of water of the
same volume as the samples being processed and carry it through the
analysis steps described in Sections 16.1.3.3 and 16.1.3.4. A blank
value larger than 5 mg should not be subtracted from the final
particulate matter mass. Causes for large blank values should be
investigated and any problems resolved before proceeding with further
analyses.
16.1.4 Calibration. Calibrate the barium perchlorate solutions as
in Method 6, Section 10.5.
16.1.5 Calculations.
16.1.5.1 Nomenclature. Same as Section 12.1 with the following
additions:

ma = Mass of clean analytical filter, mg.
md = Mass of dissolved particulate matter, mg.
me = Mass of beaker and dissolved particulate matter after
evaporation of filtrate, mg.
mp = Mass of insoluble particulate matter, mg.
mr = Mass of analytical filter, sample filter, and insoluble
particulate matter, mg.
mbk = Mass of nonsulfate particulate matter in blank sample,
mg.
mn = Mass of nonsulfate particulate matter, mg.
ms = Mass of Ammonium sulfate, mg.
N = Normality of Ba(ClO4) titrant, meq/ml.
Va = Volume of aliquot taken for titration, 20 ml.
Vc = Volume of titrant used for titration blank, ml.
Vd = Volume of filtrate evaporated, 200 ml.
Ve = Volume of eluate collected, 50 ml.
Vf = Volume of extracted sample, 500 ml.
Vi = Volume of filtrate added to ion exchange column, 20 ml.
Vt = Volume of Ba(C104)2 titrant, ml.
W = Equivalent weight of ammonium sulfate, 66.07 mg/meq.
16.1.5.2 Mass of Insoluble Particulate Matter.
[GRAPHIC] [TIFF OMITTED] TR17OC00.155

16.1.5.3 Mass of Dissolved Particulate Matter.
[GRAPHIC] [TIFF OMITTED] TR17OC00.156

16.1.5.4 Mass of Ammonium Sulfate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.157

16.1.5.5 Mass of Nonsulfate Particulate Matter.
[GRAPHIC] [TIFF OMITTED] TR17OC00.158

17.0 References

Same as Method 5, Section 17.0, with the addition of the following:

1. Mulik, J.D. and E. Sawicki. Ion Chromatographic Analysis of
Environmental Pollutants. Ann Arbor, Ann Arbor Science Publishers, Inc.
Vol. 2, 1979.
2. Sawicki, E., J.D. Mulik, and E. Wittgenstein. Ion Chromatographic
Analysis of Environmental Pollutants. Ann Arbor, Ann Arbor Science
Publishers, Inc. Vol. 1. 1978.
3. Siemer, D.D. Separation of Chloride and Bromide from Complex
Matrices Prior to Ion Chromatographic Determination. Analytical
Chemistry 52(12): 1874-1877. October 1980.
4. Small, H., T.S. Stevens, and W.C. Bauman. Novel Ion Exchange
Chromatographic Method Using Conductimetric Determination. Analytical
Chemistry. 47(11):1801. 1975.

18.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 5G--Determination of Particulate Matter Emissions From Wood
Heaters (Dilution Tunnel Sampling Location)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 4, Method 5, Method 5H, and Method 28.

[[Page 215]]

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the determination
of PM emissions from wood heaters.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 The exhaust from a wood heater is collected with a total
collection hood, and is combined with ambient dilution air. Particulate
matter is withdrawn proportionally from a single point in a sampling
tunnel, and is collected on two glass fiber filters in series. The
filters are maintained at a temperature of no greater than 32 deg.C (90
deg.F). The particulate mass is determined gravimetrically after the
removal of uncombined water.
2.2 There are three sampling train approaches described in this
method: (1) One dual-filter dry sampling train operated at about 0.015
m\3\/min (0.5 cfm), (2) One dual-filter plus impingers sampling train
operated at about 0.015 m\3\/min (0.5 cfm), and (3) two dual-filter dry
sampling trains operated simultaneously at any flow rate. Options (2)
and (3) are referenced in Section 16.0 of this method. The dual-filter
dry sampling train equipment and operation, option (1), are described in
detail in this method.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are required for sample
collection:
6.1.1 Sampling Train. The sampling train configuration is shown in
Figure 5G-1 and consists of the following components:
6.1.1.1 Probe. Stainless steel (e.g., 316 or grade more corrosion
resistant) or glass about 9.5 mm (\3/8\ in.) I.D., 0.6 m (24 in.) in
length. If made of stainless steel, the probe shall be constructed from
seamless tubing.
6.1.1.2 Pitot Tube. Type S, as described in Section 6.1 of Method
2. The Type S pitot tube assembly shall have a known coefficient,
determined as outlined in Method 2, Section 10. Alternatively, a
standard pitot may be used as described in Method 2, Section 6.1.2.
6.1.1.3 Differential Pressure Gauge. Inclined manometer or
equivalent device, as described in Method 2, Section 6.2. One manometer
shall be used for velocity head (p) readings and another
(optional) for orifice differential pressure readings (H).
6.1.1.4 Filter Holders. Two each made of borosilicate glass,
stainless steel, or Teflon, with a glass frit or stainless steel filter
support and a silicone rubber, Teflon, or Viton gasket. The holder
design shall provide a positive seal against leakage from the outside or
around the filters. The filter holders shall be placed in series with
the backup filter holder located 25 to 100 mm (1 to 4 in.) downstream
from the primary filter holder. The filter holder shall be capable of
holding a filter with a 100 mm (4 in.) diameter, except as noted in
Section 16.
6.1.1.5 Filter Temperature Monitoring System. A temperature sensor
capable of measuring temperature to within 3 deg.C
( 5 deg.F). The sensor shall be installed at the exit side
of the front filter holder so that the sensing tip of the temperature
sensor is in direct contact with the sample gas or in a thermowell as
shown in Figure 5G-1. The temperature sensor shall comply with the
calibration specifications in Method 2, Section 10.3. Alternatively, the
sensing tip of the temperature sensor may be installed at the inlet side
of the front filter holder.
6.1.1.6 Dryer. Any system capable of removing water from the sample
gas to less than 1.5 percent moisture (volume percent) prior to the
metering system. The system shall include a temperature sensor for
demonstrating that sample gas temperature exiting the dryer is less than
20 deg.C (68 deg.F).
6.1.1.7 Metering System. Same as Method 5, Section 6.1.1.9.
6.1.2 Barometer. Same as Method 5, Section 6.1.2.
6.1.3 Dilution Tunnel Gas Temperature Measurement. A temperature
sensor capable of measuring temperature to within 3 deg.C
( 5 deg.F).
6.1.4 Dilution Tunnel. The dilution tunnel apparatus is shown in
Figure 5G-2 and consists of the following components:
6.1.4.1 Hood. Constructed of steel with a minimum diameter of 0.3 m
(1 ft) on the large end and a standard 0.15 to 0.3 m (0.5 to 1 ft)
coupling capable of connecting to standard 0.15 to 0.3 m (0.5 to 1 ft)
stove pipe on the small end.
6.1.4.2 90 deg. Elbows. Steel 90 deg. elbows, 0.15 to 0.3 m (0.5 to
1 ft) in diameter for connecting mixing duct, straight duct and optional
damper assembly. There shall be at least two 90 deg. elbows upstream of
the sampling section (see Figure 5G-2).
6.1.4.3 Straight Duct. Steel, 0.15 to 0.3 m (0.5 to 1 ft) in
diameter to provide the ducting for the dilution apparatus upstream of

[[Page 216]]

the sampling section. Steel duct, 0.15 m (0.5 ft) in diameter shall be
used for the sampling section. In the sampling section, at least 1.2 m
(4 ft) downstream of the elbow, shall be two holes (velocity traverse
ports) at 90 deg. to each other of sufficient size to allow entry of the
pitot for traverse measurements. At least 1.2 m (4 ft) downstream of the
velocity traverse ports, shall be one hole (sampling port) of sufficient
size to allow entry of the sampling probe. Ducts of larger diameter may
be used for the sampling section, provided the specifications for
minimum gas velocity and the dilution rate range shown in Section 8 are
maintained. The length of duct from the hood inlet to the sampling ports
shall not exceed 9.1 m (30 ft).
6.1.4.4 Mixing Baffles. Steel semicircles (two) attached at 90 deg.
to the duct axis on opposite sides of the duct midway between the two
elbows upstream of sampling section. The space between the baffles shall
be about 0.3 m (1 ft).
6.1.4.5 Blower. Squirrel cage or other fan capable of extracting
gas from the dilution tunnel of sufficient flow to maintain the velocity
and dilution rate specifications in Section 8 and exhausting the gas to
the atmosphere.
6.2 Sample Recovery. The following items are required for sample
recovery: probe brushes, wash bottles, sample storage containers, petri
dishes, and funnel. Same as Method 5, Sections 6.2.1 through 6.2.4, and
6.2.8, respectively.
6.3 Sample Analysis. The following items are required for sample
analysis: glass weighing dishes, desiccator, analytical balance, beakers
(250-ml or smaller), hygrometer, and temperature sensor. Same as Method
5, Sections 6.3.1 through 6.3.3 and 6.3.5 through 6.3.7, respectively.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Filters. Glass fiber filters with a minimum diameter of 100
mm (4 in.), without organic binder, exhibiting at least 99.95 percent
efficiency (0.05 percent penetration) on 0.3-micron dioctyl phthalate
smoke particles. Gelman A/E 61631 has been found acceptable for this
purpose.
7.1.2 Stopcock Grease. Same as Method 5, Section 7.1.5. 7.2 Sample
Recovery. Acetone-reagent grade, same as Method 5, Section 7.2.
7.3 Sample Analysis. Two reagents are required for the sample
analysis:
7.3.1 Acetone. Same as in Section 7.2.
7.3.2 Desiccant. Anhydrous calcium sulfate, calcium chloride, or
silica gel, indicating type.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Dilution Tunnel Assembly and Cleaning. A schematic of a
dilution tunnel is shown in Figure 5G-2. The dilution tunnel dimensions
and other features are described in Section 6.1.4. Assemble the dilution
tunnel, sealing joints and seams to prevent air leakage. Clean the
dilution tunnel with an appropriately sized wire chimney brush before
each certification test.
8.2 Draft Determination. Prepare the wood heater as in Method 28,
Section 6.2.1. Locate the dilution tunnel hood centrally over the wood
heater stack exhaust. Operate the dilution tunnel blower at the flow
rate to be used during the test run. Measure the draft imposed on the
wood heater by the dilution tunnel (i.e., the difference in draft
measured with and without the dilution tunnel operating) as described in
Method 28, Section 6.2.3. Adjust the distance between the top of the
wood heater stack exhaust and the dilution tunnel hood so that the
dilution tunnel induced draft is less than 1.25 Pa (0.005 in.
H2O). Have no fire in the wood heater, close the wood heater
doors, and open fully the air supply controls during this check and
adjustment.
8.3 Pretest Ignition. Same as Method 28, Section 8.7.
8.4 Smoke Capture. During the pretest ignition period, operate the
dilution tunnel and visually monitor the wood heater stack exhaust.
Operate the wood heater with the doors closed and determine that 100
percent of the exhaust gas is collected by the dilution tunnel hood. If
less than 100 percent of the wood heater exhaust gas is collected,
adjust the distance between the wood heater stack and the dilution
tunnel hood until no visible exhaust gas is escaping. Stop the pretest
ignition period, and repeat the draft determination procedure described
in Section 8.2.
8.5 Velocity Measurements. During the pretest ignition period,
conduct a velocity traverse to identify the point of average velocity.
This single point shall be used for measuring velocity during the test
run.
8.5.1 Velocity Traverse. Measure the diameter of the duct at the
velocity traverse port location through both ports. Calculate the duct
area using the average of the two diameters. A pretest leak-check of
pitot lines as in Method 2, Section 8.1, is recommended. Place the
calibrated pitot tube at the centroid of the stack in either of the
velocity traverse ports. Adjust the damper or similar device on the
blower inlet until the velocity indicated by the pitot is approximately
220 m/min (720 ft/min). Continue to read the p and temperature
until the velocity has remained constant (less than 5 percent change)
for 1 minute. Once a constant velocity is obtained at the centroid of
the

[[Page 217]]

duct, perform a velocity traverse as outlined in Method 2, Section 8.3
using four points per traverse as outlined in Method 1. Measure the
p and tunnel temperature at each traverse point and record the
readings. Calculate the total gas flow rate using calculations contained
in Method 2, Section 12. Verify that the flow rate is 4
0.40 dscm/min (140 14 dscf/min); if not, readjust the
damper, and repeat the velocity traverse. The moisture may be assumed to
be 4 percent (100 percent relative humidity at 85 deg.F). Direct
moisture measurements (e.g., according to Method 4) are also
permissible.

Note: If burn rates exceed 3 kg/hr (6.6 lb/hr), dilution tunnel duct
flow rates greater than 4 dscm/min (140 dscfm) and sampling section duct
diameters larger than 150 mm (6 in.) are allowed. If larger ducts or
flow rates are used, the sampling section velocity shall be at least 220
m/min (720 fpm). In order to ensure measurable particulate mass catch,
it is recommended that the ratio of the average mass flow rate in the
dilution tunnel to the average fuel burn rate be less than 150:1 if
larger duct sizes or flow rates are used.

8.5.2 Testing Velocity Measurements. After obtaining velocity
traverse results that meet the flow rate requirements, choose a point of
average velocity and place the pitot and temperature sensor at that
location in the duct. Alternatively, locate the pitot and the
temperature sensor at the duct centroid and calculate a velocity
correction factor for the centroidal position. Mount the pitot to ensure
no movement during the test run and seal the port holes to prevent any
air leakage. Align the pitot opening to be parallel with the duct axis
at the measurement point. Check that this condition is maintained during
the test run (about 30-minute intervals). Monitor the temperature and
velocity during the pretest ignition period to ensure that the proper
flow rate is maintained. Make adjustments to the dilution tunnel flow
rate as necessary.
8.6 Pretest Preparation. Same as Method 5, Section 8.1.
8.7 Preparation of Sampling Train. During preparation and assembly
of the sampling train, keep all openings where contamination can occur
covered until just prior to assembly or until sampling is about to
begin.
Using a tweezer or clean disposable surgical gloves, place one
labeled (identified) and weighed filter in each of the filter holders.
Be sure that each filter is properly centered and that the gasket is
properly placed so as to prevent the sample gas stream from
circumventing the filter. Check each filter for tears after assembly is
completed.
Mark the probe with heat resistant tape or by some other method to
denote the proper distance into the stack or duct. Set up the train as
shown in Figure 5G-1.
8.8 Leak-Check Procedures.
8.8.1 Leak-Check of Metering System Shown in Figure 5G-1. That
portion of the sampling train from the pump to the orifice meter shall
be leak-checked prior to initial use and after each certification or
audit test. Leakage after the pump will result in less volume being
recorded than is actually sampled. Use the procedure described in Method
5, Section 8.4.1. Similar leak-checks shall be conducted for other types
of metering systems (i.e., without orifice meters).
8.8.2 Pretest Leak-Check. A pretest leak-check of the sampling
train is recommended, but not required. If the pretest leak check is
conducted, the procedures outlined in Method 5, Section 8.4.2 should be
used. A vacuum of 130 mm Hg (5 in. Hg) may be used instead of 380 mm Hg
(15 in. Hg).
8.8.3 Post-Test Leak-Check. A leak-check of the sampling train is
mandatory at the conclusion of each test run. The leak-check shall be
performed in accordance with the procedures outlined in Method 5,
Section 8.4.2. A vacuum of 130 mm Hg (5 in. Hg) or the highest vacuum
measured during the test run, whichever is greater, may be used instead
of 380 mm Hg (15 in. Hg).
8.9 Preliminary Determinations. Determine the pressure, temperature
and the average velocity of the tunnel gases as in Section 8.5. Moisture
content of diluted tunnel gases is assumed to be 4 percent for making
flow rate calculations; the moisture content may be measured directly as
in Method 4.
8.10 Sampling Train Operation. Position the probe inlet at the
stack centroid, and block off the openings around the probe and porthole
to prevent unrepresentative dilution of the gas stream. Be careful not
to bump the probe into the stack wall when removing or inserting the
probe through the porthole; this minimizes the chance of extracting
deposited material.
8.10.1 Begin sampling at the start of the test run as defined in
Method 28, Section 8.8.1. During the test run, maintain a sample flow
rate proportional to the dilution tunnel flow rate (within 10 percent of
the initial proportionality ratio) and a filter holder temperature of no
greater than 32 deg.C (90 deg.F). The initial sample flow rate shall
be approximately 0.015 m\3\/min (0.5 cfm).
8.10.2 For each test run, record the data required on a data sheet
such as the one shown in Figure 5G-3. Be sure to record the initial dry
gas meter reading. Record the dry gas meter readings at the beginning
and end of each sampling time increment and when sampling is halted.
Take other readings as indicated on Figure 5G-3 at least once each 10
minutes during the test run. Since the manometer level and zero may
drift because of vibrations and temperature changes, make periodic
checks during the test run.
8.10.3 For the purposes of proportional sampling rate
determinations, data from

[[Page 218]]

calibrated flow rate devices, such as glass rotameters, may be used in
lieu of incremental dry gas meter readings. Proportional rate
calculation procedures must be revised, but acceptability limits remain
the same.
8.10.4 During the test run, make periodic adjustments to keep the
temperature between (or upstream of) the filters at the proper level. Do
not change sampling trains during the test run.
8.10.5 At the end of the test run (see Method 28, Section 6.4.6),
turn off the coarse adjust valve, remove the probe from the stack, turn
off the pump, record the final dry gas meter reading, and conduct a
post-test leak-check, as outlined in Section 8.8.2. Also, leak-check the
pitot lines as described in Method 2, Section 8.1; the lines must pass
this leak-check in order to validate the velocity head data.
8.11 Calculation of Proportional Sampling Rate. Calculate percent
proportionality (see Section 12.7) to determine whether the run was
valid or another test run should be made.
8.12 Sample Recovery. Same as Method 5, Section 8.7, with the
exception of the following:
8.12.1 An acetone blank volume of about 50-ml or more may be used.
8.12.2 Treat the samples as follows:
8.12.2.1 Container Nos. 1 and 1A. Treat the two filters according
to the procedures outlined in Method 5, Section 8.7.6.1. The filters may
be stored either in a single container or in separate containers. Use
the sum of the filter tare weights to determine the sample mass
collected.
8.12.2.3 Container No. 2.
8.12.2.3.1 Taking care to see that dust on the outside of the probe
or other exterior surfaces does not get into the sample, quantitatively
recover particulate matter or any condensate from the probe and filter
holders by washing and brushing these components with acetone and
placing the wash in a labeled glass container. At least three cycles of
brushing and rinsing are required.
8.12.2.3.2 Between sampling runs, keep brushes clean and protected
from contamination.
8.12.2.3.3 After all acetone washings and particulate matter have
been collected in the sample containers, tighten the lids on the sample
containers so that the acetone will not leak out when transferred to the
laboratory weighing area. Mark the height of the fluid levels to
determine whether leakage occurs during transport. Label the containers
clearly to identify contents.
8.13 Sample Transport. Whenever possible, containers should be
shipped in such a way that they remain upright at all times.

Note: Requirements for capping and transport of sample containers
are not applicable if sample recovery and analysis occur in the same
room.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.8, 10.1-10.4................ Sampling Ensures accurate
equipment leak measurement of stack
check and gas flow rate,
calibration. sample volume.
10.5.......................... Analytical Ensure accurate and
balance precise measurement
calibration. of collected
particulate.
16.2.5........................ Simultaneous, Ensure precision of
dual-train measured particulate
sample concentration.
collection.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory record of all calibrations.

10.1 Pitot Tube. The Type S pitot tube assembly shall be calibrated
according to the procedure outlined in Method 2, Section 10.1, prior to
the first certification test and checked semiannually, thereafter. A
standard pitot need not be calibrated but shall be inspected and
cleaned, if necessary, prior to each certification test.
10.2 Volume Metering System.
10.2.1 Initial and Periodic Calibration. Before its initial use and
at least semiannually thereafter, calibrate the volume metering system
as described in Method 5, Section 10.3.1, except that the wet test meter
with a capacity of 3.0 liters/rev (0.1 ft\3\/rev) may be used. Other
liquid displacement systems accurate to within 1 percent,
may be used as calibration standards.

Note: Procedures and equipment specified in Method 5, Section 16.0,
for alternative calibration standards, including calibrated dry gas
meters and critical orifices, are allowed for calibrating the dry gas
meter in the sampling train. A dry gas meter used as a calibration
standard shall be recalibrated at least once annually.

10.2.2 Calibration After Use. After each certification or audit
test (four or more test runs conducted on a wood heater at the four burn
rates specified in Method 28), check calibration of the metering system
by performing three calibration runs at a single, intermediate flow rate
as described in Method 5, Section 10.3.2.

[[Page 219]]

Note: Procedures and equipment specified in Method 5, Section 16.0,
for alternative calibration standards are allowed for the post-test dry
gas meter calibration check.

10.2.3 Acceptable Variation in Calibration. If the dry gas meter
coefficient values obtained before and after a certification test differ
by more than 5 percent, the certification test shall either be voided
and repeated, or calculations for the certification test shall be
performed using whichever meter coefficient value (i.e., before or
after) gives the lower value of total sample volume.
10.3 Temperature Sensors. Use the procedure in Method 2, Section
10.3, to calibrate temperature sensors before the first certification or
audit test and at least semiannually, thereafter.
10.4 Barometer. Calibrate against a mercury barometer before the
first certification test and at least semiannually, thereafter. If a
mercury barometer is used, no calibration is necessary. Follow the
manufacturer's instructions for operation.
10.5 Analytical Balance. Perform a multipoint calibration (at least
five points spanning the operational range) of the analytical balance
before the first certification test and semiannually, thereafter. Before
each certification test, audit the balance by weighing at least one
calibration weight (class F) that corresponds to 50 to 150 percent of
the weight of one filter. If the scale cannot reproduce the value of the
calibration weight to within 0.1 mg, conduct the multipoint calibration
before use.

11.0 Analytical Procedure

11.1 Record the data required on a sheet such as the one shown in
Figure 5G-4. Use the same analytical balance for determining tare
weights and final sample weights.
11.2 Handle each sample container as follows:
11.2.1 Container Nos. 1 and 1A. Treat the two filters according to
the procedures outlined in Method 5, Section 11.2.1.
11.2.2 Container No. 2. Same as Method 5, Section 11.2.2, except
that the beaker may be smaller than 250 ml.
11.2.3 Acetone Blank Container. Same as Method 5, Section 11.2.4,
except that the beaker may be smaller than 250 ml.

12.0 Data Analysis and Calculations

Bws = Water vapor in the gas stream, proportion by volume
(assumed to be 0.04).
cs = Concentration of particulate matter in stack gas, dry
basis, corrected to standard conditions, g/dscm (gr/dscf).
E = Particulate emission rate, g/hr (lb/hr).
Eadj = Adjusted particulate emission rate, g/hr (lb/hr).
La = Maximum acceptable leakage rate for either a pretest or
post-test leak-check, equal to 0.00057 m\3\/min (0.020 cfm) or
4 percent of the average sampling rate, whichever is less.
Lp = Leakage rate observed during the post-test leak-check,
m\3\/min (cfm).
ma = Mass of residue of acetone blank after evaporation, mg.
maw = Mass of residue from acetone wash after evaporation,
mg.
mn = Total amount of particulate matter collected, mg.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in.
Hg).
PR = Percent of proportional sampling rate.
Ps = Absolute gas pressure in dilution tunnel, mm Hg (in.
Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
Qsd = Average gas flow rate in dilution tunnel, calculated as
in Method 2, Equation 2-8, dscm/hr (dscf/hr).
Tm = Absolute average dry gas meter temperature (see Figure
5G-3), deg.K ( deg.R).
Tmi = Absolute average dry gas meter temperature during each
10-minute interval, i, of the test run, deg.K ( deg.R).
Ts = Absolute average gas temperature in the dilution tunnel
(see Figure 5G-3), deg.K ( deg.R).
Tsi = Absolute average gas temperature in the dilution tunnel
during each 10 minute interval, i, of the test run, deg.K
( deg.R).
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Va = Volume of acetone blank, ml.
Vaw = Volume of acetone used in wash, ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm
(dcf).
Vmi = Volume of gas sample as measured by dry gas meter
during each 10-minute interval, i, of the test run, dcm.
Vm(std) = Volume of gas sample measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vs = Average gas velocity in the dilution tunnel, calculated
by Method 2, Equation 2-7, m/sec (ft/sec). The dilution tunnel
dry gas molecular weight may be assumed to be 29 g/g mole (lb/
lb mole).
Vsi = Average gas velocity in dilution tunnel during each 10-
minute interval, i, of the test run, calculated by Method 2,
Equation 2-7, m/sec (ft/sec).
Y = Dry gas meter calibration factor.
H = Average pressure differential across the orifice meter, if
used (see Figure 5G-2), mm H\2\O (in. H\2\O).

[[Page 220]]

U = Total sampling time, min.
10 = 10 minutes, length of first sampling period.
13.6 = Specific gravity of mercury.
100 = Conversion to percent.
12.2 Dry Gas Volume. Same as Method 5, Section 12.2, except that
component changes are not allowable.
12.3 Solvent Wash Blank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.159

12.4 Total Particulate Weight. Determine the total particulate
catch, mn, from the sum of the weights obtained from Container Nos. 1,
1A, and 2, less the acetone blank (see Figure 5G-4).
12.5 Particulate Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.160

Where:
K2 = 0.001 g/mg for metric units.
= 0.0154 gr/mg for English units.
12.6 Particulate Emission Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.161

Note: Particulate emission rate results produced using the sampling
train described in Section 6 and shown in Figure 5G-1 shall be adjusted
for reporting purposes by the following method adjustment factor:
[GRAPHIC] [TIFF OMITTED] TR17OC00.162

Where:

K3 = constant, 1.82 for metric units.
= constant, 0.643 for English units.

12.7 Proportional Rate Variation. Calculate PR for each 10-minute
interval, i, of the test run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.163

Alternate calculation procedures for proportional rate variation may
be used if other sample flow rate data (e.g., orifice flow meters or
rotameters) are monitored to maintain proportional sampling rates. The
proportional rate variations shall be calculated for each 10-minute
interval by comparing the stack to nozzle velocity ratio for each 10-
minute interval to the average stack to nozzle velocity ratio for the
test run. Proportional rate variation may be calculated for intervals
shorter than 10 minutes with appropriate revisions to Equation 5G-5. If
no more than 10 percent of the PR values for all the intervals exceed 90
percent PR 110 percent, and if no PR value for
any interval exceeds 80 percent PR 120 percent,
the results are acceptable. If the PR values for the test run are judged
to be unacceptable, report the test run emission results, but do not
include the results in calculating the weighted average emission rate,
and repeat the test run.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 Method 5H Sampling Train. The sampling train and sample
collection, recovery, and analysis procedures described in Method 5H,
Sections 6.1.1, 7.1, 7.2, 8.1, 8.10, 8.11, and 11.0, respectively, may
be used in lieu of similar sections in Method 5G. Operation of the
Method 5H sampling train in the dilution tunnel is as described in
Section 8.10 of this method. Filter temperatures and condenser
conditions are as described in Method 5H. No adjustment to the measured
particulate matter emission rate (Equation 5G-4, Section 12.6) is to be
applied to the particulate emission rate measured by this alternative
method.
16.2 Dual Sampling Trains. Two sampling trains may be operated
simultaneously at sample flow rates other than that specified in Section
8.10, provided that the following specifications are met.
16.2.1 Sampling Train. The sampling train configuration shall be
the same as specified in Section 6.1.1, except the probe, filter, and
filter holder need not be the same sizes as specified in the applicable
sections. Filter holders of plastic materials such as Nalgene or
polycarbonate materials may be used (the Gelman 1119 filter holder has
been found suitable for this purpose). With such materials, it is
recommended that solvents not be used in sample recovery. The filter
face velocity shall not exceed 150 mm/sec (30 ft/min) during the test
run. The dry gas meter shall be calibrated for the same flow rate range
as

[[Page 221]]

encountered during the test runs. Two separate, complete sampling trains
are required for each test run.
16.2.2 Probe Location. Locate the two probes in the dilution tunnel
at the same level (see Section 6.1.4.3). Two sample ports are necessary.
Locate the probe inlets within the 50 mm (2 in.) diameter centroidal
area of the dilution tunnel no closer than 25 mm (1 in.) apart.
16.2.3 Sampling Train Operation. Operate the sampling trains as
specified in Section 8.10, maintaining proportional sampling rates and
starting and stopping the two sampling trains simultaneously. The pitot
values as described in Section 8.5.2 shall be used to adjust sampling
rates in both sampling trains.
16.2.4 Recovery and Analysis of Sample. Recover and analyze the
samples from the two sampling trains separately, as specified in
Sections 8.12 and 11.0, respectively.
16.2.4.1 For this alternative procedure, the probe and filter
holder assembly may be weighed without sample recovery (use no solvents)
described above in order to determine the sample weight gains. For this
approach, weigh the clean, dry probe and filter holder assembly upstream
of the front filter (without filters) to the nearest 0.1 mg to establish
the tare weights. The filter holder section between the front and second
filter need not be weighed. At the end of the test run, carefully clean
the outside of the probe, cap the ends, and identify the sample (label).
Remove the filters from the filter holder assemblies as described for
container Nos. 1 and 1A in Section 8.12.2.1. Reassemble the filter
holder assembly, cap the ends, identify the sample (label), and transfer
all the samples to the laboratory weighing area for final weighing.
Requirements for capping and transport of sample containers are not
applicable if sample recovery and analysis occur in the same room.
16.2.4.2 For this alternative procedure, filters may be weighed
directly without a petri dish. If the probe and filter holder assembly
are to be weighed to determine the sample weight, rinse the probe with
acetone to remove moisture before desiccating prior to the test run.
Following the test run, transport the probe and filter holder to the
desiccator, and uncap the openings of the probe and the filter holder
assembly. Desiccate for 24 hours and weigh to a constant weight. Report
the results to the nearest 0.1 mg.
16.2.5 Calculations. Calculate an emission rate (Section 12.6) for
the sample from each sampling train separately and determine the average
emission rate for the two values. The two emission rates shall not
differ by more than 7.5 percent from the average emission rate, or 7.5
percent of the weighted average emission rate limit in the applicable
subpart of the regulations, whichever is greater. If this specification
is not met, the results are unacceptable. Report the results, but do not
include the results in calculating the weighted average emission rate.
Repeat the test run until acceptable results are achieved, report the
average emission rate for the acceptable test run, and use the average
in calculating the weighted average emission rate.

17.0 References

Same as Method 5, Section 17.0, References 1 through 11, with the
addition of the following:

1. Oregon Department of Environmental Quality. Standard Method for
Measuring the Emissions and Efficiencies of Woodstoves. June 8, 1984.
Pursuant to Oregon Administrative Rules Chapter 340, Division 21.
2. American Society for Testing and Materials. Proposed Test Methods
for Heating Performance and Emissions of Residential Wood-fired Closed
Combustion-Chamber Heating Appliances. E-6 Proposal P 180. August 1986.

[[Page 222]]

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.164

[[Page 223]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.165

[[Page 224]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.166

[[Page 225]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.167

Method 5H--Determination of Particulate Matter Emissions From Wood
Heaters From a Stack Location

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 2, Method 3, Method 5,
Method 5G, Method 6, Method 6C, Method 16A, and Method 28.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

[[Page 226]]

1.2 Applicability. This method is applicable for the determination
of PM and condensible emissions from wood heaters.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter is withdrawn proportionally from the wood
heater exhaust and is collected on two glass fiber filters separated by
impingers immersed in an ice water bath. The first filter is maintained
at a temperature of no greater than 120 deg.C (248 deg.F). The second
filter and the impinger system are cooled such that the temperature of
the gas exiting the second filter is no greater than 20 deg.C (68
deg.F). The particulate mass collected in the probe, on the filters, and
in the impingers is determined gravimetrically after the removal of
uncombined water.

3.0 Definitions

Same as in Method 6C, Section 3.0.

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are required for sample
collection:
6.1.1 Sampling Train. The sampling train configuration is shown in
Figure 5H-1. Same as Method 5, Section 6.1.1, with the exception of the
following:
6.1.1.1 Probe Nozzle. The nozzle is optional; a straight sampling
probe without a nozzle is an acceptable alternative.
6.1.1.2 Probe Liner. Same as Method 5, Section 6.1.1.2, except that
the maximum length of the sample probe shall be 0.6 m (2 ft) and probe
heating is optional.
6.1.1.3 Filter Holders. Two each of borosilicate glass, with a
glass frit or stainless steel filter support and a silicone rubber,
Teflon, or Viton gasket. The holder design shall provide a positive seal
against leakage from the outside or around the filter. The front filter
holder shall be attached immediately at the outlet of the probe and
prior to the first impinger. The second filter holder shall be attached
on the outlet of the third impinger and prior to the inlet of the fourth
(silica gel) impinger.
6.1.2 Barometer. Same as Method 5, Section 6.2.
6.1.3 Stack Gas Flow Rate Measurement System. A schematic of an
example test system is shown in Figure 5H-2. The flow rate measurement
system consists of the following components:
6.1.3.1 Sample Probe. A glass or stainless steel sampling probe.
6.1.3.2 Gas Conditioning System. A high density filter to remove
particulate matter and a condenser capable of lowering the dew point of
the gas to less than 5 deg.C (40 deg.F). Desiccant, such as Drierite,
may be used to dry the sample gas. Do not use silica gel.
6.1.3.3 Pump. An inert (e.g., Teflon or stainless steel heads)
sampling pump capable of delivering more than the total amount of sample
required in the manufacturer's instructions for the individual
instruments. A means of controlling the analyzer flow rate and a device
for determining proper sample flow rate (e.g., precision rotameter,
pressure gauge downstream of all flow controls) shall be provided at the
analyzer. The requirements for measuring and controlling the analyzer
flow rate are not applicable if data are presented that demonstrate that
the analyzer is insensitive to flow variations over the range
encountered during the test.
6.1.3.4 Carbon Monoxide (CO) Analyzer. Any analyzer capable of
providing a measure of CO in the range of 0 to 10 percent by volume at
least once every 10 minutes.
6.1.3.5 Carbon Dioxide (CO2) Analyzer. Any analyzer
capable of providing a measure of CO2 in the range of 0 to 25
percent by volume at least once every 10 minutes.

Note: Analyzers with ranges less than those specified above may be
used provided actual concentrations do not exceed the range of the
analyzer.

6.1.3.6 Manifold. A sampling tube capable of delivering the sample
gas to two analyzers and handling an excess of the total amount used by
the analyzers. The excess gas is exhausted through a separate port.
6.1.3.7 Recorders (optional). To provide a permanent record of the
analyzer outputs.
6.1.4 Proportional Gas Flow Rate System. To monitor stack flow rate
changes and provide a measurement that can be used to adjust and
maintain particulate sampling flow rates proportional to the stack gas
flow rate. A schematic of the proportional flow rate system is shown in
Figure 5H-2 and consists of the following components:
6.1.4.1 Tracer Gas Injection System. To inject a known
concentration of sulfur dioxide (SO2) into the flue. The
tracer gas injection system consists of a cylinder of SO2, a
gas cylinder regulator, a stainless steel needle valve or flow
controller, a nonreactive (stainless steel and glass) rotameter, and an
injection loop to disperse the SO2 evenly in the flue.

[[Page 227]]

6.1.4.2 Sample Probe. A glass or stainless steel sampling probe.
6.1.4.3 Gas Conditioning System. A combustor as described in Method
16A, Sections 6.1.5 and 6.1.6, followed by a high density filter to
remove particulate matter, and a condenser capable of lowering the dew
point of the gas to less than 5 deg.C (40 deg.F). Desiccant, such as
Drierite, may be used to dry the sample gas. Do not use silica gel.
6.1.4.4 Pump. Same as described in Section 6.1.3.3.
6.1.4.5 SO2 Analyzer. Any analyzer capable of providing
a measure of the SO2 concentration in the range of 0 to 1,000
ppm by volume (or other range necessary to measure the SO2
concentration) at least once every 10 minutes.
6.1.4.6 Recorder (optional). To provide a permanent record of the
analyzer outputs.

Note: Other tracer gas systems, including helium gas systems, are
acceptable for determination of instantaneous proportional sampling
rates.

6.2 Sample Recovery. Same as Method 5, Section 6.2.
6.3 Sample Analysis. Same as Method 5, Section 6.3, with the
addition of the following:
6.3.1 Separatory Funnel. Glass or Teflon, 500-ml or greater.

7.0 Reagents and Standards

7.1 Sample Collection. Same as Method 5, Section 7.1, including
deionized distilled water.
7.2 Sample Recovery. Same as Method 5, Section 7.2.
7.3 Sample Analysis. The following reagents and standards are
required for sample analysis:
7.3.1 Acetone. Same as Method 5 Section 7.2.
7.3.2 Dichloromethane (Methylene Chloride). Reagent grade, 0.001
percent residue in glass bottles.
7.3.3 Desiccant. Anhydrous calcium sulfate, calcium chloride, or
silica gel, indicating type.
7.3.4 Cylinder Gases. For the purposes of this procedure, span
value is defined as the upper limit of the range specified for each
analyzer as described in Section 6.1.3.4 or 6.1.3.5. If an analyzer with
a range different from that specified in this method is used, the span
value shall be equal to the upper limit of the range for the analyzer
used (see Note in Section 6.1.3.5).
7.3.4.1 Calibration Gases. The calibration gases for the
CO2, CO, and SO2 analyzers shall be CO2
in nitrogen (N2), CO in N2, and SO2 in
N2, respectively. CO2 and CO calibration gases may
be combined in a single cylinder. Use three calibration gases as
specified in Method 6C, Sections 7.2.1 through 7.2.3.
7.3.4.2 SO2 Injection Gas. A known concentration of
SO2 in N2. The concentration must be at least 2
percent SO2 with a maximum of 100 percent SO2.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Pretest Preparation. Same as Method 5, Section 8.1.
8.2 Calibration Gas and SO2 Injection Gas Concentration
Verification, Sampling System Bias Check, Response Time Test, and Zero
and Calibration Drift Tests. Same as Method 6C, Sections 8.2.1, 8.2.3,
8.2.4, and 8.5, respectively, except that for verification of CO and
CO2 gas concentrations, substitute Method 3 for Method 6.
8.3 Preliminary Determinations.
8.3.1 Sampling Location. The sampling location for the particulate
sampling probe shall be 2.45 0.15 m (8 0.5 ft)
above the platform upon which the wood heater is placed (i.e., the top
of the scale).
8.3.2 Sampling Probe and Nozzle. Select a nozzle, if used, sized
for the range of velocity heads, such that it is not necessary to change
the nozzle size in order to maintain proportional sampling rates. During
the run, do not change the nozzle size. Select a suitable probe liner
and probe length to effect minimum blockage.
8.4 Preparation of Particulate Sampling Train. Same as Method 5,
Section 8.3, with the exception of the following:
8.4.1 The train should be assembled as shown in Figure 5H-1.
8.4.2 A glass cyclone may not be used between the probe and filter
holder.
8.5 Leak-Check Procedures.
8.5.1 Leak-Check of Metering System Shown in Figure 5H-1. That
portion of the sampling train from the pump to the orifice meter shall
be leak-checked after each certification or audit test. Use the
procedure described in Method 5, Section 8.4.1.
8.5.2 Pretest Leak-Check. A pretest leak-check of the sampling
train is recommended, but not required. If the pretest leak-check is
conducted, the procedures outlined in Method 5, Section 8.5.2 should be
used. A vacuum of 130 mm Hg (5 in. Hg) may be used instead of 380 mm Hg
(15 in. Hg).
8.5.2 Leak-Checks During Sample Run. If, during the sampling run, a
component (e.g., filter assembly or impinger) change becomes necessary,
conduct a leak-check as described in Method 5, Section 8.4.3.
8.5.3 Post-Test Leak-Check. A leak-check is mandatory at the
conclusion of each sampling run. The leak-check shall be performed in
accordance with the procedures outlined in Method 5, Section 8.4.4,
except that a vacuum of 130 mm Hg (5 in. Hg) or the greatest vacuum
measured during the test run, whichever is greater, may be used instead
of 380 mm Hg (15 in. Hg).

[[Page 228]]

8.6 Tracer Gas Procedure. A schematic of the tracer gas injection
and sampling systems is shown in Figure 5H-2.
8.6.1 SO2 Injection Probe. Install the SO2
injection probe and dispersion loop in the stack at a location 2.9
0.15 m (9.5 0.5 ft) above the sampling
platform.
8.6.2 SO2 Sampling Probe. Install the SO2
sampling probe at the centroid of the stack at a location 4.1
0.15 m (13.5 0.5 ft) above the sampling
platform.
8.7 Flow Rate Measurement System. A schematic of the flow rate
measurement system is shown in Figure 5H-2. Locate the flow rate
measurement sampling probe at the centroid of the stack at a location
2.3 0.3 m (7.5 1 ft) above the sampling
platform.
8.8 Tracer Gas Procedure. Within 1 minute after closing the wood
heater door at the start of the test run (as defined in Method 28,
Section 8.8.1), meter a known concentration of SO2 tracer gas
at a constant flow rate into the wood heater stack. Monitor the
SO2 concentration in the stack, and record the SO2
concentrations at 10-minute intervals or more often. Adjust the
particulate sampling flow rate proportionally to the SO2
concentration changes using Equation 5H-6 (e.g., the SO2
concentration at the first 10-minute reading is measured to be 100 ppm;
the next 10 minute SO2 concentration is measured to be 75
ppm: the particulate sample flow rate is adjusted from the initial 0.15
cfm to 0.20 cfm). A check for proportional rate variation shall be made
at the completion of the test run using Equation 5H-10.
8.9 Volumetric Flow Rate Procedure. Apply stoichiometric
relationships to the wood combustion process in determining the exhaust
gas flow rate as follows:
8.9.1 Test Fuel Charge Weight. Record the test fuel charge weight
(wet) as specified in Method 28, Section 8.8.2. The wood is assumed to
have the following weight percent composition: 51 percent carbon, 7.3
percent hydrogen, 41 percent oxygen. Record the wood moisture for each
fuel charge as described in Method 28, Section 8.6.5. The ash is assumed
to have negligible effect on associated C, H, and O concentrations after
the test burn.
8.9.2 Measured Values. Record the CO and CO2
concentrations in the stack on a dry basis every 10 minutes during the
test run or more often. Average these values for the test run. Use as a
mole fraction (e.g., 10 percent CO2 is recorded as 0.10) in
the calculations to express total flow (see Equation 5H-6).
8.10 Sampling Train Operation.
8.10.1 For each run, record the data required on a data sheet such
as the one shown in Figure 5H-3. Be sure to record the initial dry gas
meter reading. Record the dry gas meter readings at the beginning and
end of each sampling time increment, when changes in flow rates are
made, before and after each leak-check, and when sampling is halted.
Take other readings as indicated on Figure 5H-3 at least once each 10
minutes during the test run.
8.10.2 Remove the nozzle cap, verify that the filter and probe
heating systems are up to temperature, and that the probe is properly
positioned. Position the nozzle, if used, facing into gas stream, or the
probe tip in the 50 mm (2 in.) centroidal area of the stack.
8.10.3 Be careful not to bump the probe tip into the stack wall
when removing or inserting the probe through the porthole; this
minimizes the chance of extracting deposited material.
8.10.4 When the probe is in position, block off the openings around
the probe and porthole to prevent unrepresentative dilution of the gas
stream.
8.10.5 Begin sampling at the start of the test run as defined in
Method 28, Section 8.8.1, start the sample pump, and adjust the sample
flow rate to between 0.003 and 0.014 m\3\/min (0.1 and 0.5 cfm). Adjust
the sample flow rate proportionally to the stack gas flow during the
test run according to the procedures outlined in Section 8. Maintain a
proportional sampling rate (within 10 percent of the desired value) and
a filter holder temperature no greater than 120 deg.C (248 deg.F).
8.10.6 During the test run, make periodic adjustments to keep the
temperature around the filter holder at the proper level. Add more ice
to the impinger box and, if necessary, salt to maintain a temperature of
less than 20 deg.C (68 deg.F) at the condenser/silica gel outlet.
8.10.7 If the pressure drop across the filter becomes too high,
making proportional sampling difficult to maintain, either filter may be
replaced during a sample run. It is recommended that another complete
filter assembly be used rather than attempting to change the filter
itself. Before a new filter assembly is installed, conduct a leak-check
(see Section 8.5.2). The total particulate weight shall include the
summation of all filter assembly catches. The total time for changing
sample train components shall not exceed 10 minutes. No more than one
component change is allowed for any test run.
8.10.8 At the end of the test run, turn off the coarse adjust
valve, remove the probe and nozzle from the stack, turn off the pump,
record the final dry gas meter reading, and conduct a post-test leak-
check, as outlined in Section 8.5.3.
8.11 Sample Recovery. Same as Method 5, Section 8.7, with the
exception of the following:
8.11.1 Blanks. The volume of the acetone blank may be about 50-ml,
rather than 200-ml; a 200-ml water blank shall also be saved for
analysis.
8.11.2 Samples.

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8.11.2.1 Container Nos. 1 and 1A. Treat the two filters according
to the procedures outlined in Method 5, Section 8.7.6.1. The filters may
be stored either in a single container or in separate containers.
8.11.2.2 Container No. 2. Same as Method 5, Section 8.7.6.2, except
that the container should not be sealed until the impinger rinse
solution is added (see Section 8.10.2.4).
8.11.2.3 Container No. 3. Treat the impingers as follows: Measure
the liquid which is in the first three impingers to within 1-ml by using
a graduated cylinder or by weighing it to within 0.5 g by using a
balance (if one is available). Record the volume or weight of liquid
present. This information is required to calculate the moisture content
of the effluent gas. Transfer the water from the first, second, and
third impingers to a glass container. Tighten the lid on the sample
container so that water will not leak out.
8.11.2.4 Rinse impingers and graduated cylinder, if used, with
acetone three times or more. Avoid direct contact between the acetone
and any stopcock grease or collection of any stopcock grease in the
rinse solutions. Add these rinse solutions to sample Container No. 2.
8.11.2.5 Container No. 4. Same as Method 5, Section 8.7.6.3
8.12 Sample Transport. Whenever possible, containers should be
transferred in such a way that they remain upright at all times.

Note: Requirements for capping and transport of sample containers
are not applicable if sample recovery and analysis occur in the same
room.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.2........................... Sampling system Ensures that bias
bias check. introduced by
measurement system,
minus analyzer, is
no greater than 3
percent of span.
8.2........................... Analyzer zero and Ensures that bias
calibration introduced by drift
drift tests. in the measurement
system output during
the run is no
greater than 3
percent of span.
8.5, 10.1, 12.13.............. Sampling Ensures accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration; sample volume.
proportional
sampling rate
verification.
10.1.......................... Analytical Ensure accurate and
balance precise measurement
calibration. of collected
particulate.
10.3.......................... Analyzer Ensures that bias
calibration introduced by
error check. analyzer calibration
error is no greater
than 2 percent of
span.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory record of all calibrations.

10.1 Volume Metering System, Temperature Sensors, Barometer, and
Analytical Balance. Same as Method 5G, Sections 10.2 through 10.5,
respectively.
10.2 SO2 Injection Rotameter. Calibrate the
SO2 injection rotameter system with a soap film flowmeter or
similar direct volume measuring device with an accuracy of 2 percent.
Operate the rotameter at a single reading for at least three calibration
runs for 10 minutes each. When three consecutive calibration flow rates
agree within 5 percent, average the three flow rates, mark the rotameter
at the calibrated setting, and use the calibration flow rate as the
SO2 injection flow rate during the test run. Repeat the
rotameter calibration before the first certification test and
semiannually thereafter.
10.3. Gas Analyzers. Same as Method 6C, Section 10.0.

11.0 Analytical Procedure

11.1 Record the data required on a sheet such as the one shown in
Figure 5H-4.
11.2 Handle each sample container as follows:
11.2.1 Container Nos. 1 and 1A. Treat the two filters according to
the procedures outlined in Method 5, Section 11.2.1.
11.2.2 Container No. 2. Same as Method 5, Section 11.2.2, except
that the beaker may be smaller than 250-ml.
11.2.3 Container No. 3. Note the level of liquid in the container
and confirm on the analysis sheet whether leakage occurred during
transport. If a noticeable amount of leakage has occurred, either void
the sample or use methods, subject to the approval of the Administrator,
to correct the final results. Determination of sample leakage is not
applicable if sample recovery and analysis occur in the same room.
Measure the liquid in this container either volumetrically to within 1-
ml or gravimetrically to within 0.5 g. Transfer the contents to a 500-ml
or larger separatory funnel. Rinse the container with water, and add to
the separatory funnel. Add 25-ml of dichloromethane to the separatory
funnel, stopper and vigorously shake 1 minute, let

[[Page 230]]

separate and transfer the dichloromethane (lower layer) into a tared
beaker or evaporating dish. Repeat twice more. It is necessary to rinse
Container No. 3 with dichloromethane. This rinse is added to the
impinger extract container. Transfer the remaining water from the
separatory funnel to a tared beaker or evaporating dish and evaporate to
dryness at 104 deg.C (220 deg.F). Desiccate and weigh to a constant
weight. Evaporate the combined impinger water extracts at ambient
temperature and pressure. Desiccate and weigh to a constant weight.
Report both results to the nearest 0.1 mg.
11.2.4 Container No. 4. Weigh the spent silica gel (or silica gel
plus impinger) to the nearest 0.5 g using a balance.
11.2.5 Acetone Blank Container. Same as Method 5, Section 11.2.4,
except that the beaker may be smaller than 250 ml.
11.2.6 Dichloromethane Blank Container. Treat the same as the
acetone blank.
11.2.7 Water Blank Container. Transfer the water to a tared 250 ml
beaker and evaporate to dryness at 104 deg.C (220 deg.F). Desiccate
and weigh to a constant weight.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

a = Sample flow rate adjustment factor.
BR = Dry wood burn rate, kg/hr (lb/hr), from Method 28, Section 8.3.
Bws = Water vapor in the gas stream, proportion by volume.
Cs = Concentration of particulate matter in stack gas, dry
basis, corrected to standard conditions, g/dscm (g/dscf).
E = Particulate emission rate, g/hr (lb/hr).
H = Average pressure differential across the orifice meter (see
Figure 5H-1), mm H2O (in. H2O).
La = Maximum acceptable leakage rate for either a post-test
leak-check or for a leak-check following a component change;
equal to 0.00057 cmm (0.020 cfm) or 4 percent of the average
sampling rate, whichever is less.
L1 = Individual leakage rate observed during the leak-check
conducted before a component change, cmm (cfm).
Lp = Leakage rate observed during the post-test leak-check,
cmm (cfm).
mn = Total amount of particulate matter collected, mg.
Ma = Mass of residue of solvent after evaporation, mg.
NC = Grams of carbon/gram of dry fuel (lb/lb), equal to
0.0425.
NT = Total dry moles of exhaust gas/kg of dry wood burned, g-
moles/kg (lb-moles/lb).
PR = Percent of proportional sampling rate.
Pbar = Barometric pressure at the sampling site, mm Hg
(in.Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in.Hg).
Qsd = Total gas flow rate, dscm/hr (dscf/hr).
S1 = Concentration measured at the SO2 analyzer
for the first 10-minute interval, ppm.
Si = Concentration measured at the SO2 analyzer
for the ``ith'' 10 minute interval, ppm.
Tm = Absolute average dry gas meter temperature (see Figure
5H-3), deg.K ( deg.R).
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Va = volume of solvent blank, ml.
Vaw = Volume of solvent used in wash, ml.
Vlc = Total volume of liquid collected in impingers and
silica gel (see Figure 5H-4), ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm
(dcf).
Vm(std) = Volume of gas sample measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vmi(std) = Volume of gas sample measured by the dry gas meter
during the ``ith'' 10-minute interval, dscm (dscf).
Vw(std) = Volume of water vapor in the gas sample, corrected
to standard conditions, scm (scf).
Wa = Weight of residue in solvent wash, mg.
Y = Dry gas meter calibration factor.
YCO = Measured mole fraction of CO (dry), average from
Section 8.2, g/g-mole (lb/lb-mole).
YCO2 = Measured mole fraction of CO2 (dry),
average from Section 8.2, g/g-mole (lb/lb-mole).
YHC = Assumed mole fraction of HC (dry), g/g-mole (lb/lb-
mole); = 0.0088 for catalytic wood heaters; = 0.0132 for non-
catalytic wood heaters; = 0.0080 for pellet-fired wood
heaters.
10 = Length of first sampling period, min.
13.6 = Specific gravity of mercury.
100 = Conversion to percent.
= Total sampling time, min.
1 = Sampling time interval, from the beginning of a
run until the first component change, min.
12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 5H-3).
12.3 Dry Gas Volume. Same as Method 5, Section 12.3.
12.4 Volume of Water Vapor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.168

Where:

K2 = 0.001333 m³/ml for metric units.
K2 = 0.04707 ft³/ml for English units.

12.5 Moisture Content.

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[GRAPHIC] [TIFF OMITTED] TR17OC00.169

12.6 Solvent Wash Blank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.170

12.7 Total Particulate Weight. Determine the total particulate
catch from the sum of the weights obtained from containers 1, 2, 3, and
4 less the appropriate solvent blanks (see Figure 5H-4).

Note: Refer to Method 5, Section 8.5 to assist in calculation of
results involving two filter assemblies.
12.8 Particulate Concentration.

[GRAPHIC] [TIFF OMITTED] TR17OC00.171

12.9 Sample Flow Rate Adjustment.
[GRAPHIC] [TIFF OMITTED] TR17OC00.172

12.10 Carbon Balance for Total Moles of Exhaust Gas (dry)/kg of
Wood Burned in the Exhaust Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.173

Where:

K3 = 1000 g/kg for metric units.
K3 = 1.0 lb/lb for English units.
Note: The NOX/SOX portion of the gas is
assumed to be negligible.

12.11 Total Stack Gas Flow Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.174

Where:
K4 = 0.02406 dscm/g-mole for metric units.
K4 = 384.8 dscf/lb-mole for English units.
12.12 Particulate Emission Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.175

12.13 Proportional Rate Variation. Calculate PR for each 10-minute
interval, i, of the test run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.176

12.14 Acceptable Results. If no more than 15 percent of the PR
values for all the intervals fall outside the range 90 percent
PR 110 percent, and if no PR value for any
interval falls outside the range 75 PR 125
percent, the results are acceptable. If the PR values for the test runs
are judged to be unacceptable, report the test run emission results, but
do not include the test run results in calculating the weighted average
emission rate, and repeat the test.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Method 5G, Section 17.0.

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17.0 Tables, Diagrams, Flowcharts, and Validation Data
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[GRAPHIC] [TIFF OMITTED] TR17OC00.178

[[Page 234]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.179

[[Page 235]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.180

Method 5I--Determination of Low Level Particulate Matter Emissions From
Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Certain information is contained in other
EPA procedures found in this part. Therefore, to obtain reliable
results, persons using this method should have experience with and a
thorough knowledge of the following Methods: Methods 1, 2, 3, 4 and 5.

1. Scope and Application.

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

[[Page 236]]

1.2 Applicability. This method is applicable for the determination
of low level particulate matter (PM) emissions from stationary sources.
The method is most effective for total PM catches of 50 mg or less. This
method was initially developed for performing correlation of manual PM
measurements to PM continuous emission monitoring systems (CEMS),
however it is also useful for other low particulate concentration
applications.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods. Method 5I requires the use of paired trains.
Acceptance criteria for the identification of data quality outliers from
the paired trains are provided in Section 12.2 of this Method.

2. Summary of Method.

2.1. Description. The system setup and operation is essentially
identical to Method 5. Particulate is withdrawn isokinetically from the
source and collected on a 47 mm glass fiber filter maintained at a
temperature of 120 14 deg.C (248 25 deg.F).
The PM mass is determined by gravimetric analysis after the removal of
uncombined water. Specific measures in this procedure designed to
improve system performance at low particulate levels include:

1. Improved sample handling procedures
2 Light weight sample filter assembly
3. Use of low residue grade acetone

Accuracy is improved through the minimization of systemic errors
associated with sample handling and weighing procedures. High purity
reagents, all glass, grease free, sample train components, and light
weight filter assemblies and beakers, each contribute to the overall
objective of improved precision and accuracy at low particulate
concentrations.
2.2 Paired Trains. This method must be performed using a paired
train configuration. These trains may be operated as co-located trains
(to trains operating collecting from one port) or as simultaneous trains
(separate trains operating from different ports at the same time).
Procedures for calculating precision of the paired trains are provided
in Section 12.
2.3 Detection Limit. a. Typical detection limit for manual
particulate testing is 0.5 mg. This mass is also cited as the accepted
weight variability limit in determination of ``constant weight'' as
cited in Section 8.1.2 of this Method. EPA has performed studies to
provide guidance on minimum PM catch. The minimum detection limit (MDL)
is the minimum concentration or amount of an analyte that can be
determined with a specified degree of confidence to be different from
zero. We have defined the minimum or target catch as a concentration or
amount sufficiently larger than the MDL to ensure that the results are
reliable and repeatable. The particulate matter catch is the product of
the average particulate matter concentration on a mass per volume basis
and the volume of gas collected by the sample train. The tester can
generally control the volume of gas collected by increasing the sampling
time or to a lesser extent by increasing the rate at which sample is
collected. If the tester has a reasonable estimate of the PM
concentration from the source, the tester can ensure that the target
catch is collected by sampling the appropriate gas volume.
b. However, if the source has a very low particulate matter
concentration in the stack, the volume of gas sampled may need to be
very large which leads to unacceptably long sampling times. When
determining compliance with an emission limit, EPA guidance has been
that the tester does not always have to collect the target catch.
Instead, we have suggested that the tester sample enough stack gas, that
if the source were exactly at the level of the emission standard, the
sample catch would equal the target catch. Thus, if at the end of the
test the catch were smaller than the target, we could still conclude
that the source is in compliance though we might not know the exact
emission level. This volume of gas becomes a target volume that can be
translated into a target sampling time by assuming an average sampling
rate. Because the MDL forms the basis for our guidance on target
sampling times, EPA has conducted a systematic laboratory study to
define what is the MDL for Method 5 and determined the Method to have a
calculated practical quantitation limit (PQL) of 3 mg of PM and an MDL
of 1 mg.
c. Based on these results, the EPA has concluded that for PM
testing, the target catch must be no less than 3 mg. Those sample
catches between 1 mg and 3 mg are between the detection limit and the
limit of quantitation. If a tester uses the target catch to estimate a
target sampling time that results in sample catches that are less than 3
mg, you should not automatically reject the results. If the tester
calculated the target sampling time as described above by assuming that
the source was at the level of the emission limit, the results would
still be valid for determining that the source was in compliance. For
purposes other than determining compliance, results should be divided
into two categories--those that fall between 3 mg and 1 mg and those
that are below 1 mg. A sample catch between 1 and 3 mg may be used for
such purposes as calculating emission rates with the understanding that
the resulting emission rates can have a high degree of uncertainty.
Results of less than 1 mg should not be used for calculating emission
rates or pollutant concentrations.
d. When collecting small catches such as 3 mg, bias becomes an
important issue. Source testers must use extreme caution to reach

[[Page 237]]

the PQL of 3 mg by assuring that sampling probes are very clean (perhaps
confirmed by low blank weights) before use in the field. They should
also use low tare weight sample containers, and establish a well-
controlled balance room to weigh the samples.

3. Definitions.

3.1 Light Weight Filter Housing. A smaller housing that allows the
entire filtering system to be weighed before and after sample
collection. (See. 6.1.3)
3.2 Paired Train. Sample systems trains may be operated as co-
located trains (two sample probes attached to each other in the same
port) or as simultaneous trains (two separate trains operating from
different ports at the same time).

4. Interferences.

a. There are numerous potential interferents that may be encountered
during performance of Method 5I sampling and analyses. This Method
should be considered more sensitive to the normal interferents typically
encountered during particulate testing because of the low level
concentrations of the flue gas stream being sampled.
b. Care must be taken to minimize field contamination, especially to
the filter housing since the entire unit is weighed (not just the filter
media). Care must also be taken to ensure that no sample is lost during
the sampling process (such as during port changes, removal of the filter
assemblies from the probes, etc.).
c. Balance room conditions are a source of concern for analysis of
the low level samples. Relative humidity, ambient temperatures
variations, air draft, vibrations and even barometric pressure can
affect consistent reproducible measurements of the sample media.
Ideally, the same analyst who performs the tare weights should perform
the final weights to minimize the effects of procedural differences
specific to the analysts.
d. Attention must also be provided to weighing artifacts caused by
electrostatic charges which may have to be discharged or neutralized
prior to sample analysis. Static charge can affect consistent and
reliable gravimetric readings in low humidity environments. Method 5I
recommends a relative humidity of less than 50 percent in the weighing
room environment used for sample analyses. However, lower humidity may
be encountered or required to address sample precision problems. Low
humidity conditions can increase the effects of static charge.
e. Other interferences associated with typical Method 5 testing
(sulfates, acid gases, etc.) are also applicable to Method 5I.

5. Safety.

Disclaimer. This method may involve hazardous materials, operations,
and equipment. This test method may not address all of the safety
concerns associated with its use. It is the responsibility of the user
to establish appropriate safety and health practices and to determine
the applicability and observe all regulatory limitations before using
this method.

6. Equipment and Supplies.

6.1 Sample Collection Equipment and Supplies. The sample train is
nearly identical in configuration to the train depicted in Figure 5-1 of
Method 5. The primary difference in the sample trains is the lightweight
Method 5I filter assembly that attaches directly to the exit to the
probe. Other exceptions and additions specific to Method 5I include:
6.1.1 Probe Nozzle. Same as Method 5, with the exception that it
must be constructed of borosilicate or quartz glass tubing.
6.1.2 Probe Liner. Same as Method 5, with the exception that it
must be constructed of borosilicate or quartz glass tubing.
6.1.3 Filter Holder. The filter holder is constructed of
borosilicate or quartz glass front cover designed to hold a 47-mm glass
fiber filter, with a wafer thin stainless steel (SS) filter support, a
silicone rubber or Viton O-ring, and Teflon tape seal. This holder
design will provide a positive seal against leakage from the outside or
around the filter. The filter holder assembly fits into a SS filter
holder and attaches directly to the outlet of the probe. The tare weight
of the filter, borosilicate or quartz glass holder, SS filter support,
O-ring and Teflon tape seal generally will not exceed approximately 35
grams. The filter holder is designed to use a 47-mm glass fiber filter
meeting the quality criteria in of Method 5. These units are
commercially available from several source testing equipment vendors.
Once the filter holder has been assembled, desiccated and tared, protect
it from external sources of contamination by covering the front socket
with a ground glass plug. Secure the plug with an impinger clamp or
other item that will ensure a leak-free fitting.
6.2 Sample Recovery Equipment and Supplies. Same as Method 5, with
the following exceptions:
6.2.1 Probe-Liner and Probe-Nozzle Brushes. Teflon or nylon bristle
brushes with stainless steel wire handles, should be used to clean the
probe. The probe brush must have extensions (at least as long as the
probe) of Teflon, nylon or similarly inert material. The brushes must be
properly sized and shaped for brushing out the probe liner and nozzle.
6.2.2 Wash Bottles. Two Teflon wash bottles are recommended
however, polyethylene wash bottles may be used at the option of the
tester. Acetone should not be stored in

[[Page 238]]

polyethylene bottles for longer than one month.
6.2.3 Filter Assembly Transport. A system should be employed to
minimize contamination of the filter assemblies during transport to and
from the field test location. A carrying case or packet with clean
compartments of sufficient size to accommodate each filter assembly can
be used. This system should have an air tight seal to further minimize
contamination during transport to and from the field.
6.3 Analysis Equipment and Supplies. Same as Method 5, with the
following exception:
6.3.1 Lightweight Beaker Liner. Teflon or other lightweight beaker
liners are used for the analysis of the probe and nozzle rinses. These
light weight liners are used in place of the borosilicate glass beakers
typically used for the Method 5 weighings in order to improve sample
analytical precision.
6.3.2 Anti-static Treatment. Commercially available gaseous anti-
static rinses are recommended for low humidity situations that
contribute to static charge problems.

7. Reagents and Standards.

7.1 Sampling Reagents. The reagents used in sampling are the same
as Method 5 with the following exceptions:
7.1.1 Filters. The quality specifications for the filters are
identical to those cited for Method 5. The only difference is the filter
diameter of 47 millimeters.
7.1.2 Stopcock Grease. Stopcock grease cannot be used with this
sampling train. We recommend that the sampling train be assembled with
glass joints containing O-ring seals or screw-on connectors, or similar.
7.1.3 Acetone. Low residue type acetone, 0.001 percent
residue, purchased in glass bottles is used for the recovery of
particulate matter from the probe and nozzle. Acetone from metal
containers generally has a high residue blank and should not be used.
Sometimes, suppliers transfer acetone to glass bottles from metal
containers; thus, acetone blanks must be run prior to field use and only
acetone with low blank values (0.001 percent residue, as
specified by the manufacturer) must be used. Acetone blank correction is
not allowed for this method; therefore, it is critical that high purity
reagents be purchased and verified prior to use.
7.1.4 Gloves. Disposable, powder-free, latex surgical gloves, or
their equivalent are used at all times when handling the filter housings
or performing sample recovery.
7.2 Standards. There are no applicable standards or audit samples
commercially available for Method 5I analyses.

8. Sample Collection, Preservation, Storage, and Transport.

8.1 Pretest Preparation. Same as Method 5 with several exceptions
specific to filter assembly and weighing.
8.1.1 Filter Assembly. Uniquely identify each filter support before
loading filters into the holder assembly. This can be done with an
engraving tool or a permanent marker. Use powder free latex surgical
gloves whenever handling the filter holder assemblies. Place the O-ring
on the back of the filter housing in the O-ring groove. Place a 47 mm
glass fiber filter on the O-ring with the face down. Place a stainless
steel filter holder against the back of the filter. Carefully wrap 5 mm
(\1/4\ inch) wide Teflon'' tape one timearound the outside of the filter
holder overlapping the stainless steel filter support by approximately
2.5 mm (\1/8\ inch). Gently brush the Teflon tape down on the back of
the stainless steel filter support. Store the filter assemblies in their
transport case until time for weighing or field use.
8.1.2 Filter Weighing Procedures. a. Desiccate the entire filter
holder assemblies at 20 5.6 deg.C (68
10 deg.F) and ambient pressure for at least 24 hours. Weigh at intervals
of at least 6 hours to a constant weight, i.e., 0.5 mg change from
previous weighing. Record the results to the nearest 0.1 mg. During each
weighing, the filter holder assemblies must not be exposed to the
laboratory atmosphere for a period greater than 2 minutes and a relative
humidity above 50 percent. Lower relative humidity may be required in
order to improve analytical precision. However, low humidity conditions
increase static charge to the sample media.
b. Alternatively (unless otherwise specified by the Administrator),
the filters holder assemblies may be oven dried at 105 deg.C (220 deg.F)
for a minimum of 2 hours, desiccated for 2 hours, and weighed. The
procedure used for the tare weigh must also be used for the final weight
determination.
c. Experience has shown that weighing uncertainties are not only
related to the balance performance but to the entire weighing procedure.
Therefore, before performing any measurement, establish and follow
standard operating procedures, taking into account the sampling
equipment and filters to be used.
8.2 Preliminary Determinations. Select the sampling site, traverse
points, probe nozzle, and probe length as specified in Method 5.
8.3 Preparation of Sampling Train. Same as Method 5, Section 8.3,
with the following exception: During preparation and assembly of the
sampling train, keep all openings where contamination can occur covered
until justbefore assembly or until sampling is about to begin. Using
gloves, place a labeled

[[Page 239]]

(identified) and weighed filter holder assembly into the stainless steel
holder. Then place this whole unit in the Method 5 hot box, and attach
it to the probe. Do not use stopcock grease.
8.4 Leak-Check Procedures. Same as Method 5.
8.5 Sampling Train Operation.
8.5.1. Operation. Operate the sampling train in a manner consistent
with those described in Methods 1, 2, 4 and 5 in terms of the number of
sample points and minimum time per point. The sample rate and total gas
volume should be adjusted based on estimated grain loading of the source
being characterized. The total sampling time must be a function of the
estimated mass of particulate to be collected for the run. Targeted mass
to be collected in a typical Method 5I sample train should be on the
order of 10 to 20 mg. Method 5I is most appropriate for total collected
masses of less than 50 milligrams, however, there is not an exact
particulate loading cutoff, and it is likely that some runs may exceed
50 mg. Exceeding 50 mg (or less than 10 mg) for the sample mass does not
necessarily justify invalidating a sample run if all other Method
criteria are met.
8.5.2 Paired Train. This Method requires PM samples be collected
with paired trains.
8.5.2.1 It is important that the systems be operated truly
simultaneously. This implies that both sample systems start and stop at
the same times. This also means that if one sample system is stopped
during the run, the other sample systems must also be stopped until the
cause has been corrected.
8.5.2.2 Care should be taken to maintain the filter box temperature
of the paired trains as close as possible to the Method required
temperature of 120 14 deg.C (248 25 deg.F). If
separate ovens are being used for simultaneously operated trains, it is
recommended that the oven temperature of each train be maintained within
14 deg.C ( 25 deg.F) of each other.
8.5.2.3 The nozzles for paired trains need not be identically
sized.
8.5.2.4 Co-located sample nozzles must be within the same plane
perpendicular to the gas flow. Co-located nozzles and pitot assemblies
should be within a 6.0 cm x 6.0 cm square (as cited for a quadruple
train in Reference Method 301).
8.5.3 Duplicate gas samples for molecular weight determination need
not be collected.
8.6 Sample Recovery. Same as Method 5 with several exceptions
specific to the filter housing.
8.6.1 Before moving the sampling train to the cleanup site, remove
the probe from the train and seal the nozzle inlet and outlet of the
probe. Be careful not to lose any condensate that might be present. Cap
the filter inlet using a standard ground glass plug and secure the cap
with an impinger clamp. Remove the umbilical cord from the last impinger
and cap the impinger. If a flexible line is used between the first
impinger condenser and the filter holder, disconnect the line at the
filter holder and let any condensed water or liquid drain into the
impingers or condenser.
8.6.2 Transfer the probe and filter-impinger assembly to the
cleanup area. This area must be clean and protected from the wind so
that the possibility of losing any of the sample will be minimized.
8.6.3 Inspect the train prior to and during disassembly and note
any abnormal conditions such as particulate color, filter loading,
impinger liquid color, etc.
8.6.4 Container No. 1, Filter Assembly. Carefully remove the cooled
filter holder assembly from the Method 5 hot box and place it in the
transport case. Use a pair of clean gloves to handle the filter holder
assembly.
8.6.5 Container No. 2, Probe Nozzle and Probe Liner Rinse. Rinse
the probe and nozzle components with acetone. Be certain that the probe
and nozzle brushes have been thoroughly rinsed prior to use as they can
be a source of contamination.
8.6.6 All Other Train Components. (Impingers) Same as Method 5.
8.7 Sample Storage and Transport. Whenever possible, containers
should be shipped in such a way that they remain upright at all times.
All appropriate dangerous goods shipping requirements must be observed
since acetone is a flammable liquid.

9. Quality Control.

9.1 Miscellaneous Field Quality Control Measures.
9.1.1 A quality control (QC) check of the volume metering system at
the field site is suggested before collecting the sample using the
procedures in Method 5, Section 4.4.1.
9.1.2 All other quality control checks outlined in Methods 1, 2, 4
and 5 also apply to Method 5I. This includes procedures such as leak-
checks, equipment calibration checks, and independent checks of field
data sheets for reasonableness and completeness.
9.2 Quality Control Samples.
9.2.1 Required QC Sample. A laboratory reagent blank must be
collected and analyzed for each lot of acetone used for a field program
to confirm that it is of suitable purity. The particulate samples cannot
be blank corrected.
9.2.2 Recommended QC Samples. These samples may be collected and
archived for future analyses.
9.2.2.1 A field reagent blank is a recommended QC sample collected
from a portion of the acetone used for cleanup of the probe and nozzle.
Take 100 ml of this acetone directly from the wash bottle being used and
place it in a glass sample container labeled ``field acetone reagent
blank.'' At least one field reagent blank is recommended for every

[[Page 240]]

five runs completed. The field reagent blank samples demonstrate the
purity of the acetone was maintained throughout the program.
9.2.2.2 A field bias blank train is a recommended QC sample. This
sample is collected by recovering a probe and filter assembly that has
been assembled, taken to the sample location, leak checked, heated,
allowed to sit at the sample location for a similar duration of time as
a regular sample run, leak-checked again, and then recovered in the same
manner as a regular sample. Field bias blanks are not a Method
requirement, however, they are recommended and are very useful for
identifying sources of contamination in emission testing samples. Field
bias blank train results greater than 5 times the method detection limit
may be considered problematic.

10. Calibration and Standardization Same as Method 5, Section 5.

11. Analytical Procedures.

11.1 Analysis. Same as Method 5, Sections 11.1--11.2.4, with the
following exceptions:
11.1.1 Container No. 1. Same as Method 5, Section 11.2.1, with the
following exception: Use disposable gloves to remove each of the filter
holder assemblies from the desiccator, transport container, or sample
oven (after appropriate cooling).
11.1.2 Container No. 2. Same as Method 5, Section 11.2.2, with the
following exception: It is recommended that the contents of Container
No. 2 be transferred to a 250 ml beaker with a Teflon liner or similar
container that has a minimal tare weight before bringing to dryness.

12. Data Analysis and Calculations.

12.1 Particulate Emissions. The analytical results cannot be blank
corrected for residual acetone found in any of the blanks. All other
sample calculations are identical to Method 5.
12.2 Paired Trains Outliers. a. Outliers are identified through the
determination of precision and any systemic bias of the paired trains.
Data that do not meet this criteria should be flagged as a data quality
problem. The primary reason for performing dual train sampling is to
generate information to quantify the precision of the Reference Method
data. The relative standard deviation (RSD) of paired data is the
parameter used to quantify data precision. RSD for two simultaneously
gathered data points is determined according to:
[GRAPHIC] [TIFF OMITTED] TR30SE99.008

where, Ca and Cb are concentration values determined from trains A and B
respectively. For RSD calculation, the concentration units are
unimportant so long as they are consistent.
b. A minimum precision criteria for Reference Method PM data is that
RSD for any data pair must be less than 10% as long as the mean PM
concentration is greater than 10 mg/dscm. If the mean PM concentration
is less than 10 mg/dscm higher RSD values are acceptable. At mean PM
concentration of 1 mg/dscm acceptable RSD for paired trains is 25%.
Between 1 and 10 mg/dscm acceptable RSD criteria should be linearly
scaled from 25% to 10%. Pairs of manual method data exceeding these RSD
criteria should be eliminated from the data set used to develop a PM
CEMS correlation or to assess RCA. If the mean PM concentration is less
than 1 mg/dscm, RSD does not apply and the mean result is acceptable.

13. Method Performance. [Reserved]

14. Pollution Prevention. [Reserved]

15. Waste Management. [Reserved]

16. Alternative Procedures. Same as Method 5.

17. Bibliography. Same as Method 5.

18. Tables, Diagrams, Flowcharts and Validation Data. Figure 5I-1 is a
schematic of the sample train.

[[Page 241]]

[GRAPHIC] [TIFF OMITTED] TR30SE99.009

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A see the List of CFR Sections Affected, which appears in the
Finding Aids section of the printed volume and on GPO Access.

[[Page 242]]

Appendix A-4 to Part 60--Test Methods 6 through 10B

Method 6--Determination of sulfur dioxide emissions from stationary
sources
Method 6A--Determination of sulfur dioxide, moisture, and carbon dioxide
emissions from fossil fuel combustion sources
Method 6B--Determination of sulfur dioxide and carbon dioxide daily
average emissions from fossil fuel combustion sources
Method 6C--Determination of Sulfur Dioxide Emissions From Stationary
Sources (Instrumental Analyzer Procedure)
Method 7--Determination of nitrogen oxide emissions from stationary
sources
Method 7A--Determination of nitrogen oxide emissions from stationary
sources--Ion chromatographic method
Method 7B--Determination of nitrogen oxide emissions from stationary
sources (Ultraviolet spectrophotometry)
Method 7C--Determination of nitrogen oxide emissions from stationary
sources--Alkaline-permanganate/colorimetric method
Method 7D--Determination of nitrogen oxide emissions from stationary
sources--Alkaline-permanganate/ion chromatographic method
Method 7E--Determination of Nitrogen Oxides Emissions From Stationary
Sources (Instrumental Analyzer Procedure)
Method 8--Determination of sulfuric acid mist and sulfur dioxide
emissions from stationary sources
Method 9--Visual determination of the opacity of emissions from
stationary sources
Alternate method 1--Determination of the opacity of emissions from
stationary sources remotely by lidar
Method 10--Determination of carbon monoxide emissions from stationary
sources
Method 10A--Determination of carbon monoxide emissions in certifying
continuous emission monitoring systems at petroleum refineries
Method 10B--Determination of carbon monoxide emissions from stationary
sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that

[[Page 243]]

the techniques or alternatives are in fact applicable and are properly
executed; (2) including a written description of the alternative method
in the test report (the written method must be clear and must be capable
of being performed without additional instruction, and the the degree of
detail should be similar to the detail contained in the test methods);
and (3) providing any rationale or supporting data necessary to show the
validity of the alternative in the particular application. Failure to
meet these requirements can result in the Administrator's disapproval of
the alternative.

Method 6--Determination of Sulfur Dioxide Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, and Method 8.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
SO2............................... 7449-09-5 3.4 mg SO2/m³
(2.12 x 10)-7 lb/
ft3
------------------------------------------------------------------------

1.2 Applicability. This method applies to the measurement of sulfur
dioxide (SO²) emissions from stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the sampling point in the stack.
The SO² and the sulfur trioxide, including those fractions in
any sulfur acid mist, are separated. The SO² fraction is
measured by the barium-thorin titration method.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Free Ammonia. Free ammonia interferes with this method by
reacting with SO² to form particulate sulfite and by reacting
with the indicator. If free ammonia is present (this can be determined
by knowledge of the process and/or noticing white particulate matter in
the probe and isopropanol bubbler), alternative methods, subject to the
approval of the Administrator are required. One approved alternative is
listed in Reference 13 of Section 17.0.
4.2 Water-Soluble Cations and Fluorides. The cations and fluorides
are removed by a glass wool filter and an isopropanol bubbler;
therefore, they do not affect the SO2 analysis. When samples
are collected from a gas stream with high concentrations of metallic
fumes (i.e., very fine cation aerosols) a high-efficiency glass fiber
filter must be used in place of the glass wool plug (i.e., the one in
the probe) to remove the cation interferent.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are required for sample
collection:
6.1.1 Sampling Train. A schematic of the sampling train is shown in
Figure 6-1. The sampling equipment described in Method 8 may be
substituted in place of the midget impinger equipment of Method 6.
However, the Method 8 train must be modified to include a heated filter
between the probe and isopropanol impinger, and the operation of the
sampling train and sample analysis must be at the flow rates and
solution volumes defined in Method 8. Alternatively, SO2 may
be determined simultaneously with particulate

[[Page 244]]

matter and moisture determinations by either (1) replacing the water in
a Method 5 impinger system with a 3 percent H2O2
solution, or (2) replacing the Method 5 water impinger system with a
Method 8 isopropanol-filter-H2O2 system. The
analysis for SO2 must be consistent with the procedure of
Method 8. The Method 6 sampling train consists of the following
components:
6.1.1.1 Probe. Borosilicate glass or stainless steel (other
materials of construction may be used, subject to the approval of the
Administrator), approximately 6 mm (0.25 in.) inside diameter, with a
heating system to prevent water condensation and a filter (either in-
stack or heated out-of-stack) to remove particulate matter, including
sulfuric acid mist. A plug of glass wool is a satisfactory filter.
6.1.1.2 Bubbler and Impingers. One midget bubbler with medium-
coarse glass frit and borosilicate or quartz glass wool packed in top
(see Figure 6-1) to prevent sulfuric acid mist carryover, and three 30-
ml midget impingers. The midget bubbler and midget impingers must be
connected in series with leak-free glass connectors. Silicone grease may
be used, if necessary, to prevent leakage. A midget impinger may be used
in place of the midget bubbler.

Note: Other collection absorbers and flow rates may be used, subject
to the approval of the Administrator, but the collection efficiency must
be shown to be at least 99 percent for each test run and must be
documented in the report. If the efficiency is found to be acceptable
after a series of three tests, further documentation is not required. To
conduct the efficiency test, an extra absorber must be added and
analyzed separately. This extra absorber must not contain more than 1
percent of the total SO2.
6.1.1.3 Glass Wool. Borosilicate or quartz.
6.1.1.4 Stopcock Grease. Acetone-insoluble, heat-stable silicone
grease may be used, if necessary.
6.1.1.5 Temperature Sensor. Dial thermometer, or equivalent, to
measure temperature of gas leaving impinger train to within 1 deg.C (2
deg.F).
6.1.1.6 Drying Tube. Tube packed with 6- to 16- mesh indicating-
type silica gel, or equivalent, to dry the gas sample and to protect the
meter and pump. If silica gel is previously used, dry at 177 deg.C (350
deg.F) for 2 hours. New silica gel may be used as received.
Alternatively, other types of desiccants (equivalent or better) may be
used, subject to the approval of the Administrator.
6.1.1.7 Valve. Needle valve, to regulate sample gas flow rate.
6.1.1.8 Pump. Leak-free diaphragm pump, or equivalent, to pull gas
through the train. Install a small surge tank between the pump and rate
meter to negate the pulsation effect of the diaphragm pump on the rate
meter.
6.1.1.9 Rate Meter. Rotameter, or equivalent, capable of measuring
flow rate to within 2 percent of the selected flow rate of about 1
liter/min (0.035 cfm).
6.1.1.10 Volume Meter. Dry gas meter (DGM), sufficiently accurate
to measure the sample volume to within 2 percent, calibrated at the
selected flow rate and conditions actually encountered during sampling,
and equipped with a temperature sensor (dial thermometer, or equivalent)
capable of measuring temperature accurately to within 3 deg.C (5.4
deg.F). A critical orifice may be used in place of the DGM specified in
this section provided that it is selected, calibrated, and used as
specified in Section 16.0.
6.1.2 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). See the
Note in Method 5, Section 6.1.2.
6.1.3 Vacuum Gauge and Rotameter. At least 760-mm Hg (30-in. Hg)
gauge and 0- to 40-ml/min rotameter, to be used for leak-check of the
sampling train.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Wash Bottles. Two polyethylene or glass bottles, 500-ml.
6.2.2 Storage Bottles. Polyethylene bottles, 100-ml, to store
impinger samples (one per sample).
6.3 Sample Analysis. The following equipment is needed for sample
analysis:
6.3.1 Pipettes. Volumetric type, 5-ml, 20-ml (one needed per
sample), and 25-ml sizes.
6.3.2 Volumetric Flasks. 100-ml size (one per sample) and 1000-ml
size.
6.3.3 Burettes. 5- and 50-ml sizes.
6.3.4 Erlenmeyer Flasks. 250-ml size (one for each sample, blank,
and standard).
6.3.5 Dropping Bottle. 125-ml size, to add indicator.
6.3.6 Graduated Cylinder. 100-ml size.
6.3.7 Spectrophotometer. To measure absorbance at 352 nm.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents must conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society. Where such specifications are not
available, use the best available grade.

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Water. Deionized distilled to conform to ASTM Specification D
1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17). The
KMnO4 test for oxidizable organic matter may be omitted when
high concentrations of organic matter are not expected to be present.
7.1.2 Isopropanol, 80 Percent by Volume. Mix 80 ml of isopropanol
with 20 ml of water.

[[Page 245]]

7.1.2.1 Check each lot of isopropanol for peroxide impurities as
follows: Shake 10 ml of isopropanol with 10 ml of freshly prepared 10
percent potassium iodide solution. Prepare a blank by similarly treating
10 ml of water. After 1 minute, read the absorbance at 352 nm on a
spectrophotometer using a 1-cm path length. If absorbance exceeds 0.1,
reject alcohol for use.
7.1.2.2 Peroxides may be removed from isopropanol by redistilling
or by passage through a column of activated alumina; however, reagent
grade isopropanol with suitably low peroxide levels may be obtained from
commercial sources. Rejection of contaminated lots may, therefore, be a
more efficient procedure.
7.1.3 Hydrogen Peroxide (H2O2), 3 Percent by
Volume. Add 10 ml of 30 percent H2O2 to 90 ml of
water. Prepare fresh daily.
7.1.4 Potassium Iodide Solution, 10 Percent Weight by Volume (w/v).
Dissolve 10.0 g of KI in water, and dilute to 100 ml. Prepare when
needed.
7.2 Sample Recovery. The following reagents are required for sample
recovery:
7.2.1 Water. Same as in Section 7.1.1.
7.2.2 Isopropanol, 80 Percent by Volume. Same as in Section 7.1.2.
7.3 Sample Analysis. The following reagents and standards are
required for sample analysis:
7.3.1 Water. Same as in Section 7.1.1.
7.3.2 Isopropanol, 100 Percent.
7.3.3 Thorin Indicator. 1-(o-arsonophenylazo)-2-naphthol-3,6-
disulfonic acid, disodium salt, or equivalent. Dissolve 0.20 g in 100 ml
of water.
7.3.4 Barium Standard Solution, 0.0100 N. Dissolve 1.95 g of barium
perchlorate trihydrate [Ba(ClO4)2 3H2O]
in 200 ml water, and dilute to 1 liter with isopropanol. Alternatively,
1.22 g of barium chloride dihydrate [BaCl2 2H2O]
may be used instead of the barium perchlorate trihydrate. Standardize as
in Section 10.5.
7.3.5 Sulfuric Acid Standard, 0.0100 N. Purchase or standardize to
0.0002 N against 0.0100 N NaOH which has previously been
standardized against potassium acid phthalate (primary standard grade).
7.3.6 Quality Assurance Audit Samples. When making compliance
determinations, audit samples, if available must be obtained from the
appropriate EPA Regional Office or from the responsible enforcement
authority and analyzed in conjunction with the field samples.

Note: The responsible enforcement authority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Storage and Transport

8.1 Preparation of Sampling Train. Measure 15 ml of 80 percent
isopropanol into the midget bubbler and 15 ml of 3 percent
H2O2 into each of the first two midget impingers.
Leave the final midget impinger dry. Assemble the train as shown in
Figure 6-1. Adjust the probe heater to a temperature sufficient to
prevent water condensation. Place crushed ice and water around the
impingers.
8.2 Sampling Train Leak-Check Procedure. A leak-check prior to the
sampling run is recommended, but not required. A leak-check after the
sampling run is mandatory. The leak-check procedure is as follows:
8.2.1 Temporarily attach a suitable (e.g., 0- to 40- ml/min)
rotameter to the outlet of the DGM, and place a vacuum gauge at or near
the probe inlet. Plug the probe inlet, pull a vacuum of at least 250 mm
Hg (10 in. Hg), and note the flow rate as indicated by the rotameter. A
leakage rate in excess of 2 percent of the average sampling rate is not
acceptable.

Note: Carefully (i.e., slowly) release the probe inlet plug before
turning off the pump.

8.2.2 It is suggested (not mandatory) that the pump be leak-checked
separately, either prior to or after the sampling run. To leak-check the
pump, proceed as follows: Disconnect the drying tube from the probe-
impinger assembly. Place a vacuum gauge at the inlet to either the
drying tube or the pump, pull a vacuum of 250 mm Hg (10 in. Hg), plug or
pinch off the outlet of the flow meter, and then turn off the pump. The
vacuum should remain stable for at least 30 seconds.
If performed prior to the sampling run, the pump leak-check shall
precede the leak-check of the sampling train described immediately
above; if performed after the sampling run, the pump leak-check shall
follow the sampling train leak-check.
8.2.3 Other leak-check procedures may be used, subject to the
approval of the Administrator.
8.3 Sample Collection.
8.3.1 Record the initial DGM reading and barometric pressure. To
begin sampling, position the tip of the probe at the sampling point,
connect the probe to the bubbler, and start the pump. Adjust the sample
flow to a constant rate of approximately 1.0 liter/min as indicated by
the rate meter. Maintain this constant rate ( 10 percent)
during the entire sampling run.
8.3.2 Take readings (DGM volume, temperatures at DGM and at
impinger outlet, and rate meter flow rate) at least every 5 minutes. Add
more ice during the run to keep the temperature of the gases leaving the
last impinger at 20 deg.C (68 deg.F) or less.
8.3.3 At the conclusion of each run, turn off the pump, remove the
probe from the

[[Page 246]]

stack, and record the final readings. Conduct a leak-check as described
in Section 8.2. (This leak-check is mandatory.) If a leak is detected,
void the test run or use procedures acceptable to the Administrator to
adjust the sample volume for the leakage.
8.3.4 Drain the ice bath, and purge the remaining part of the train
by drawing clean ambient air through the system for 15 minutes at the
sampling rate. Clean ambient air can be provided by passing air through
a charcoal filter or through an extra midget impinger containing 15 ml
of 3 percent H2O2. Alternatively, ambient air
without purification may be used.
8.4 Sample Recovery. Disconnect the impingers after purging.
Discard the contents of the midget bubbler. Pour the contents of the
midget impingers into a leak-free polyethylene bottle for shipment.
Rinse the three midget impingers and the connecting tubes with water,
and add the rinse to the same storage container. Mark the fluid level.
Seal and identify the sample container.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
7.1.2.................... Isopropanol check.. Ensure acceptable level
of peroxide impurities
in isopropanol.
8.2, 10.1-10.4........... Sampling equipment Ensure accurate
leak-check and measurement of stack
calibration. gas flow rate, sample
volume.
10.5..................... Barium standard Ensure precision of
solution normality
standardization. determination.
11.2.3................... Replicate Ensure precision of
titrations. titration
determinations
11.3..................... Audit sample Evaluate analyst's
analysis. technique and standards
preparation.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Volume Metering System.
10.1.1 Initial Calibration.
10.1.1.1 Before its initial use in the field, leak-check the
metering system (drying tube, needle valve, pump, rate meter, and DGM)
as follows: Place a vacuum gauge at the inlet to the drying tube and
pull a vacuum of 250 mm Hg (10 in. Hg). Plug or pinch off the outlet of
the flow meter, and then turn off the pump. The vacuum must remain
stable for at least 30 seconds. Carefully release the vacuum gauge
before releasing the flow meter end.
10.1.1.2 Remove the drying tube, and calibrate the metering system
(at the sampling flow rate specified by the method) as follows: Connect
an appropriately sized wet-test meter (e.g., 1 liter per revolution) to
the inlet of the needle valve. Make three independent calibration runs,
using at least five revolutions of the DGM per run. Calculate the
calibration factor Y (wet-test meter calibration volume divided by the
DGM volume, both volumes adjusted to the same reference temperature and
pressure) for each run, and average the results (Yi). If any
Y-value deviates by more than 2 percent from (Yi), the
metering system is unacceptable for use. If the metering system is
acceptable, use (Yi) as the calibration factor for subsequent
test runs.
10.1.2 Post-Test Calibration Check. After each field test series,
conduct a calibration check using the procedures outlined in Section
10.1.1.2, except that three or more revolutions of the DGM may be used,
and only two independent runs need be made. If the average of the two
post-test calibration factors does not deviate by more than 5 percent
from Yi, then Yi is accepted as the DGM
calibration factor (Y), which is used in Equation 6-1 to calculate
collected sample volume (see Section 12.2). If the deviation is more
than 5 percent, recalibrate the metering system as in Section 10.1.1,
and determine a post-test calibration factor (Yf). Compare
Yi and Yf; the smaller of the two factors is
accepted as the DGM calibration factor. If recalibration indicates that
the metering system is unacceptable for use, either void the test run or
use methods, subject to the approval of the Administrator, to determine
an acceptable value for the collected sample volume.
10.1.3 DGM as a Calibration Standard. A DGM may be used as a
calibration standard for volume measurements in place of the wet-test
meter specified in Section 10.1.1.2, provided that it is calibrated
initially and recalibrated periodically according to the same procedures
outlined in Method 5, Section 10.3 with the following exceptions: (a)
the DGM is calibrated against a wet-test meter having a capacity of 1
liter/rev (0.035 ft³/rev) or 3 liters/rev (0.1
ft³/rev) and having the capability of measuring volume to
within 1 percent; (b) the DGM is calibrated at 1 liter/min (0.035 cfm);
and (c) the meter box of the Method 6 sampling train is calibrated at
the same flow rate.
10.2 Temperature Sensors. Calibrate against mercury-in-glass
thermometers.
10.3 Rate Meter. The rate meter need not be calibrated, but should
be cleaned and maintained according to the manufacturer's instructions.
10.4 Barometer. Calibrate against a mercury barometer.
10.5 Barium Standard Solution. Standardize the barium perchlorate
or chloride solution against 25 ml of standard sulfuric acid to which
100 ml of 100 percent isopropanol

[[Page 247]]

has been added. Run duplicate analyses. Calculate the normality using
the average of duplicate analyses where the titrations agree within 1
percent or 0.2 ml, whichever is larger.

11.0 Analytical Procedure

11.1 Sample Loss Check. Note level of liquid in container and
confirm whether any sample was lost during shipment; note this finding
on the analytical data sheet. If a noticeable amount of leakage has
occurred, either void the sample or use methods, subject to the approval
of the Administrator, to correct the final results.
11.2 Sample Analysis.
11.2.1 Transfer the contents of the storage container to a 100-ml
volumetric flask, dilute to exactly 100 ml with water, and mix the
diluted sample.
11.2.2 Pipette a 20-ml aliquot of the diluted sample into a 250-ml
Erlenmeyer flask and add 80 ml of 100 percent isopropanol plus two to
four drops of thorin indicator. While stirring the solution, titrate to
a pink endpoint using 0.0100 N barium standard solution.
11.2.3 Repeat the procedures in Section 11.2.2, and average the
titration volumes. Run a blank with each series of samples. Replicate
titrations must agree within 1 percent or 0.2 ml, whichever is larger.

Note: Protect the 0.0100 N barium standard solution from evaporation
at all times.

11.3 Audit Sample Analysis.
11.3.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, an audit sample, if
available, must be analyzed.
11.3.2 Concurrently analyze the audit sample and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.3.3 The same analyst, analytical reagents, and analytical system
must be used for the compliance samples and the audit sample. If this
condition is met, duplicate auditing of subsequent compliance analyses
for the same enforcement agency within a 30-day period is waived. An
audit sample set may not be used to validate different sets of
compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both enforcement
agencies.
11.4 Audit Sample Results.
11.4.1 Calculate the audit sample concentrations and submit results
using the instructions provided with the audit samples.
11.4.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.4.3 The concentrations of the audit samples obtained by the
analyst must agree within 5 percent of the actual concentration. If the
5 percent specification is not met, reanalyze the compliance and audit
samples, and include initial and reanalysis values in the test report.
11.4.4 Failure to meet the 5-percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to determine
the compliance or noncompliance status of the affected facility.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature.

Ca = Actual concentration of SO2 in audit sample,
mg/dscm.
Cd = Determined concentration of SO2 in audit
sample, mg/dscm.
CSO2 = Concentration of SO2, dry basis, corrected
to standard conditions, mg/dscm (lb/dscf).
N = Normality of barium standard titrant, meq/ml.
Pbar = Barometric pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
RE = Relative error of QA audit sample analysis, percent
Tm = Average DGM absolute temperature, deg.K ( deg.R).
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Va = Volume of sample aliquot titrated, ml.
Vm = Dry gas volume as measured by the DGM, dcm (dcf).
Vm(std) = Dry gas volume measured by the DGM, corrected to
standard conditions, dscm (dscf).
Vsoln = Total volume of solution in which the SO2 sample is
contained, 100 ml.
Vt = Volume of barium standard titrant used for the sample
(average of replicate titration), ml.
Vtb = Volume of barium standard titrant used for the blank,
ml.
Y = DGM calibration factor.

12.2 Dry Sample Gas Volume, Corrected to Standard Conditions.

[[Page 248]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.181

Where:

K1 = 0.3855 deg.K/mm Hg for metric units,
K1 = 17.65 deg.R/in. Hg for English units.

12.3 SO2 Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.182

Where:

K2 = 32.03 mg SO2/meq for metric units,
K2 = 7.061 x 10^-5 lb SO2/meq for
English units.

12.4 Relative Error for QA Audit Samples.
[GRAPHIC] [TIFF OMITTED] TR17OC00.183

13.0 Method Performance

13.1 Range. The minimum detectable limit of the method has been
determined to be 3.4 mg SO2/m³ (2.12 x
10^-7 lb/ft³). Although no upper limit has been
established, tests have shown that concentrations as high as 80,000 mg/
m³ (0.005 lb/ft³) of SO2 can be
collected efficiently at a rate of 1.0 liter/min (0.035 cfm) for 20
minutes in two midget impingers, each containing 15 ml of 3 percent
H2O2. Based on theoretical calculations, the upper
concentration limit in a 20 liter (0.7 ft³) sample is about
93,300 mg/m³ (0.00583 lb/ft³).

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 Nomenclature. Same as Section 12.1, with the following
additions:

Bwa = Water vapor in ambient air, proportion by volume.
Ma = Molecular weight of the ambient air saturated at
impinger temperature, g/g-mole (lb/lb-mole).
Ms = Molecular weight of the sample gas saturated at impinger
temperature, g/g-mole (lb/lb-mole).
Pc = Inlet vacuum reading obtained during the calibration
run, mm Hg (in. Hg).
Psr = Inlet vacuum reading obtained during the sampling run,
mm Hg (in. Hg).
Qstd = Volumetric flow rate through critical orifice, scm/min
(scf/min).
Qstd = Average flow rate of pre-test and post-test
calibration runs, scm/min (scf/min).
Tamb = Ambient absolute temperature of air, deg.K ( deg.R).
Vsb = Volume of gas as measured by the soap bubble meter,
m\3\ (ft\3\).

Vsb(std) = Volume of gas as measured by the soap bubble
meter, corrected to standard conditions, scm (scf).
= Soap bubble travel time, min.
s = Time, min.

16.2 Critical Orifices for Volume and Rate Measurements. A critical
orifice may be used in place of the DGM specified in Section 6.1.1.10,
provided that it is selected, calibrated, and used as follows:
16.2.1 Preparation of Sampling Train. Assemble the sampling train
as shown in Figure 6-2. The rate meter and surge tank are optional but
are recommended in order to detect changes in the flow rate.

Note: The critical orifices can be adapted to a Method 6 type
sampling train as follows: Insert sleeve type, serum bottle stoppers
into two reducing unions. Insert the needle into the stoppers as shown
in Figure 6-3.
16.2.2 Selection of Critical Orifices.
16.2.2.1 The procedure that follows describes the use of hypodermic
needles and stainless steel needle tubings, which have been found
suitable for use as critical orifices. Other materials and critical
orifice designs may be used provided the orifices act as true critical
orifices, (i.e., a critical vacuum can be obtained) as described in this
section. Select a critical orifice that is sized to operate at the
desired flow rate. The needle sizes and tubing lengths shown in Table 6-
1 give the following approximate flow rates.
16.2.2.2 Determine the suitability and the appropriate operating
vacuum of the critical orifice as follows: If applicable, temporarily
attach a rate meter and surge tank to the outlet of the sampling train,
if said equipment is not present (see Section 16.2.1). Turn on the pump
and adjust the valve to give an outlet vacuum reading corresponding to
about half of the atmospheric pressure. Observe the rate meter reading.
Slowly increase the vacuum until a stable reading is

[[Page 249]]

obtained on the rate meter. Record the critical vacuum, which is the
outlet vacuum when the rate meter first reaches a stable value. Orifices
that do not reach a critical value must not be used.
16.2.3 Field Procedures.
16.2.3.1 Leak-Check Procedure. A leak-check before the sampling run
is recommended, but not required. The leak-check procedure is as
follows: Temporarily attach a suitable (e.g., 0-40 ml/min) rotameter and
surge tank, or a soap bubble meter and surge tank to the outlet of the
pump. Plug the probe inlet, pull an outlet vacuum of at least 250 mm Hg
(10 in. Hg), and note the flow rate as indicated by the rotameter or
bubble meter. A leakage rate in excess of 2 percent of the average
sampling rate (Qstd) is not acceptable. Carefully release the
probe inlet plug before turning off the pump.
16.2.3.2 Moisture Determination. At the sampling location, prior to
testing, determine the percent moisture of the ambient air using the wet
and dry bulb temperatures or, if appropriate, a relative humidity meter.
16.2.3.3 Critical Orifice Calibration. At the sampling location,
prior to testing, calibrate the entire sampling train (i.e., determine
the flow rate of the sampling train when operated at critical
conditions). Attach a 500-ml soap bubble meter to the inlet of the
probe, and operate the sampling train at an outlet vacuum of 25 to 50 mm
Hg (1 to 2 in. Hg) above the critical vacuum. Record the information
listed in Figure 6-4. Calculate the standard volume of air measured by
the soap bubble meter and the volumetric flow rate using the equations
below:
[GRAPHIC] [TIFF OMITTED] TR17OC00.184

[GRAPHIC] [TIFF OMITTED] TR17OC00.185

16.2.3.4 Sampling.
16.2.3.4.1 Operate the sampling train for sample collection at the same
vacuum used during the calibration run. Start the watch and pump
simultaneously. Take readings (temperature, rate meter, inlet vacuum,
and outlet vacuum) at least every 5 minutes. At the end of the sampling
run, stop the watch and pump simultaneously.
16.2.3.4.2 Conduct a post-test calibration run using the calibration
procedure outlined in Section 16.2.3.3. If the Qstd obtained
before and after the test differ by more than 5 percent, void the test
run; if not, calculate the volume of the gas measured with the critical
orifice using Equation 6-6 as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.186

16.2.3.4.3 If the percent difference between the molecular weight of
the ambient air at saturated conditions and the sample gas is more that
3 percent, then the molecular weight of the gas sample must
be considered in the calculations using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.187

Note: A post-test leak-check is not necessary because the post-test
calibration run results will indicate whether there is any leakage.
16.2.3.4.4 Drain the ice bath, and purge the sampling train using
the procedure described in Section 8.3.4.
16.3 Elimination of Ammonia Interference. The following alternative
procedures must be used in addition to those specified in the method
when sampling at sources having ammonia emissions.
16.3.1 Sampling. The probe shall be maintained at 275 deg.C (527
deg.F) and equipped with a high-efficiency in-stack filter (glass fiber)
to remove particulate matter. The filter material shall be unreactive to
SO2. Whatman 934AH (formerly Reeve Angel 934AH) filters
treated as described in Reference 10 in Section 17.0 of Method 5 is an
example of a filter

[[Page 250]]

that has been shown to work. Where alkaline particulate matter and
condensed moisture are present in the gas stream, the filter shall be
heated above the moisture dew point but below 225 deg.C (437 deg.F).
16.3.2 Sample Recovery. Recover the sample according to Section 8.4
except for discarding the contents of the midget bubbler. Add the
bubbler contents, including the rinsings of the bubbler with water, to a
separate polyethylene bottle from the rest of the sample. Under normal
testing conditions where sulfur trioxide will not be present
significantly, the tester may opt to delete the midget bubbler from the
sampling train. If an approximation of the sulfur trioxide concentration
is desired, transfer the contents of the midget bubbler to a separate
polyethylene bottle.
16.3.3 Sample Analysis. Follow the procedures in Sections 11.1 and
11.2, except add 0.5 ml of 0.1 N HCl to the Erlenmeyer flask and mix
before adding the indicator. The following analysis procedure may be
used for an approximation of the sulfur trioxide concentration. The
accuracy of the calculated concentration will depend upon the ammonia to
SO2 ratio and the level of oxygen present in the gas stream.
A fraction of the SO2 will be counted as sulfur trioxide as
the ammonia to SO2 ratio and the sample oxygen content
increases. Generally, when this ratio is 1 or less and the oxygen
content is in the range of 5 percent, less than 10 percent of the
SO2 will be counted as sulfur trioxide. Analyze the peroxide
and isopropanol sample portions separately. Analyze the peroxide portion
as described above. Sulfur trioxide is determined by difference using
sequential titration of the isopropanol portion of the sample. Transfer
the contents of the isopropanol storage container to a 100-ml volumetric
flask, and dilute to exactly 100 ml with water. Pipette a 20-ml aliquot
of this solution into a 250-ml Erlenmeyer flask, add 0.5 ml of 0.1 N
HCl, 80 ml of 100 percent isopropanol, and two to four drops of thorin
indicator. Titrate to a pink endpoint using 0.0100 N barium perchlorate.
Repeat and average the titration volumes that agree within 1 percent or
0.2 ml, whichever is larger. Use this volume in Equation 6-2 to
determine the sulfur trioxide concentration. From the flask containing
the remainder of the isopropanol sample, determine the fraction of
SO2 collected in the bubbler by pipetting 20-ml aliquots into
250-ml Erlenmeyer flasks. Add 5 ml of 3 percent
H2O2, 100 ml of 100 percent isopropanol, and two
to four drips of thorin indicator, and titrate as before. From this
titration volume, subtract the titrant volume determined for sulfur
trioxide, and add the titrant volume determined for the peroxide
portion. This final volume constitutes Vt, the volume of
barium perchlorate used for the SO2 sample.

17.0 References

1. Atmospheric Emissions from Sulfuric Acid Manufacturing Processes.
U.S. DHEW, PHS, Division of Air Pollution. Public Health Service
Publication No. 999-AP-13. Cincinnati, OH. 1965.
2. Corbett, P.F. The Determination of SO2 and
SO3 in Flue Gases. Journal of the Institute of Fuel. 24:237-
243. 1961.
3. Matty, R.E., and E.K. Diehl. Measuring Flue-Gas SO2
and SO3. Power. 101:94-97. November 1957.
4. Patton, W.F., and J.A. Brink, Jr. New Equipment and Techniques
for Sampling Chemical Process Gases. J. Air Pollution Control
Association. 13:162. 1963.
5. Rom, J.J. Maintenance, Calibration, and Operation of Isokinetic
Source Sampling Equipment. Office of Air Programs, U.S. Environmental
Protection Agency. Research Triangle Park, NC. APTD-0576. March 1972.
6. Hamil, H.F., and D.E. Camann. Collaborative Study of Method for
the Determination of Sulfur Dioxide Emissions from Stationary Sources
(Fossil-Fuel Fired Steam Generators). U.S. Environmental Protection
Agency, Research Triangle Park, NC. EPA-650/4-74-024. December 1973.
7. Annual Book of ASTM Standards. Part 31; Water, Atmospheric
Analysis. American Society for Testing and Materials. Philadelphia, PA.
1974. pp. 40-42.
8. Knoll, J.E., and M.R. Midgett. The Application of EPA Method 6 to
High Sulfur Dioxide Concentrations. U.S. Environmental Protection
Agency. Research Triangle Park, NC. EPA-600/4-76-038. July 1976.
9. Westlin, P.R., and R.T. Shigehara. Procedure for Calibrating and
Using Dry Gas Volume Meters as Calibration Standards. Source Evaluation
Society Newsletter. 3(1):17-30. February 1978.
10. Yu, K.K. Evaluation of Moisture Effect on Dry Gas Meter
Calibration. Source Evaluation Society Newsletter. 5(1):24-28. February
1980.
11. Lodge, J.P., Jr., et al. The Use of Hypodermic Needles as
Critical Orifices in Air Sampling. J. Air Pollution Control Association.
16:197-200. 1966.
12. Shigehara, R.T., and C.B. Sorrell. Using Critical Orifices as
Method 5 CalibrationStandards. Source Evaluation Society Newsletter.
10:4-15. August 1985.
13. Curtis, F., Analysis of Method 6 Samples in the Presence of
Ammonia. Source Evaluation Society Newsletter. 13(1):9-15 February 1988.

[[Page 251]]

18.0 Tables, Diagrams, Flowcharts and Validation Data

Table 6-1.--Approximate Flow Rates for Various Needle Sizes
------------------------------------------------------------------------
Needle
Needle size (gauge) length Flow rate
(cm) (ml/min)
------------------------------------------------------------------------
21............................................ 7.6 1,100
22............................................ 2.9 1,000
22............................................ 3.8 900
23............................................ 3.8 500
23............................................ 5.1 450
24............................................ 3.2 400
------------------------------------------------------------------------

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Method 6A--Determination of Sulfur Dioxide, Moisture, and Carbon Dioxide
From Fossil Fuel Combustion Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, Method 6, and Method 19.

1.0 Scope and Application

1.1 Analytes.

[[Page 256]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
SO2............................... 7449-09-05 3.4 mg SO2/m³
(2.12 x 10^-7 lb/
ft³)
CO2............................... 124-38-9 N/A
H2O............................... 7732-18-5 N/A
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of sulfur dioxide (SO2) emissions from fossil fuel combustion
sources in terms of concentration (mg/dscm or lb/dscf) and in terms of
emission rate (ng/J or lb/10⁶ Btu) and for the determination
of carbon dioxide (CO2) concentration (percent). Moisture
content (percent), if desired, may also be determined by this method.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from a sampling point in the stack.
The SO2 and the sulfur trioxide, including those fractions in
any sulfur acid mist, are separated. The SO2 fraction is
measured by the barium-thorin titration method. Moisture and
CO2 fractions are collected in the same sampling train, and
are determined gravimetrically.

3.0 Definitions. [Reserved]

4.0 Interferences

Same as Method 6, Section 4.0.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 6, Section 6.1, with the
exception of the following:
6.1.1 Sampling Train. A schematic of the sampling train used in
this method is shown in Figure 6A-1.
6.1.1.1 Impingers and Bubblers. Two 30=ml midget impingers with a
1=mm restricted tip and two 30=ml midget bubblers with unrestricted
tips. Other types of impingers and bubblers (e.g., Mae West for
SO2 collection and rigid cylinders containing Drierite for
moisture absorbers), may be used with proper attention to reagent
volumes and levels, subject to the approval of the Administrator.
6.1.1.2 CO2 Absorber. A sealable rigid cylinder or
bottle with an inside diameter between 30 and 90 mm , a length between
125 and 250 mm, and appropriate connections at both ends. The filter may
be a separate heated unit or may be within the heated portion of the
probe. If the filter is within the sampling probe, the filter should not
be within 15 cm of the probe inlet or any unheated section of the probe,
such as the connection to the first bubbler. The probe and filter should
be heated to at least 20 deg.C (68 deg.F) above the source
temperature, but not greater than 120 deg.C (248 deg.F). The filter
temperature (i.e., the sample gas temperature) should be monitored to
assure the desired temperature is maintained. A heated Teflon connector
may be used to connect the filter holder or probe to the first impinger.

Note: For applications downstream of wet scrubbers, a heated out-of-
stack filter (either borosilicate glass wool or glass fiber mat) is
necessary.

6.2 Sample Recovery. Same as Method 6, Section 6.2.
6.3 Sample Analysis. Same as Method 6, Section 6.3, with the
addition of a balance to measure within 0.05 g.

7.0 Reagents and Standards

7.1 Sample Collection. Same as Method 6, Section 7.1, with the
addition of the following:
7.1.1 Drierite. Anhydrous calcium sulfate (CaSO4)
desiccant, 8 mesh, indicating type is recommended.

Note: Do not use silica gel or similar desiccant in this
application.

7.1.2 CO2 Absorbing Material. Ascarite II. Sodium
hydroxide-coated silica, 8- to 20-mesh.
7.2 Sample Recovery and Analysis. Same as Method 6, Sections 7.2
and 7.3, respectively.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Preparation of Sampling Train.
8.1.1 Measure 15 ml of 80 percent isopropanol into the first midget
bubbler and 15 ml of 3 percent hydrogen peroxide into

[[Page 257]]

each of the two midget impingers (the second and third vessels in the
train) as described in Method 6, Section 8.1. Insert the glass wool into
the top of the isopropanol bubbler as shown in Figure 6A-1. Place about
25 g of Drierite into the second midget bubbler (the fourth vessel in
the train). Clean the outside of the bubblers and impingers and allow
the vessels to reach room temperature. Weigh the four vessels
simultaneously to the nearest 0.1 g, and record this initial weight
(mwi).
8.1.2 With one end of the CO2 absorber sealed, place
glass wool into the cylinder to a depth of about 1 cm (0.5 in.). Place
about 150 g of CO2 absorbing material in the cylinder on top
of the glass wool, and fill the remaining space in the cylinder with
glass wool. Assemble the cylinder as shown in Figure 6A-2. With the
cylinder in a horizontal position, rotate it around the horizontal axis.
The CO2 absorbing material should remain in position during
the rotation, and no open spaces or channels should be formed. If
necessary, pack more glass wool into the cylinder to make the
CO2 absorbing material stable. Clean the outside of the
cylinder of loose dirt and moisture and allow the cylinder to reach room
temperature. Weigh the cylinder to the nearest 0.1 g, and record this
initial weight (mai).
8.1.3 Assemble the train as shown in Figure 6A-1. Adjust the probe
heater to a temperature sufficient to prevent condensation (see Note in
Section 6.1). Place crushed ice and water around the impingers and
bubblers. Mount the CO2 absorber outside the water bath in a
vertical flow position with the sample gas inlet at the bottom. Flexible
tubing (e.g., Tygon) may be used to connect the last SO2
absorbing impinger to the moisture absorber and to connect the moisture
absorber to the CO2 absorber. A second, smaller
CO2 absorber containing Ascarite II may be added in-line
downstream of the primary CO2 absorber as a breakthrough
indicator. Ascarite II turns white when CO2 is absorbed.
8.2 Sampling Train Leak-Check Procedure and Sample Collection. Same
as Method 6, Sections 8.2 and 8.3, respectively.
8.3 Sample Recovery.
8.3.1 Moisture Measurement. Disconnect the isopropanol bubbler, the
SO2 impingers, and the moisture absorber from the sample
train. Allow about 10 minutes for them to reach room temperature, clean
the outside of loose dirt and moisture, and weigh them simultaneously in
the same manner as in Section 8.1. Record this final weight
(mwf).
8.3.2 Peroxide Solution. Discard the contents of the isopropanol
bubbler and pour the contents of the midget impingers into a leak-free
polyethylene bottle for shipping. Rinse the two midget impingers and
connecting tubes with water, and add the washing to the same storage
container.
8.3.3 CO2 Absorber. Allow the CO2 absorber to
warm to room temperature (about 10 minutes), clean the outside of loose
dirt and moisture, and weigh to the nearest 0.1 g in the same manner as
in Section 8.1. Record this final weight (maf). Discard used
Ascarite II material.

9.0 Quality Control

Same as Method 6, Section 9.0.

10.0 Calibration and Standardization

Same as Method 6, Section 10.0.

11.0 Analytical Procedure

11.1 Sample Analysis. The sample analysis procedure for
SO2 is the same as that specified in Method 6, Section 11.0.
11.2 Quality Assurance (QA) Audit Samples. Analysis of QA audit
samples is required only when this method is used for compliance
determinations. Obtain an audit sample set as directed in Section 7.3.6
of Method 6. Analyze the audit samples, and report the results as
directed in Section 11.3 of Method 6. Acceptance criteria for the audit
results are the same as those in Method 6.

12.0 Data Analysis and Calculations

Same as Method 6, Section 12.0, with the addition of the following:
12.1 Nomenclature.

Cw = Concentration of moisture, percent.
CCO2 = Concentration of CO2, dry basis, percent.
ESO2 = Emission rate of SO2, ng/J (lb/
10⁶ Btu).
FC = Carbon F-factor from Method 19 for the fuel burned,
dscm/J (dscf/10⁶ Btu).
mwi = Initial weight of impingers, bubblers, and moisture
absorber, g.
mwf = Final weight of impingers, bubblers, and moisture
absorber, g.
mai = Initial weight of CO2 absorber, g.
maf = Final weight of CO2 absorber, g.
mSO2 = Mass of SO2 collected, mg.
VCO2(std) = Equivalent volume of CO2 collected at
standard conditions, dscm (dscf).
Vw(std) = Equivalent volume of moisture collected at standard
conditions, scm (scf).

12.2 CO2 Volume Collected, Corrected to Standard
Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.192

Where:

K3 = Equivalent volume of gaseous CO2 at standard
conditions, 5.467 x 10^-\4\ dscm/g (1.930 x
10^-\2\ dscf/g).

12.3 Moisture Volume Collected, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.193

Where:

[[Page 258]]

K4 = Equivalent volume of water vapor at standard conditions,
1.336 x 10^-\3\ scm/g (4.717 x 10^-\2\
scf/g).

12.4 SO2 Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.194

Where:

K2 = 32.03 mg SO2/meq. SO2 (7.061 x
10^-\5\ lb SO2/meq. SO2)

12.5 CO2 Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.195

12.6 Moisture Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.196

13.0 Method Performance

13.1 Range and Precision. The minimum detectable limit and the
upper limit for the measurement of SO2 are the same as for
Method 6. For a 20-liter sample, this method has a precision of
0.5 percent CO2 for concentrations between 2.5
and 25 percent CO2 and 1.0 percent moisture for
moisture concentrations greater than 5 percent.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Methods

If the only emission measurement desired is in terms of emission
rate of SO2 (ng/J or lb/10\6\ Btu), an abbreviated procedure
may be used. The differences between the above procedure and the
abbreviated procedure are described below.
16.1 Sampling Train. The sampling train is the same as that shown
in Figure 6A-1 and as described in Section 6.1, except that the dry gas
meter is not needed.
16.2 Preparation of the Sampling Train. Follow the same procedure
as in Section 8.1, except do not weigh the isopropanol bubbler, the
SO2 absorbing impingers, or the moisture absorber.
16.3 Sampling Train Leak-Check Procedure and Sample Collection.
Leak-check and operate the sampling train as described in Section 8.2,
except that dry gas meter readings, barometric pressure, and dry gas
meter temperatures need not be recorded during sampling.
16.4 Sample Recovery. Follow the procedure in Section 8.3, except
do not weigh the isopropanol bubbler, the SO2 absorbing
impingers, or the moisture absorber.
16.5 Sample Analysis. Analysis of the peroxide solution and QA
audit samples is the same as that described in Sections 11.1 and 11.2,
respectively.
16.6 Calculations.
16.6.1 SO2 Collected.
[GRAPHIC] [TIFF OMITTED] TR17OC00.197

Where:

K2 = 32.03 mg SO2/meq. SO2
K2 = 7.061 x 10^-\5\ lb SO2/meq.
SO2

16.6.2 Sulfur Dioxide Emission Rate.
[GRAPHIC] [TIFF OMITTED] TR17OC00.198

Where:

K5 = 1.829 x 10\9\ mg/dscm

[[Page 259]]

K2 = 0.1142 lb/dscf

17.0 References

Same as Method 6, Section 17.0, References 1 through 8, with the
addition of the following:

1. Stanley, Jon and P.R. Westlin. An Alternate Method for Stack Gas
Moisture Determination. Source Evaluation Society Newsletter. 3(4).
November 1978.
2. Whittle, Richard N. and P.R. Westlin. Air Pollution Test Report:
Development and Evaluation of an Intermittent Integrated SO2/
CO2 Emission Sampling Procedure. Environmental Protection
Agency, Emission Standard and Engineering Division, Emission Measurement
Branch. Research Triangle Park, NC. December 1979. 14 pp.

[[Page 260]]

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.199

[[Page 261]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.410

Method 6B--Determination of Sulfur Dioxide and Carbon Dioxide Daily
Average Emissions From Fossil Fuel Combustion Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, Method 6, and Method 6A.

1.0 Scope and Application

1.1 Analytes.

[[Page 262]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Sulfur dioxide (SO2).............. 7449-09-05 3.4 mg SO2/m\3\
(2.12 x 10^-\7\ lb/
ft\3\)
Carbon dioxide (CO2).............. 124-38-9 N/A
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of SO2 emissions from combustion sources in terms of
concentration (ng/dscm or lb/dscf) and emission rate (ng/J or lb/10\6\
Btu), and for the determination of CO2 concentration
(percent) on a daily (24 hours) basis.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the sampling point in the stack
intermittently over a 24-hour or other specified time period. The
SO2 fraction is measured by the barium-thorin titration
method. Moisture and CO2 fractions are collected in the same
sampling train, and are determined gravimetrically.

3.0 Definitions. [Reserved]

4.0 Interferences

Same as Method 6, Section 4.0.

5.0 Safety

6.0 Equipment and Supplies

Same as Method 6A, Section 6.0, with the following exceptions and
additions:
6.1 The isopropanol bubbler is not used. An empty bubbler for the
collection of liquid droplets, that does not allow direct contact
between the collected liquid and the gas sample, may be included in the
sampling train.
6.2 For intermittent operation, include an industrial timer-switch
designed to operate in the ``on'' position at least 2 minutes
continuously and ``off'' the remaining period over a repeating cycle.
The cycle of operation is designated in the applicable regulation. At a
minimum, the sampling operation should include at least 12, equal,
evenly-spaced periods per 24 hours.
6.3 Stainless steel sampling probes, type 316, are not recommended
for use with Method 6B because of potential sample contamination due to
corrosion. Glass probes or other types of stainless steel, e.g.,
Hasteloy or Carpenter 20, are recommended for long-term use.
Note: For applications downstream of wet scrubbers, a heated out-of-
stack filter (either borosilicate glass wool or glass fiber mat) is
necessary. Probe and filter heating systems capable of maintaining a
sample gas temperature of between 20 and 120 deg.C (68 and 248 deg.F)
at the filter are also required in these cases. The electric supply for
these heating systems should be continuous and separate from the timed
operation of the sample pump.

7.0 Reagents and Standards

Same as Method 6A, Section 7.0, with the following exceptions:
7.1 Isopropanol is not used for sampling.
7.2 The hydrogen peroxide absorbing solution shall be diluted to no
less than 6 percent by volume, instead of 3 percent as specified in
Methods 6 and 6A.
7.3 If the Method 6B sampling train is to be operated in a low
sample flow condition (less than 100 ml/min or 0.21 ft\3\/hr), molecular
sieve material may be substituted for Ascarite II as the CO2
absorbing material. The recommended molecular sieve material is Union
Carbide \1/16\ inch pellets, 5 A deg., or equivalent. Molecular sieve
material need not be discarded following the sampling run, provided that
it is regenerated as per the manufacturer's instruction. Use of
molecular sieve material at flow rates higher than 100 ml/min (0.21
ft\3\/hr) may cause erroneous CO2 results.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Preparation of Sampling Train. Same as Method 6A, Section 8.1,
with the addition of the following:
8.1.1 The sampling train is assembled as shown in Figure 6A-1 of
Method 6A, except that the isopropanol bubbler is not included.
8.1.2 Adjust the timer-switch to operate in the ``on'' position
from 2 to 4 minutes on a 2-hour repeating cycle or other cycle specified
in the applicable regulation. Other timer sequences may be used with the
restriction that the total sample volume collected is between 25 and 60
liters (0.9 and 2.1 ft ³) for the amounts of sampling
reagents prescribed in this method.
8.1.3 Add cold water to the tank until the impingers and bubblers
are covered at least two-thirds of their length. The impingers and
bubbler tank must be covered and protected from intense heat and direct
sunlight. If freezing conditions exist, the impinger solution and the
water bath must be protected.

Note: Sampling may be conducted continuously if a low flow-rate
sample pump [20

[[Page 263]]

to 40 ml/min (0.04 to 0.08 ft³/hr) for the reagent volumes
described in this method] is used. If sampling is continuous, the timer-
switch is not necessary. In addition, if the sample pump is designed for
constant rate sampling, the rate meter may be deleted. The total gas
volume collected should be between 25 and 60 liters (0.9 and 2.1
ft³) for the amounts of sampling reagents prescribed in this
method.

8.2 Sampling Train Leak-Check Procedure. Same as Method 6, Section
8.2.
8.3 Sample Collection.
8.3.1 The probe and filter (either in-stack, out-of-stack, or both)
must be heated to a temperature sufficient to prevent water
condensation.
8.3.2 Record the initial dry gas meter reading. To begin sampling,
position the tip of the probe at the sampling point, connect the probe
to the first impinger (or filter), and start the timer and the sample
pump. Adjust the sample flow to a constant rate of approximately 1.0
liter/min (0.035 cfm) as indicated by the rotameter. Observe the
operation of the timer, and determine that it is operating as intended
(i.e., the timer is in the ``on'' position for the desired period, and
the cycle repeats as required).
8.3.3 One time between 9 a.m. and 11 a.m. during the 24-hour
sampling period, record the dry gas meter temperature (Tm)
and the barometric pressure (P(bar)).
8.3.4 At the conclusion of the run, turn off the timer and the
sample pump, remove the probe from the stack, and record the final gas
meter volume reading. Conduct a leak-check as described in Section 8.2.
If a leak is found, void the test run or use procedures acceptable to
the Administrator to adjust the sample volume for leakage. Repeat the
steps in Sections 8.3.1 to 8.3.4 for successive runs.
8.4 Sample Recovery. The procedures for sample recovery (moisture
measurement, peroxide solution, and CO2 absorber) are the
same as those in Method 6A, Section 8.3.

9.0 Quality Control

Same as Method 6, Section 9.0., with the exception of the
isopropanol-check.

10.0 Calibration and Standardization

Same as Method 6, Section 10.0, with the addition of the following:
10.1 Periodic Calibration Check. After 30 days of operation of the
test train, conduct a calibration check according to the same procedures
as the post-test calibration check (Method 6, Section 10.1.2). If the
deviation between initial and periodic calibration factors exceeds 5
percent, use the smaller of the two factors in calculations for the
preceding 30 days of data, but use the most recent calibration factor
for succeeding test runs.

11.0 Analytical Procedures

11.1 Sample Loss Check and Analysis. Same as Method 6, Sections
11.1 and 11.2, respectively.
11.2 Quality Assurance (QA) Audit Samples. Analysis of QA audit
samples is required only when this method is used for compliance
determinations. Obtain an audit sample set as directed in Section 7.3.6
of Method 6. Analyze the audit samples at least once for every 30 days
of sample collection, and report the results as directed in Section 11.3
of Method 6. The analyst performing the sample analyses shall perform
the audit analyses. If more than one analyst performs the sample
analyses during the 30-day sampling period, each analyst shall perform
the audit analyses and all audit results shall be reported. Acceptance
criteria for the audit results are the same as those in Method 6.

12.0 Data Analysis and Calculations

Same as Method 6A, Section 12.0, except that Pbar and
Tm correspond to the values recorded in Section 8.3.3 of this
method. The values are as follows:

Pbar = Initial barometric pressure for the test period, mm
Hg.
Tm = Absolute meter temperature for the test period, deg.K.

13.0 Method Performance

13.1 Range.
13.1.1 Sulfur Dioxide. Same as Method 6.
13.1.2 Carbon Dioxide. Not determined.
13.2 Repeatability and Reproducibility. EPA-sponsored collaborative
studies were undertaken to determine the magnitude of repeatability and
reproducibility achievable by qualified testers following the procedures
in this method. The results of the studies evolve from 145 field tests
including comparisons with Methods 3 and 6. For measurements of emission
rates from wet, flue gas desulfurization units in (ng/J), the
repeatability (intra-laboratory precision) is 8.0 percent and the
reproducibility (inter-laboratory precision) is 11.1 percent.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Methods

Same as Method 6A, Section 16.0, except that the timer is needed and
is operated as outlined in this method.

17.0 References

Same as Method 6A, Section 17.0, with the addition of the following:

1. Butler, Frank E., et. al. The Collaborative Test of Method 6B:
Twenty-Four-Hour Analysis of SO2 and CO2. JAPCA.
Vol. 33, No. 10. October 1983.

[[Page 264]]

18.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 6C--Determination of Sulfur Dioxide Emissions From Stationary
Sources (Instrumental Analyzer Procedure)

1. Applicability and Principle

1.1 Applicability. This method is applicable to the determination
of sulfur dioxide (SO2) concentrations in controlled and
uncontrolled emissions from stationary sources only when specified
within the regulations.
1.2 Principle. A gas sample is continuously extracted from a stack,
and a portion of the sample is conveyed to an instrumental analyzer for
determination of SO2 gas concentration using an ultraviolet
(UV), nondispersive infrared (NDIR), or fluorescence analyzer.
Performance specifications and test procedures are provided to ensure
reliable data.

2. Range and Sensitivity

2.1 Analytical Range. The analytical range is determined by the
instrumental design. For this method, a portion of the analytical range
is selected by choosing the span of the monitoring system. The span of
the monitoring system shall be selected such that the pollutant gas
concentration equivalent to the emission standard is not less than 30
percent of the span. If at any time during a run the measured gas
concentration exceeds the span, the run shall be considered invalid.
2.2 Sensitivity. The minimum detectable limit depends on the
analytical range, span, and signal-to-noise ratio of the measurement
system. For a well designed system, the minimum detectable limit should
be less than 2 percent of the span.

3. Definitions

3.1 Measurement System. The total equipment required for the
determination of gas concentration. The measurement system consists of
the following major subsystems:
3.1.1 Sample Interface. That portion of a system used for one or
more of the following: sample acquisition, sample transport, sample
conditioning, or protection of the analyzers from the effects of the
stack effluent.
3.1.2 Gas Analyzer. That portion of the system that senses the gas
to be measured and generates an output proportional to its
concentration.
3.1.3 Data Recorder. A strip chart recorder, analog computer, or
digital recorder for recording measurement data from the analyzer
output.
3.2 Span. The upper limit of the gas concentration measurement
range displayed on the data recorder.
3.3 Calibration Gas. A known concentration of a gas in an
appropriate diluent gas.
3.4 Analyzer Calibration Error. The difference between the gas
concentration exhibited by the gas analyzer and the known concentration
of the calibration gas when the calibration gas is introduced directly
to the analyzer.
3.5 Sampling System Bias. The difference between the gas
concentrations exhibited by the measurement system when a known
concentration gas is introduced at the outlet of the sampling probe and
when the same gas is introduced directly to the analyzer.
3.6 Zero Drift. The difference in the measurement system output
reading from the initial calibration response at the zero concentration
level after a stated period of operation during which no unscheduled
maintenance, repair, or adjustment took place.
3.7 Calibration Drift. The difference in the measurement system
output reading from the initial calibration response at a mid-range
calibration value after a stated period of operation during which no
unscheduled maintenance, repair, or adjustment took place.
3.8 Response Time. The amount of time required for the measurement
system to display 95 percent of a step change in gas concentration on
the data recorder.
3.9 Interference Check. A method for detecting analytical
interferences and excessive biases through direct comparison of gas
concentrations provided by the measurement system and by a modified
Method 6 procedure. For this check, the modified Method 6 samples are
acquired at the sample by-pass discharge vent.
3.10 Calibration Curve. A graph or other systematic method of
establishing the relationship between the analyzer response and the
actual gas concentration introduced to the analyzer.

4. Measurement System Performance Specifications

4.1 Analyzer Calibration Error. Less than 2 percent of
the span for the zero, mid-range, and high-range calibration gases.
4.2 Sampling System Bias. Less than 5 percent of the
span for the zero, and mid- or high-range calibration gases.
4.3 Zero Drift. Less than 3 percent of the span over
the period of each run.
4.4 Calibration Drift. Less than 3 percent of the span
over the period of each run.
4.5 Interference Check. Less than 7 percent of the
modified Method 6 result for each run.

5. Apparatus and Reagents

5.1 Measurement System. Any measurement system for SO2
that meets the specifications of this method. A schematic of an
acceptable measurement system is shown in Figure 6C-1. The essential
components of the measurement system are described below:
5.1.1 Sample Probe. Glass, stainless steel, or equivalent, of
sufficient length to traverse the sample points. The sampling probe
shall be heated to prevent condensation.

[[Page 265]]

5.1.2 Sample Line. Heated (sufficient to prevent condensation)
stainless steel or Teflon tubing, to transport the sample gas to the
moisture removal system.
5.1.3 Sample Transport Lines. Stainless steel or Teflon tubing, to
transport the sample from the moisture removal system to the sample
pump, sample flow rate control, and sample gas manifold.
5.1.4 Calibration Valve Assembly. A three-way valve assembly, or
equivalent, for blocking the sample gas flow and introducing calibration
gases to the measurement system at the outlet of the sampling probe when
in the calibration mode.
5.1.5 Moisture Removal System. A refrigerator-type condenser or
similar device (e.g., permeation dryer), to remove condensate
continuously from the sample gas while maintaining minimal contact
between the condensate and the sample gas. The moisture removal system
is not necessary for analyzers that can measure gas concentrations on a
wet basis; for these analyzers, (1) heat the sample line and all
interface components up to the inlet of the analyzer sufficiently to
prevent condensation, and (2) determine the moisture content and correct
the measured gas concentrations to a dry basis using appropriate
methods, subject to the approval of the Administrator. The determination
of sample moisture content is not necessary for pollutant analyzers that
measure concentrations on a wet basis when (1) a wet basis
CO2 analyzer operated according to Method 3A is used to
obtain simultaneous measurements, and (2) the pollutant/CO2
measurements are used to determine emissions in units of the standard.
5.1.6 Particulate Filter. An in-stack or heated (sufficient to
prevent water condensation) out-of-stack filter. The filter shall be
borosilicate or quartz glass wool, or glass fiber mat. Additional
filters at the inlet or outlet of the moisture removal system and inlet
of the analyzer may be used to prevent accumulation of particulate
material in the measurement system and extend the useful life of the
components. All filters shall be fabricated of materials that are
nonreactive to the gas being sampled.
5.1.7 Sample Pump. A leak-free pump, to pull the sample gas through
the system at a flow rate sufficient to minimize the response time of
the measurement system. The pump may be constructed of any material that
is nonreactive to the gas being sampled.
5.1.8 Sample Flow Rate Control. A sample flow rate control valve
and rotameter, or equivalent, to maintain a constant sampling rate
within 10 percent.
(Note: The tester may elect to install a back-pressure regulator to
maintain the sample gas manifold at a constant pressure in order to
protect the analyzer(s) from overpressurization, and to minimize the
need for flow rate adjustments.)
5.1.9 Sample Gas Manifold. A sample gas manifold, to divert a
portion of the sample gas stream to the analyzer, and the remainder to
the by-pass discharge vent. The sample gas manifold should also include
provisions for introducing calibration gases directly to the analyzer.
The manifold may be constructed of any material that is nonreactive to
the gas being sampled.
5.1.10 Gas Analyzer. A UV or NDIR absorption or fluorescence
analyzer, to determine continuously the SO2 concentration in
the sample gas stream. The analyzer shall meet the applicable
performance specifications of Section 4. A means of controlling the
analyzer flow rate and a device for determining proper sample flow rate
(e.g., precision rotameter, pressure gauge downstream of all flow
controls, etc.) shall be provided at the analyzer.
(Note: Housing the analyzer(s) in a clean, thermally-stable,
vibration-free environment will minimize drift in the analyzer
calibration.)
5.1.11 Data Recorder. A strip chart recorder, analog computer, or
digital recorder, for recording measurement data. The data recorder
resolution (i.e., readability) shall be 0.5 percent of span.
Alternatively, a digital or analog meter having a resolution of 0.5
percent of span may be used to obtain the analyzer responses and the
readings may be recorded manually. If this alternative is used, the
readings shall be obtained at equally spaced intervals over the duration
of the sampling run. For sampling run durations of less than 1 hour,
measurements at 1-minute intervals or a minimum of 30 measurements,
whichever is less restrictive, shall be obtained. For sampling run
durations greater than 1 hour, measurements at 2-minute intervals or a
minimum of 96 measurements, whichever is less restrictive, shall be
obtained.
5.2 Method 6 Apparatus and Reagents. The apparatus and reagents
described in Method 6, and shown by the schematic of the sampling train
in Figure 6C-2, to conduct the interference check.
5.3 SO2 Calibration Gases. The calibration gases for the
gas analyzer shall be SO2 in N2 or SO2
in air. Alternatively, SO2/CO2, SO2/
O2, or SO2/CO2/O2 gas
mixtures in N2 may be used. For fluorescence-based analyzers,
the O2 and CO2 concentrations of the calibration
gases as introduced to the analyzer shall be within 1 percent (absolute)
O2 and 1 percent (absolute) CO2 of the
O2 and Co2 concentrations of the effluent samples
as introduced to the analyzer. Alternatively, for fluorescence-based
analyzers, use calibration blends of SO2 in air and the
nomographs provided by the vendor to determine the quenching correction
factor (the effluent O2 and CO2 concentrations
must be known). Use three calibration gases as specified below:

[[Page 266]]

5.3.1 High-Range Gas. Concentration equivalent to 80 to 100 percent
of the span.
5.3.2 Mid-Range Gas. Concentration equivalent to 40 to 60 percent
of the span.
5.3.3 Zero Gas. Concentration of less than 0.25 percent of the
span. Purified ambient air may be used for the zero gas by passing air
through a charcoal filter, or through one or more impingers containing a
solution of 3 percent H2O2.

6. Measurement System Performance Test Procedures

Perform the following procedures before measurement of emissions
(Section 7).
6.1 Calibration Gas Concentration Verification. There are two
alternatives for establishing the concentrations of calibration gases.
Alternative Number 1 is preferred.
6.1.1 Alternative Number 1--Use of calibration gases that are
analyzed following the Environmental Protection Agency Traceability
Protocol Number 1 (see Citation 1 in the Bibliography). Obtain a
certification from the gas manufacturer that Protocol Number 1 was
followed.
6.1.2 Alternative Number 2--Use of calibration gases not prepared
according to Protocol Number 1. If this alternative is chosen, obtain
gas mixtures with a manufacturer's tolerance not to exceed 2
percent of the tag value. Within 6 months before the emission test,
analyze each of the calibration gases in triplicate using Method 6.
Citation 2 in the Bibliography describes procedures and techniques that
may be used for this analysis. Record the results on a data sheet
(example is shown in Figure 6C-3). Each of the individual SO2
analytical results for each calibration gas shall be within 5 percent
(or 5 ppm, whichever is greater) of the triplicate set average;
otherwise, discard the entire set, and repeat the triplicate analyses.
If the average of the triplicate analyses is within 5 percent of the
calibration gas manufacturer's cylinder tag value, use the tag value;
otherwise, conduct at least three additional analyses until the results
of six consecutive runs agree with 5 percent (or 5 ppm, whichever is
greater) of their average. Then use this average for the cylinder value.
6.2 Measurement System Preparation. Assemble the measurement system
by following the manufacturer's written instructions for preparing and
preconditioning the gas analyzer and, as applicable, the other system
components. Introduce the calibration gases in any sequence, and make
all necessary adjustments to calibrate the analyzer and the data
recorder. Adjust system components to achieve correct sampling rates.
6.3 Analyzer Calibration Error. Conduct the analyzer calibration
error check by introducing calibration gases to the measurement system
at any point upstream of the gas analyzer as follows:
6.3.1 After the measurement system has been prepared for use,
introduce the zero, mid-range, and high-range gases to the analyzer.
During this check, make no adjustments to the system except those
necessary to achieve the correct calibration gas flow rate at the
analyzer. Record the analyzer responses to each calibration gas on a
form similar to Figure 6C-4.
Note: A calibration curve established prior to the analyzer
calibration error check may be used to convert the analyzer response to
the equivalent gas concentration introduced to the analyzer. However,
the same correction procedure shall be used for all effluent and
calibration measurements obtained during the test.
6.3.2 The analyzer calibration error check shall be considered
invalid if the gas concentration displayed by the analyzer exceeds
2 percent of the span for any of the calibration gases. If
an invalid calibration is exhibited, take corrective action, and repeat
the analyzer calibration error check until acceptable performance is
achieved.
6.4 Sampling System Bias Check. Perform the sampling system bias
check by introducing calibration gases at the calibration valve
installed at the outlet of the sampling probe. A zero gas and either the
mid-range or high-range gas, whichever most closely approximates the
effluent concentrations, shall be used for this check as follows:
6.4.1 Introduce the upscale calibration gas, and record the gas
concentration displayed by the analyzer on a form similar to Figure 6C-
5. Then introduce zero gas, and record the gas concentration displayed
by the analyzer. During the sampling system bias check, operate the
system at the normal sampling rate, and make no adjustments to the
measurement system other than those necessary to achieve proper
calibration gas flow rates at the analyzer. Alternately introduce the
zero and upscale gases until a stable response is achieved. The tester
shall determine the measurement system response time by observing the
times required to achieve a stable response for both the zero and
upscale gases. Note the longer of the two times as the response time.
6.4.2 The sampling system bias check shall be considered invalid if
the difference between the gas concentrations displayed by the
measurement system for the analyzer calibration error check and for the
sampling system bias check exceeds 5 percent of the span for
either the zero or upscale calibration gas. If an invalid calibration is
exhibited, take corrective action, and repeat the sampling system bias
check until acceptable performance is achieved. If adjustment to the
analyzer is required, first repeat the analyzer calibration error check,
then repeat the sampling system bias check.

[[Page 267]]

7. Emission Test Procedure

7.1 Selection of Sampling Site and Sampling Points. Select a
measurement site and sampling points using the same criteria that are
applicable to Method 6.
7.2 Interference Check Preparation. For each individual analyzer,
conduct an interference check for at least three runs during the initial
field test on a particular source category. Retain the results, and
report them with each test performed on that source category.
If an interference check is being performed, assemble the modified
Method 6 train (flow control valve, two midget impingers containing 3
percent H2O2, and dry gas meter) as shown in
Figure 6C-2. Install the sampling train to obtain a sample at the
measurement system sample by-pass discharge vent. Record the initial dry
gas meter reading.
7.3 Sample Collection. Position the sampling probe at the first
measurement point, and begin sampling at the same rate as used during
the sampling system bias check. Maintain constant rate sampling (i.e.,
10 percent) during the entire run. The sampling time per run
shall be the same as for Method 6 plus twice the system response time.
For each run, use only those measurements obtained after twice response
time of the measurement system has elapsed, to determine the average
effluent concentration. If an interference check is being performed,
open the flow control valve on the modified Method 6 train concurrent
with the initiation of the sampling period, and adjust the flow to 1
liter per minute (10 percent).
(Note: If a pump is not used in the modified Method 6 train, caution
should be exercised in adjusting the flow rate since overpressurization
of the impingers may cause leakage in the impinger train, resulting in
positively biased results).
7.4 Zero and Calibration Drift Tests. Immediately preceding and
following each run, or if adjustments are necessary for the measurement
system during the run, repeat the sampling system bias check procedure
described in Section 6.4 (Make no adjustments to the measurement system
until after the drift checks are completed.) Record and analyzer's
responses on a form similar to Figure 6C-5.
7.4.1 If either the zero or upscale calibration value exceeds the
sampling system bias specification, then the run is considered invalid.
Repeat both the analyzer calibration error check procedure (Section 6.3)
and the sampling system bias check procedure (Section 6.4) before
repeating the run.
7.4.2 If both the zero and upscale calibration values are within
the sampling system bias specification, then use the average of the
initial and final bias check values to calculate the gas concentration
for the run. If the zero or upscale calibration drift value exceeds the
drift limits, based on the difference between the sampling system bias
check responses immediately before and after the run, repeat both the
analyzer calibration error check procedure (Section 6.3) and the
sampling system bias check procedure (Section 6.4) before conducting
additional runs.
7.5 Interference Check (if performed). After completing the run,
record the final dry gas meter reading, meter temperature, and
barometric pressure. Recover and analyze the contents of the midget
impingers, and determine the SO2 gas concentration using the
procedures of Method 6. (It is not necessary to analyze EPA performance
audit samples for Method 6.) Determine the average gas concentration
exhibited by the analyzer for the run. If the gas concentrations
provided by the analyzer and the modified Method 6 differ by more than 7
percent of the modified Method 6 result, the run is invalidated.

8. Emission Calculation

The average gas effluent concentration is determined from the
average gas concentration displayed by the gas analyzer, and is adjusted
for the zero and upscale sampling system bias checks, as determined in
accordance with Section 7.4. The average gas concentration displayed by
the analyzer may be determined by integration of the area under the
curve for chart recorders, or by averaging all of the effluent
measurements. Alternatively, the average may be calculated from
measurements recorded at equally spaced intervals over the entire
duration of the run. For sampling run durations of less than 1 hour,
measurements at 1-minute intervals or a minimum of 30 measurements,
whichever is less restrictive, shall be used. For sampling run durations
greater than 1 hour, measurements at 2-minute intervals or a minimum of
96 measurements, whichever is less restrictive, shall be used. Calculate
the effluent gas concentration using Equation 6C-1.
[GRAPHIC] [TIFF OMITTED] TC16NO91.150

Where:

Cgas = Effluent gas concentration, dry basis, ppm.
C = Average gas concentration indicated by gas analyzer, dry basis, ppm.
Co = Average of initial and final system calibration bias
check responses for the zero gas, ppm.
Cm = Average of initial and final system calibration bias
check responses for the upscale calibration gas, ppm.
Cma = Actual concentration of the upscale calibration gas,
ppm.

9. Bibliography

[[Page 268]]

1. Traceability Protocol for Establishing True Concentrations of
Gases Used for Calibrations and Audits of Continuous Source Emission
Monitors: Protocol Number 1. U.S. Environmental Protection Agency,
Quality Assurance Division. Research Triangle Park, NC. June 1978.
2. Westlin, Peter R. and J. W. Brown. Methods for Collecting and
Analyzing Gas Cylinder Samples. Source Evaluation Society Newsletter.
3(3):5-15. September 1978.
[GRAPHIC] [TIFF OMITTED] TC01JN92.141

Figure 6C-3--Analysis of Calibration Gases

Date____________________________________________________________________
Analytic method used

[[Page 269]]

________________________________________________________________________

------------------------------------------------------------------------
Gas concentration (indicate units)
--------------------------------------
High-range
Zero ^a Mid-range ^b ^c
------------------------------------------------------------------------
Sample run:
1.............................. ........... ........... ...........
2.............................. ........... ........... ...........
3.............................. ........... ........... ...........
Average...................... ........... ........... ...........
Maximum percent deviation........ ........... ........... ...........
------------------------------------------------------------------------
^a Average must be less than 0.25 percent of span.
^b Average must be 50 to 60 percent of span.
^c Average must be 80 to 90 percent of span.

Figure 6C-4--Analyzer calibration data

Source identification:__________________________________________________
Test personnel:_________________________________________________________
Date:___________________________________________________________________
Analyzer calibration data for sampling
runs:_________________________________________________________________
Span:___________________________________________________________________

----------------------------------------------------------------------------------------------------------------
Analyzer
Cylinder calibration Absolute Difference
value response difference (percent of
(indicate (indicate (indicate span)
units) units) units)
----------------------------------------------------------------------------------------------------------------
Zero gas.................................................... ........... ........... ........... ...........
Mid-range gas............................................... ........... ........... ........... ...........
High-range gas.............................................. ........... ........... ........... ...........
----------------------------------------------------------------------------------------------------------------

Figure 6C-5--System calibration bias and drift data

Source identification:__________________________________________________
Test personnel:_________________________________________________________
Date:___________________________________________________________________
Run number:_____________________________________________________________
Span:___________________________________________________________________

----------------------------------------------------------------------------------------------------------------
Initial values Final values
----------------------------------------------------
Analyzer System cal. System cal. Drift
calibration System bias System bias (percent of
response calibration (percent of calibration (percent of span)
response span) response span)
----------------------------------------------------------------------------------------------------------------
Zero gas.......................... ........... ........... ........... ........... ........... ...........
Upscale gas....................... ........... ........... ........... ........... ........... ...........
----------------------------------------------------------------------------------------------------------------

[GRAPHIC] [TIFF OMITTED] TC16NO91.151

Method 7--Determination of Nitrogen Oxide Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1 and Method 5.

[[Page 270]]

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9
Nitrogen dioxide (NO2)........ 10102-44-0 2-400 mg/dscm
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the measurement of
nitrogen oxides (NOX) emitted from stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sample methods.

2.0 Summary of Method

A grab sample is collected in an evacuated flask containing a dilute
sulfuric acid-hydrogen peroxide absorbing solution, and the nitrogen
oxides, except nitrous oxide, are measured colorimetrically using the
phenoldisulfonic acid (PDS) procedure.

3.0 Definitions. [Reserved]

4.0 Interferences

Biased results have been observed when sampling under conditions of
high sulfur dioxide concentrations (above 2000 ppm).

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. A schematic of the sampling train used in
performing this method is shown in Figure 7-1. Other grab sampling
systems or equipment, capable of measuring sample volume to within 2.0
percent and collecting a sufficient sample volume to allow analytical
reproducibility to within 5 percent, will be considered acceptable
alternatives, subject to the approval of the Administrator. The
following items are required for sample collection:
6.1.1 Probe. Borosilicate glass tubing, sufficiently heated to
prevent water condensation and equipped with an in-stack or heated out-
of-stack filter to remove particulate matter (a plug of glass wool is
satisfactory for this purpose). Stainless steel or Teflon tubing may
also be used for the probe. Heating is not necessary if the probe
remains dry during the purging period.
6.1.2 Collection Flask. Two-liter borosilicate, round bottom flask,
with short neck and 24/40 standard taper opening, protected against
implosion or breakage.
6.1.3 Flask Valve. T-bore stopcock connected to a 24/40 standard
taper joint.
6.1.4 Temperature Gauge. Dial-type thermometer, or other
temperature gauge, capable of measuring 1 deg.C (2 deg.F) intervals
from -5 to 50 deg.C (23 to 122 deg.F).
6.1.5 Vacuum Line. Tubing capable of withstanding a vacuum of 75 mm
(3 in.) Hg absolute pressure, with ``T'' connection and T-bore stopcock.
6.1.6 Vacuum Gauge. U-tube manometer, 1 meter (39 in.), with 1 mm
(0.04 in.) divisions, or other gauge capable of measuring pressure to
within 2.5 mm (0.10 in.) Hg.
6.1.7 Pump. Capable of evacuating the collection flask to a
pressure equal to or less than 75 mm (3 in.) Hg absolute.
6.1.8 Squeeze Bulb. One-way.
6.1.9 Volumetric Pipette. 25-ml.
6.1.10 Stopcock and Ground Joint Grease. A high-vacuum, high-
temperature chlorofluorocarbon grease is required.

[[Page 271]]

Halocarbon 25-5S has been found to be effective.
6.1.11 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm (0.1 in.) Hg. See NOTE
in Method 5, Section 6.1.2.
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Graduated Cylinder. 50-ml with 1 ml divisions.
6.2.2 Storage Containers. Leak-free polyethylene bottles.
6.2.3 Wash Bottle. Polyethylene or glass.
6.2.4 Glass Stirring Rod.
6.2.5 Test Paper for Indicating pH. To cover the pH range of 7 to
14.
6.3 Analysis. The following items are required for analysis:
6.3.1 Volumetric Pipettes. Two 1-ml, two 2-ml, one 3-ml, one 4-ml,
two 10-ml, and one 25-ml for each sample and standard.
6.3.2 Porcelain Evaporating Dishes. 175- to 250-ml capacity with
lip for pouring, one for each sample and each standard. The Coors No.
45006 (shallowform, 195-ml) has been found to be satisfactory.
Alternatively, polymethyl pentene beakers (Nalge No. 1203, 150-ml), or
glass beakers (150-ml) may be used. When glass beakers are used, etching
of the beakers may cause solid matter to be present in the analytical
step; the solids should be removed by filtration.
6.3.3 Steam Bath. Low-temperature ovens or thermostatically
controlled hot plates kept below 70 deg.C (160 deg.F) are acceptable
alternatives.
6.3.4 Dropping Pipette or Dropper. Three required.
6.3.5 Polyethylene Policeman. One for each sample and each
standard.
6.3.6 Graduated Cylinder. 100-ml with 1-ml divisions.
6.3.7 Volumetric Flasks. 50-ml (one for each sample and each
standard), 100-ml (one for each sample and each standard, and one for
the working standard KNO3 solution), and 1000-ml (one).
6.3.8 Spectrophotometer. To measure at 410 nm.
6.3.9 Graduated Pipette. 10-ml with 0.1-ml divisions.
6.3.10 Test Paper for Indicating pH. To cover the pH range of 7 to
14.
6.3.11 Analytical Balance. To measure to within 0.1 mg.

7.0 Reagents and Standards

Unless otherwise indicated, it is intended that all reagents conform
to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available; otherwise, use the best available grade.
7.1 Sample Collection. The following reagents are required for
sampling:
7.1.1 Water. Deionized distilled to conform to ASTM D 1193-77 or 91
Type 3 (incorporated by reference--see Sec. 60.17). The KMnO4
test for oxidizable organic matter may be omitted when high
concentrations of organic matter are not expected to be present.
7.1.2 Absorbing Solution. Cautiously add 2.8 ml concentrated
H2SO4 to a 1-liter flask partially filled with
water. Mix well, and add 6 ml of 3 percent hydrogen peroxide, freshly
prepared from 30 percent hydrogen peroxide solution. Dilute to 1 liter
of water and mix well. The absorbing solution should be used within 1
week of its preparation. Do not expose to extreme heat or direct
sunlight.
7.2 Sample Recovery. The following reagents are required for sample
recovery:
7.2.1 Water. Same as in 7.1.1.
7.2.2 Sodium Hydroxide, 1 N. Dissolve 40 g NaOH in water, and
dilute to 1 liter.
7.3 Analysis. The following reagents and standards are required for
analysis:
7.3.1 Water. Same as in 7.1.1.
7.3.2 Fuming Sulfuric Acid. 15 to 18 percent by weight free sulfur
trioxide. HANDLE WITH CAUTION.
7.3.3 Phenol. White solid.
7.3.4 Sulfuric Acid. Concentrated, 95 percent minimum assay.
7.3.5 Potassium Nitrate (KNO3). Dried at 105 to 110
deg.C (221 to 230 deg.F) for a minimum of 2 hours just prior to
preparation of standard solution.
7.3.6 Standard KNO3 Solution. Dissolve exactly 2.198 g
of dried KNO3 in water, and dilute to 1 liter with water in a
1000-ml volumetric flask.
7.3.7 Working Standard KNO3 Solution. Dilute 10 ml of
the standard solution to 100 ml with water. One ml of the working
standard solution is equivalent to 100 g nitrogen dioxide
(NO2).
7.3.8 Phenoldisulfonic Acid Solution. Dissolve 25 g of pure white
phenol solid in 150 ml concentrated sulfuric acid on a steam bath. Cool,
add 75 ml fuming sulfuric acid (15 to 18 percent by weight free sulfur
trioxide--HANDLE WITH CAUTION), and heat at 100 deg.C (212 deg.F) for
2 hours. Store in a dark, stoppered bottle.
7.3.9 Concentrated Ammonium Hydroxide.
7.3.10 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, audit samples may be obtained
from the appropriate EPA Regional Office or from the responsible
enforcement authority.

Note: The responsible enforcement authority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Storage and Transport

8.1 Sample Collection.
8.1.1 Flask Volume. The volume of the collection flask and flask
valve combination must be known prior to sampling. Assemble

[[Page 272]]

the flask and flask valve, and fill with water to the stopcock. Measure
the volume of water to 10 ml. Record this volume on the
flask.
8.1.2 Pipette 25 ml of absorbing solution into a sample flask,
retaining a sufficient quantity for use in preparing the calibration
standards. Insert the flask valve stopper into the flask with the valve
in the ``purge'' position. Assemble the sampling train as shown in
Figure 7-1, and place the probe at the sampling point. Make sure that
all fittings are tight and leak-free, and that all ground glass joints
have been greased properly with a high-vacuum, high temperature
chlorofluorocarbon-based stopcock grease. Turn the flask valve and the
pump valve to their ``evacuate'' positions. Evacuate the flask to 75 mm
(3 in.) Hg absolute pressure, or less. Evacuation to a pressure
approaching the vapor pressure of water at the existing temperature is
desirable. Turn the pump valve to its ``vent'' position, and turn off
the pump. Check for leakage by observing the manometer for any pressure
fluctuation. (Any variation greater than 10 mm (0.4 in.) Hg over a
period of 1 minute is not acceptable, and the flask is not to be used
until the leakage problem is corrected. Pressure in the flask is not to
exceed 75 mm (3 in.) Hg absolute at the time sampling is commenced.)
Record the volume of the flask and valve (Vf), the flask
temperature (Ti), and the barometric pressure. Turn the flask
valve counterclockwise to its ``purge'' position, and do the same with
the pump valve. Purge the probe and the vacuum tube using the squeeze
bulb. If condensation occurs in the probe and the flask valve area, heat
the probe, and purge until the condensation disappears. Next, turn the
pump valve to its ``vent'' position. Turn the flask valve clockwise to
its ``evacuate'' position, and record the difference in the mercury
levels in the manometer. The absolute internal pressure in the flask
(Pi) is equal to the barometric pressure less the manometer
reading. Immediately turn the flask valve to the ``sample'' position,
and permit the gas to enter the flask until pressures in the flask and
sample line (i.e., duct, stack) are equal. This will usually require
about 15 seconds; a longer period indicates a plug in the probe, which
must be corrected before sampling is continued. After collecting the
sample, turn the flask valve to its ``purge'' position, and disconnect
the flask from the sampling train.
8.1.3 Shake the flask for at least 5 minutes.
8.1.4 If the gas being sampled contains insufficient oxygen for the
conversion of NO to NO2 (e.g., an applicable subpart of the
standards may require taking a sample of a calibration gas mixture of NO
in N2), then introduce oxygen into the flask to permit this
conversion. Oxygen may be introduced into the flask by one of three
methods: (1) Before evacuating the sampling flask, flush with pure
cylinder oxygen, then evacuate flask to 75 mm (3 in.) Hg absolute
pressure or less; or (2) inject oxygen into the flask after sampling; or
(3) terminate sampling with a minimum of 50 mm (2 in.) Hg vacuum
remaining in the flask, record this final pressure, and then vent the
flask to the atmosphere until the flask pressure is almost equal to
atmospheric pressure.
8.2 Sample Recovery. Let the flask sit for a minimum of 16 hours,
and then shake the contents for 2 minutes.
8.2.1 Connect the flask to a mercury filled U-tube manometer. Open
the valve from the flask to the manometer, and record the flask
temperature (Tf), the barometric pressure, and the difference
between the mercury levels in the manometer. The absolute internal
pressure in the flask (Pf) is the barometric pressure less
the manometer reading. Transfer the contents of the flask to a leak-free
polyethylene bottle. Rinse the flask twice with 5 ml portions of water,
and add the rinse water to the bottle. Adjust the pH to between 9 and 12
by adding 1 N NaOH, dropwise (about 25 to 35 drops). Check the pH by
dipping a stirring rod into the solution and then touching the rod to
the pH test paper. Remove as little material as possible during this
step. Mark the height of the liquid level so that the container can be
checked for leakage after transport. Label the container to identify
clearly its contents. Seal the container for shipping.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.4.......................... Audit sample Evaluate analytical
analysis. technique,
preparation of
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Spectrophotometer.
10.1.1 Optimum Wavelength Determination.
10.1.1.1 Calibrate the wavelength scale of the spectrophotometer
every 6 months. The calibration may be accomplished by using an energy
source with an intense line emission such as a mercury lamp, or by using
a series of glass filters spanning the measuring range of the
spectrophotometer. Calibration materials are available commercially and
from the National Institute of Standards and Technology. Specific
details on the use of

[[Page 273]]

such materials should be supplied by the vendor; general information
about calibration techniques can be obtained from general reference
books on analytical chemistry. The wavelength scale of the
spectrophotometer must read correctly within 5 nm at all calibration
points; otherwise, repair and recalibrate the spectrophotometer. Once
the wavelength scale of the spectrophotometer is in proper calibration,
use 410 nm as the optimum wavelength for the measurement of the
absorbance of the standards and samples.
10.1.1.2 Alternatively, a scanning procedure may be employed to
determine the proper measuring wavelength. If the instrument is a
double-beam spectrophotometer, scan the spectrum between 400 and 415 nm
using a 200 g NO2 standard solution in the sample
cell and a blank solution in the reference cell. If a peak does not
occur, the spectrophotometer is probably malfunctioning and should be
repaired. When a peak is obtained within the 400 to 415 nm range, the
wavelength at which this peak occurs shall be the optimum wavelength for
the measurement of absorbance of both the standards and the samples. For
a single-beam spectrophotometer, follow the scanning procedure described
above, except scan separately the blank and standard solutions. The
optimum wavelength shall be the wavelength at which the maximum
difference in absorbance between the standard and the blank occurs.
10.1.2 Determination of Spectrophotometer Calibration Factor
Kc. Add 0 ml, 2.0 ml, 4.0 ml, 6.0 ml, and 8.0 ml of the
KNO3 working standard solution (1 ml = 100 g
NO2) to a series of five 50-ml volumetric flasks. To each
flask, add 25 ml of absorbing solution and 10 ml water. Add 1 N NaOH to
each flask until the pH is between 9 and 12 (about 25 to 35 drops).
Dilute to the mark with water. Mix thoroughly, and pipette a 25-ml
aliquot of each solution into a separate porcelain evaporating dish.
Beginning with the evaporation step, follow the analysis procedure of
Section 11.2 until the solution has been transferred to the 100-ml
volumetric flask and diluted to the mark. Measure the absorbance of each
solution at the optimum wavelength as determined in Section 10.2.1. This
calibration procedure must be repeated on each day that samples are
analyzed. Calculate the spectrophotometer calibration factor as shown in
Section 12.2.
10.1.3 Spectrophotometer Calibration Quality Control. Multiply the
absorbance value obtained for each standard by the Kc factor
(reciprocal of the least squares slope) to determine the distance each
calibration point lies from the theoretical calibration line. The
difference between the calculated concentration values and the actual
concentrations (i.e., 100, 200, 300, and 400 g NO2)
should be less than 7 percent for all standards.
10.2 Barometer. Calibrate against a mercury barometer.
10.3 Temperature Gauge. Calibrate dial thermometers against
mercury-in-glass thermometers.
10.4 Vacuum Gauge. Calibrate mechanical gauges, if used, against a
mercury manometer such as that specified in Section 6.1.6.
10.5 Analytical Balance. Calibrate against standard weights.

11.0 Analytical Procedures

11.1 Sample Loss Check. Note the level of the liquid in the
container, and confirm whether any sample was lost during shipment. Note
this on the analytical data sheet. If a noticeable amount of leakage has
occurred, either void the sample or use methods, subject to the approval
of the Administrator, to correct the final results.
11.2 Sample Preparation. Immediately prior to analysis, transfer
the contents of the shipping container to a 50 ml volumetric flask, and
rinse the container twice with 5 ml portions of water. Add the rinse
water to the flask, and dilute to mark with water; mix thoroughly.
Pipette a 25-ml aliquot into the porcelain evaporating dish. Return any
unused portion of the sample to the polyethylene storage bottle.
Evaporate the 25-ml aliquot to dryness on a steam bath, and allow to
cool. Add 2 ml phenoldisulfonic acid solution to the dried residue, and
triturate thoroughly with a polyethylene policeman. Make sure the
solution contacts all the residue. Add 1 ml water and 4 drops of
concentrated sulfuric acid. Heat the solution on a steam bath for 3
minutes with occasional stirring. Allow the solution to cool, add 20 ml
water, mix well by stirring, and add concentrated ammonium hydroxide,
dropwise, with constant stirring, until the pH is 10 (as determined by
pH paper). If the sample contains solids, these must be removed by
filtration (centrifugation is an acceptable alternative, subject to the
approval of the Administrator) as follows: Filter through Whatman No. 41
filter paper into a 100-ml volumetric flask. Rinse the evaporating dish
with three 5-ml portions of water. Filter these three rinses. Wash the
filter with at least three 15-ml portions of water. Add the filter
washings to the contents of the volumetric flask, and dilute to the mark
with water. If solids are absent, the solution can be transferred
directly to the 100-ml volumetric flask and diluted to the mark with
water.
11.3 Sample Analysis. Mix the contents of the flask thoroughly, and
measure the absorbance at the optimum wavelength used for the standards
(Section 10.2.1), using the blank solution as a zero reference. Dilute
the sample and the blank with equal volumes of water if the absorbance
exceeds A4, the absorbance of the 400-g
NO2 standard (see Section 10.2.2).
11.4 Audit Sample Analysis.

[[Page 274]]

11.4.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, an audit sample must be
analyzed, subject to availability.
11.4.2 Concurrently analyze the audit sample and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.4.3 The same analyst, analytical reagents, and analytical system
must be used for the compliance samples and the audit sample. If this
condition is met, duplicate auditing of subsequent compliance analyses
for the same enforcement agency within a 30-day period is waived. An
audit sample set may not be used to validate different sets of
compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both enforcement
agencies.
11.5 Audit Sample Results.
11.5.1 Calculate the audit sample concentrations and submit results
using the instructions provided with the audit samples.
11.5.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.5.3 The concentrations of the audit samples obtained by the
analyst must agree within 5 percent of the actual concentration. If the
5 percent specification is not met, reanalyze the compliance and audit
samples, and include initial and reanalysis values in the test report.
11.5.4 Failure to meet the 5-percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to determine
the compliance or noncompliance status of the affected facility.

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculations.
12.1 Nomenclature.

A = Absorbance of sample.
A1 = Absorbance of the 100-g NO2
standard.
A2 = Absorbance of the 200-g NO2
standard.
A3 = Absorbance of the 300-g NO2
standard.
A4 = Absorbance of the 400-g NO2
standard.
C = Concentration of NOX as NO2, dry basis,
corrected to standard conditions, mg/dsm\3\ (lb/dscf).
Cd = Determined audit sample concentration, mg/dscm.
Ca = Actual audit sample concentration, mg/dscm.
F = Dilution factor (i.e., 25/5, 25/10, etc., required only if sample
dilution was needed to reduce the absorbance into the range of
the calibration).
Kc = Spectrophotometer calibration factor.
m = Mass of NOX as NO2 in gas sample, g.
Pf = Final absolute pressure of flask, mm Hg (in. Hg).
Pi = Initial absolute pressure of flask, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
RE = Relative error for QA audit samples, percent.
Tf = Final absolute temperature of flask, deg.K ( deg.R).
Ti = Initial absolute temperature of flask, deg.K ( deg.R).
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Vsc = Sample volume at standard conditions (dry basis), ml.
Vf = Volume of flask and valve, ml.
Va = Volume of absorbing solution, 25 ml.

12.2 Spectrophotometer Calibration Factor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.200

12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.201

[[Page 275]]

Where:

K1 = 0.3858 deg.K/mm Hg for metric units,
K1 = 17.65 deg.R/in. Hg for English units.

12.4 Total g NO2 per sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.202

Where:
2 = 50/25, the aliquot factor.

Note: If other than a 25-ml aliquot is used for analysis, the factor
2 must be replaced by a corresponding factor.
12.5 Sample Concentration, Dry Basis, Corrected to Standard
Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.203

Where:
K2 = 10\3\ (mg/m\3\)/(g/ml) for metric units,
K2 = 6.242 x 10^-\5\ (lb/scf)/(g/ml) for
English units.
12.6 Relative Error for QA Audit Samples.
[GRAPHIC] [TIFF OMITTED] TR17OC00.204

13.0 Method Performance

13.1 Range. The analytical range of the method has been determined
to be 2 to 400 milligrams NOX (as NO2) per dry
standard cubic meter, without having to dilute the sample.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Standard Methods of Chemical Analysis. 6th ed. New York, D. Van
Nostrand Co., Inc. 1962. Vol. 1, pp. 329-330.
2. Standard Method of Test for Oxides of Nitrogen in Gaseous
Combustion Products (Phenoldisulfonic Acid Procedure). In: 1968 Book of
ASTM Standards, Part 26. Philadelphia, PA. 1968. ASTM Designation D
1608-60, pp. 725-729.
3. Jacob, M.B. The Chemical Analysis of Air Pollutants. New York.
Interscience Publishers, Inc. 1960. Vol. 10, pp. 351-356.
4. Beatty, R.L., L.B. Berger, and H.H. Schrenk. Determination of
Oxides of Nitrogen by the Phenoldisulfonic Acid Method. Bureau of Mines,
U.S. Dept. of Interior. R.I. 3687. February 1943.
5. Hamil, H.F. and D.E. Camann. Collaborative Study of Method for
the Determination of Nitrogen Oxide Emissions from Stationary Sources
(Fossil Fuel-Fired Steam Generators). Southwest Research Institute
Report for Environmental Protection Agency. Research Triangle Park, NC.
October 5, 1973.
6. Hamil, H.F. and R.E. Thomas. Collaborative Study of Method for
the Determination of Nitrogen Oxide Emissions from Stationary Sources
(Nitric Acid Plants). Southwest Research Institute Report for
Environmental Protection Agency. Research Triangle Park, NC. May 8,
1974.
7. Stack Sampling Safety Manual (Draft). U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standards,
Research Triangle Park, NC. September 1978.

[[Page 276]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.205

Method 7A--Determination of Nitrogen Oxide Emissions From Stationary
Sources (Ion Chromatographic Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 3, Method 5, and
Method 7.

[[Page 277]]

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9 ....................
Nitrogen dioxide (NO2)........ 10102-44-0 65-655 ppmv
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of NOX emissions from stationary sources.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

A grab sample is collected in an evacuated flask containing a dilute
sulfuric acid-hydrogen peroxide absorbing solution. The nitrogen oxides,
excluding nitrous oxide (N2O), are oxidized to nitrate and
measured by ion chromatography.

3.0 Definitions [Reserved]

4.0 Interferences

Biased results have been observed when sampling under conditions of
high sulfur dioxide concentrations (above 2000 ppm).

5.0 Safety

5.1 This method may involve hazardous materials, operations, and
equipment. This test method may not address all of the safety problems
associated with its use. It is the responsibility of the user of this
test method to establish appropriate safety and health practices and to
determine the applicability of regulatory limitations prior to
performing this test method.
5.2 Corrosive reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burns as thermal
burns.
5.2.1 Hydrogen Peroxide (H2O2). Irritating to
eyes, skin, nose, and lungs.
5.2.2 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 3 mg/m³ will cause lung damage in uninitiated. 1 mg/
m³ for 8 hours will cause lung damage or, in higher
concentrations, death. Provide ventilation to limit inhalation. Reacts
violently with metals and organics.

6.0 Equipment and Supplies

6.1 Sample Collection. Same as in Method 7, Section 6.1.
6.2 Sample Recovery. Same as in Method 7, Section 6.2, except the
stirring rod and pH paper are not needed.
6.3 Analysis. For the analysis, the following equipment and
supplies are required. Alternative instrumentation and procedures will
be allowed provided the calibration precision requirement in Section
10.1.2 and audit accuracy requirement in Section 11.3 can be met.
6.3.1 Volumetric Pipets. Class A;1-, 2-, 4-, 5-ml (two for the set
of standards and one per sample), 6-, 10-, and graduated 5-ml sizes.
6.3.2 Volumetric Flasks. 50-ml (two per sample and one per
standard), 200-ml, and 1-liter sizes.
6.3.3 Analytical Balance. To measure to within 0.1 mg.
6.3.4 Ion Chromatograph. The ion chromatograph should have at least
the following components:
6.3.4.1 Columns. An anion separation or other column capable of
resolving the nitrate ion from sulfate and other species present and a
standard anion suppressor column (optional). Suppressor columns are
produced as proprietary items; however, one can be produced in the
laboratory using the resin available from BioRad Company, 32nd and
Griffin Streets, Richmond, California. Peak resolution can be optimized
by varying the eluent strength or column flow rate, or by experimenting
with alternative columns that may offer more efficient separation. When
using guard columns with the stronger reagent to protect the separation
column, the analyst should allow rest periods between injection
intervals to purge possible sulfate buildup in the guard column.
6.3.4.2 Pump. Capable of maintaining a steady flow as required by
the system.
6.3.4.3 Flow Gauges. Capable of measuring the specified system flow
rate.
6.3.4.4 Conductivity Detector.
6.3.4.5 Recorder. Compatible with the output voltage range of the
detector.

7.0 Reagents and Standards

Unless otherwise indicated, it is intended that all reagents conform
to the specifications established by the Committee on Analytical
Reagents of the American Chemical

[[Page 278]]

Society, where such specifications are available; otherwise, use the
best available grade.
7.1 Sample Collection. Same as Method 7, Section 7.1.
7.2 Sample Recovery. Same as Method 7, Section 7.1.1.
7.3 Analysis. The following reagents and standards are required for
analysis:
7.3.1 Water. Same as Method 7, Section 7.1.1.
7.3.2 Stock Standard Solution, 1 mg NO2/ml. Dry an
adequate amount of sodium nitrate (NaNO3) at 105 to 110
deg.C (221 to 230 deg.F) for a minimum of 2 hours just before preparing
the standard solution. Then dissolve exactly 1.847 g of dried
NaNO3 in water, and dilute to l liter in a volumetric flask.
Mix well. This solution is stable for 1 month and should not be used
beyond this time.
7.3.3 Working Standard Solution, 25 g/ml. Dilute 5 ml of
the standard solution to 200 ml with water in a volumetric flask, and
mix well.
7.3.4 Eluent Solution. Weigh 1.018 g of sodium carbonate
(Na2CO3) and 1.008 g of sodium bicarbonate
(NaHCO3), and dissolve in 4 liters of water. This solution is
0.0024 M Na2CO3/0.003 M NaHCO3. Other
eluents appropriate to the column type and capable of resolving nitrate
ion from sulfate and other species present may be used.
7.3.5 Quality Assurance Audit Samples. Same as Method 7, Section
7.3.8.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling. Same as in Method 7, Section 8.1.
8.2 Sample Recovery. Same as in Method 7, Section 8.2, except
delete the steps on adjusting and checking the pH of the sample. Do not
store the samples more than 4 days between collection and analysis.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... Ion chromatograph Ensure linearity of
calibration. ion chromatograph
response to
standards.
11.3.......................... Audit sample Evaluate analytical
analysis. technique,
preparation of
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

10.1 Ion Chromatograph.
10.1.1 Determination of Ion Chromatograph Calibration Factor S.
Prepare a series of five standards by adding 1.0, 2.0, 4.0, 6.0, and
10.0 ml of working standard solution (25 g/ml) to a series of
five 50-ml volumetric flasks. (The standard masses will equal 25, 50,
100, 150, and 250 g.) Dilute each flask to the mark with water,
and mix well. Analyze with the samples as described in Section 11.2, and
subtract the blank from each value. Prepare or calculate a linear
regression plot of the standard masses in g (x-axis) versus
their peak height responses in millimeters (y-axis). (Take peak height
measurements with symmetrical peaks; in all other cases, calculate peak
areas.) From this curve, or equation, determine the slope, and calculate
its reciprocal to denote as the calibration factor, S.
10.1.2 Ion Chromatograph Calibration Quality Control. If any point
on the calibration curve deviates from the line by more than 7 percent
of the concentration at that point, remake and reanalyze that standard.
This deviation can be determined by multiplying S times the peak height
response for each standard. The resultant concentrations must not differ
by more than 7 percent from each known standard mass (i.e., 25, 50, 100,
150, and 250 g).
10.2 Conductivity Detector. Calibrate according to manufacturer's
specifications prior to initial use.
10.3 Barometer. Calibrate against a mercury barometer.
10.4 Temperature Gauge. Calibrate dial thermometers against
mercury-in-glass thermometers.
10.5 Vacuum Gauge. Calibrate mechanical gauges, if used, against a
mercury manometer such as that specified in Section 6.1.6 of Method 7.
10.6 Analytical Balance. Calibrate against standard weights.

11.0 Analytical Procedures

11.1 Sample Preparation.
11.1.1 Note on the analytical data sheet, the level of the liquid
in the container, and whether any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the
final results. Immediately before analysis, transfer the contents of the
shipping container to a 50-ml volumetric flask, and rinse the container
twice with 5 ml portions of water. Add the rinse water to the flask, and
dilute to the mark with water. Mix thoroughly.
11.1.2 Pipet a 5-ml aliquot of the sample into a 50-ml volumetric
flask, and dilute to the mark with water. Mix thoroughly. For each set
of determinations, prepare a reagent blank by diluting 5 ml of absorbing
solution

[[Page 279]]

to 50 ml with water. (Alternatively, eluent solution may be used instead
of water in all sample, standard, and blank dilutions.)
11.2 Analysis.
11.2.1 Prepare a standard calibration curve according to Section
10.1.1. Analyze the set of standards followed by the set of samples
using the same injection volume for both standards and samples. Repeat
this analysis sequence followed by a final analysis of the standard set.
Average the results. The two sample values must agree within 5 percent
of their mean for the analysis to be valid. Perform this duplicate
analysis sequence on the same day. Dilute any sample and the blank with
equal volumes of water if the concentration exceeds that of the highest
standard.
11.2.2 Document each sample chromatogram by listing the following
analytical parameters: injection point, injection volume, nitrate and
sulfate retention times, flow rate, detector sensitivity setting, and
recorder chart speed.
11.3 Audit Sample Analysis. Same as Method 7, Section 11.4.

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculations.
12.1 Sample Volume. Calculate the sample volume Vsc (in ml), on a
dry basis, corrected to standard conditions, using Equation 7-2 of
Method 7.
12.2 Sample Concentration of NOX as NO2.
12.2.1 Calculate the sample concentration C (in mg/dscm) as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.206

Where:

H = Sample peak height, mm.
S = Calibration factor, g/mm.
F = Dilution factor (required only if sample dilution was needed to
reduce the concentration into the range of calibration),
dimensionless.
10⁴ = 1:10 dilution times conversion factor of: (mg/10\3\
g)(10\6\ ml/m\3\).

12.2.2 If desired, the concentration of NO2 may be
calculated as ppm NO2 at standard conditions as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.207

Where:

0.5228 = ml/mg NO2.

13.0 Method Performance

13.1 Range. The analytical range of the method is from 125 to 1250
mg NOX/m³ as NO2 (65 to 655 ppmv), and
higher concentrations may be analyzed by diluting the sample. The lower
detection limit is approximately 19 mg/m\3\ (10 ppmv), but may vary
among instruments.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Mulik, J.D., and E. Sawicki. Ion Chromatographic Analysis of
Environmental Pollutants. Ann Arbor, Ann Arbor Science Publishers, Inc.
Vol. 2, 1979.
2. Sawicki, E., J.D. Mulik, and E. Wittgenstein. Ion Chromatographic
Analysis of Environmental Pollutants. Ann Arbor, Ann Arbor Science
Publishers, Inc. Vol. 1. 1978.
3. Siemer, D.D. Separation of Chloride and Bromide from Complex
Matrices Prior to Ion Chromatographic Determination. Anal. Chem.
52(12):1874-1877. October 1980.
4. Small, H., T.S. Stevens, and W.C. Bauman. Novel Ion Exchange
Chromatographic Method Using Conductimetric Determination. Anal. Chem.
47(11):1801. 1975.
5. Yu, K.K., and P.R. Westlin. Evaluation of Reference Method 7
Flask Reaction Time. Source Evaluation Society Newsletter. 4(4).
November 1979. 10 pp.
6. Stack Sampling Safety Manual (Draft). U.S. Environmental
Protection Agency, Office of Air Quality Planning and Standard, Research
Triangle Park, NC. September 1978.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 7B--Determination of Nitrogen Oxide Emissions From Stationary
Sources (Ultraviolet Spectrophotometric Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 5, and Method 7.

1.0 Scope and Application

1.1 Analytes.

[[Page 280]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9
Nitrogen dioxide (NO2)........ 10102-44-0 30-786 ppmv
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of NOX emissions from nitric acid plants.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A grab sample is collected in an evacuated flask containing a
dilute sulfuric acid-hydrogen peroxide absorbing solution; the
NOX, excluding nitrous oxide (N2O), are measured
by ultraviolet spectrophotometry.

3.0 Definition. [Reserved]

4.0 Interferences. [Reserved]

5.0 Safety

5.1 This method may involve hazardous materials, operations, and
equipment. This test method may not address all of the safety problems
associated with its use. It is the responsibility of the user of this
test method to establish appropriate safety and health practices and to
determine the applicability of regulatory limitations prior to
performing this test method.
5.2 Corrosive reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Hydrogen Peroxide (H2O2). Irritating to
eyes, skin, nose, and lungs.
5.2.2 Sodium Hydroxide (NaOH). Causes severe damage to eyes and
skin. Inhalation causes irritation to nose, throat, and lungs. Reacts
exothermically with limited amounts of water.
5.2.3 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 3 mg/m \3\ will cause lung damage in uninitiated. 1 mg/m \3\ for
8 hours will cause lung damage or, in higher concentrations, death.
Provide ventilation to limit inhalation. Reacts violently with metals
and organics.

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 7, Section 6.1.
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Wash Bottle. Polyethylene or glass.
6.2.2 Volumetric Flasks. 100-ml (one for each sample).
6.3 Analysis. The following items are required for analysis:
6.3.1 Volumetric Pipettes. 5-, 10-, 15-, and 20-ml to make
standards and sample dilutions.
6.3.2 Volumetric Flasks. 1000- and 100-ml for preparing standards
and dilution of samples.
6.3.3 Spectrophotometer. To measure ultraviolet absorbance at 210
nm.
6.3.4 Analytical Balance. To measure to within 0.1 mg.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents are to conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society, where such specifications are available.
Otherwise, use the best available grade.

7.1 Sample Collection. Same as Method 7, Section 7.1. It is
important that the amount of hydrogen peroxide in the absorbing solution
not be increased. Higher concentrations of peroxide may interfere with
sample analysis.
7.2 Sample Recovery. Same as Method 7, Section 7.2.
7.3 Analysis. Same as Method 7, Sections 7.3.1, 7.3.3, and 7.3.4,
with the addition of the following:
7.3.1 Working Standard KNO3 Solution. Dilute 10 ml of
the standard solution to 1000 ml with water. One milliliter of the
working standard is equivalent to 10 g NO2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sample Collection. Same as Method 7, Section 8.1.
8.2 Sample Recovery.
8.2.1 Let the flask sit for a minimum of 16 hours, and then shake
the contents for 2 minutes.
8.2.2 Connect the flask to a mercury filled U-tube manometer. Open
the valve from the flask to the manometer, and record the flask
temperature (Tf), the barometric pressure, and the difference
between the mercury levels in the manometer. The absolute internal

[[Page 281]]

pressure in the flask (Pf) is the barometric pressure less
the manometer reading.
8.2.3 Transfer the contents of the flask to a leak-free wash
bottle. Rinse the flask three times with 10-ml portions of water, and
add to the bottle. Mark the height of the liquid level so that the
container can be checked for leakage after transport. Label the
container to identify clearly its contents. Seal the container for
shipping.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.......................... Spectrophometer Ensures linearity of
calibration. spectrophotometer
response to
standards.
11.4.......................... Audit sample Evaluates analytical
analysis. technique and
preparation of
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

Same as Method 7, Sections 10.2 through 10.5, with the addition of
the following:
10.1 Determination of Spectrophotometer Standard Curve. Add 0 ml, 5
ml, 10 ml, 15 ml, and 20 ml of the KNO3 working standard
solution (1 ml = 10 g NO2) to a series of five 100-
ml volumetric flasks. To each flask, add 5 ml of absorbing solution.
Dilute to the mark with water. The resulting solutions contain 0.0, 50,
100, 150, and 200 g NO2, respectively. Measure the
absorbance by ultraviolet spectrophotometry at 210 nm, using the blank
as a zero reference. Prepare a standard curve plotting absorbance vs.
g NO2.

Note: If other than a 20-ml aliquot of sample is used for analysis,
then the amount of absorbing solution in the blank and standards must be
adjusted such that the same amount of absorbing solution is in the blank
and standards as is in the aliquot of sample used.

10.1.1 Calculate the spectrophotometer calibration factor as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.208

Where:

Mi = Mass of NO2 in standard i, g.
Ai = Absorbance of NO2 standard i.
n = Total number of calibration standards.

10.1.2 For the set of calibration standards specified here,
Equation 7B-1 simplifies to the following:
[GRAPHIC] [TIFF OMITTED] TR17OC00.209

10.2 Spectrophotometer Calibration Quality Control. Multiply the
absorbance value obtained for each standard by the Kc factor
(reciprocal of the least squares slope) to determine the distance each
calibration point lies from the theoretical calibration line. The
difference between the calculated concentration values and the actual
concentrations (i.e., 50, 100, 150, and 200 g NO2)
should be less than 7 percent for all standards.

11.0 Analytical Procedures

12.0 Data Analysis and Calculations

Same as Method 7, Section 12.0, except replace Section 12.3 with the
following:
12.1 Total g NO2 Per Sample.

[[Page 282]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.211

Where:

5 = 100/20, the aliquot factor.

Note: If other than a 20-ml aliquot is used for analysis, the factor
5 must be replaced by a corresponding factor.

13.0 Method Performance

13.1 Range. The analytical range of the method as outlined has been
determined to be 57 to 1500 milligrams NOX (as
NO2) per dry standard cubic meter, or 30 to 786 parts per
million by volume (ppmv) NOX.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. National Institute for Occupational Safety and Health.
Recommendations for Occupational Exposure to Nitric Acid. In:
Occupational Safety and Health Reporter. Washington, D.C. Bureau of
National Affairs, Inc. 1976. p. 149.
2. Rennie, P.J., A.M. Sumner, and F.B. Basketter. Determination of
Nitrate in Raw, Potable, and Waste Waters by Ultraviolet
Spectrophotometry. Analyst. 104:837. September 1979.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 7C--Determination of Nitrogen Oxide Emissions From Stationary
Sources (Alkaline Permanganate/Colorimetric Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 3, Method 6 and
Method 7.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS no. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9 ....................
Nitrogen dioxide (NO2)........ 10102-44-07 ppmv
------------------------------------------------------------------------

1.2 Applicability. This method applies to the measurement of
NOX emissions from fossil-fuel fired steam generators,
electric utility plants, nitric acid plants, or other sources as
specified in the regulations.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

An integrated gas sample is extracted from the stack and passed
through impingers containing an alkaline potassium permanganate
solution; NOX (NO + NO2) emissions are oxidized to
NO2 and NO3. Then NO3^-is
reduced to NO2^-with cadmium, and the
NO2^-is analyzed colorimetrically.

3.0 Definitions. [Reserved]

4.0 Interferences

Possible interferents are sulfur dioxides (SO2) and
ammonia (NH3).
4.1 High concentrations of SO2 could interfere because
SO2 consumes MnO4 (as does NOX) and,
therefore, could reduce the NOX collection efficiency.
However, when sampling emissions from a coal-fired electric utility
plant burning 2.1 percent sulfur coal with no control of SO2
emissions, collection efficiency was not reduced. In fact, calculations
show that sampling 3000 ppm SO2 will reduce the
MnO4 concentration by only 5 percent if all the
SO2 is consumed in the first impinger.
4.2 Ammonia (NH3) is slowly oxidized to
NO3^- by the absorbing solution. At 100 ppm
NH3 in the gas stream, an interference of 6 ppm
NOX (11 mg NO2/m\3\) was observed when the sample
was analyzed 10 days after collection. Therefore, the method may not be
applicable to plants using NH3 injection to control
NOX emissions unless means are taken to correct the results.
An equation has been developed to allow quantification of the
interference and is discussed in Reference 5 of Section 16.0.

5.0 Safety

[[Page 283]]

5.2 Corrosive Reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water for at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burns as thermal
burns.
5.2.1 Hydrochloric Acid (HCl). Highly toxic and corrosive. Causes
severe damage to skin. Vapors are highly irritating to eyes, skin, nose,
and lungs, causing severe damage. May cause bronchitis, pneumonia, or
edema of lungs. Exposure to vapor concentrations of 0.13 to 0.2 percent
can be lethal in minutes. Will react with metals, producing hydrogen.
5.2.2 Oxalic Acid (COOH)2. Poisonous. Irritating to
eyes, skin, nose, and throat.
5.2.3 Sodium Hydroxide (NaOH). Causes severe damage to eye tissues
and to skin. Inhalation causes irritation to nose, throat, and lungs.
Reacts exothermically with small amounts of water.
5.2.4 Potassium Permanganate (KMnO4). Caustic, strong
oxidizer. Avoid bodily contact with.

6.0 Equipment and Supplies

6.1 Sample Collection and Sample Recovery. A schematic of the
Method 7C sampling train is shown in Figure 7C-1, and component parts
are discussed below. Alternative apparatus and procedures are allowed
provided acceptable accuracy and precision can be demonstrated to the
satisfaction of the Administrator.
6.1.1 Probe. Borosilicate glass tubing, sufficiently heated to
prevent water condensation and equipped with an in-stack or heated out-
of-stack filter to remove particulate matter (a plug of glass wool is
satisfactory for this purpose). Stainless steel or Teflon tubing may
also be used for the probe.
6.1.2 Impingers. Three restricted-orifice glass impingers, having
the specifications given in Figure 7C-2, are required for each sampling
train. The impingers must be connected in series with leak-free glass
connectors. Stopcock grease may be used, if necessary, to prevent
leakage. (The impingers can be fabricated by a glass blower if not
available commercially.)
6.1.3 Glass Wool, Stopcock Grease, Drying Tube, Valve, Pump,
Barometer, and Vacuum Gauge and Rotameter. Same as in Method 6, Sections
6.1.1.3, 6.1.1.4, 6.1.1.6, 6.1.1.7, 6.1.1.8, 6.1.2, and 6.1.3,
respectively.
6.1.4 Rate Meter. Rotameter, or equivalent, accurate to within 2
percent at the selected flow rate of between 400 and 500 ml/min (0.014
to 0.018 cfm). For rotameters, a range of 0 to 1 liter/min (0 to 0.035
cfm) is recommended.
6.1.5 Volume Meter. Dry gas meter (DGM) capable of measuring the
sample volume under the sampling conditions of 400 to 500 ml/min (0.014
to 0.018 cfm) for 60 minutes within an accuracy of 2 percent.
6.1.6 Filter. To remove NOX from ambient air, prepared
by adding 20 g of 5-angstrom molecular sieve to a cylindrical tube
(e.g., a polyethylene drying tube).
6.1.7 Polyethylene Bottles. 1-liter, for sample recovery.
6.1.8 Funnel and Stirring Rods. For sample recovery.
6.2 Sample Preparation and Analysis.
6.2.1 Hot Plate. Stirring type with 50- by 10-mm Teflon-coated
stirring bars.
6.2.2 Beakers. 400-, 600-, and 1000-ml capacities.
6.2.3 Filtering Flask. 500-ml capacity with side arm.
6.2.4 Buchner Funnel. 75-mm ID, with spout equipped with a 13-mm ID
by 90-mm long piece of Teflon tubing to minimize possibility of
aspirating sample solution during filtration.
6.2.5 Filter Paper. Whatman GF/C, 7.0-cm diameter.
6.2.6 Stirring Rods.
6.2.7 Volumetric Flasks. 100-, 200- or 250-, 500-, and 1000-ml
capacity.
6.2.8 Watch Glasses. To cover 600- and 1000-ml beakers.
6.2.9 Graduated Cylinders. 50- and 250-ml capacities.
6.2.10 Pipettes. Class A.
6.2.11 pH Meter. To measure pH from 0.5 to 12.0.
6.2.12 Burette. 50-ml with a micrometer type stopcock. (The
stopcock is Catalog No. 8225-t-05, Ace Glass, Inc., Post Office Box 996,
Louisville, Kentucky 50201.) Place a glass wool plug in bottom of
burette. Cut off burette at a height of 43 cm (17 in.) from the top of
plug, and have a blower attach a glass funnel to top of burette such
that the diameter of the burette remains essentially unchanged. Other
means of attaching the funnel are acceptable.
6.2.13 Glass Funnel. 75-mm ID at the top.
6.2.14 Spectrophotometer. Capable of measuring absorbance at 540
nm; 1-cm cells are adequate.
6.2.15 Metal Thermometers. Bimetallic thermometers, range 0 to 150
deg.C (32 to 300 deg.F).
6.2.16 Culture Tubes. 20-by 150-mm, Kimax No. 45048.
6.2.17 Parafilm ``M.'' Obtained from American Can Company,
Greenwich, Connecticut 06830.
6.2.18 CO2 Measurement Equipment. Same as in Method 3,
Section 6.0.

7.0 Reagents and Standards

[[Page 284]]

7.1 Sample Collection.
7.1.1 Water. Deionized distilled to conform to ASTM Specification D
1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17).
7.1.2 Potassium Permanganate, 4.0 Percent (w/w), Sodium Hydroxide,
2.0 Percent (w/w) solution (KMnO4/NaOH solution). Dissolve
40.0 g of KMnO4 and 20.0 g of NaOH in 940 ml of water.
7.2 Sample Preparation and Analysis.
7.2.1 Water. Same as in Section 7.1.1.
7.2.2 Oxalic Acid Solution. Dissolve 48 g of oxalic acid
[(COOH)22H2O] in water, and dilute to
500 ml. Do not heat the solution.
7.2.3 Sodium Hydroxide, 0.5 N. Dissolve 20 g of NaOH in water, and
dilute to 1 liter.
7.2.4 Sodium Hydroxide, 10 N. Dissolve 40 g of NaOH in water, and
dilute to 100 ml.
7.2.5 Ethylenediamine Tetraacetic Acid (EDTA) Solution, 6.5 percent
(w/v). Dissolve 6.5 g of EDTA (disodium salt) in water, and dilute to
100 ml. Dissolution is best accomplished by using a magnetic stirrer.
7.2.6 Column Rinse Solution. Add 20 ml of 6.5 percent EDTA solution
to 960 ml of water, and adjust the pH to between 11.7 and 12.0 with 0.5
N NaOH.
7.2.7 Hydrochloric Acid (HCl), 2 N. Add 86 ml of concentrated HCl
to a 500 ml-volumetric flask containing water, dilute to volume, and mix
well. Store in a glass-stoppered bottle.
7.2.8 Sulfanilamide Solution. Add 20 g of sulfanilamide (melting
point 165 to 167 deg.C (329 to 333 deg.F)) to 700 ml of water. Add,
with mixing, 50 ml concentrated phosphoric acid (85 percent), and dilute
to 1000 ml. This solution is stable for at least 1 month, if
refrigerated.
7.2.9 N-(1-Naphthyl)-Ethylenediamine Dihydrochloride (NEDA)
Solution. Dissolve 0.5 g of NEDA in 500 ml of water. An aqueous solution
should have one absorption peak at 320 nm over the range of 260 to 400
nm. NEDA that shows more than one absorption peak over this range is
impure and should not be used. This solution is stable for at least 1
month if protected from light and refrigerated.
7.2.10 Cadmium. Obtained from Matheson Coleman and Bell, 2909
Highland Avenue, Norwood, Ohio 45212, as EM Laboratories Catalog No.
2001. Prepare by rinsing in 2 N HCl for 5 minutes until the color is
silver-grey. Then rinse the cadmium with water until the rinsings are
neutral when tested with pH paper. CAUTION: H2 is liberated
during preparation. Prepare in an exhaust hood away from any flame or
combustion source.
7.2.11 Sodium Sulfite (NaNO2) Standard Solution, Nominal
Concentration, 1000 g NO2^-/ml. Desiccate
NaNO2 overnight. Accurately weigh 1.4 to 1.6 g of NaNO2
(assay of 97 percent NaNO2 or greater), dissolve in water,
and dilute to 1 liter. Calculate the exact NO2-concentration
using Equation 7C-1 in Section 12.2. This solution is stable for at
least 6 months under laboratory conditions.
7.2.12 Potassium Nitrate (KNO3) Standard Solution. Dry
KNO3 at 110 deg.C (230 deg.F) for 2 hours, and cool in a
desiccator. Accurately weigh 9 to 10 g of KNO3 to within 0.1
mg, dissolve in water, and dilute to 1 liter. Calculate the exact
NO3^- concentration using Equation 7C-2 in Section
12.3. This solution is stable for 2 months without preservative under
laboratory conditions.
7.2.13 Spiking Solution. Pipette 7 ml of the KNO3
standard into a 100-ml volumetric flask, and dilute to volume.
7.2.14 Blank Solution. Dissolve 2.4 g of KMnO4 and 1.2 g
of NaOH in 96 ml of water. Alternatively, dilute 60 ml of
KMnO4/NaOH solution to 100 ml.
7.2.15 Quality Assurance Audit Samples. Same as in Method 7,
Section 7.3.10. When requesting audit samples, specify that they be in
the appropriate concentration range for Method 7C.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Preparation of Sampling Train. Add 200 ml of KMnO4/
NaOH solution (Section 7.1.2) to each of three impingers, and assemble
the train as shown in Figure 7C-1. Adjust the probe heater to a
temperature sufficient to prevent water condensation.
8.2 Leak-Checks. Same as in Method 6, Section 8.2.
8.3 Sample Collection.
8.3.1 Record the initial DGM reading and barometric pressure.
Determine the sampling point or points according to the appropriate
regulations (e.g., Sec. 60.46(b)(5) of 40 CFR Part 60). Position the tip
of the probe at the sampling point, connect the probe to the first
impinger, and start the pump. Adjust the sample flow to a value between
400 and 500 ml/min (0.014 and 0.018 cfm). CAUTION: DO NOT EXCEED THESE
FLOW RATES. Once adjusted, maintain a constant flow rate during the
entire sampling run. Sample for 60 minutes. For relative accuracy (RA)
testing of continuous emission monitors, the minimum sampling time is 1
hour, sampling 20 minutes at each traverse point.

Note: When the SO2 concentration is greater than 1200
ppm, the sampling time may have to be reduced to 30 minutes to eliminate
plugging of the impinger orifice with MnO2. For RA tests with
SO2 greater than 1200 ppm, sample for 30 minutes (10 minutes
at each point).

8.3.2 Record the DGM temperature, and check the flow rate at least
every 5 minutes. At the conclusion of each run, turn off the pump,
remove the probe from the stack, and record the final readings. Divide
the sample volume by the sampling time to determine the average flow
rate. Conduct the mandatory post-test leak-check. If a leak is found,

[[Page 285]]

void the test run, or use procedures acceptable to the Administrator to
adjust the sample volume for the leakage.
8.4 CO2 Measurement. During sampling, measure the
CO2 content of the stack gas near the sampling point using
Method 3. The single-point grab sampling procedure is adequate, provided
the measurements are made at least three times (near the start, midway,
and before the end of a run), and the average CO2
concentration is computed. The Orsat or Fyrite analyzer may be used for
this analysis.
8.5 Sample Recovery. Disconnect the impingers. Pour the contents of
the impingers into a 1-liter polyethylene bottle using a funnel and a
stirring rod (or other means) to prevent spillage. Complete the
quantitative transfer by rinsing the impingers and connecting tubes with
water until the rinsings are clear to light pink, and add the rinsings
to the bottle. Mix the sample, and mark the solution level. Seal and
identify the sample container.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.2, 10.1-10.3................ Sampling Ensure accurate
equipment leak- measurement of
check and sample volume.
calibration.
10.4.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.3.......................... Spiked sample Ensure reduction
analysis. efficiency of
column.
11.6.......................... Audit sample Evaluate analytical
analysis. technique,
preparation of
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

10.1 Volume Metering System. Same as Method 6, Section 10.1. For
detailed instructions on carrying out these calibrations, it is
suggested that Section 3.5.2 of Reference 4 of Section 16.0 be
consulted.
10.2 Temperature Sensors and Barometer. Same as in Method 6,
Sections 10.2 and 10.4, respectively.
10.3 Check of Rate Meter Calibration Accuracy (Optional).
Disconnect the probe from the first impinger, and connect the filter.
Start the pump, and adjust the rate meter to read between 400 and 500
ml/min (0.014 and 0.018 cfm). After the flow rate has stabilized, start
measuring the volume sampled, as recorded by the dry gas meter and the
sampling time. Collect enough volume to measure accurately the flow
rate. Then calculate the flow rate. This average flow rate must be less
than 500 ml/min (0.018 cfm) for the sample to be valid; therefore, it is
recommended that the flow rate be checked as above prior to each test.
10.4 Spectrophotometer.
10.4.1 Dilute 5.0 ml of the NaNO2 standard solution to
200 ml with water. This solution nominally contains 25 g
NO2^-/ml. Use this solution to prepare calibration
standards to cover the range of 0.25 to 3.00 g
NO2^-/ml. Prepare a minimum of three standards each
for the linear and slightly nonlinear (described below) range of the
curve. Use pipettes for all additions.
10.4.2 Measure the absorbance of the standards and a water blank as
instructed in Section 11.5. Plot the net absorbance vs. g
NO2^-/ml. Draw a smooth curve through the points.
The curve should be linear up to an absorbance of approximately 1.2 with
a slope of approximately 0.53 absorbance units/g
NO2^-/ml. The curve should pass through the origin.
The curve is slightly nonlinear from an absorbance of 1.2 to 1.6.

11.0 Analytical Procedures

11.1 Sample Stability. Collected samples are stable for at least
four weeks; thus, analysis must occur within 4 weeks of collection.
11.2 Sample Preparation.
11.2.1 Prepare a cadmium reduction column as follows: Fill the
burette with water. Add freshly prepared cadmium slowly, with tapping,
until no further settling occurs. The height of the cadmium column
should be 39 cm (15 in). When not in use, store the column under rinse
solution.

Note: The column should not contain any bands of cadmium fines. This
may occur if regenerated cadmium is used and will greatly reduce the
column lifetime.

11.2.2 Note the level of liquid in the sample container, and
determine whether any sample was lost during shipment. If a noticeable
amount of leakage has occurred, the volume lost can be determined from
the difference between initial and final solution levels, and this value
can then be used to correct the analytical result. Quantitatively
transfer the contents to a 1-liter volumetric flask, and dilute to
volume.

[[Page 286]]

11.2.3 Take a 100-ml aliquot of the sample and blank (unexposed
KMnO4/NaOH) solutions, and transfer to 400-ml beakers
containing magnetic stirring bars. Using a pH meter, add concentrated
H2SO4 with stirring until a pH of 0.7 is obtained.
Allow the solutions to stand for 15 minutes. Cover the beakers with
watch glasses, and bring the temperature of the solutions to 50 deg.C
(122 deg.F). Keep the temperature below 60 deg.C (140 deg.F).
Dissolve 4.8 g of oxalic acid in a minimum volume of water,
approximately 50 ml, at room temperature. Do not heat the solution. Add
this solution slowly, in increments, until the KMnO4 solution
becomes colorless. If the color is not completely removed, prepare some
more of the above oxalic acid solution, and add until a colorless
solution is obtained. Add an excess of oxalic acid by dissolving 1.6 g
of oxalic acid in 50 ml of water, and add 6 ml of this solution to the
colorless solution. If suspended matter is present, add concentrated
H2SO4 until a clear solution is obtained.
11.2.4 Allow the samples to cool to near room temperature, being
sure that the samples are still clear. Adjust the pH to between 11.7 and
12.0 with 10 N NaOH. Quantitatively transfer the mixture to a Buchner
funnel containing GF/C filter paper, and filter the precipitate. Filter
the mixture into a 500-ml filtering flask. Wash the solid material four
times with water. When filtration is complete, wash the Teflon tubing,
quantitatively transfer the filtrate to a 500-ml volumetric flask, and
dilute to volume. The samples are now ready for cadmium reduction.
Pipette a 50-ml aliquot of the sample into a 150-ml beaker, and add a
magnetic stirring bar. Pipette in 1.0 ml of 6.5 percent EDTA solution,
and mix.
11.3 Determine the correct stopcock setting to establish a flow
rate of 7 to 9 ml/min of column rinse solution through the cadmium
reduction column. Use a 50-ml graduated cylinder to collect and measure
the solution volume. After the last of the rinse solution has passed
from the funnel into the burette, but before air entrapment can occur,
start adding the sample, and collect it in a 250-ml graduated cylinder.
Complete the quantitative transfer of the sample to the column as the
sample passes through the column. After the last of the sample has
passed from the funnel into the burette, start adding 60 ml of column
rinse solution, and collect the rinse solution until the solution just
disappears from the funnel. Quantitatively transfer the sample to a 200-
ml volumetric flask (a 250-ml flask may be required), and dilute to
volume. The samples are now ready for NO2-analysis.

Note: Two spiked samples should be run with every group of samples
passed through the column. To do this, prepare two additional 50-ml
aliquots of the sample suspected to have the highest NO2-
concentration, and add 1 ml of the spiking solution to these aliquots.
If the spike recovery or column efficiency (see Section 12.2) is below
95 percent, prepare a new column, and repeat the cadmium reduction.
11.4 Repeat the procedures outlined in Sections 11.2 and 11.3 for
each sample and each blank.
11.5 Sample Analysis. Pipette 10 ml of sample into a culture tube.
Pipette in 10 ml of sulfanilamide solution and 1.4 ml of NEDA solution.
Cover the culture tube with parafilm, and mix the solution. Prepare a
blank in the same manner using the sample from treatment of the
unexposed KMnO4/NaOH solution. Also, prepare a calibration
standard to check the slope of the calibration curve. After a 10-minute
color development interval, measure the absorbance at 540 nm against
water. Read g NO2^-/ml from the
calibration curve. If the absorbance is greater than that of the highest
calibration standard, use less than 10 ml of sample, and repeat the
analysis. Determine the NO2^-concentration using
the calibration curve obtained in Section 10.4.
Note: Some test tubes give a high blank NO2^-
value but culture tubes do not.

11.6 Audit Sample Analysis. Same as in Method 7, Section 11.4.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature.

B = Analysis of blank, g NO2^-/ml.
C = Concentration of NOX as NO2, dry basis, mg/
dsm³.
E = Column efficiency, dimensionless
K2 = 10^-3 mg/g.
m = Mass of NOX, as NO2, in sample, g.
Pbar = Barometric pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
s = Concentration of spiking solution, g NO3/ml.
S = Analysis of sample, g NO2^-/ml.
Tm = Average dry gas meter absolute temperature, deg.K.
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Vm(std) = Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm (dscf).
Vm = Dry gas volume as measured by the dry gas meter, scm
(scf).
x = Analysis of spiked sample, g NO2^-/ml.
X = Correction factor for CO2 collection = 100/(100 -
%CO2(V/V)).
y = Analysis of unspiked sample, g NO2^-/
ml.
Y = Dry gas meter calibration factor.
1.0 ppm NO = 1.247 mg NO/m³ at STP.
1.0 ppm NO2 = 1.912 mg NO2/m³ at STP.

[[Page 287]]

1 ft³ = 2.832 x 10^-2 m³.

12.2 NO2 Concentration. Calculate the NO2
concentration of the solution (see Section 7.2.11) using the following
equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.212

12.3 NO3 Concentration. Calculate the NO3
concentration of the KNO3 solution (see Section 7.2.12) using
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.213

12.4 Sample Volume, Dry Basis, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.214

K1 = 0.3855 deg.K/mm Hg for metric units.
K1 = 17.65 deg.R/in. Hg for English units.

12.5 Efficiency of Cadmium Reduction Column. Calculate this value as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.215

200 = Final volume of sample and blank after passing through the column,
ml.
1.0 = Volume of spiking solution added, ml.
46.01 = g NO2^-/mole.
62.01 = g NO3^-/mole.

12.6 Total g NO2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.216

500 = Total volume of prepared sample, ml.
50 = Aliquot of prepared sample processed through cadmium column, ml.
100 = Aliquot of KMnO4/NaOH solution, ml.
1000 = Total volume of KMnO4/NaOH solution, ml.

12.7 Sample Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.217

13.0 Method Performance

13.1 Precision. The intra-laboratory relative standard deviation
for a single measurement is 2.8 and 2.9 percent at 201 and 268 ppm
NOX, respectively.
13.2 Bias. The method does not exhibit any bias relative to Method
7.

[[Page 288]]

13.3 Range. The lower detectable limit is 13 mg NOX/
m³, as NO2 (7 ppm NOX) when sampling at
500 ml/min for 1 hour. No upper limit has been established; however,
when using the recommended sampling conditions, the method has been
found to collect NOX emissions quantitatively up to 1782 mg
NOX/m³, as NO2 (932 ppm
NOX).

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Margeson, J.H., W.J. Mitchell, J.C. Suggs, and M.R. Midgett.
Integrated Sampling and Analysis Methods for Determining NOX
Emissions at Electric Utility Plants. U.S. Environmental Protection
Agency, Research Triangle Park, NC. Journal of the Air Pollution Control
Association. 32:1210-1215. 1982.
2. Memorandum and attachment from J.H. Margeson, Source Branch,
Quality Assurance Division, Environmental Monitoring Systems Laboratory,
to The Record, EPA. March 30, 1983. NH3 Interference in
Methods 7C and 7D.
3. Margeson, J.H., J.C. Suggs, and M.R. Midgett. Reduction of
Nitrate to Nitrite with Cadmium. Anal. Chem. 52:1955-57. 1980.
4. Quality Assurance Handbook for Air Pollution Measurement Systems.
Volume III--Stationary Source Specific Methods. U.S. Environmental
Protection Agency. Research Triangle Park, NC. Publication No. EPA-600/
4-77-027b. August 1977.
5. Margeson, J.H., et al. An Integrated Method for Determining
NOX Emissions at Nitric Acid Plants. Analytical Chemistry. 47
(11):1801. 1975.

[[Page 289]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.218

[[Page 290]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.219

Method 7D--Determination of Nitrogen Oxide Emissions From Stationary
Sources (Alkaline-Permanganate/Ion Chromatographic Method)

Note: This method is not inclusive with respect to specifications
(e.g., equipment and supplies) and procedures (e.g., sampling and
analytical) essential to its performance. Some material is incorporated
by reference from other methods in this part. Therefore, to obtain
reliable results, persons using this method should have a thorough
knowledge of at least the following additional test methods: Method 1,
Method 3, Method 6, Method 7, and Method 7C.

1.0 Scope and Application

1.1 Analytes.

[[Page 291]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX), as NO2,
including:
Nitric oxide (NO)............. 10102-43-9
Nitrogen dioxide (NO2)........ 10102-44-0 7 ppmv
------------------------------------------------------------------------

2.0 Summary of Method

An integrated gas sample is extracted from the stack and passed
through impingers containing an alkaline-potassium permanganate
solution; NOX (NO + NO2) emissions are oxidized to
NO3^-. Then NO3^- is analyzed
by ion chromatography.

3.0 Definitions [Reserved]

4.0 Interferences

Same as in Method 7C, Section 4.0.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection and Sample Recovery. Same as Method 7C,
Section 6.1. A schematic of the sampling train used in performing this
method is shown in Figure 7C-1 of Method 7C.
6.2 Sample Preparation and Analysis.
6.2.1 Magnetic Stirrer. With 25- by 10-mm Teflon-coated stirring
bars.
6.2.2 Filtering Flask. 500-ml capacity with sidearm.
6.2.3 Buchner Funnel. 75-mm ID, with spout equipped with a 13-mm ID
by 90-mm long piece of Teflon tubing to minimize possibility of
aspirating sample solution during filtration.
6.2.4 Filter Paper. Whatman GF/C, 7.0-cm diameter.
6.2.5 Stirring Rods.
6.2.6 Volumetric Flask. 250-ml.
6.2.7 Pipettes. Class A.
6.2.8 Erlenmeyer Flasks. 250-ml.
6.2.9 Ion Chromatograph. Equipped with an anion separator column to
separate NO3^-, H3⁺
suppressor, and necessary auxiliary equipment. Nonsuppressed and other
forms of ion chromatography may also be used provided that adequate
resolution of NO3^- is obtained. The system must
also be able to resolve and detect NO2^-.

7.0 Reagents and Standards

7.1 Sample Collection.
7.1.1 Water. Deionized distilled to conform to ASTM specification D
1193-77 or 91 Type 3 (incorporated by reference--see Sec. 60.17).
7.1.2 Potassium Permanganate, 4.0 Percent (w/w), Sodium Hydroxide,
2.0 Percent (w/w). Dissolve 40.0 g of KMnO4 and 20.0 g of
NaOH in 940 ml of water.
7.2 Sample Preparation and Analysis.
7.2.1 Water. Same as in Section 7.1.1.
7.2.2 Hydrogen Peroxide (H2O2), 5 Percent.
Dilute 30 percent H2O2 1:5 (v/v) with water.
7.2.3 Blank Solution. Dissolve 2.4 g of KMnO4 and 1.2 g
of NaOH in 96 ml of water. Alternatively, dilute 60 ml of
KMnO4/NaOH solution to 100 ml.
7.2.4 KNO3 Standard Solution. Dry KNO3 at 110
deg.C for 2 hours, and cool in a desiccator. Accurately weigh 9 to 10 g
of KNO3 to within 0.1 mg, dissolve in water, and dilute to 1
liter. Calculate the exact NO3^- concentration
using Equation 7D-1 in Section 12.2.

[[Page 292]]

This solution is stable for 2 months without preservative under
laboratory conditions.
7.2.5 Eluent, 0.003 M NaHCO3/0.0024 M
Na2CO3. Dissolve 1.008 g NaHCO3 and
1.018 g Na2CO3 in water, and dilute to 4 liters.
Other eluents capable of resolving nitrate ion from sulfate and other
species present may be used.
7.2.6 Quality Assurance Audit Samples. Same as Method 7, Section
7.3.10. When requesting audit samples, specify that they be in the
appropriate concentration range for Method 7D.
8.0 Sample Collection, Preservation, Transport, and Storage.
8.1 Sampling. Same as in Method 7C, Section 8.1.
8.2 Sample Recovery. Same as in Method 7C, Section 8.2.
8.3 Sample Preparation for Analysis.
Note: Samples must be analyzed within 28 days of collection.

8.3.1 Note the level of liquid in the sample container, and
determine whether any sample was lost during shipment. If a noticeable
amount of leakage has occurred, the volume lost can be determined from
the difference between initial and final solution levels, and this value
can then be used to correct the analytical result. Quantitatively
transfer the contents to a 1-liter volumetric flask, and dilute to
volume.
8.3.2 Sample preparation can be started 36 hours after collection.
This time is necessary to ensure that all NO2^- is
converted to NO3^- in the collection solution. Take
a 50-ml aliquot of the sample and blank, and transfer to 250-ml
Erlenmeyer flasks. Add a magnetic stirring bar. Adjust the stirring rate
to as fast a rate as possible without loss of solution. Add 5 percent
H2O2 in increments of approximately 5 ml using a
5-ml pipette. When the KMnO4 color appears to have been
removed, allow the precipitate to settle, and examine the supernatant
liquid. If the liquid is clear, the H2O2 addition
is complete. If the KMnO4 color persists, add more
H2O2, with stirring, until the supernatant liquid
is clear.

Note: The faster the stirring rate, the less volume of
H2O2 that will be required to remove the
KMnO4.) Quantitatively transfer the mixture to a Buchner
funnel containing GF/C filter paper, and filter the precipitate. The
spout of the Buchner funnel should be equipped with a 13-mm ID by 90-mm
long piece of Teflon tubing. This modification minimizes the possibility
of aspirating sample solution during filtration. Filter the mixture into
a 500-ml filtering flask. Wash the solid material four times with water.
When filtration is complete, wash the Teflon tubing, quantitatively
transfer the filtrate to a 250-ml volumetric flask, and dilute to
volume. The sample and blank are now ready for
NO3^-analysis.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.2, 10.1-10.3................ Sampling Ensure accurate
equipment leak- measurement of
check and sample volume.
calibration.
10.4.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.3.......................... Spiked sample Ensure reduction
analysis. efficiency of
column.
11.6.......................... Audit sample Evaluate analytical
analysis. technique,
preparation of
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardizations

10.1 Dry Gas Meter (DGM) System.
10.1.1 Initial Calibration. Same as in Method 6, Section 10.1.1.
For detailed instructions on carrying out this calibration, it is
suggested that Section 3.5.2 of Citation 4 in Section 16.0 of Method 7C
be consulted.
10.1.2 Post-Test Calibration Check. Same as in Method 6, Section
10.1.2.
10.2 Thermometers for DGM and Barometer. Same as in Method 6,
Sections 10.2 and 10.4, respectively.
10.3 Ion Chromatograph.
10.3.1 Dilute a given volume (1.0 ml or greater) of the
KNO3 standard solution to a convenient volume with water, and
use this solution to prepare calibration standards. Prepare at least
four standards to cover the range of the samples being analyzed. Use
pipettes for all additions. Run standards as instructed in Section 11.2.
Determine peak height or area, and plot the individual values versus
concentration in g NO3^-/ml.
10.3.2 Do not force the curve through zero. Draw a smooth curve
through the points. The curve should be linear. With the linear curve,
use linear regression to determine the calibration equation.

11.0 Analytical Procedures

11.1 The following chromatographic conditions are recommended:
0.003 M NaHCO3/0.0024 Na2CO3 eluent
solution (Section 7.2.5), full scale range, 3 MHO; sample loop,
0.5 ml; flow rate, 2.5 ml/min. These conditions should give a
NO3^- retention time of approximately 15 minutes
(Figure 7D-1).
11.2 Establish a stable baseline. Inject a sample of water, and
determine whether any NO3^- appears in the
chromatogram. If NO3^-

[[Page 293]]

is present, repeat the water load/injection procedure approximately five
times; then re-inject a water sample and observe the chromatogram. When
no NO3^- is present, the instrument is ready for
use. Inject calibration standards. Then inject samples and a blank.
Repeat the injection of the calibration standards (to compensate for any
drift in response of the instrument). Measure the
NO3^- peak height or peak area, and determine the
sample concentration from the calibration curve.

11.3 Audit Analysis. Same as in Method 7, Section 11.4

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature. Same as in Method 7C, Section 12.1.
12.2 NO3^- concentration. Calculate the
NO3^- concentration in the KNO3 standard
solution (see Section 7.2.4) using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.220

12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions. Same
as in Method 7C, Section 12.4.
12.4 Total g NO2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.221

Where:

250 = Volume of prepared sample, ml.
1000 = Total volume of KMnO4 solution, ml.
50 = Aliquot of KMnO4/NaOH solution, ml.
46.01 = Molecular weight of NO3^-.
62.01 = Molecular weight of NO3^-.

12.5 Sample Concentration. Same as in Method 7C, Section 12.7.

13.0 Method Performance

13.1 Precision. The intra-laboratory relative standard deviation for a
single measurement is approximately 6 percent at 200 to 270 ppm
NOx.
13.2 Bias. The method does not exhibit any bias relative to Method 7.
13.3 Range. The lower detectable limit is similar to that of Method 7C.
No upper limit has been established; however, when using the recommended
sampling conditions, the method has been found to collect NOX
emissions quantitatively up to 1782 mg NOX/m\3\, as
NO2 (932 ppm NOx).

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Method 7C, Section 16.0, References 1, 2, 4, and 5.

[[Page 294]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.222

Method 7E--Determination of Nitrogen Oxides Emissions From Stationary
Sources (Instrumental Analyzer Procedure)

1. Applicability and Principle

1.1 Applicability. This method is applicable to the determination
of nitrogen oxides (NOx) concentrations in emissions from
stationary sources only when specified within the regulations.
1.2 Principle. A gas simple is continuously extracted from a stack,
and a portion of the sample is conveyed to an instrumental
chemiluminescent analyzer for determination of NOx
concentration. Performance specifications and test procedures are
provided to ensure reliable data.

2. Range and Sensitivity

Same as Method 6C, Sections 2.1 and 2.2.

3. Definitions

3.1 Measurement System. The total equipment required for the
determination of NOx concentration. The measurement system
consists of the following major subsystems:
3.1.1 Sample Interface, Gas Analyzer, and Data Recorder. Same as
Method 6C, Sections 3.1.1, 3.1.2, and 3.1.3.
3.1.2 NO2 to NO Converter. A device that converts the
nitrogen dioxide (NO2) in the sample gas to nitrogen oxide
(NO).
3.2 Span, Calibration Gas, Analyzer Calibration Error, Sampling
System Bias, Zero Drift, Calibration Drift, and Response Time. Same as
Method 6C, Sections 3.2 through 3.8.
3.3 Interference Response. The output response of the measurement
system to a component in the sample gas, other than the gas component
being measured.

4. Measurement System Performance Specifications

Same as Method 6C, Sections 4.1 through 4.4.

5. Apparatus and Reagents

5.1 Measurement System. Any measurement system for NOx
that meets the specifications of this method. A schematic of an
acceptable measurement system is shown in Figure 6C-1 of Method 6C. The
essential components of the measurement system are described below:

[[Page 295]]

5.1.1 Sample Probe, Sample Line, Calibration Valve Assembly,
Moisture Removal System, Particulate Filter, Sample Pump, Sample Flow
Rate Control, Sample Gas Manifold, and Data Recorder. Same as Method 6C,
Sections 5.1.1 through 5.1.9, and 5.1.11.
5.1.2 NO2 to NO Converter. That portion of the system
that converts the nitrogen dioxide (NO2) in the sample gas to
nitrogen oxide (NO). An NO2 to NO converter is not necessary
if data are presented to demonstrate that the NO2 portion of
the exhaust gas is less than 5 percent of the total NOx
concentration.
5.1.3 NOx Analyzer. An analyzer based on the principles
of chemiluminescence, to determine continuously the NOx
concentration in the sample gas stream. The analyzer shall meet the
applicable performance specifications of Section 4. A means of
controlling the analyzer flow rate and a device for determining proper
sample flow rate (e.g., precision rotameter, pressure gauge downstream
of all flow controls, etc.) shall be provided at the analyzer.
5.2 NOx Calibration Gases. The calibration gases for the
NOx analyzer shall be NO in N2. Three calibration
gases, as specified in Sections 5.3.1 through 5.3.3. of Method 6C, shall
be used. Ambient air may be used for the zero gas.

6. Measurement System Performance Test Procedures

Perform the following procedures before measurement of emissions
(Section 7).
6.1 Calibration Gas Concentration Verification. Follow Section 6.1
of Method 6C, except if calibration gas analysis is required, use Method
7, and change all 5 percent performance values to 10 percent (or 10 ppm,
whichever is greater).
6.2 Interference Response. Conduct an interference response test of
the analyzer prior to its initial use in the field. Thereafter, recheck
the measurement system if changes are made in the instrumentation that
could alter the interference response (e.g., changes in the gas
detector). Conduct the interference response in accordance with Section
5.4 of Method 20.
6.3 Measurement System Preparation, Analyzer Calibration Error, and
Sample System Bias Check. Follow Sections 6.2 through 6.4 of Method 6C.
6.4 NO2 to NO Conversion Efficiency. Unless data are
presented to demonstrate that the NO2 concentration within
the sample stream is not greater than 5 percent of the NOx
concentration, conduct an NO2 to NO conversion efficiency
test in accordance with Section 5.6 of Method 20.

7. Emission Test Procedure

7.1 Selection of Sampling Site and Sampling Points. Select a
measurement site and sampling points using the same criteria that are
applicable to tests performed using Method 7.
7.2 Sample Collection. Position the sampling probe at the first
measurement point, and begin sampling at the same rate as used during
the system calibration drift test. Maintain constant rate sampling
(i.e., 10 percent) during the entire run. The sampling time
per run shall be the same as the total time required to perform a run
using Method 7, plus twice the system response time. For each run, use
only those measurements obtained after twice the response time of the
measurement system has elapsed, to determine the average effluent
concentration.
7.3 Zero and Calibration Drift Test. Follow Section 7.4 of Method
6C.

8. Emission Calculation

Follow Section 8 of Method 6C.

9. Bibliography

Same as bibliography of Method 6C.

Method 8--Determination of Sulfuric Acid and Sulfur Dioxide Emissions
From Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, and Method 6.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Sulfuric acid, including: 7664-93-9, 7449- 0.05 mg/m³ (0.03 x
Sulfuric acid (H2SO4) mist, 11-9. 10^-7 lb/ft³).
Sulfur trioxide (SO3).
Sulfur dioxide (SO2).......... 7449-09-5........ 1.2 mg/m³ (3 x 10^-9
lb/ft³).
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of H2SO4 (including H2SO4
mist and SO3) and gaseous SO2 emissions from
stationary sources.

[[Page 296]]

Note: Filterable particulate matter may be determined along with
H2SO4 and SO2 (subject to the approval
of the Administrator) by inserting a heated glass fiber filter between
the probe and isopropanol impinger (see Section 6.1.1 of Method 6). If
this option is chosen, particulate analysis is gravimetric only;
sulfuric acid is not determined separately.

1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

A gas sample is extracted isokinetically from the stack. The
H2SO4 and the SO2 are separated, and
both fractions are measured separately by the barium-thorin titration
method.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Possible interfering agents of this method are fluorides, free
ammonia, and dimethyl aniline. If any of these interfering agents is
present (this can be determined by knowledge of the process),
alternative methods, subject to the approval of the Administrator, are
required.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as Method 5, Section 6.1, with the
following additions and exceptions:
6.1.1 Sampling Train. A schematic of the sampling train used in
this method is shown in Figure 8-1; it is similar to the Method 5
sampling train, except that the filter position is different, and the
filter holder does not have to be heated. See Method 5, Section 6.1.1,
for details and guidelines on operation and maintenance.
6.1.1.1 Probe Liner. Borosilicate or quartz glass, with a heating
system to prevent visible condensation during sampling. Do not use metal
probe liners.
6.1.1.2 Filter Holder. Borosilicate glass, with a glass frit filter
support and a silicone rubber gasket. Other gasket materials (e.g.,
Teflon or Viton) may be used, subject to the approval of the
Administrator. The holder design shall provide a positive seal against
leakage from the outside or around the filter. The filter holder shall
be placed between the first and second impingers. Do not heat the filter
holder.
6.1.1.3 Impingers. Four, of the Greenburg-Smith design, as shown in
Figure 8-1. The first and third impingers must have standard tips. The
second and fourth impingers must be modified by replacing the insert
with an approximately 13-mm (\1/2\-in.) ID glass tube, having an
unconstricted tip located 13 mm (\1/2\ in.) from the bottom of the
impinger. Similar collection systems, subject to the approval of the
Administrator, may be used.
6.1.1.4 Temperature Sensor. Thermometer, or equivalent, to measure
the temperature of the gas leaving the impinger train to within 1 deg.C
(2 deg.F).
6.2 Sample Recovery. The following items are required for sample
recovery:
6.2.1 Wash Bottles. Two polyethylene or glass bottles, 500-ml.
6.2.2 Graduated Cylinders. Two graduated cylinders (volumetric
flasks may be used), 250-ml, 1-liter.
6.2.3 Storage Bottles. Leak-free polyethylene bottles, 1-liter size
(two for each sampling run).
6.2.4 Trip Balance. 500-g capacity, to measure to 0.5
g (necessary only if a moisture content analysis is to be done).
6.3 Analysis. The following items are required for sample analysis:
6.3.1 Pipettes. Volumetric 10-ml, 100-ml.
6.3.2 Burette. 50-ml.
6.3.3 Erlenmeyer Flask. 250-ml (one for each sample, blank, and
standard).
6.3.4 Graduated Cylinder. 100-ml.
6.3.5 Dropping Bottle. To add indicator solution, 125-ml size.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Filters and Silica Gel. Same as in Method 5, Sections 7.1.1
and 7.1.2, respectively.
7.1.2 Water. Same as in Method 6, Section 7.1.1.
7.1.3 Isopropanol, 80 Percent by Volume. Mix 800 ml of isopropanol
with 200 ml of water.

Note: Check for peroxide impurities using the procedure outlined in
Method 6, Section 7.1.2.1.
7.1.4 Hydrogen Peroxide (H\2\O\2\), 3 Percent by Volume. Dilute 100
ml of 30 percent H2O2) to 1 liter with water.
Prepare fresh daily.
7.1.5 Crushed Ice.

[[Page 297]]

7.2 Sample Recovery. The reagents and standards required for sample
recovery are:
7.2.1 Water. Same as in Section 7.1.2.
7.2.2 Isopropanol, 80 Percent. Same as in Section 7.1.3.
7.3 Sample Analysis. Same as Method 6, Section 7.3.
7.3.1 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, audit samples may be obtained
from the appropriate EPA Regional Office or from the responsible
enforcement authority.

Note: The responsible enforcement authority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. Same as Method 5, Section 8.1, except that
filters should be inspected but need not be desiccated, weighed, or
identified. If the effluent gas can be considered dry (i.e., moisture-
free), the silica gel need not be weighed.
8.2 Preliminary Determinations. Same as Method 5, Section 8.2.
8.3 Preparation of Sampling Train. Same as Method 5, Section 8.3,
with the following exceptions:
8.3.1 Use Figure 8-1 instead of Figure 5-1.
8.3.2 Replace the second sentence of Method 5, Section 8.3.1 with:
Place 100 ml of 80 percent isopropanol in the first impinger, 100 ml of
3 percent H2O2 in both the second and third
impingers; retain a portion of each reagent for use as a blank solution.
Place about 200 g of silica gel in the fourth impinger.
8.3.3 Ignore any other statements in Section 8.3 of Method 5 that
are obviously not applicable to the performance of Method 8.

Note: If moisture content is to be determined by impinger analysis,
weigh each of the first three impingers (plus absorbing solution) to the
nearest 0.5 g, and record these weights. Weigh also the silica gel (or
silica gel plus container) to the nearest 0.5 g, and record.)

8.4 Metering System Leak-Check Procedure. Same as Method 5, Section
8.4.1.
8.5 Pretest Leak-Check Procedure. Follow the basic procedure in
Method 5, Section 8.4.2, noting that the probe heater shall be adjusted
to the minimum temperature required to prevent condensation, and also
that verbage such as ``* * * plugging the inlet to the filter holder * *
* '' found in Section 8.4.2.2 of Method 5 shall be replaced by `` * * *
plugging the inlet to the first impinger * * * ''. The pretest leak-
check is recommended, but is not required.
8.6 Sampling Train Operation. Follow the basic procedures in Method
5, Section 8.5, in conjunction with the following special instructions:
8.6.1 Record the data on a sheet similar to that shown in Figure 8-
2 (alternatively, Figure 5-2 in Method 5 may be used). The sampling rate
shall not exceed 0.030 m\3\/min (1.0 cfm) during the run. Periodically
during the test, observe the connecting line between the probe and first
impinger for signs of condensation. If condensation does occur, adjust
the probe heater setting upward to the minimum temperature required to
prevent condensation. If component changes become necessary during a
run, a leak-check shall be performed immediately before each change,
according to the procedure outlined in Section 8.4.3 of Method 5 (with
appropriate modifications, as mentioned in Section 8.5 of this method);
record all leak rates. If the leakage rate(s) exceeds the specified
rate, the tester shall either void the run or plan to correct the sample
volume as outlined in Section 12.3 of Method 5. Leak-checks immediately
after component changes are recommended, but not required. If these
leak-checks are performed, the procedure in Section 8.4.2 of Method 5
(with appropriate modifications) shall be used.
8.6.2 After turning off the pump and recording the final readings
at the conclusion of each run, remove the probe from the stack. Conduct
a post-test (mandatory) leak-check as outlined in Section 8.4.4 of
Method 5 (with appropriate modifications), and record the leak rate. If
the post-test leakage rate exceeds the specified acceptable rate, either
correct the sample volume, as outlined in Section 12.3 of Method 5, or
void the run.
8.6.3 Drain the ice bath and, with the probe disconnected, purge
the remaining part of the train by drawing clean ambient air through the
system for 15 minutes at the average flow rate used for sampling.

Note: Clean ambient air can be provided by passing air through a
charcoal filter. Alternatively, ambient air (without cleaning) may be
used.
8.7 Calculation of Percent Isokinetic. Same as Method 5, Section
8.6.
8.8 Sample Recovery. Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the sampling period. Allow
the probe to cool. Treat the samples as follows:
8.8.1 Container No. 1.
8.8.1.1 If a moisture content analysis is to be performed, clean
and weigh the first impinger (plus contents) to the nearest 0.5 g, and
record this weight.
8.8.1.2 Transfer the contents of the first impinger to a 250-ml
graduated cylinder. Rinse the probe, first impinger, all connecting
glassware before the filter, and the front half of the filter holder
with 80 percent isopropanol. Add the isopropanol rinse solution to the
cylinder. Dilute the contents of the cylinder to 225 ml with 80 percent

[[Page 298]]

isopropanol, and transfer the cylinder contents to the storage
container. Rinse the cylinder with 25 ml of 80 percent isopropanol, and
transfer the rinse to the storage container. Add the filter to the
solution in the storage container and mix. Seal the container to protect
the solution against evaporation. Mark the level of liquid on the
container, and identify the sample container.
8.8.2 Container No. 2.
8.8.2.1 If a moisture content analysis is to be performed, clean
and weigh the second and third impingers (plus contents) to the nearest
0.5 g, and record the weights. Also, weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g, and record the weight.
8.8.2.2 Transfer the solutions from the second and third impingers
to a 1-liter graduated cylinder. Rinse all connecting glassware
(including back half of filter holder) between the filter and silica gel
impinger with water, and add this rinse water to the cylinder. Dilute
the contents of the cylinder to 950 ml with water. Transfer the solution
to a storage container. Rinse the cylinder with 50 ml of water, and
transfer the rinse to the storage container. Mark the level of liquid on
the container. Seal and identify the sample container.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
7.1.3......................... Isopropanol check Ensure acceptable
level of peroxide
impurities in
isopropanol.
8.4, 8.5, 10.1................ Sampling Ensure accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume.
10.2.......................... Barium standard Ensure normality
solution determination.
standardization.
11.2.......................... Replicate Ensure precision of
titrations. titration
determinations.
11.3.......................... Audit sample Evaluate analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

10.1 Sampling Equipment. Same as Method 5, Section 10.0.
10.2 Barium Standard Solution. Same as Method 6, Section 10.5.

11.0 Analytical Procedure

11.1. Sample Loss. Same as Method 6, Section 11.1.
11.2. Sample Analysis.
11.2.1 Container No. 1. Shake the container holding the isopropanol
solution and the filter. If the filter breaks up, allow the fragments to
settle for a few minutes before removing a sample aliquot. Pipette a
100-ml aliquot of this solution into a 250-ml Erlenmeyer flask, add 2 to
4 drops of thorin indicator, and titrate to a pink endpoint using 0.0100
N barium standard solution. Repeat the titration with a second aliquot
of sample, and average the titration values. Replicate titrations must
agree within 1 percent or 0.2 ml, whichever is greater.
11.2.2 Container No. 2. Thoroughly mix the solution in the
container holding the contents of the second and third impingers.
Pipette a 10-ml aliquot of sample into a 250-ml Erlenmeyer flask. Add 40
ml of isopropanol, 2 to 4 drops of thorin indicator, and titrate to a
pink endpoint using 0.0100 N barium standard solution. Repeat the
titration with a second aliquot of sample, and average the titration
values. Replicate titrations must agree within 1 percent or 0.2 ml,
whichever is greater.
11.2.3 Blanks. Prepare blanks by adding 2 to 4 drops of thorin
indicator to 100 ml of 80 percent isopropanol. Titrate the blanks in the
same manner as the samples.
11.3 Audit Sample Analysis.
11.3.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, EPA audit samples must be
analyzed, subject to availability.
11.3.2 Concurrently analyze audit samples and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.

Note: It is recommended that known quality control samples be
analyzed prior to the compliance and audit sample analyses to optimize
the system accuracy and precision. These quality control samples may be
obtained by contacting the appropriate EPA regional Office or the
responsible enforcement authority.

11.3.3 The same analyst, analytical reagents, and analytical system
shall be used for the compliance samples and the EPA audit samples. If
this condition is met, duplicate auditing of subsequent compliance
analyses for the same enforcement agency within a 30-day period is
waived. Audit samples may not be used to validate different compliance
samples under the jurisdiction of separate enforcement agencies, unless
prior arrangements have been made with both enforcement agencies.

[[Page 299]]

11.4 Audit Sample Results.
11.4.1 Calculate the audit sample concentrations in mg/dscm and
submit results using the instructions provided with the audit samples.
11.4.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.4.3 The concentrations of the audit samples obtained by the
analyst shall agree within 5 percent of the actual concentrations. If
the 5 percent specification is not met, reanalyze the compliance and
audit samples, and include initial and reanalysis values in the test
report.
11.4.4 Failure to meet the 5 percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to determine
the compliance or noncompliance status of the affected facility.

12.0 Data Analysis and Calculations

Carry out calculations retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature. Same as Method 5, Section 12.1, with the
following additions and exceptions:

Ca = Actual concentration of SO2 in audit sample,
mg/dscm.
Cd = Determined concentration of SO2 in audit
sample, mg/dscm.
CH2SO4 = Sulfuric acid (including SO3)
concentration, g/dscm (lb/dscf).
CSO2 = Sulfur dioxide concentration, g/dscm (lb/dscf).
N = Normality of barium perchlorate titrant, meq/ml.
RE = Relative error of QA audit sample analysis, percent
Va = Volume of sample aliquot titrated, 100 ml for
H2SO4 and 10 ml for SO2.
Vsoln = Total volume of solution in which the sample is
contained, 250 ml for the SO2 sample and 1000 ml
for the H2SO4 sample.
Vt = Volume of barium standard solution titrant used for the
sample, ml.
Vtb = Volume of barium standard solution titrant used for the
blank, ml.

12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 8-2).
12.3 Dry Gas Volume. Same as Method 5, Section 12.3.
12.4 Volume of Water Vapor Condensed and Moisture Content.
Calculate the volume of water vapor using Equation 5-2 of Method 5; the
weight of water collected in the impingers and silica gel can be
converted directly to milliliters (the specific gravity of water is 1 g/
ml). Calculate the moisture content of the stack gas (Bws)
using Equation 5-3 of Method 5. The Note in Section 12.5 of Method 5
also applies to this method. Note that if the effluent gas stream can be
considered dry, the volume of water vapor and moisture content need not
be calculated.
12.5 Sulfuric Acid Mist (Including SO3) Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.223

Where:

K3 = 0.04904 g/meq for metric units,
K3 = 1.081 x 10^-4 lb/meq for English units.

12.6 Sulfur Dioxide Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.224

Where:

K4 = 0.03203 g/meq for metric units,
K4 = 7.061 x 10^-5 lb/meq for English units.

12.7 Isokinetic Variation. Same as Method 5, Section 12.11.
12.8 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate, if needed, using
data obtained in this method and the equations in Sections 12.6 and 12.7
of Method 2.
12.9 Relative Error (RE) for QA Audit Samples. Same as Method 6,
Section 12.4.

13.0 Method Performance

13.1 Analytical Range. Collaborative tests have shown that the
minimum detectable limits of the method are 0.06 mg/m³ (4 x
10^-9

[[Page 300]]

lb/ft³) for H2SO4 and 1.2 mg/
m³ (74 x 10^-9 lb/ft³) for
SO2. No upper limits have been established. Based on
theoretical calculations for 200 ml of 3 percent
H2O2 solution, the upper concentration limit for
SO2 in a 1.0 m³ (35.3 ft³) gas sample
is about 12,000 mg/m³ (7.7 x 10^-4 lb/
ft³). The upper limit can be extended by increasing the
quantity of peroxide solution in the impingers.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Section 17.0 of Methods 5 and 6.

[[Page 301]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.225

[[Page 302]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.226

Method 9--Visual Determination of the Opacity of Emissions From
Stationary Sources

Many stationary sources discharge visible emissions into the
atmosphere; these emissions are usually in the shape of a plume. This
method involves the determination of plume opacity by qualified
observers. The method includes procedures for the training and
certification of observers, and procedures to be used in the field for
determination of plume opacity. The appearance of a plume as viewed by
an observer depends upon a number of variables, some of which may be
controllable and some of which may not be controllable in the field.
Variables which can be controlled to an extent to which they no longer
exert a significant influence upon

[[Page 303]]

plume appearance include: Angle of the observer with respect to the
plume; angle of the observer with respect to the sun; point of
observation of attached and detached steam plume; and angle of the
observer with respect to a plume emitted from a rectangular stack with a
large length to width ratio. The method includes specific criteria
applicable to these variables.
Other variables which may not be controllable in the field are
luminescence and color contrast between the plume and the background
against which the plume is viewed. These variables exert an influence
upon the appearance of a plume as viewed by an observer, and can affect
the ability of the observer to accurately assign opacity values to the
observed plume. Studies of the theory of plume opacity and field studies
have demonstrated that a plume is most visible and presents the greatest
apparent opacity when viewed against a contrasting background. It
follows from this, and is confirmed by field trials, that the opacity of
a plume, viewed under conditions where a contrasting background is
present can be assigned with the greatest degree of accuracy. However,
the potential for a positive error is also the greatest when a plume is
viewed under such contrasting conditions. Under conditions presenting a
less contrasting background, the apparent opacity of a plume is less and
approaches zero as the color and luminescence contrast decrease toward
zero. As a result, significant negative bias and negative errors can be
made when a plume is viewed under less contrasting conditions. A
negative bias decreases rather than increases the possibility that a
plant operator will be cited for a violation of opacity standards due to
observer error.
Studies have been undertaken to determine the magnitude of positive
errors which can be made by qualified observers while reading plumes
under contrasting conditions and using the procedures set forth in this
method. The results of these studies (field trials) which involve a
total of 769 sets of 25 readings each are as follows:
(1) For black plumes (133 sets at a smoke generator), 100 percent of
the sets were read with a positive error \1\ of less than 7.5 percent
opacity; 99 percent were read with a positive error of less than 5
percent opacity.
---------------------------------------------------------------------------

\1\ For a set, positive error = average opacity determined by
observers' 25 observations--average opacity determined from
transmissometer's 25 recordings.
---------------------------------------------------------------------------

(2) For white plumes (170 sets at a smoke generator, 168 sets at a
coal-fired power plant, 298 sets at a sulfuric acid plant), 99 percent
of the sets were read with a positive error of less than 7.5 percent
opacity; 95 percent were read with a positive error of less than 5
percent opacity.
The positive observational error associated with an average of
twenty-five readings is therefore established. The accuracy of the
method must be taken into account when determining possible violations
of applicable opacity standards.

1. Principle and Applicability

1.1 Principle. The opacity of emissions from stationary sources is
determined visually by a qualified observer.
1.2 Applicability. This method is applicable for the determination
of the opacity of emissions from stationary sources pursuant to
Sec. 60.11(b) and for qualifying observers for visually determining
opacity of emissions.

2. Procedures

The observer qualified in accordance with section 3 of this method
shall use the following procedures for visually determining the opacity
of emissions:
2.1 Position. The qualified observer shall stand at a distance
sufficient to provide a clear view of the emissions with the sun
oriented in the 140 deg. sector to his back. Consistent with maintaining
the above requirement, the observer shall, as much as possible, make his
observations from a position such that his line of vision is
approximately perpendicular to the plume direction, and when observing
opacity of emissions from rectangular outlets (e.g., roof monitors, open
baghouses, noncircular stacks), approximately perpendicular to the
longer axis of the outlet. The observer's line of sight should not
include more than one plume at a time when multiple stacks are involved,
and in any case the observer should make his observations with his line
of sight perpendicular to the longer axis of such a set of multiple
stacks (e.g., stub stacks on baghouses).
2.2 Field Records. The observer shall record the name of the plant,
emission location, type facility, observer's name and affiliation, a
sketch of the observer's position relative to the source, and the date
on a field data sheet (Figure 9-1). The time, estimated distance to the
emission location, approximate wind direction, estimated wind speed,
description of the sky condition (presence and color of clouds), and
plume background are recorded on a field data sheet at the time opacity
readings are initiated and completed.
2.3 Observations. Opacity observations shall be made at the point of
greatest opacity in that portion of the plume where condensed water
vapor is not present. The observer shall not look continuously at the
plume, but instead shall observe the plume momentarily at 15-second
intervals.
2.3.1 Attached Steam Plumes. When condensed water vapor is present
within the

[[Page 304]]

plume as it emerges from the emission outlet, opacity observations shall
be made beyond the point in the plume at which condensed water vapor is
no longer visible. The observer shall record the approximate distance
from the emission outlet to the point in the plume at which the
observations are made.
2.3.2 Detached Steam Plume. When water vapor in the plume condenses
and becomes visible at a distinct distance from the emission outlet, the
opacity of emissions should be evaluated at the emission outlet prior to
the condensation of water vapor and the formation of the steam plume.
2.4 Recording Observations. Opacity observations shall be recorded
to the nearest 5 percent at 15-second intervals on an observational
record sheet. (See Figure 9-2 for an example.) A minimum of 24
observations shall be recorded. Each momentary observation recorded
shall be deemed to represent the average opacity of emissions for a 15-
second period.
2.5 Data Reduction. Opacity shall be determined as an average of 24
consecutive observations recorded at 15-second intervals. Divide the
observations recorded on the record sheet into sets of 24 consecutive
observations. A set is composed of any 24 consecutive observations. Sets
need not be consecutive in time and in no case shall two sets overlap.
For each set of 24 observations, calculate the average by summing the
opacity of the 24 observations and dividing this sum by 24. If an
applicable standard specifies an averaging time requiring more than 24
observations, calculate the average for all observations made during the
specified time period. Record the average opacity on a record sheet.
(See Figure 9-1 for an example.)

3. Qualifications and Testing

3.1 Certification Requirements. To receive certification as a
qualified observer, a candidate must be tested and demonstrate the
ability to assign opacity readings in 5 percent increments to 25
different black plumes and 25 different white plumes, with an error not
to exceed 15 percent opacity on any one reading and an average error not
to exceed 7.5 percent opacity in each category. Candidates shall be
tested according to the procedures described in section 3.2. Smoke
generators used pursuant to section 3.2 shall be equipped with a smoke
meter which meets the requirements of section 3.3.
The certification shall be valid for a period of 6 months, at which
time the qualification procedure must be repeated by any observer in
order to retain certification.
3.2 Certification Procedure. The certification test consists of
showing the candidate a complete run of 50 plumes--25 black plumes and
25 white plumes--generated by a smoke generator. Plumes within each set
of 25 black and 25 white runs shall be presented in random order. The
candidate assigns an opacity value to each plume and records his
observation on a suitable form. At the completion of each run of 50
readings, the score of the candidate is determined. If a candidate fails
to qualify, the complete run of 50 readings must be repeated in any
retest. The smoke test may be administered as part of a smoke school or
training program, and may be preceded by training or familiarization
runs of the smoke generator during which candidates are shown black and
white plumes of known opacity.
3.3 Smoke Generator Specifications. Any smoke generator used for the
purposes of section 3.2 shall be equipped with a smoke meter installed
to measure opacity across the diameter of the smoke generator stack. The
smoke meter output shall display instack opacity based upon a pathlength
equal to the stack exit diameter, on a full 0 to 100 percent chart
recorder scale. The smoke meter optical design and performance shall
meet the specifications shown in Table 9-1. The smoke meter shall be
calibrated as prescribed in section 3.3.1 prior to the conduct of each
smoke reading test. At the completion of each test, the zero and span
drift shall be checked and if the drift exceeds ^plus-minus1
percent opacity, the condition shall be corrected prior to conducting
any subsequent test runs. The smoke meter shall be demonstrated, at the
time of installation, to meet the specifications listed in Table 9-1.
This demonstration shall be repeated following any subsequent repair or
replacement of the photocell or associated electronic circuitry
including the chart recorder or output meter, or every 6 months,
whichever occurs first.

Table 9-1--Smoke Meter Design and Performance Specifications
------------------------------------------------------------------------
Parameter Specification
------------------------------------------------------------------------
a. Light source.......................... Incandescent lamp operated at
nominal rated voltage.
b. Spectral response of photocell........ Photopic (daylight spectral
response of the human eye--
Citation 3).
c. Angle of view......................... 15 deg. maximum total angle.
d. Angle of projection................... 15 deg. maximum total angle.
e. Calibration error..................... ^plus-minus3% opacity,
maximum.
f. Zero and span drift................... ^plus-minus1% opacity, 30
minutes
g. Response time......................... 5 seconds.
------------------------------------------------------------------------

3.3.1 Calibration. The smoke meter is calibrated after allowing a
minimum of 30 minutes warmup by alternately producing simulated opacity
of 0 percent and 100 percent. When stable response at 0 percent or 100
percent is noted, the smoke meter is adjusted to produce an output of 0
percent or 100 percent, as appropriate. This calibration shall be
repeated until stable 0 percent and 100

[[Page 305]]

percent readings are produced without adjustment. Simulated 0 percent
and 100 percent opacity values may be produced by alternately switching
the power to the light source on and off while the smoke generator is
not producing smoke.
3.3.2 Smoke Meter Evaluation. The smoke meter design and performance
are to be evaluated as follows:
3.3.2.1 Light Source. Verify from manufacturer's data and from
voltage measurements made at the lamp, as installed, that the lamp is
operated within ^plus-minus5 percent of the nominal rated
voltage.
3.3.2.2 Spectral Response of Photocell. Verify from manufacturer's
data that the photocell has a photopic response; i.e., the spectral
sensitivity of the cell shall closely approximate the standard spectral-
luminosity curve for photopic vision which is referenced in (b) of Table
9-1.

[[Page 306]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.154

Figure 9-2--Observation Record
Page ____ of ____
Company........................... Observer.............. ........
Location.......................... Type facility......... ........
Test Number....................... Point of emissions.... ........
Date..............................

[[Page 307]]

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Seconds Steam plume (check if applicable)
Hr. Min. ----------------------------------------------------------------------------- Comments
0 15 30 45 Attached Detached
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Figure 9-2--Observation Record--(Continued)
Page ____ of ____
Company........................... Observer.............. ........
Location.......................... Type facility......... ........
Test Number....................... Point of emissions.... ........
Date..............................

[[Page 308]]

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3.3.2.3 Angle of View. Check construction geometry to ensure that
the total angle of view of the smoke plume, as seen by the photocell,
does not exceed 15 deg.. The total angle of view may be calculated from:
-¹d/2L, where -¹d/2L, where plus-minus2 percent shall be used. Care should be taken when
inserting the filters to prevent stray light from affecting the meter.
Make a total of five nonconsecutive readings for each filter. The
maximum error on any one reading shall be 3 percent opacity.
3.3.2.6 Zero and Span Drift. Determine the zero and span drift by
calibrating and operating the smoke generator in a normal manner over a
1-hour period. The drift is measured by checking the zero and span at
the end of this period.
3.3.2.7 Response Time. Determine the response time by producing the
series of five simulated 0 percent and 100 percent opacity values and
observing the time required to reach stable response. Opacity values of
0 percent and 100 percent may be simulated by alternately switching the
power to the light source off and on while the smoke generator is not
operating.

4. Bibliography.

1. Air Pollution Control District Rules and Regulations, Los Angeles
County Air Pollution Control District, Regulation IV, Prohibitions, Rule
50.
2. Weisburd, Melvin I., Field Operations and Enforcement Manual for
Air, U.S. Environmental Protection Agency, Research Triangle Park, NC.
APTD-1100, August 1972, pp. 4.1-4.36.
3. Condon, E.U., and Odishaw, H., Handbook of Physics, McGraw-Hill
Co., New York, NY, 1958, Table 3.1, p. 6-52.

Alternate Method 1--Determination of the Opacity of Emissions From
Stationary Sources Remotely by Lidar

This alternate method provides the quantitative determination of the
opacity of an emissions plume remotely by a mobile lidar system (laser
radar; Light Detection and Ranging). The method includes procedures for
the calibration of the lidar and procedures to be used in the field for
the lidar determination of plume opacity. The lidar is used to measure
plume opacity during either day or nighttime hours because it contains
its own pulsed light source or transmitter. The operation of the lidar
is not dependent upon ambient lighting conditions (light, dark, sunny or
cloudy).
The lidar mechanism or technique is applicable to measuring plume
opacity at numerous wavelengths of laser radiation. However, the
performance evaluation and calibration test results given in support of
this method apply only to a lidar that employs a ruby (red light) laser
[Reference 5.1].

1. Principle and Applicability

1.1 Principle. The opacity of visible emissions from stationary
sources (stacks, roof vents, etc.) is measured remotely by a mobile
lidar (laser radar).
1.2 Applicability. This method is applicable for the remote
measurement of the opacity of visible emissions from stationary sources
during both nighttime and daylight conditions, pursuant to 40 CFR
Sec. 60.11(b). It is also applicable for the calibration and performance
verification of the mobile lidar for the measurement of the opacity of
emissions. A performance/design specification for a basic lidar system
is also incorporated into this method.
1.3 Definitions.
Azimuth angle: The angle in the horizontal plane that designates
where the laser beam is pointed. It is measured from an arbitrary fixed
reference line in that plane.
Backscatter: The scattering of laser light in a direction opposite
to that of the incident laser beam due to reflection from particulates
along the beam's atmospheric path which may include a smoke plume.
Backscatter signal: The general term for the lidar return signal
which results from laser light being backscattered by atmospheric and
smoke plume particulates.
Convergence distance: The distance from the lidar to the point of
overlap of the lidar receiver's field-of-view and the laser beam.
Elevation angle: The angle of inclination of the laser beam
referenced to the horizontal plane.
Far region: The region of the atmosphere's path along the lidar
line-of-sight beyond or behind the plume being measured.
Lidar: Acronym for Light Detection and Ranging.
Lidar range: The range or distance from the lidar to a point of
interest along the lidar line-of-sight.
Near region: The region of the atmospheric path along the lidar
line-of-sight between the lidar's convergence distance and the plume
being measured.
Opacity: One minus the optical transmittance of a smoke plume,
screen target, etc.
Pick interval: The time or range intervals in the lidar backscatter
signal whose minimum average amplitude is used to calculate opacity. Two
pick intervals are required, one in the near region and one in the far
region.
Plume: The plume being measured by lidar.
Plume signal: The backscatter signal resulting from the laser light
pulse passing through a plume.

[[Page 310]]

1/R\2\correction: The correction made for the systematic decrease in
lidar backscatter signal amplitude with range.
Reference signal: The backscatter signal resulting from the laser
light pulse passing through ambient air.
Sample interval: The time period between successive samples for a
digital signal or between successive measurements for an analog signal.
Signal spike: An abrupt, momentary increase and decrease in signal
amplitude.
Source: The source being tested by lidar.
Time reference: The time (to) when the laser pulse
emerges from the laser, used as the reference in all lidar time or range
measurements.

2. Procedures

The mobile lidar calibrated in accordance with Paragraph 3 of this
method shall use the following procedures for remotely measuring the
opacity of stationary source emissions:
2.1 Lidar Position. The lidar shall be positioned at a distance
from the plume sufficient to provide an unobstructed view of the source
emissions. The plume must be at a range of at least 50 meters or three
consecutive pick intervals (whichever is greater) from the lidar's
transmitter/receiver convergence distance along the line-of-sight. The
maximum effective opacity measurement distance of the lidar is a
function of local atmospheric conditions, laser beam diameter, and plume
diameter. The test position of the lidar shall be selected so that the
diameter of the laser beam at the measurement point within the plume
shall be no larger than three-fourths the plume diameter. The beam
diameter is calculated by Equation (AM1-1):

D(lidar)=A+R0.75 D(Plume) (AM1-1)
Where:

D(Plume)=diameter of the plume (cm),
=laser beam divergence measured in radians
R=range from the lidar to the source (cm)
D(Lidar)=diameter of the laser beam at range R (cm),
A=diameter of the laser beam or pulse where it leaves the laser.

The lidar range, R, is obtained by aiming and firing the laser at the
emissions source structure immediately below the outlet. The range value
is then determined from the backscatter signal which consists of a
signal spike (return from source structure) and the atmospheric
backscatter signal [Reference 5.1]. This backscatter signal should be
recorded.
When there is more than one source of emissions in the immediate
vicinity of the plume, the lidar shall be positioned so that the laser
beam passes through only a single plume, free from any interference of
the other plumes for a minimum of 50 meters or three consecutive pick
intervals (whichever is greater) in each region before and beyond the
plume along the line-of-sight (determined from the backscatter signals).
The lidar shall initially be positioned so that its line-of-sight is
approximately perpendicular to the plume.
When measuring the opacity of emissions from rectangular outlets
(e.g., roof monitors, open baghouses, noncircular stacks, etc.), the
lidar shall be placed in a position so that its line-of-sight is
approximately perpendicular to the longer (major) axis of the outlet.
2.2 Lidar Operational Restrictions. The lidar receiver shall not be
aimed within an angle of ^plus-minus 15 deg. (cone angle) of
the sun.
This method shall not be used to make opacity measurements if
thunderstorms, snowstorms, hail storms, high wind, high-ambient dust
levels, fog or other atmospheric conditions cause the reference signals
to consistently exceed the limits specified in Section 2.3.
2.3 Reference Signal Requirements. Once placed in its proper
position for opacity measurement, the laser is aimed and fired with the
line-of-sight near the outlet height and rotated horizontally to a
position clear of the source structure and the associated plume. The
backscatter signal obtained from this position is called the ambient-air
or reference signal. The lidar operator shall inspect this signal
[Section V of Reference 5.1] to: (1) determine if the lidar line-of-
sight is free from interference from other plumes and from physical
obstructions such as cables, power lines, etc., for a minimum of 50
meters or three consecutive pick intervals (whichever is greater) in
each region before and beyond the plume, and (2) obtain a qualitative
measure of the homogeneity of the ambient air by noting any signal
spikes.
Should there be any signal spikes on the reference signal within a
minimum of 50 meters or three consecutive pick intervals (whichever is
greater) in each region before and beyond the plume, the laser shall be
fired three more times and the operator shall inspect the reference
signals on the display. If the spike(s) remains, the azimuth angle shall
be changed and the above procedures conducted again. If the spike(s)
disappears in all three reference signals, the lidar line-of-sight is
acceptable if there is shot-to-shot consistency and there is no
interference from other plumes.
Shot-to-shot consistency of a series of reference signals over a
period of twenty seconds is verified in either of two ways. (1) The
lidar operator shall observe the reference signal amplitudes. For shot-
to-shot consistency the ratio of Rf to Rn
[amplitudes of the near and far region pick intervals (Section 2.6.1)]
shall vary by not more than ^plus-minus 6% between shots; or
(2) the lidar operator shall accept any one of the reference signals and
treat the other two as plume signals; then

[[Page 311]]

the opacity for each of the subsequent reference signals is calculated
(Equation AM1-2). For shot-to-shot consistency, the opacity values shall
be within ^plus-minus 3% of 0% opacity and the associated
So values less than or equal to 8% (full scale) [Section
2.6].
If a set of reference signals fails to meet the requirements of this
section, then all plume signals [Section 2.4] from the last set of
acceptable reference signals to the failed set shall be discarded.
2.3.1 Initial and Final Reference Signals. Three reference signals
shall be obtained within a 90-second time period prior to any data run.
A final set of three reference signals shall be obtained within three
(3) minutes after the completion of the same data run.
2.3.2 Temporal Criterion for Additional Reference Signals. An
additional set of reference signals shall be obtained during a data run
if there is a change in wind direction or plume drift of 30 deg. or more
from the direction that was prevalent when the last set of reference
signals was obtained. An additional set of reference signals shall also
be obtained if there is an increase in value of SIn (near
region standard deviation, Equation AM1-5) or SIf (far region
standard deviation, Equation AM1-6) that is greater than 6% (full scale)
over the respective values calculated from the immediately previous
plume signal, and this increase in value remains for 30 seconds or
longer. An additional set of reference signals shall also be obtained if
there is a change in amplitude in either the near or the far region of
the plume signal, that is greater than 6% of the near signal amplitude
and this change in amplitude remains for 30 seconds or more.
2.4 Plume Signal Requirements. Once properly aimed, the lidar is
placed in operation with the nominal pulse or firing rate of six pulses/
minute (1 pulse/10 seconds). The lidar operator shall observe the plume
backscatter signals to determine the need for additional reference
signals as required by Section 2.3.2. The plume signals are recorded
from lidar start to stop and are called a data run. The length of a data
run is determined by operator discretion. Short-term stops of the lidar
to record additional reference signals do not constitute the end of a
data run if plume signals are resumed within 90 seconds after the
reference signals have been recorded, and the total stop or interrupt
time does not exceed 3 minutes.
2.4.1 Non-hydrated Plumes. The laser shall be aimed at the region
of the plume which displays the greatest opacity. The lidar operator
must visually verify that the laser is aimed clearly above the source
exit structure.
2.4.2 Hydrated Plumes. The lidar will be used to measure the
opacity of hydrated or so-called steam plumes. As listed in the
reference method, there are two types, i.e., attached and detached steam
plumes.
2.4.2.1 Attached Steam Plumes. When condensed water vapor is
present within a plume, lidar opacity measurements shall be made at a
point within the residual plume where the condensed water vapor is no
longer visible. The laser shall be aimed into the most dense region
(region of highest opacity) of the residual plume.
During daylight hours the lidar operator locates the most dense
portion of the residual plume visually. During nighttime hours a high-
intensity spotlight, night vision scope, or low light level TV, etc.,
can be used as an aid to locate the residual plume. If visual
determination is ineffective, the lidar may be used to locate the most
dense region of the residual plume by repeatedly measuring opacity,
along the longitudinal axis or center of the plume from the emissions
outlet to a point just beyond the steam plume. The lidar operator should
also observe color differences and plume reflectivity to ensure that the
lidar is aimed completely within the residual plume. If the operator
does not obtain a clear indication of the location of the residual
plume, this method shall not be used.
Once the region of highest opacity of the residual plume has been
located, aiming adjustments shall be made to the laser line-of-sight to
correct for the following: movement to the region of highest opacity out
of the lidar line-of-sight (away from the laser beam) for more than 15
seconds, expansion of the steam plume (air temperature lowers and/or
relative humidity increases) so that it just begins to encroach on the
field-of-view of the lidar's optical telescope receiver, or a decrease
in the size of the steam plume (air temperature higher and/or relative
humidity decreases) so that regions within the residual plume whose
opacity is higher than the one being monitored, are present.
2.4.2.2 Detached Steam Plumes. When the water vapor in a hydrated
plume condenses and becomes visible at a finite distance from the stack
or source emissions outlet, the opacity of the emissions shall be
measured in the region of the plume clearly above the emissions outlet
and below condensation of the water vapor.
During daylight hours the lidar operators can visually determine if
the steam plume is detached from the stack outlet. During nighttime
hours a high-intensity spotlight, night vision scope, low light level
TV, etc., can be used as an aid in determining if the steam plume is
detached. If visual determination is ineffective, the lidar may be used
to determine if the steam plume is detached by repeatedly measuring
plume opacity from the outlet to the steam plume along the plume's
longitudinal axis or center line. The lidar operator should also observe
color differences and plume reflectivity to detect a

[[Page 312]]

detached plume. If the operator does not obtain a clear indication of
the location of the detached plume, this method shall not be used to
make opacity measurements between the outlet and the detached plume.
Once the determination of a detached steam plume has been confirmed,
the laser shall be aimed into the region of highest opacity in the plume
between the outlet and the formation of the steam plume. Aiming
adjustments shall be made to the lidar's line-of-sight within the plume
to correct for changes in the location of the most dense region of the
plume due to changes in wind direction and speed or if the detached
steam plume moves closer to the source outlet encroaching on the most
dense region of the plume. If the detached steam plume should move too
close to the source outlet for the lidar to make interference-free
opacity measurements, this method shall not be used.
2.5 Field Records. In addition to the recording recommendations
listed in other sections of this method the following records should be
maintained. Each plume measured should be uniquely identified. The name
of the facility, type of facility, emission source type, geographic
location of the lidar with respect to the plume, and plume
characteristics should be recorded. The date of the test, the time
period that a source was monitored, the time (to the nearest second) of
each opacity measurement, and the sample interval should also be
recorded. The wind speed, wind direction, air temperature, relative
humidity, visibility (measured at the lidar's position), and cloud cover
should be recorded at the beginning and end of each time period for a
given source. A small sketch depicting the location of the laser beam
within the plume should be recorded.
If a detached or attached steam plume is present at the emissions
source, this fact should be recorded. Figures AM1-I and AM1-II are
examples of logbook forms that may be used to record this type of data.
Magnetic tape or paper tape may also be used to record data.

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[[Page 314]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.156

[[Page 315]]

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2.6 Opacity Calculation and Data Analysis. Referring to the
reference signal and plume signal in Figure AM1-III, the measured
opacity (Op) in percent for each lidar measurement is
calculated using Equation AM1-2. (Op=1-Tp; Tp
is the plume transmittance.)

[[Page 316]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.158

Where:

In=near-region pick interval signal amplitude, plume signal,
1/R\2\corrected,
If=far-region pick interval signal amplitude, plume signal,
1/R\2\corrected,
Rn=near-region pick interval signal amplitude, reference
signal, 1/R\2\corrected, and
Rf=far-region pick interval signal amplitude, reference
signal, 1/R\2\corrected.
The 1/R\2\ correction to the plume and reference signal amplitudes
is made by multiplying the amplitude for each successive sample interval
from the time reference, by the square of the lidar time (or range)
associated with that sample interval [Reference 5.1].
The first step in selecting the pick intervals for Equation AM1-2 is
to divide the plume signal amplitude by the reference signal amplitude
at the same respective ranges to obtain a ``normalized'' signal. The
pick intervals selected using this normalized signal, are a minimum of
15 m (100 nanoseconds) in length and consist of at least 5 contiguous
sample intervals. In addition, the following criteria, listed in order
of importance, govern pick interval selection. (1) The intervals shall
be in a region of the normalized signal where the reference signal meets
the requirements of Section 2.3 and is everywhere greater than zero. (2)
The intervals (near and far) with the minimum average amplitude are
chosen. (3) If more than one interval with the same minimum average
amplitude is found, the interval closest to the plume is chosen. (4) The
standard deviation, So, for the calculated opacity shall be
8% or less. (So is calculated by Equation AM1-7).
If So is greater than 8%, then the far pick interval
shall be changed to the next interval of minimal average amplitude. If
So is still greater than 8%, then this procedure is repeated
for the far pick interval. This procedure may be repeated once again for
the near pick interval, but if So remains greater than 8%,
the plume signal shall be discarded.
The reference signal pick intervals, Rn and
Rf, must be chosen over the same time interval as the plume
signal pick intervals, In and If, respectively
[Figure AM1-III]. Other methods of selecting pick intervals may be used
if they give equivalent results. Field-oriented examples of pick
interval selection are available in Reference 5.1.
The average amplitudes for each of the pick intervals,
In, If, Rn, Rf, shall be
calculated by averaging the respective individual amplitudes of the
sample intervals from the plume signal and the associated reference
signal each corrected for 1/R\2\. The amplitude of In shall
be calculated according to Equation (AM-3).
[GRAPHIC] [TIFF OMITTED] TC01JN92.159

Where:

Ini=the amplitude of the ith sample interval (near-region),
=sum of the individual amplitudes for the sample intervals,
m=number of sample intervals in the pick interval, and
In=average amplitude of the near-region pick interval.
Similarly, the amplitudes for If, Rn, and
Rf are calculated with the three expressions in Equation
(AM1-4).
[GRAPHIC] [TIFF OMITTED] TC01JN92.160

The standard deviation, SIn, of the set of amplitudes for
the near-region pick interval, In, shall be calculated using
Equation (AM1-5).
Similarly, the standard deviations SIf, SRn,
and SRf are calculated with the three expressions in Equation
(AM1-6).

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[GRAPHIC] [TIFF OMITTED] TC01JN92.162

The standard deviation, So, for each associated opacity
value, Op, shall be calculated using Equation (AM1-7).
[GRAPHIC] [TIFF OMITTED] TC01JN92.163

The calculated values of In, If,
Rn, Rf, SIn, SIf,
SRn, SRf, Op, and So should
be recorded. Any plume signal with an So greater than 8%
shall be discarded.
2.6.1 Azimuth Angle Correction. If the azimuth angle correction to
opacity specified in this section is performed, then the elevation angle
correction specified in Section 2.6.2 shall not be performed. When
opacity is measured in the residual region of an attached steam plume,
and the lidar line-of-sight is not perpendicular to the plume, it may be
necessary to correct the opacity measured by the lidar to obtain the
opacity that would be measured on a path perpendicular to the plume. The
following method, or any other method which produces equivalent results,
shall be used to determine the need for a correction, to calculate the
correction, and to document the point within the plume at which the
opacity was measured.
Figure AM1-IV(b) shows the geometry of the opacity correction. L' is
the path through the plume along which the opacity measurement is made.
P' is the path perpendicular to the plume at the same point. The angle
/2-p, measured along the path L' shall be corrected to
obtain the corrected opacity, Opc, for the path P', using
Equation (AM1-8).
[GRAPHIC] [TIFF OMITTED] TC01JN92.164

[[Page 318]]

The correction in Equation (AM1-8) shall be performed if the inequality
in Equation (AM1-9) is true.

[GRAPHIC] [TIFF OMITTED] TC01JN92.165

Figure AM1-IV(a) shows the geometry used to calculate s=range from lidar to source*...............................
s=elevation angle of Rs*.................
Rp=range from lidar to plume at the opacity measurement
point*..................................................................
p=elevation angle of Rp*.................
Ra=range from lidar to plume at some arbitrary point,
Pa, so the drift angle of the plume can be determined*.......
a=elevation angle of Ra*.................
=angle between Rp and Ra.......................
R's=projection of Rs in the horizontal plane
R'p=projection of Rp in the horizontal plane......

[[Page 320]]

R'a=projection of Ra in the horizontal plane
'=angle between R's and R'p*............
'=angle between R'p and R'a*.............
R=distance from the source to the opacity measurement point
projected in the horizontal plane.......................................
Rp to the
point in the plume Pa..............................................
[GRAPHIC] [TIFF OMITTED] TC01JN92.167

The correction angle =Cos^-1 (Cosp Cosa
Cos'+Sinp
Sina),

and
Rp2+Ra2-2 Rp Ra
Cos)^1/2

R, the distance from the source to the opacity
measurement point projected in the horizontal plane, shall be determined
using Equation AM1-11.
[GRAPHIC] [TIFF OMITTED] TC01JN92.168

Where:
R's=Rs Cos s, and
R'p=Rp Cos p.

In the special case where the plume centerline at the opacity
measurement point is horizontal, parallel to the ground, Equation AM1-12
may be used to determine s=(R'\2\s+Rp\2\Sin\2\p)
^1/2.

If the angle 30 deg. or
150 deg., the azimuth angle correction shall not be
performed and the associated opacity value shall be discarded.
2.6.2 Elevation Angle Correction. An individual lidar-measured
opacity, Op, shall be corrected for elevation angle if the
laser elevation or inclination angle, p [Figure AM1-
V], is greater than or equal to the value calculated in Equation AM1-13.
[GRAPHIC] [TIFF OMITTED] TC01JN92.170

The measured opacity, Op, along the lidar path L, is adjusted
to obtain the corrected opacity, Opc, for the actual plume
(horizontal) path, P, by using Equation (AM1-14).

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Where:

p=lidar elevation or inclination angle,
Op=measured opacity along path L, and
Opc=corrected opacity for the actual plume thickness P.
The values for p, Op and Opc
should be recorded.

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2.6.3 Determination of Actual Plume Opacity. Actual opacity of the
plume shall be determined by Equation AM1-15.
[GRAPHIC] [TIFF OMITTED] TC01JN92.173

2.6.4 Calculation of Average Actual Plume Opacity. The average of
the actual plume opacity, Opa, shall be calculated as the
average of the consecutive individual actual opacity values,
Opa, by Equation AM1-16.

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[GRAPHIC] [TIFF OMITTED] TC01JN92.174

Where:

(Opa)k=the kth actual opacity value in an
averaging interval containing n opacity values; k is a summing
index.
=the sum of the individual actual opacity values.
n=the number of individual actual opacity values contained in the
averaging interval.
Opa=average actual opacity calculated over the averaging
interval.

3. Lidar Performance Verification

The lidar shall be subjected to two types of performance
verifications that shall be performed in the field. The annual
calibration, conducted at least once a year, shall be used to directly
verify operation and performance of the entire lidar system. The routine
verification, conducted for each emission source measured, shall be used
to insure proper performance of the optical receiver and associated
electronics.
3.1 Annual Calibration Procedures. Either a plume from a smoke
generator or screen targets shall be used to conduct this calibration.
If the screen target method is selected, five screens shall be
fabricated by placing an opaque mesh material over a narrow frame (wood,
metal extrusion, etc.). The screen shall have a surface area of at least
one square meter. The screen material should be chosen for precise
optical opacities of about 10, 20, 40, 60, and 80%. Opacity of each
target shall be optically determined and should be recorded. If a smoke
generator plume is selected, it shall meet the requirements of Section
3.3 of Reference Method 9. This calibration shall be performed in the
field during calm (as practical) atmospheric conditions. The lidar shall
be positioned in accordance with Section 2.1.
The screen targets must be placed perpendicular to and coincident
with the lidar line-of-sight at sufficient height above the ground
(suggest about 30 ft) to avoid ground-level dust contamination.
Reference signals shall be obtained just prior to conducting the
calibration test.
The lidar shall be aimed through the center of the plume within 1
stack diameter of the exit, or through the geometric center of the
screen target selected. The lidar shall be set in operation for a 6-
minute data run at a nominal pulse rate of 1 pulse every 10 seconds.
Each backscatter return signal and each respective opacity value
obtained from the smoke generator transmissometer, shall be obtained in
temporal coincidence. The data shall be analyzed and reduced in
accordance with Section 2.6 of this method. This calibration shall be
performed for 0% (clean air), and at least five other opacities
(nominally 10, 20, 40, 60, and 80%).
The average of the lidar opacity values obtained during a 6-minute
calibration run shall be calculated and should be recorded. Also the
average of the opacity values obtained from the smoke generator
transmissometer for the same 6-minute run shall be calculated and should
be recorded.
Alternate calibration procedures that do not meet the above
requirements but produce equivalent results may be used.
3.2 Routine Verification Procedures. Either one of two techniques
shall be used to conduct this verification. It shall be performed at
least once every 4 hours for each emission source measured. The
following parameters shall be directly verified.
1) The opacity value of 0% plus a minimum of 5 (nominally 10, 20,
40, 60, and 80%) opacity values shall be verified through the PMT
detector and data processing electronics.
2) The zero-signal level (receiver signal with no optical signal
from the source present) shall be inspected to insure that no spurious
noise is present in the signal. With the entire lidar receiver and
analog/digital electronics turned on and adjusted for normal operating
performance, the following procedures shall be used for Techniques 1 and
2, respectively.
3.2.1 Procedure for Technique 1. This test shall be performed with
no ambient or stray light reaching the PMT detector. The narrow band
filter (694.3 nanometers peak) shall be removed from its position in
front of the PMT detector. Neutral density filters of nominal opacities
of 10, 20, 40, 60, and 80% shall be used. The recommended test
configuration is depicted in Figure AM1-VI.

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[GRAPHIC] [TIFF OMITTED] TC01JN92.175

The zero-signal level shall be measured and should be recorded, as
indicated in Figure AM1-VI(a). This simulated clear-air or 0% opacity
value shall be tested in using the selected light source depicted in
Figure AM1-VI(b).
The light source either shall be a continuous wave (CW) laser with
the beam mechanically chopped or a light emitting diode controlled with
a pulse generator (rectangular pulse). (A laser beam may have to be
attenuated so as not to saturate the PMT detector). This signal level
shall be measured

[[Page 325]]

and should be recorded. The opacity value is calculated by taking two
pick intervals [Section 2.6] about 1 microsecond apart in time and using
Equation (AM1-2) setting the ratio Rn/Rf=1. This
calculated value should be recorded.
The simulated clear-air signal level is also employed in the optical
test using the neutral density filters. Using the test configuration in
Figure AM1-VI(c), each neutral density filter shall be separately placed
into the light path from the light source to the PMT detector. The
signal level shall be measured and should be recorded. The opacity value
for each filter is calculated by taking the signal level for that
respective filter (If), dividing it by the 0% opacity signal
level (In) and performing the remainder of the calculation by
Equation (AM1-2) with Rn/Rf=1. The calculated
opacity value for each filter should be recorded.
The neutral density filters used for Technique 1 shall be calibrated
for actual opacity with accuracy of ^plus-minus2% or better.
This calibration shall be done monthly while the filters are in use and
the calibrated values should be recorded.
3.2.2 Procedure for Technique 2. An optical generator (built-in
calibration mechanism) that contains a light-emitting diode (red light
for a lidar containing a ruby laser) is used. By injecting an optical
signal into the lidar receiver immediately ahead of the PMT detector, a
backscatter signal is simulated. With the entire lidar receiver
electronics turned on and adjusted for normal operating performance, the
optical generator is turned on and the simulation signal (corrected for
1/R\2\) is selected with no plume spike signal and with the opacity
value equal to 0%. This simulated clear-air atmospheric return signal is
displayed on the system's video display. The lidar operator then makes
any fine adjustments that may be necessary to maintain the system's
normal operating range.
The opacity values of 0% and the other five values are selected one
at a time in any order. The simulated return signal data should be
recorded. The opacity value shall be calculated. This measurement/
calculation shall be performed at least three times for each selected
opacity value. While the order is not important, each of the opacity
values from the optical generator shall be verified. The calibrated
optical generator opacity value for each selection should be recorded.
The optical generator used for Technique 2 shall be calibrated for
actual opacity with an accuracy of ^plus-minus1% or better.
This calibration shall be done monthly while the generator is in use and
calibrated value should be recorded.
Alternate verification procedures that do not meet the above
requirements but produce equivalent results may be used.
3.3 Deviation. The permissible error for the annual calibration and
routine verification are:
3.3.1 Annual Calibration Deviation.
3.3.1.1 Smoke Generator. If the lidar-measured average opacity for
each data run is not within ^plus-minus5% (full scale) of the
respective smoke generator's average opacity over the range of 0%
through 80%, then the lidar shall be considered out of calibration.
3.3.1.2 Screens. If the lidar-measured average opacity for each
data run is not within ^plus-minus3% (full scale) of the
laboratory-determined opacity for each respective simulation screen
target over the range of 0% through 80%, then the lidar shall be
considered out of calibration.
3.3.2 Routine Verification Error. If the lidar-measured average
opacity for each neutral density filter (Technique 1) or optical
generator selection (Technique 2) is not within ^plus-minus3%
(full scale) of the respective laboratory calibration value then the
lidar shall be considered non-operational.

4. Performance/Design Specification for Basic Lidar System

4.1 Lidar Design Specification. The essential components of the
basic lidar system are a pulsed laser (transmitter), optical receiver,
detector, signal processor, recorder, and an aiming device that is used
in aiming the lidar transmitter and receiver. Figure AM1-VII shows a
functional block diagram of a basic lidar system.

[[Page 326]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.176

4.2 Performance Evaluation Tests. The owner of a lidar system shall
subject such a lidar system to the performance verification tests
described in Section 3, prior to first use of this method. The annual
calibration shall be performed for three separate, complete

[[Page 327]]

runs and the results of each should be recorded. The requirements of
Section 3.3.1 must be fulfilled for each of the three runs.
Once the conditions of the annual calibration are fulfilled the
lidar shall be subjected to the routine verification for three separate
complete runs. The requirements of Section 3.3.2 must be fulfilled for
each of the three runs and the results should be recorded. The
Administrator may request that the results of the performance evaluation
be submitted for review.

5. References

5.1 The Use of Lidar for Emissions Source Opacity Determination,
U.S. Environmental Protection Agency, National Enforcement
Investigations Center, Denver, CO. EPA-330/1-79-003-R, Arthur W.
Dybdahl, current edition [NTIS No. PB81-246662].
5.2 Field Evaluation of Mobile Lidar for the Measurement of Smoke
Plume Opacity, U.S. Environmental Protection Agency, National
Enforcement Investigations Center, Denver, CO. EPA/NEIC-TS-128, February
1976.
5.3 Remote Measurement of Smoke Plume Transmittance Using Lidar, C.
S. Cook, G. W. Bethke, W. D. Conner (EPA/RTP). Applied Optics 11, pg
1742. August 1972.
5.4 Lidar Studies of Stack Plumes in Rural and Urban Environments,
EPA-650/4-73-002, October 1973.
5.5 American National Standard for the Safe Use of Lasers ANSI Z
136.1-176, March 8, 1976.
5.6 U.S. Army Technical Manual TB MED 279, Control of Hazards to
Health from Laser Radiation, February 1969.
5.7 Laser Institute of America Laser Safety Manual, 4th Edition.
5.8 U.S. Department of Health, Education and Welfare, Regulations
for the Administration and Enforcement of the Radiation Control for
Health and Safety Act of 1968, January 1976.
5.9 Laser Safety Handbook, Alex Mallow, Leon Chabot, Van Nostrand
Reinhold Co., 1978.

Method 10--Determination of Carbon Monoxide Emissions From Stationary
Sources

1. Principle and Applicability

1.1 Principle. An integrated or continuous gas sample is extracted
from a sampling point and analyzed for carbon monoxide (CO) content
using a Luft-type nondispersive infrared analyzer (NDIR) or equivalent.
1.2 Applicability. This method is applicable for the determination
of carbon monoxide emissions from stationary sources only when specified
by the test procedures for determining compliance with new source
performance standards. The test procedure will indicate whether a
continuous or an integrated sample is to be used.

2. Range and Sensitivity

2.1 Range. 0 to 1,000 ppm.
2.2 Sensitivity. Minimum detectable concentration is 20 ppm for a 0
to 1,000 ppm span.

3. Interferences

Any substance having a strong absorption of infrared energy will
interfere to some extent. For example, discrimination ratios for water
(H2O) and carbon dioxide (CO2) are 3.5 percent
H2O per 7 ppm CO and 10 percent CO2 per 10 ppm CO,
respectively, for devices measuring in the 1,500 to 3,000 ppm range. For
devices measuring in the 0 to 100 ppm range, interference ratios can be
as high as 3.5 percent H2O per 25 ppm CO and 10 percent
CO2 per 50 ppm CO. The use of silica gel and ascarite traps
will alleviate the major interference problems. The measured gas volume
must be corrected if these traps are used.

4. Precision and Accuracy

4.1 Precision. The precision of most NDIR analyzers is approximately
^plus-minus2 percent of span.
4.2 Accuracy. The accuracy of most NDIR analyzers is approximately
^plus-minus5 percent of span after calibration.

5. Apparatus

5.1 Continuous Sample (Figure 10-1).
5.1.1 Probe. Stainless steel or sheathed Pyrex\1\ glass, equipped
with a filter to remove particulate matter.
---------------------------------------------------------------------------

\1\ Mention of trade names or specific products does not constitute
endorsement by the Environmental Protection Agency.
---------------------------------------------------------------------------

5.1.2 Air-Cooled Condenser or Equivalent. To remove any excess
moisture.
5.2 Integrated Sample (Figure 10-2).
5.2.1 Probe. Stainless steel or sheathed Pyrex glass, equipped with
a filter to remove particulate matter.
5.2.2 Air-Cooled Condenser or Equivalent. To remove any excess
moisture.
5.2.3 Valve. Needle valve, or equivalent, to adjust flow rate.
5.2.4 Pump. Leak-free diaphragm type, or equivalent, to transport
gas.
5.2.5 Rate Meter. Rotameter, or equivalent, to measure a flow range
from 0 to 1.0 liter per min (0.035 cfm).
5.2.6 Flexible Bag. Tedlar, or equivalent, with a capacity of 60 to
90 liters (2 to 3 ft\3\). Leak-test the bag in the laboratory before
using by evacuating bag with a pump followed by a dry gas meter. When
evacuation is complete, there should be no flow through the meter.
5.2.7 Pitot Tube. Type S, or equivalent, attached to the probe so
that the sampling rate can be regulated proportional to the stack gas
velocity when velocity is varying with the time or a sample traverse is
conducted.
5.3 Analysis (Figure 10-3).

[[Page 328]]

5.3.1 Carbon Monoxide Analyzer. Nondispersive infrared spectrometer,
or equivalent. This instrument should be demonstrated, preferably by the
manufacturer, to meet or exceed manufacturer's specifications and those
described in this method.
5.3.2 Drying Tube. To contain approximately 200 g of silica gel.
5.3.3 Calibration Gas. Refer to section 6.1.
5.3.4 Filter. As recommended by NDIR manufacturer.
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[GRAPHIC] [TIFF OMITTED] TC01JN92.178

5.3.5 CO2 Removal Tube. To contain approximately 500 g of
ascarite.
5.3.6 Ice Water Bath. For ascarite and silica gel tubes.
5.3.7 Valve. Needle valve, or equivalent, to adjust flow rate
5.3.8 Rate Meter. Rotameter or equivalent to measure gas flow rate
of 0 to 1.0 liter per min (0.035 cfm) through NDIR.
5.3.9 Recorder (optional). To provide permanent record of NDIR
readings.

6. Reagents

6.1 Calibration Gases. Known concentration of CO in nitrogen
(N2) for instrument span, prepurified grade of N2
for zero, and two additional concentrations corresponding approximately
to 60 percent and 30 percent span. The span concentration shall not
exceed 1.5 times the applicable source performance standard. The
calibration gases shall be certified by the manufacturer to be within
^plus-minus2 percent of the specified concentration.
[GRAPHIC] [TIFF OMITTED] TC01JN92.179

6.2 Silica Gel. Indicating type, 6 to 16 mesh, dried at 175 deg.C
(347 deg.F) for 2 hours.
6.3 Ascarite. Commercially available.

7. Procedure

7.1 Sampling.
7.1.1 Continuous Sampling. Set up the equipment as shown in Figure
10-1 making sure all connections are leak free. Place the probe in the
stack at a sampling point and purge the sampling line. Connect the
analyzer and begin drawing sample into the analyzer. Allow 5 minutes for
the system to stabilize, then record the analyzer reading as required by
the test procedure. (See section 7.2 and 8). CO2 content of
the gas may be determined by using the Method 3 integrated sample
procedure, or by weighing the ascarite CO2 removal tube and
computing CO2 concentration from the gas volume sampled and
the weight gain of the tube.
7.1.2 Integrated Sampling. Evacuate the flexible bag. Set up the
equipment as shown in Figure 10-2 with the bag disconnected. Place the
probe in the stack and purge the sampling line. Connect the bag, making
sure that all connections are leak free. Sample at a rate proportional
to the stack velocity. CO2 content of the gas may be
determined by using the Method 3 integrated sample procedures, or by
weighing the ascarite CO2 removal tube and computing CO2
concentration from the gas volume sampled and the weight gain of the
tube.
7.2 CO Analysis. Assemble the apparatus as shown in Figure 10-3,
calibrate the instrument, and perform other required operations as
described in section 8. Purge analyzer with N2 prior to
introduction of each sample. Direct the sample stream through the
instrument for the test period, recording the readings. Check the zero
and span again after the test to assure that any drift or malfunction is
detected. Record the sample data on Table 10-1.

8. Calibration

Assemble the apparatus according to Figure 10-3. Generally an
instrument requires a warm-up period before stability is obtained.
Follow the manufacturer's instructions for specific procedure. Allow a
minimum time of 1 hour for warm-up. During this time check

[[Page 329]]

the sample conditioning apparatus, i.e., filter, condenser, drying tube,
and CO2 removal tube, to ensure that each component is in
good operating condition. Zero and calibrate the instrument according to
the manufacturer's procedures using, respectively, nitrogen and the
calibration gases.

Table 10-1--Field data
------------------------------------------------------------------------
Comments
------------------------------------------------------------------------
Location.................................. ............................
Test...................................... ............................
Date...................................... ............................
Operator.................................. ............................
------------------------------------------------------------------------

Rotameter setting, liters per
Clock time minute (cubic feet per minute)
------------------------------------------------------------------------

------------------------------------------------------------------------

9. Calculation

Calculate the concentration of carbon monoxide in the stack using
Equation 10-1.
CCO!stack=CCO!NDIR(1-Fco2)
Eq. 10-1
Where:

CCO!stack=Concentration of CO in stack, ppm by volume (dry
basis).
CCO!NDIR=Concentration of CO measured by NDIR analyzer, ppm
by volume (dry basis).
FCO!2=Volume fraction of CO2 in sample, i.e.,
percent CO2 from Orsat analysis divided by 100.

10. Alternative Procedures

10.1 Interference Trap. The sample conditioning system described in
Method 10A, sections 2.1.2 and 4.2, may be used as an alternative to the
silica gel and ascarite traps.

11. Bibliography

1. McElroy, Frank, The Intertech NDIR-CO Analyzer, Presented at 11th
Methods Conference on Air Pollution, University of California,
Berkeley, CA. April 1, 1970.
2. Jacobs, M. B., et al., Continuous Determination of Carbon Monoxide
and Hydrocarbons in Air by a Modified Infrared Analyzer, J.
Air Pollution Control Association, 9(2): 110-114. August 1959.
3. MSA LIRA Infrared Gas and Liquid Analyzer Instruction Book, Mine
Safety Appliances Co., Technical Products Division,
Pittsburgh, PA.
4. Models 215A, 315A, and 415A Infrared Analyzers, Beckman Instruments,
Inc., Beckman Instructions 1635-B, Fullerton, CA. October
1967.
5. Continuous CO Monitoring System, Model A5611, Intertech Corp.,
Princeton, NJ.
6. UNOR Infrared Gas Analyzers, Bendix Corp., Ronceverte, WV

Addenda

A. Performance Specifications for NDIR Carbon Monoxide Analyzers
Range (minimum)........................... 0-1000 ppm.
Output (minimum).......................... 0-10mV.
Minimum detectable sensitivity............ 20 ppm.
Rise time, 90 percent (maximum)........... 30 seconds.
Fall time, 90 percent (maximum)........... 30 seconds.
Zero drift (maximum)...................... 10% in 8 hours.
Span drift (maximum)...................... 10% in 8 hours.
Precision (minimum)....................... ^plus-minus2% of full scale.
Noise (maximum)........................... ^plus-minus1% of full scale.
Linearity (maximum deviation)............. 2% of full scale.
Interference rejection ratio.............. CO2--1000 to 1, H2O--500 to
1.
------------------------------------------------------------------------

B. Definitions of Performance Specifications.
Range-- The minimum and maximum measurement limits.
Output-- Electrical signal which is proportional to the measurement;
intended for connection to readout or data processing devices. Usually
expressed as millivolts or milliamps full scale at a given impedance.
Full scale-- The maximum measuring limit for a given range.
Minimum detectable sensitivity-- The smallest amount of input
concentration that can be detected as the concentration approaches zero.
Accuracy-- The degree of agreement between a measured value and the
true value; usually expressed as ^plus-minus percent of full
scale.
Time to 90 percent response-- The time interval from a step change
in the input concentration at the instrument inlet to a reading of 90
percent of the ultimate recorded concentration.
Rise Time (90 percent)--The interval between initial response time
and time to 90 percent response after a step increase in the inlet
concentration.
Fall Time (90 percent)--The interval between initial response time
and time to 90 percent response after a step decrease in the inlet
concentration.
Zero Drift-- The change in instrument output over a stated time
period, usually 24 hours, of unadjusted continuous operation when the
input concentration is zero; usually expressed as percent full scale.
Span Drift-- The change in instrument output over a stated time
period, usually 24 hours, of unadjusted continuous operation when the
input concentration is a stated upscale value; usually expressed as
percent full scale.
Precision-- The degree of agreement between repeated measurements of
the same concentration, expressed as the average deviation of the single
results from the mean.
Noise--Spontaneous deviations from a mean output not caused by input
concentration changes.

[[Page 330]]

Linearity--The maximum deviation between an actual instrument
reading and the reading predicted by a straight line drawn between upper
and lower calibration points.

Method 10A--Determination of Carbon Monoxide Emissions in Certifying
Continuous Emission Monitoring Systems at Petroleum Refineries

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 4, and Method 5.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Carbon monoxide (CO).............. 630-08-0 3 ppmv
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of CO emissions at petroleum refineries. This method serves as the
reference method in the relative accuracy test for nondispersive
infrared (NDIR) CO continuous emission monitoring systems (CEMS) that
are required to be installed in petroleum refineries on fluid catalytic
cracking unit catalyst regenerators (Sec. 60.105(a)(2) of this part).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

An integrated gas sample is extracted from the stack, passed through
an alkaline permanganate solution to remove sulfur oxides and nitrogen
oxides, and collected in a Tedlar bag. The CO concentration in the
sample is measured spectrophotometrically using the reaction of CO with
p-sulfaminobenzoic acid.

3.0 Definitions. [Reserved]

4.0 Interferences

Sulfur oxides, nitric oxide, and other acid gases interfere with the
colorimetric reaction. They are removed by passing the sampled gas
through an alkaline potassium permanganate scrubbing solution. Carbon
dioxide (CO2) does not interfere, but, because it is removed
by the scrubbing solution, its concentration must be measured
independently and an appropriate volume correction made to the sampled
gas.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train shown in Figure 10A-1 is
required for sample collection. Component parts are described below:
6.1.1 Probe. Stainless steel, sheathed Pyrex glass, or equivalent,
equipped with a glass wool plug to remove particulate matter.
6.1.2 Sample Conditioning System. Three Greenburg-Smith impingers
connected in series with leak-free connections.
6.1.3 Pump. Leak-free pump with stainless steel and Teflon parts to
transport sample at a flow rate of 300 ml/min (0.01 ft\3\/min) to the
flexible bag.
6.1.4 Surge Tank. Installed between the pump and the rate meter to
eliminate the pulsation effect of the pump on the rate meter.
6.1.5 Rate Meter. Rotameter, or equivalent, to measure flow rate at
300 ml/min (0.01 ft\3\/min). Calibrate according to Section 10.2.
6.1.6 Flexible Bag. Tedlar, or equivalent, with a capacity of 10
liters (0.35 ft\3\) and equipped with a sealing quick-connect plug. The
bag must be leak-free according to Section 8.1. For protection, it is
recommended that the bag be enclosed within a rigid container.

[[Page 331]]

6.1.7 Valves. Stainless-steel needle valve to adjust flow rate, and
stainless-steel three-way valve, or equivalent.
6.1.8 CO2 Analyzer. Fyrite, or equivalent, to measure
CO2 concentration to within O.5 percent.
6.1.9 Volume Meter. Dry gas meter, capable of measuring the sample
volume under calibration conditions of 300 ml/min (0.01 ft\3\/min) for
10 minutes.
6.1.10 Pressure Gauge. A water filled U-tube manometer, or
equivalent, of about 30 cm (12 in.) to leak-check the flexible bag.
6.2 Sample Analysis.
6.2.1 Spectrophotometer. Single- or double-beam to measure
absorbance at 425 and 600 nm. Slit width should not exceed 20 nm.
6.2.2 Spectrophotometer Cells. 1-cm pathlength.
6.2.3 Vacuum Gauge. U-tube mercury manometer, 1 meter (39 in.),
with 1-mm divisions, or other gauge capable of measuring pressure to
within 1 mm Hg.
6.2.4 Pump. Capable of evacuating the gas reaction bulb to a
pressure equal to or less than 40 mm Hg absolute, equipped with coarse
and fine flow control valves.
6.2.5 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 1 mm Hg.
6.2.6 Reaction Bulbs. Pyrex glass, 100-ml with Teflon stopcock
(Figure 10A-2), leak-free at 40 mm Hg, designed so that 10 ml of the
colorimetric reagent can be added and removed easily and accurately.
Commercially available gas sample bulbs such as Supelco Catalog No. 2-
2161 may also be used.
6.2.7 Manifold. Stainless steel, with connections for three
reaction bulbs and the appropriate connections for the manometer and
sampling bag as shown in Figure 10A-3.
6.2.8 Pipets. Class A, 10-ml size.
6.2.9 Shaker Table. Reciprocating-stroke type such as Eberbach
Corporation, Model 6015. A rocking arm or rotary-motion type shaker may
also be used. The shaker must be large enough to accommodate at least
six gas sample bulbs simultaneously. It may be necessary to construct a
table top extension for most commercial shakers to provide sufficient
space for the needed bulbs (Figure 10A-4).
6.2.10 Valve. Stainless steel shut-off valve.
6.2.11 Analytical Balance. Capable of weighing to 0.1 mg.

7.0 Reagents and Standards

Unless otherwise indicated, all reagents shall conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society, where such specifications are available;
otherwise, the best available grade shall be used.
7.1 Sample Collection.
7.1.1 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91, Type 3 (incorporated by reference--see Sec. 60.17). If high
concentrations of organic matter are not expected to be present, the
potassium permanganate test for oxidizable organic matter may be
omitted.
7.1.2 Alkaline Permanganate Solution, 0.25 M KMnO4/1.5 M
Sodium Hydroxide (NaOH). Dissolve 40 g KMnO4 and 60 g NaOH in
approximately 900 ml water, cool, and dilute to 1 liter.
7.2 Sample Analysis.
7.2.1 Water. Same as in Section 7.1.1.
7.2.2 1 M Sodium Hydroxide Solution. Dissolve 40 g NaOH in
approximately 900 ml of water, cool, and dilute to 1 liter.
7.2.3 0.1 M NaOH Solution. Dilute 50 ml of the 1 M NaOH solution
prepared in Section 7.2.2 to 500 ml.
7.2.4 0.1 M Silver Nitrate (AgNO3) Solution. Dissolve
8.5 g AgNO3 in water, and dilute to 500 ml.
7.2.5 0.1 M Para-Sulfaminobenzoic Acid (p-SABA) Solution. Dissolve
10.0 g p-SABA in 0.1 M NaOH, and dilute to 500 ml with 0.1 M NaOH.
7.2.6 Colorimetric Solution. To a flask, add 100 ml of 0.1 M p-SABA
solution and 100 ml of 0.1 M AgNO3 solution. Mix, and add 50
ml of 1 M NaOH with shaking. The resultant solution should be clear and
colorless. This solution is acceptable for use for a period of 2 days.
7.2.7 Standard Gas Mixtures. Traceable to National Institute of
Standards and Technology (NIST) standards and containing between 50 and
1000 ppm CO in nitrogen. At least two concentrations are needed to span
each calibration range used (Section 10.3). The calibration gases must
be certified by the manufacturer to be within 2 percent of the specified
concentrations.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sample Bag Leak-Checks. While a bag leak-check is required
after bag use, it should also be done before the bag is used for sample
collection. The bag should be leak-checked in the inflated and deflated
condition according to the following procedure:
8.1.1 Connect the bag to a water manometer, and pressurize the bag
to 5 to 10 cm H2O (2 to 4 in H2O). Allow the bag
to stand for 60 minutes. Any displacement in the water manometer
indicates a leak.
8.1.2 Evacuate the bag with a leakless pump that is connected to
the downstream side of a flow indicating device such as a 0- to 100-ml/
min rotameter or an impinger containing water. When the bag is
completely evacuated, no flow should be evident if the bag is leak-free.
8.2 Sample Collection.
8.2.1 Evacuate the Tedlar bag completely using a vacuum pump.
Assemble the apparatus as shown in Figure 10A-1. Loosely pack glass wool
in the tip of the probe. Place 400

[[Page 332]]

ml of alkaline permanganate solution in the first two impingers and 250
ml in the third. Connect the pump to the third impinger, and follow this
with the surge tank, rate meter, and 3-way valve. Do not connect the
Tedlar bag to the system at this time.
8.2.2 Leak-check the sampling system by plugging the probe inlet,
opening the 3-way valve, and pulling a vacuum of approximately 250 mm Hg
on the system while observing the rate meter for flow. If flow is
indicated on the rate meter, do not proceed further until the leak is
found and corrected.
8.2.3 Purge the system with sample gas by inserting the probe into
the stack and drawing the sample gas through the system at 300 ml/min
10 percent for 5 minutes. Connect the evacuated Tedlar bag
to the system, record the starting time, and sample at a rate of 300 ml/
min for 30 minutes, or until the Tedlar bag is nearly full. Record the
sampling time, the barometric pressure, and the ambient temperature.
Purge the system as described above immediately before each sample.
8.2.4 The scrubbing solution is adequate for removing sulfur oxides
and nitrogen oxides from 50 liters (1.8 ft\3\) of stack gas when the
concentration of each is less than 1,000 ppm and the CO2
concentration is less than 15 percent. Replace the scrubber solution
after every fifth sample.
8.3 Carbon Dioxide Measurement. Measure the CO2 content
in the stack to the nearest 0.5 percent each time a CO sample is
collected. A simultaneous grab sample analyzed by the Fyrite analyzer is
acceptable.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.
10.1 Gas Bulb Calibration. Weigh the empty bulb to the nearest 0.1
g. Fill the bulb to the stopcock with water, and again weigh to the
nearest 0.1 g. Subtract the tare weight, and calculate the volume in
liters to three significant figures using the density of water at the
measurement temperature. Record the volume on the bulb. Alternatively,
mark an identification number on the bulb, and record the volume in a
notebook.
10.2 Rate Meter Calibration. Assemble the system as shown in Figure
10A-1 (the impingers may be removed), and attach a volume meter to the
probe inlet. Set the rotameter at 300 ml/min, record the volume meter
reading, start the pump, and pull ambient air through the system for 10
minutes. Record the final volume meter reading. Repeat the procedure and
average the results to determine the volume of gas that passed through
the system.
10.3 Spectrophotometer Calibration Curve.
10.3.1 Collect the standards as described in Section 8.2. Prepare
at least two sets of three bulbs as standards to span the 0 to 400 or
400 to 1000 ppm range. If any samples span both concentration ranges,
prepare a calibration curve for each range using separate reagent
blanks. Prepare a set of three bulbs containing colorimetric reagent but
no CO to serve as a reagent blank. Analyze each standard and blank
according to the sample analysis procedure of Section 11.0 Reject the
standard set where any of the individual bulb absorbances differs from
the set mean by more than 10 percent.
10.3.2 Calculate the average absorbance for each set (3 bulbs) of
standards using Equation 10A-1 and Table 10A-1. Construct a graph of
average absorbance for each standard against its corresponding
concentration. Draw a smooth curve through the points. The curve should
be linear over the two concentration ranges discussed in Section 13.3.

11.0 Analytical Procedure

11.1 Assemble the system shown in Figure 10A-3, and record the
information required in Table 10A-1 as it is obtained. Pipet 10.0 ml of
the colorimetric reagent into each gas reaction bulb, and attach the
bulbs to the system. Open the stopcocks to the reaction bulbs, but leave
the valve to the Tedlar bag closed. Turn on the pump, fully open the
coarse-adjust flow valve, and slowly open the fine-adjust valve until
the pressure is reduced to at least 40 mm Hg. Now close the coarse
adjust valve, and observe the manometer to be certain that the system is
leak-free. Wait a minimum of 2 minutes. If the pressure has increased
less than 1 mm Hg, proceed as described below. If a leak is present,
find and correct it before proceeding further.
11.2 Record the vacuum pressure (Pv) to the nearest 1 mm
Hg, and close the reaction

[[Page 333]]

bulb stopcocks. Open the Tedlar bag valve, and allow the system to come
to atmospheric pressure. Close the bag valve, open the pump coarse
adjust valve, and evacuate the system again. Repeat this fill/evacuation
procedure at least twice to flush the manifold completely. Close the
pump coarse adjust valve, open the Tedlar bag valve, and let the system
fill to atmospheric pressure. Open the stopcocks to the reaction bulbs,
and let the entire system come to atmospheric pressure. Close the bulb
stopcocks, remove the bulbs, record the room temperature and barometric
pressure (Pbar, to nearest mm Hg), and place the bulbs on the
shaker table with their main axis either parallel to or perpendicular to
the plane of the table top. Purge the bulb-filling system with ambient
air for several minutes between samples. Shake the samples for exactly 2
hours.
11.3 Immediately after shaking, measure the absorbance (A) of each
bulb sample at 425 nm if the concentration is less than or equal to 400
ppm CO or at 600 nm if the concentration is above 400 ppm.
Note: This may be accomplished with multiple bulb sets by
sequentially collecting sets and adding to the shaker at staggered
intervals, followed by sequentially removing sets from the shaker for
absorbance measurement after the two-hour designated intervals have
elapsed.
11.4 Use a small portion of the sample to rinse a spectrophotometer
cell several times before taking an aliquot for analysis. If one cell is
used to analyze multiple samples, rinse the cell with deionized
distilled water several times between samples. Prepare and analyze
standards and a reagent blank as described in Section 10.3. Use water as
the reference. Reject the analysis if the blank absorbance is greater
than 0.1. All conditions should be the same for analysis of samples and
standards. Measure the absorbances as soon as possible after shaking is
completed.
11.5 Determine the CO concentration of each bag sample using the
calibration curve for the appropriate concentration range as discussed
in Section 10.3.

12.0 Calculations and Data Analysis

Carry out calculations retaining at least one extra decimal figure
beyond that of the acquired data. Round off figures after final
calculation.
12.1 Nomenclature.

A = Sample absorbance, uncorrected for the reagent blank.
Ar = Absorbance of the reagent blank.
As = Average sample absorbance per liter, units/liter.
Bw = Moisture content in the bag sample.
C = CO concentration in the stack gas, dry basis, ppm.
Cb = CO concentration of the bag sample, dry basis, ppm.
Cg = CO concentration from the calibration curve, ppm.
F = Volume fraction of CO2 in the stack.
n = Number of reaction bulbs used per bag sample.
Pb = Barometric pressure, mm Hg.
Pv = Residual pressure in the sample bulb after evacuation,
mm Hg.
Pw = Vapor pressure of H2O in the bag (from Table
10A-2), mm Hg.
Vb = Volume of the sample bulb, liters.
Vr = Volume of reagent added to the sample bulb, 0.0100
liter.

12.2 Average Sample Absorbance per Liter. Calculate As
for each gas bulb using Equation 10A-1, and record the value in Table
10A-1. Calculate the average As for each bag sample, and
compare the three values to the average. If any single value differs by
more than 10 percent from the average, reject this value, and calculate
a new average using the two remaining values.
[GRAPHIC] [TIFF OMITTED] TR17OC00.227

Note: A and Ar must be at the same wavelength.
12.3 CO Concentration in the Bag. Calculate Cb using
Equations 10A-2 and 10A-3. If condensate is visible in the Tedlar bag,
calculate Bw using Table 10A-2 and the temperature and
barometric pressure in the analysis room. If condensate is not visible,
calculate Bw using the temperature and barometric pressure at
the sampling site.
[GRAPHIC] [TIFF OMITTED] TR17OC00.228

[GRAPHIC] [TIFF OMITTED] TR17OC00.229

12.4 CO Concentration in the Stack.
[GRAPHIC] [TIFF OMITTED] TR17OC00.230

13.0 Method Performance

13.1 Precision. The estimated intralaboratory standard deviation of
the method is 3 percent of the mean for gas samples analyzed in
duplicate in the concentration range of 39 to 412 ppm. The
interlaboratory precision has not been established.
13.2 Accuracy. The method contains no significant biases when
compared to an NDIR analyzer calibrated with NIST standards.
13.3 Range. Approximately 3 to 1800 ppm CO. Samples having
concentrations below 400 ppm are analyzed at 425 nm, and samples having
concentrations above 400 ppm are analyzed at 600 nm.

[[Page 334]]

13.4 Sensitivity. The detection limit is 3 ppmv based on a change
in concentration equal to three times the standard deviation of the
reagent blank solution.
13.5 Stability. The individual components of the colorimetric
reagent are stable for at least 1 month. The colorimetric reagent must
be used within 2 days after preparation to avoid excessive blank
correction. The samples in the Tedlar bag should be stable for at least
1 week if the bags are leak-free.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Butler, F.E., J.E. Knoll, and M.R. Midgett. Development and
Evaluation of Methods for Determining Carbon Monoxide Emissions. U.S.
Environmental Protection Agency, Research Triangle Park, N.C. June 1985.
33 pp.
2. Ferguson, B.B., R.E. Lester, and W.J. Mitchell. Field Evaluation
of Carbon Monoxide and Hydrogen Sulfide Continuous Emission Monitors at
an Oil Refinery. U.S. Environmental Protection Agency, Research Triangle
Park, N.C. Publication No. EPA-600/4-82-054. August 1982. 100 pp.
3. Lambert, J.L., and R.E. Weins. Induced Colorimetric Method for
Carbon Monoxide. Analytical Chemistry. 46(7):929-930. June 1974.
4. Levaggi, D.A., and M. Feldstein. The Colorimetric Determination
of Low Concentrations of Carbon Monoxide. Industrial Hygiene Journal.
25:64-66. January-February 1964.
5. Repp, M. Evaluation of Continuous Monitors For Carbon Monoxide in
Stationary Sources. U.S. Environmental Protection Agency. Research
Triangle Park, N.C. Publication No. EPA-600/2-77-063. March 1977. 155
pp.
6. Smith, F., D.E. Wagoner, and R.P. Donovan. Guidelines for
Development of a Quality Assurance Program: Volume VIII--Determination
of CO Emissions from Stationary Sources by NDIR Spectrometry. U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA-650/4-74-005-h. February 1975. 96 pp.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 335]]

Table 10A-1.--Data Recording Sheet for Samples Analyzed in Triplicate
--------------------------------------------------------------------------------------------------------------------------------------------------------
Partial
Room Bulb Reagent pressure Shaking Abs
Sample No./type temp Stack Bulb vol. vol. in of gas in Pb, mm time, versus A-Ar As Avg As
deg.C %CO2 No. liters bulb, bulb, mm Hg min water
liter Hg
--------------------------------------------------------------------------------------------------------------------------------------------------------
blank
--------------------------------------------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------
Std. 1
------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------
Std. 2
------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------
Sample 1
------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------
Sample 2
------------------------------------------------------------------------------------------------------------------

--------------------------------------------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------

------------------------------------------------------------------------------------------------------------------
Sample 3
--------------------------------------------------------------------------------------------------------------------------------------------------------

[[Page 336]]

Table 10A-2.--Moisture Correction
----------------------------------------------------------------------------------------------------------------
Vapor Vapor
Temperature deg.C pressure of Temperature pressure of
H2,O, mm Hg deg.C H2, mm Hg
----------------------------------------------------------------------------------------------------------------
4............................................................... 6.1 18 15.5
6............................................................... 7.0 20 17.5
8............................................................... 8.0 22 19.8
10.............................................................. 9.2 24 22.4
12.............................................................. 10.5 26 25.2
14.............................................................. 12.0 28 28.3
16.............................................................. 13.6 30 31.8
----------------------------------------------------------------------------------------------------------------

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[[Page 338]]

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[[Page 339]]

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Method 10B--Determination of Carbon Monoxide Emissions From Stationary
Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Carbon monoxide (CO)............. 630-08-0 Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method applies to the measurement of CO
emissions at petroleum refineries and from other sources when specified
in an applicable subpart of the regulations.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the sampling point,
passed through a conditioning system to remove interferences, and
collected in a Tedlar bag. The CO is separated from the sample by gas
chromatography (GC) and catalytically reduced to methane
(CH4) which is determined by flame ionization detection
(FID). The analytical portion of this method is identical to applicable
sections in Method 25 detailing CO measurement.

[[Page 340]]

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Carbon dioxide (CO2) and organics potentially can
interfere with the analysis. Most of the CO2 is removed from
the sample by the alkaline permanganate conditioning system; any
residual CO2 and organics are separated from the CO by GC.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. Same as in Method 10A, Section 6.1.
6.2 Sample Analysis. A GC/FID analyzer, capable of quantifying CO
in the sample and consisting of at least the following major components,
is required for sample analysis. [Alternatively, complete Method 25
analytical systems (Method 25, Section 6.3) are acceptable alternatives
when calibrated for CO and operated in accordance with the Method 25
analytical procedures (Method 25, Section 11.0).]
6.2.1 Separation Column. A column capable of separating CO from
CO2 and organic compounds that may be present. A 3.2-mm (\1/
8\-in.) OD stainless steel column packed with 1.7 m (5.5 ft.) of 60/80
mesh Carbosieve S-II (available from Supelco) has been used successfully
for this purpose.
6.2.2 Reduction Catalyst. Same as in Method 25, Section 6.3.1.2.
6.2.3 Sample Injection System. Same as in Method 25, Section
6.3.1.4, equipped to accept a sample line from the Tedlar bag.
6.2.4 Flame Ionization Detector. Meeting the linearity
specifications of Section 10.3 and having a minimal instrument range of
10 to 1,000 ppm CO.
6.2.5 Data Recording System. Analog strip chart recorder or digital
integration system, compatible with the FID, for permanently recording
the analytical results.

7.0 Reagents and Standards

7.1 Sample Collection. Same as in Method 10A, Section 7.1.
7.2 Sample Analysis.
7.2.1 Carrier, Fuel, and Combustion Gases. Same as in Method 25,
Sections 7.2.1, 7.2.2, and 7.2.3, respectively.
7.2.2 Calibration Gases. Three standard gases with nominal CO
concentrations of 20, 200, and 1,000 ppm CO in nitrogen. The calibration
gases shall be certified by the manufacturer to be 2
percent of the specified concentrations.
7.2.3 Reduction Catalyst Efficiency Check Calibration Gas. Standard
CH4 gas with a nominal concentration of 1,000 ppm in air.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as in Method 10A, Section 8.0.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.0........................... Sample bag/ Ensures that negative
sampling system bias introduced
leak-checks. through leakage is
minimized.
10.1.......................... Carrier gas blank Ensures that positive
check. bias introduced by
contamination of
carrier gas is less
than 5 ppmv.
10.2.......................... Reduction Ensures that negative
catalyst bias introduced by
efficiency check. inefficient
reduction catalyst
is less than 5
percent.
10.3.......................... Analyzer Ensures linearity of
calibration. analyzer response to
standards.
11.2.......................... Triplicate sample Ensures precision of
analyses. analytical results.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Carrier Gas Blank Check. Analyze each new tank of carrier gas
with the GC analyzer according to Section 11.2 to check for
contamination. The corresponding concentration must be less than 5 ppm
for the tank to be acceptable for use.
10.2 Reduction Catalyst Efficiency Check. Prior to initial use, the
reduction catalyst shall be tested for reduction efficiency. With the
heated reduction catalyst bypassed, make triplicate injections of the
1,000 ppm CH4 gas (Section 7.2.3) to calibrate the analyzer.
Repeat the procedure using 1,000 ppm CO gas (Section 7.2.2) with the
catalyst in operation. The reduction catalyst operation is acceptable if
the CO response is within 5 percent of the certified gas value.
10.3 Analyzer Calibration. Perform this test before the system is
first placed into operation. With the reduction catalyst in operation,
conduct a linearity check of the analyzer using the standards specified
in Section 7.2.2. Make triplicate injections of each calibration gas,
and then calculate the average response factor (area/ppm) for each gas,
as

[[Page 341]]

well as the overall mean of the response factor values. The instrument
linearity is acceptable if the average response factor of each
calibration gas is within 2.5 percent of the overall mean value and if
the relative standard deviation (calculated in Section 12.8 of Method
25) for each set of triplicate injections is less than 2 percent. Record
the overall mean of the response factor values as the calibration
response factor (R).

11.0 Analytical Procedure

11.1 Preparation for Analysis. Before putting the GC analyzer into
routine operation, conduct the calibration procedures listed in Section
10.0. Establish an appropriate carrier flow rate and detector
temperature for the specific instrument used.
11.2 Sample Analysis. Purge the sample loop with sample, and then
inject the sample. Analyze each sample in triplicate, and calculate the
average sample area (A). Determine the bag CO concentration according to
Section 12.2.

12.0 Calculations and Data Analysis

Carry out calculations retaining at least one extra significant
figure beyond that of the acquired data. Round off results only after
the final calculation.
12.1 Nomenclature.

A = Average sample area.
Bw = Moisture content in the bag sample, fraction.
C = CO concentration in the stack gas, dry basis, ppm.
Cb = CO concentration in the bag sample, dry basis, ppm.
F = Volume fraction of CO2 in the stack, fraction.
Pbar = Barometric pressure, mm Hg.
Pw = Vapor pressure of the H2O in the bag (from
Table 10A-2, Method 10A), mm Hg.
R = Mean calibration response factor, area/ppm.

12.2 CO Concentration in the Bag. Calculate Cb using
Equations 10B-1 and 10B-2. If condensate is visible in the Tedlar bag,
calculate Bw using Table 10A-2 of Method 10A and the
temperature and barometric pressure in the analysis room. If condensate
is not visible, calculate Bw using the temperature and
barometric pressure at the sampling site.
[GRAPHIC] [TIFF OMITTED] TR17OC00.235

[GRAPHIC] [TIFF OMITTED] TR17OC00.236

12.3 CO Concentration in the Stack
[GRAPHIC] [TIFF OMITTED] TR17OC00.237

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as in Method 25, Section 16.0, with the addition of the
following:

1. Butler, F.E, J.E. Knoll, and M.R. Midgett. Development and
Evaluation of Methods for Determining Carbon Monoxide Emissions. Quality
Assurance Division, Environmental Monitoring Systems Laboratory, U.S.
Environmental Protection Agency, Research Triangle Park, NC. June 1985.
33 pp.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A see the List of CFR Sections Affected, which appears in the
Finding Aids section of the printed volume and on GPO Access.

Appendix A-5 to Part 60--Test Methods 11 through 15A

Method 11--Determination of hydrogen sulfide content of fuel gas streams
in petroleum refineries
Method 12--Determination of inorganic lead emissions from stationary
sources
Method 13A--Determination of total fluoride emissions from stationary
sources--SPADNS zirconium lake method
Method 13B--Determination of total fluoride emissions from stationary
sources--Specific ion electrode method
Method 14--Determination of fluoride emissions from potroom roof
monitors for primary aluminum plants
Method 14A-- Determination of Total Fluoride Emissions from Selected
Sources at Primary Aluminum Production Facilities
Method 15--Determination of hydrogen sulfide, carbonyl sulfide, and
carbon disulfide emissions from stationary sources
Method 15A--Determination of total reduced sulfur emissions from sulfur
recovery plants in petroleum refineries
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.

[[Page 342]]

Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the the degree of detail should be similar to the detail contained
in the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 11--Determination of Hydrogen Sulfide Content of Fuel Gas Streams
in Petroleum Refineries

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Hydrogen sulfide (H2S)........... 7783-06-4 8 mg/m\3\--740 mg/
m\3\, (6 ppm--520
ppm).
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the H2S content of fuel gas streams at petroleum
refineries.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A sample is extracted from a source and passed through a series
of midget impingers containing a cadmium sulfate (CdSO4)
solution; H2S is absorbed, forming cadmium sulfide (CdS). The
latter compound is then measured iodometrically.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Any compound that reduces iodine (I2) or oxidizes
the iodide ion will interfere in this procedure, provided it is
collected in the

[[Page 343]]

CdSO4 impingers. Sulfur dioxide in concentrations of up to
2,600 mg/m\3\ is removed with an impinger containing a hydrogen peroxide
(H2O2) solution. Thiols precipitate with
H2S. In the absence of H2S, only traces of thiols
are collected. When methane-and ethane-thiols at a total level of 300
mg/m\3\ are present in addition to H2S, the results vary from
2 percent low at an H2S concentration of 400 mg/m\3\ to 14
percent high at an H2S concentration of 100 mg/m\3\. Carbonyl
sulfide at a concentration of 20 percent does not interfere. Certain
carbonyl-containing compounds react with iodine and produce recurring
end points. However, acetaldehyde and acetone at concentrations of 1 and
3 percent, respectively, do not interfere.
4.2 Entrained H2O2 produces a negative
interference equivalent to 100 percent of that of an equimolar quantity
of H2S. Avoid the ejection of H2O2 into
the CdSO4 impingers.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The following items are needed for sample
collection:
6.1.1 Sampling Line. Teflon tubing, 6- to 7- mm (\1/4\-in.) ID, to
connect the sampling train to the sampling valve.
6.1.2 Impingers. Five midget impingers, each with 30-ml capacity.
The internal diameter of the impinger tip must be 1 mm 0.05
mm. The impinger tip must be positioned 4 to 6 mm from the bottom of the
impinger.
6.1.3 Tubing. Glass or Teflon connecting tubing for the impingers.
6.1.4 Ice Water Bath. To maintain absorbing solution at a low
temperature.
6.1.5 Drying Tube. Tube packed with 6- to 16- mesh indicating-type
silica gel, or equivalent, to dry the gas sample and protect the meter
and pump. If the silica gel has been used previously, dry at 175 deg.C
(350 deg.F) for 2 hours. New silica gel may be used as received.
Alternatively, other types of desiccants (equivalent or better) may be
used, subject to approval of the Administrator.
Note: Do not use more than 30 g of silica gel. Silica gel adsorbs
gases such as propane from the fuel gas stream, and use of excessive
amounts of silica gel could result in errors in the determination of
sample volume.
6.1.6 Sampling Valve. Needle valve, or equivalent, to adjust gas
flow rate. Stainless steel or other corrosion-resistant material.
6.1.7 Volume Meter. Dry gas meter (DGM), sufficiently accurate to
measure the sample volume within 2 percent, calibrated at the selected
flow rate (about 1.0 liter/min) and conditions actually encountered
during sampling. The meter shall be equipped with a temperature sensor
(dial thermometer or equivalent) capable of measuring temperature to
within 3 deg.C (5.4 deg.F). The gas meter should have a petcock, or
equivalent, on the outlet connector which can be closed during the leak-
check. Gas volume for one revolution of the meter must not be more than
10 liters.
6.1.8 Rate Meter. Rotameter, or equivalent, to measure flow rates
in the range from 0.5 to 2 liters/min (1 to 4 ft\3\/hr).
6.1.9 Graduated Cylinder. 25-ml size.
6.1.10 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg). In many
cases, the barometric reading may be obtained from a nearby National
Weather Service station, in which case, the station value (which is the
absolute barometric pressure) shall be requested and an adjustment for
elevation differences between the weather station and the sampling point
shall be applied at a rate of minus 2.5 mm Hg (0.1 in Hg) per 30 m (100
ft) elevation increase or vice-versa for elevation decrease.
6.1.11 U-tube Manometer. 0-; to 30-cm water column, for leak-check
procedure.
6.1.12 Rubber Squeeze Bulb. To pressurize train for leak-check.
6.1.13 Tee, Pinchclamp, and Connecting Tubing. For leak-check.
6.1.14 Pump. Diaphragm pump, or equivalent. Insert a small surge
tank between the pump and rate meter to minimize the pulsation effect of
the diaphragm pump on the rate meter. The pump is used for the air purge
at the end of the sample run; the pump

[[Page 344]]

is not ordinarily used during sampling, because fuel gas streams are
usually sufficiently pressurized to force sample gas through the train
at the required flow rate. The pump need not be leak-free unless it is
used for sampling.
6.1.15 Needle Valve or Critical Orifice. To set air purge flow to 1
liter/min.
6.1.16 Tube Packed with Active Carbon. To filter air during purge.
6.1.17 Volumetric Flask. One 1000-ml.
6.1.18 Volumetric Pipette. One 15-ml.
6.1.19 Pressure-Reduction Regulator. Depending on the sampling
stream pressure, a pressure-reduction regulator may be needed to reduce
the pressure of the gas stream entering the Teflon sample line to a safe
level.
6.1.20 Cold Trap. If condensed water or amine is present in the
sample stream, a corrosion-resistant cold trap shall be used immediately
after the sample tap. The trap shall not be operated below 0 deg.C (32
deg.F) to avoid condensation of C3 or C4
hydrocarbons.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Sample Container. Iodine flask, glass-stoppered, 500-ml size.
6.2.2 Volumetric Pipette. One 50-ml.
6.2.3 Graduated Cylinders. One each 25- and 250-ml.
6.2.4 Erlenmeyer Flasks. 125-ml.
6.2.5 Wash Bottle.
6.2.6 Volumetric Flasks. Three 1000-ml.
6.3 Sample Analysis. The following items are needed for sample
analysis:
6.3.1 Flask. Glass-stoppered iodine flask, 500-ml.
6.3.2 Burette. 50-ml.
6.3.3 Erlenmeyer Flask. 125-ml.
6.3.4 Volumetric Pipettes. One 25-ml; two each 50- and 100-ml.
6.3.5 Volumetric Flasks. One 1000-ml; two 500-ml.
6.3.6 Graduated Cylinders. One each 10- and 100-ml.

7.0 Reagents and Standards

Note: Unless otherwise indicated, it is intended that all reagents
conform to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available. Otherwise, use the best available grade.
7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 CdSO4 Absorbing Solution. Dissolve 41 g of
3CdSO48H2O and 15 ml of 0.1 M sulfuric acid in a
1-liter volumetric flask that contains approximately \3/4\ liter of
water. Dilute to volume with deionized, distilled water. Mix thoroughly.
The pH should be 3 0.1. Add 10 drops of Dow-Corning
Antifoam B. Shake well before use. This solution is stable for at least
one month. If Antifoam B is not used, a more labor-intensive sample
recovery procedure is required (see Section 11.2).
7.1.2 Hydrogen Peroxide, 3 Percent. Dilute 30 percent
H2O2 to 3 percent as needed. Prepare fresh daily.
7.1.3 Water. Deionized distilled to conform to ASTM D 1193-77 or
91, Type 3 (incorporated by reference--see Sec. 60.17). The
KMnO4 test for oxidizable organic matter may be omitted when
high concentrations of organic matter are not expected to be present.
7.2 Sample Recovery. The following reagents are needed for sample
recovery:
7.2.1 Water. Same as Section 7.1.3.
7.2.2 Hydrochloric Acid (HCl) Solution, 3 M. Add 240 ml of
concentrated HCl (specific gravity 1.19) to 500 ml of water in a 1-liter
volumetric flask. Dilute to 1 liter with water. Mix thoroughly.
7.2.3 Iodine (I2) Solution, 0.1 N. Dissolve 24 g of
potassium iodide (KI) in 30 ml of water. Add 12.7 g of resublimed iodine
(I2) to the KI solution. Shake the mixture until the
I2 is completely dissolved. If possible, let the solution
stand overnight in the dark. Slowly dilute the solution to 1 liter with
water, with swirling. Filter the solution if it is cloudy. Store
solution in a brown-glass reagent bottle.
7.2.4 Standard I2 Solution, 0.01 N. Pipette 100.0 ml of
the 0.1 N iodine solution into a 1-liter volumetric flask, and dilute to
volume with water. Standardize daily as in Section 10.2.1. This solution
must be protected from light. Reagent bottles and flasks must be kept
tightly stoppered.
7.3 Sample Analysis. The following reagents and standards are
needed for sample analysis:
7.3.1 Water. Same as in Section 7.1.3.
7.3.2 Standard Sodium Thiosulfate Solution, 0.1 N. Dissolve 24.8 g
of sodium thiosulfate pentahydrate
(Na2S2O35H2O) or
15.8 g of anhydrous sodium thiosulfate
(Na2S2O3) in 1 liter of water, and add
0.01 g of anhydrous sodium carbonate (Na2CO3) and
0.4 ml of chloroform (CHCl3) to stabilize. Mix thoroughly by
shaking or by aerating with nitrogen for approximately 15 minutes, and
store in a glass-stoppered, reagent bottle. Standardize as in Section
10.2.2.
7.3.3 Standard Sodium Thiosulfate Solution, 0.01 N. Pipette 50.0 ml
of the standard 0.1 N Na2S2O3 solution
into a volumetric flask, and dilute to 500 ml with water.
Note: A 0.01 N phenylarsine oxide (C6H5AsO)
solution may be prepared instead of 0.01 N
Na2S2O3 (see Section 7.3.4).
7.3.4 Standard Phenylarsine Oxide Solution, 0.01 N. Dissolve 1.80 g
of (C6H5AsO) in 150 ml of 0.3 N sodium hydroxide.
After settling, decant 140 ml of this solution into 800 ml of water.
Bring the solution to pH 6-7 with 6 N HCl, and dilute to 1 liter with
water. Standardize as in Section 10.2.3.
7.3.5 Starch Indicator Solution. Suspend 10 g of soluble starch in
100 ml of water, and add 15 g of potassium hydroxide (KOH) pellets. Stir
until dissolved, dilute with 900 ml

[[Page 345]]

of water, and let stand for 1 hour. Neutralize the alkali with
concentrated HCl, using an indicator paper similar to Alkacid test
ribbon, then add 2 ml of glacial acetic acid as a preservative.
Note: Test starch indicator solution for decomposition by titrating
with 0.01 N I2 solution, 4 ml of starch solution in 200 ml of
water that contains 1 g of KI. If more than 4 drops of the 0.01 N
I2 solution are required to obtain the blue color, a fresh
solution must be prepared.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling Train Preparation. Assemble the sampling train as
shown in Figure 11-1, connecting the five midget impingers in series.
Place 15 ml of 3 percent H2O2 solution in the
first impinger. Leave the second impinger empty. Place 15 ml of the
CdSO4 solution in the third, fourth, and fifth impingers.
Place the impinger assembly in an ice water bath container, and place
water and crushed ice around the impingers. Add more ice during the run,
if needed.
8.2 Leak-Check Procedure.
8.2.1 Connect the rubber bulb and manometer to the first impinger,
as shown in Figure 11-1. Close the petcock on the DGM outlet. Pressurize
the train to 25 cm water with the bulb, and close off the tubing
connected to the rubber bulb. The train must hold 25 cm water pressure
with not more than a 1 cm drop in pressure in a 1-minute interval.
Stopcock grease is acceptable for sealing ground glass joints.
8.2.2 If the pump is used for sampling, it is recommended, but not
required, that the pump be leak-checked separately, either prior to or
after the sampling run. To leak-check the pump, proceed as follows:
Disconnect the drying tube from the impinger assembly. Place a vacuum
gauge at the inlet to either the drying tube or the pump, pull a vacuum
of 250 mm Hg (10 in. Hg), plug or pinch off the outlet of the flow
meter, and then turn off the pump. The vacuum should remain stable for
at least 30 seconds. If performed prior to the sampling run, the pump
leak-check should precede the leak-check of the sampling train described
immediately above; if performed after the sampling run, the pump leak-
check should follow the sampling train leak-check.
8.3 Purge the connecting line between the sampling valve and the
first impinger by disconnecting the line from the first impinger,
opening the sampling valve, and allowing process gas to flow through the
line for one to two minutes. Then, close the sampling valve, and
reconnect the line to the impinger train. Open the petcock on the dry
gas meter outlet. Record the initial DGM reading.
8.4 Open the sampling valve, and then adjust the valve to obtain a
rate of approximately 1 liter/min (0.035 cfm). Maintain a constant
(10 percent) flow rate during the test. Record the DGM
temperature.
8.5 Sample for at least 10 minutes. At the end of the sampling
time, close the sampling valve, and record the final volume and
temperature readings. Conduct a leak-check as described in Section 8.2
above.
8.6 Disconnect the impinger train from the sampling line. Connect
the charcoal tube and the pump as shown in Figure 11-1. Purge the train
[at a rate of 1 liter/min (0.035 ft\3\/min)] with clean ambient air for
15 minutes to ensure that all H2S is removed from the
H2O2. For sample recovery, cap the open ends, and
remove the impinger train to a clean area that is away from sources of
heat. The area should be well lighted, but not exposed to direct
sunlight.
8.7 Sample Recovery.
8.7.1 Discard the contents of the H2O2
impinger. Carefully rinse with water the contents of the third, fourth,
and fifth impingers into a 500-ml iodine flask.
Note: The impingers normally have only a thin film of CdS remaining
after a water rinse. If Antifoam B was not used or if significant
quantities of yellow CdS remain in the impingers, the alternative
recovery procedure in Section 11.2 must be used.
8.7.2 Proceed to Section 11 for the analysis.

9.0 Quality Control

10.0 Calibration and Standardization

Note: Maintain a log of all calibrations.
10.1 Calibration. Calibrate the sample collection equipment as
follows.
10.1.1 Dry Gas Meter.
10.1.1.1 Initial Calibration. The DGM shall be calibrated before
its initial use in the field. Proceed as follows: First, assemble the
following components in series: Drying tube, needle valve, pump,
rotameter, and DGM. Then, leak-check the metering system as follows:
Place a vacuum gauge (at least 760 mm Hg) at the inlet to the drying
tube, and pull a vacuum of 250 mm Hg (10 in. Hg); plug or pinch off the
outlet of the flow meter, and

[[Page 346]]

then turn off the pump. The vacuum shall remain stable for at least 30
seconds. Carefully release the vacuum gauge before releasing the flow
meter end. Next, calibrate the DGM (at the sampling flow rate specified
by the method) as follows: Connect an appropriately sized wet-test meter
(e.g., 1 liter per revolution) to the inlet of the drying tube. Make
three independent calibration runs, using at least five revolutions of
the DGM per run. Calculate the calibration factor, Y (wet-test meter
calibration volume divided by the DGM volume, both volumes adjusted to
the same reference temperature and pressure), for each run, and average
the results. If any Y value deviates by more than 2 percent from the
average, the DGM is unacceptable for use. Otherwise, use the average as
the calibration factor for subsequent test runs.
10.1.1.2 Post-Test Calibration Check. After each field test series,
conduct a calibration check as in Section 10.1.1.1, above, except for
the following two variations: (a) three or more revolutions of the DGM
may be used and (b) only two independent runs need be made. If the
calibration factor does not deviate by more than 5 percent from the
initial calibration factor (determined in Section 10.1.1.1), then the
DGM volumes obtained during the test series are acceptable. If the
calibration factor deviates by more than 5 percent, recalibrate the DGM
as in Section 10.1.1.1, and for the calculations, use the calibration
factor (initial or recalibration) that yields the lower gas volume for
each test run.
10.1.2 Temperature Sensors. Calibrate against mercury-in-glass
thermometers.
10.1.3 Rate Meter. The rate meter need not be calibrated, but
should be cleaned and maintained according to the manufacturer's
instructions.
10.1.4 Barometer. Calibrate against a mercury barometer.
10.2 Standardization.
10.2.1 Iodine Solution Standardization. Standardize the 0.01 N
I2 solution daily as follows: Pipette 25 ml of the
I2 solution into a 125-ml Erlenmeyer flask. Add 2 ml of 3 M
HCl. Titrate rapidly with standard 0.01 N
Na2S2O3 solution or with 0.01 N
C6H5AsO until the solution is light yellow, using
gentle mixing. Add four drops of starch indicator solution, and continue
titrating slowly until the blue color just disappears. Record the volume
of Na2S2O3 solution used,
VSI, or the volume of C6H5AsO solution
used, VAI, in ml. Repeat until replicate values agree within
0.05 ml. Average the replicate titration values which agree within 0.05
ml, and calculate the exact normality of the I2 solution
using Equation 11-3. Repeat the standardization daily.
10.2.2 Sodium Thiosulfate Solution Standardization. Standardize the
0.1 N Na2S2O3 solution as follows:
Oven-dry potassium dichromate (K2Cr2O7)
at 180 to 200 deg.C (360 to 390 deg.F). To the nearest milligram,
weigh 2 g of the dichromate (W). Transfer the dichromate to a 500-ml
volumetric flask, dissolve in water, and dilute to exactly 500 ml. In a
500-ml iodine flask, dissolve approximately 3 g of KI in 45 ml of water,
then add 10 ml of 3 M HCl solution. Pipette 50 ml of the dichromate
solution into this mixture. Gently swirl the contents of the flask once,
and allow it to stand in the dark for 5 minutes. Dilute the solution
with 100 to 200 ml of water, washing down the sides of the flask with
part of the water. Titrate with 0.1 N
Na2S2O3 until the solution is light
yellow. Add 4 ml of starch indicator and continue titrating slowly to a
green end point. Record the volume of
Na2S2O3 solution used, VS,
in ml. Repeat until replicate values agree within 0.05 ml. Calculate the
normality using Equation 11-1. Repeat the standardization each week or
after each test series, whichever time is shorter.
10.2.3 Phenylarsine Oxide Solution Standardization. Standardize the
0.01 N C6H5AsO (if applicable) as follows: Oven-
dry K2Cr2O7 at 180 to 200 deg.C (360
to 390 deg.F). To the nearest milligram, weigh 2 g of the dichromate
(W). Transfer the dichromate to a 500-ml volumetric flask, dissolve in
water, and dilute to exactly 500 ml. In a 500-ml iodine flask, dissolve
approximately 0.3 g of KI in 45 ml of water, then add 10 ml of 3 M HCl.
Pipette 5 ml of the dichromate solution into the iodine flask. Gently
swirl the contents of the flask once, and allow it to stand in the dark
for 5 minutes. Dilute the solution with 100 to 200 ml of water, washing
down the sides of the flask with part of the water. Titrate with 0.01 N
C6H5AsO until the solution is light yellow. Add 4
ml of starch indicator, and continue titrating slowly to a green end
point. Record the volume of C6H5AsO used,
VA, in ml. Repeat until replicate analyses agree within 0.05
ml. Calculate the normality using Equation 11-2. Repeat the
standardization each week or after each test series, whichever time is
shorter.

11.0 Analytical Procedure

Conduct the titration analyses in a clean area away from direct
sunlight.
11.1 Pipette exactly 50 ml of 0.01 N I2 solution into a
125-ml Erlenmeyer flask. Add 10 ml of 3 M HCl to the solution.
Quantitatively rinse the acidified I2 into the iodine flask.
Stopper the flask immediately, and shake briefly.
11.2 Use these alternative procedures if Antifoam B was not used or
if significant quantities of yellow CdS remain in the impingers. Extract
the remaining CdS from the third, fourth, and fifth impingers using the
acidified I2 solution. Immediately after pouring the
acidified I2 into an impinger, stopper it and shake for a few
moments, then transfer the liquid to the iodine flask. Do not transfer
any rinse portion from one impinger

[[Page 347]]

to another; transfer it directly to the iodine flask. Once the acidified
I2 solution has been poured into any glassware containing
CdS, the container must be tightly stoppered at all times except when
adding more solution, and this must be done as quickly and carefully as
possible. After adding any acidified I2 solution to the
iodine flask, allow a few minutes for absorption of the H2S
before adding any further rinses. Repeat the I2 extraction
until all CdS is removed from the impingers. Extract that part of the
connecting glassware that contains visible CdS. Quantitatively rinse all
the I2 from the impingers, connectors, and the beaker into
the iodine flask using water. Stopper the flask and shake briefly.
11.3 Allow the iodine flask to stand about 30 minutes in the dark
for absorption of the H2S into the I2, then
complete the titration analysis as outlined in Sections 11.5 and 11.6.

Note: Iodine evaporates from acidified I2 solutions.
Samples to which acidified I2 has been added may not be
stored, but must be analyzed in the time schedule stated above.

11.4 Prepare a blank by adding 45 ml of CdSO4 absorbing
solution to an iodine flask. Pipette exactly 50 ml of 0.01 N
I2 solution into a 125-ml Erlenmeyer flask. Add 10 ml of 3 M
HCl. Stopper the flask, shake briefly, let stand 30 minutes in the dark,
and titrate with the samples.

Note: The blank must be handled by exactly the same procedure as
that used for the samples.

11.5 Using 0.01 N Na2S2O3 solution
(or 0.01 N C6H5AsO, if applicable), rapidly
titrate each sample in an iodine flask using gentle mixing, until
solution is light yellow. Add 4 ml of starch indicator solution, and
continue titrating slowly until the blue color just disappears. Record
the volume of Na2S2O3 solution used,
VTT, or the volume of C6H5AsO solution
used, VAT, in ml.
11.6 Titrate the blanks in the same manner as the samples. Run
blanks each day until replicate values agree within 0.05 ml. Average the
replicate titration values which agree within 0.05 ml.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures only after
the final calculation.
12.1 Nomenclature.

CH2S = Concentration of H2S at standard
conditions, mg/dscm.
NA = Normality of standard C6H5AsO
solution, g-eq/liter.
NI = Normality of standard I2 solution, g-eq/
liter.
NS = Normality of standard (0.1 N)
Na2S2O3 solution, g-eq/liter.
NT = Normality of standard (0.01 N)
Na2S2O3 solution, assumed to
be 0.1 NS, g-eq/liter.
Pbar = Barometric pressure at the sampling site, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
Tm = Average DGM temperature, deg.K.
Tstd = Standard absolute temperature, 293 deg.K.
VA = Volume of C6H5AsO solution used
for standardization, ml.
VAI = Volume of standard C6H5AsO
solution used for titration analysis, ml.
VI = Volume of standard I2 solution used for
standardization, ml.
VIT = Volume of standard I2 solution used for
titration analysis, normally 50 ml.
Vm = Volume of gas sample at meter conditions, liters.
Vm(std) = Volume of gas sample at standard conditions,
liters.
VSI = Volume of ``0.1 N
Na2S2O3 solution used for
standardization, ml.
VT = Volume of standard (0.01 N)
Na2S2O3 solution used in
standardizing iodine solution (see Section 10.2.1), ml.
VTT = Volume of standard (~0.01 N)
Na2S2O3 solution used for
titration analysis, ml.
W = Weight of K2Cr2O7 used to
standardize Na2s2O3 or
C6H5AsO solutions, as applicable (see
Sections 10.2.2 and 10.2.3), g.
Y = DGM calibration factor.

12.2 Normality of the Standard (0.1 N) Sodium Thiosulfate
Solution.
[GRAPHIC] [TIFF OMITTED] TR17OC00.238

Where:

2.039 = Conversion factor
= (6 g-eq I2/mole K2Cr2O7)
(1,000 ml/liter)/(294.2 g
K2Cr2O7/mole) (10 aliquot
factor)

12.3 Normality of Standard Phenylarsine Oxide Solution (if
applicable).
[GRAPHIC] [TIFF OMITTED] TR17OC00.239

Where:

0.2039 = Conversion factor.
= (6 g-eq I2/mole K2Cr2O7)
(1,000 ml/liter)/(294.2 g
K2Cr2O7/mole) (100 aliquot
factor)

12.4 Normality of Standard Iodine Solution.
[GRAPHIC] [TIFF OMITTED] TR17OC00.240

Note: If C6H5AsO is used instead of
Na2S2O3, replace NT and
VT in Equation 11-3 with NA and VAS,
respectively (see Sections 10.2.1 and 10.2.3).

12.5 Dry Gas Volume. Correct the sample volume measured by the DGM
to standard conditions (20 deg.C and 760 mm Hg).

[[Page 348]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.241

12.6 Concentration of H2S. Calculate the concentration
of H2S in the gas stream at standard conditions using
Equation 11-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.242

Where:

17.04 x 10\3\ = Conversion factor
= (34.07 g/mole H2S) (1,000 liters/m\3\) (1,000mg/g)/(1,000
ml/liter) (2H2S eq/mole)

Note: If C6H5AsO is used instead of
NaS22O3, replace NA and VAT
in Equation 11-5 with NA and VAT, respectively
(see Sections 11.5 and 10.2.3).

13.0 Method Performance

13.1 Precision. Collaborative testing has shown the intra-
laboratory precision to be 2.2 percent and the inter-laboratory
precision to be 5 percent.
13.2 Bias. The method bias was shown to be -4.8 percent when only
H2S was present. In the presence of the interferences cited
in Section 4.0, the bias was positive at low H2S
concentration and negative at higher concentrations. At 230 mg
H2S/m\3\, the level of the compliance standard, the bias was
+2.7 percent. Thiols had no effect on the precision.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Determination of Hydrogen Sulfide, Ammoniacal Cadmium Chloride
Method. API Method 772-54. In: Manual on Disposal of Refinery Wastes,
Vol. V: Sampling and Analysis of Waste Gases and Particulate Matter.
American Petroleum Institute, Washington, D.C. 1954.
2. Tentative Method of Determination of Hydrogen Sulfide and
Mercaptan Sulfur in Natural Gas. Natural Gas Processors Association,
Tulsa, OK. NGPA Publication No. 2265-65. 1965.
3. Knoll, J.D., and M.R. Midgett. Determination of Hydrogen Sulfide
in Refinery Fuel Gases. Environmental Monitoring Series, Office of
Research and Development, USEPA. Research Triangle Park, NC 27711. EPA
600/4-77-007.
4. Scheil, G.W., and M.C. Sharp. Standardization of Method 11 at a
Petroleum Refinery. Midwest Research Institute Draft Report for USEPA.
Office of Research and Development. Research Triangle Park, NC 27711.
EPA Contract No. 68-02-1098. August 1976. EPA 600/4-77-088a (Volume 1)
and EPA 600/4-77-088b (Volume 2).

[[Page 349]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.243

Method 12--Determination of Inorganic Lead Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

1.0 Scope and Application

1.1 Analytes.

[[Page 350]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Inorganic Lead Compounds as lead 7439-92-1 see Section 13.3.
(Pb).
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of inorganic lead emissions from stationary sources, only as specified
in an applicable subpart of the regulations.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate and gaseous Pb emissions are withdrawn
isokinetically from the source and are collected on a filter and in
dilute nitric acid. The collected samples are digested in acid solution
and are analyzed by atomic absorption spectrophotometry using an air/
acetylene flame.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Copper. High concentrations of copper may interfere with the
analysis of Pb at 217.0 nm. This interference can be avoided by
analyzing the samples at 283.3 nm.
4.2 Matrix Effects. Analysis for Pb by flame atomic absorption
spectrophotometry is sensitive to the chemical composition and to the
physical properties (e.g., viscosity, pH) of the sample. The analytical
procedure requires the use of the Method of Standard Additions to check
for these matrix effects, and requires sample analysis using the Method
of Standard Additions if significant matrix effects are found to be
present.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. A schematic of the sampling train used in
performing this method is shown in Figure 12-1 in Section 18.0; it is
similar to the Method 5 train. The following items are needed for sample
collection:
6.1.1 Probe Nozzle, Probe Liner, Pitot Tube, Differential Pressure
Gauge, Filter Holder, Filter Heating System, Temperature Sensor,
Metering System, Barometer, and Gas Density Determination Equipment.
Same as Method 5, Sections 6.1.1.1 through 6.1.1.7, 6.1.1.9, 6.1.2, and
6.1.3, respectively.
6.1.2 Impingers. Four impingers connected in series with leak-free
ground glass fittings or any similar leak-free noncontaminating fittings
are needed. For the first, third, and fourth impingers, use the
Greenburg-Smith design, modified by replacing the tip with a 1.3 cm (\1/
2\ in.) ID glass tube extending to about 1.3 cm (\1/2\ in.) from the
bottom of the flask. For the second impinger, use the Greenburg-Smith
design with the standard tip.
6.1.3 Temperature Sensor. Place a temperature sensor, capable of
measuring temperature to within 1 deg.C (2 deg.F) at the outlet of the
fourth impinger for monitoring purposes.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Probe-Liner and Probe-Nozzle Brushes, Petri Dishes, Graduated
Cylinder and/or Balance, Plastic Storage Containers, and Funnel and
Rubber Policeman. Same as Method 5, Sections 6.2.1 and 6.2.4 through
6.2.7, respectively.
6.2.2 Wash Bottles. Glass (2).
6.2.3 Sample Storage Containers. Chemically resistant, borosilicate
glass bottles, for 0.1 N nitric acid (HNO3) impinger and
probe solutions and washes, 1000-ml. Use screw-cap liners that are
either rubber-backed Teflon or leak-free and resistant to chemical
attack by 0.1 N HNO3. (Narrow mouth glass bottles have been
found to be less prone to leakage.)
6.2.4 Funnel. Glass, to aid in sample recovery.
6.3 Sample Analysis. The following items are needed for sample
analysis:
6.3.1 Atomic Absorption Spectrophotometer. With lead hollow cathode
lamp and burner for air/acetylene flame.
6.3.2 Hot Plate.

[[Page 351]]

6.3.3 Erlenmeyer Flasks. 125-ml, 24/40 standard taper.
6.3.4 Membrane Filters. Millipore SCWPO 4700, or equivalent.
6.3.5 Filtration Apparatus. Millipore vacuum filtration unit, or
equivalent, for use with the above membrane filter.
6.3.6 Volumetric Flasks. 100-ml, 250-ml, and 1000-ml.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are needed for sample
collection:
7.1.1 Filter. Gelman Spectro Grade, Reeve Angel 934 AH, MSA 1106
BH, all with lot assay for Pb, or other high-purity glass fiber filters,
without organic binder, exhibiting at least 99.95 percent efficiency
(0.05 percent penetration) on 0.3 micron dioctyl phthalate smoke
particles. Conduct the filter efficiency test using ASTM D 2986-71, 78,
or 95a (incorporated by reference--see Sec. 60.17) or use test data from
the supplier's quality control program.
7.1.2 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method
5, Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
7.1.3 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91, Type 3 (incorporated by reference--see Sec. 60.17). If high
concentrations of organic matter are not expected to be present, the
potassium permanganate test for oxidizable organic matter may be
omitted.
7.1.4 Nitric Acid, 0.1 N. Dilute 6.5 ml of concentrated
HNO3 to 1 liter with water. (It may be desirable to run
blanks before field use to eliminate a high blank on test samples.)
7.2 Sample Recovery. 0.1 N HNO3 (Same as in Section
7.1.4 above).
7.3 Sample Analysis. The following reagents and standards are
needed for sample analysis:
7.3.1 Water. Same as in Section 7.1.3.
7.3.2 Nitric Acid, Concentrated.
7.3.3 Nitric Acid, 50 Percent (v/v). Dilute 500 ml of concentrated
HNO3 to 1 liter with water.
7.3.4 Stock Lead Standard Solution, 1000 g Pb/ml. Dissolve
0.1598 g of lead nitrate [Pb(NO3)2] in about 60 ml
water, add 2 ml concentrated HNO3, and dilute to 100 ml with
water.
7.3.5 Working Lead Standards. Pipet 0.0, 1.0, 2.0, 3.0, 4.0, and
5.0 ml of the stock lead standard solution (Section 7.3.4) into 250-ml
volumetric flasks. Add 5 ml of concentrated HNO3 to each
flask, and dilute to volume with water. These working standards contain
0.0, 4.0, 8.0, 12.0, 16.0, and 20.0 g Pb/ml, respectively.
Prepare, as needed, additional standards at other concentrations in a
similar manner.
7.3.6 Air. Suitable quality for atomic absorption
spectrophotometry.
7.3.7 Acetylene. Suitable quality for atomic absorption
spectrophotometry.
7.3.8 Hydrogen Peroxide, 3 Percent (v/v). Dilute 10 ml of 30
percent H2O2 to 100 ml with water.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. Follow the same general procedure given in
Method 5, Section 8.1, except that the filter need not be weighed.
8.2 Preliminary Determinations. Follow the same general procedure
given in Method 5, Section 8.2.
8.3 Preparation of Sampling Train. Follow the same general
procedure given in Method 5, Section 8.3, except place 100 ml of 0.1 N
HNO3 (instead of water) in each of the first two impingers.
As in Method 5, leave the third impinger empty and transfer
approximately 200 to 300 g of preweighed silica gel from its container
to the fourth impinger. Set up the train as shown in Figure 12-1.
8.4 Leak-Check Procedures. Same as Method 5, Section 8.4.
8.5 Sampling Train Operation. Same as Method 5, Section 8.5.
8.6 Calculation of Percent Isokinetic. Same as Method 5, Section
8.6.
8.7 Sample Recovery. Same as Method 5, Sections 8.7.1 through
8.7.6.1, with the addition of the following:
8.7.1 Container No. 2 (Probe).
8.7.1.1 Taking care that dust on the outside of the probe or other
exterior surfaces does not get into the sample, quantitatively recover
sample matter and any condensate from the probe nozzle, probe fitting,
probe liner, and front half of the filter holder by washing these
components with 0.1 N HNO3 and placing the wash into a glass
sample storage container. Measure and record (to the nearest 2 ml) the
total amount of 0.1 N HNO3 used for these rinses. Perform the
0.1 N HNO3 rinses as follows:
8.7.1.2 Carefully remove the probe nozzle, and rinse the inside
surfaces with 0.1 N HNO3 from a wash bottle while brushing
with a stainless steel, Nylon-bristle brush. Brush until the 0.1 N
HNO3 rinse shows no visible particles, then make a final
rinse of the inside surface with 0.1 N HNO3.
8.7.1.3 Brush and rinse with 0.1 N HNO3 the inside parts
of the Swagelok fitting in a similar way until no visible particles
remain.
8.7.1.4 Rinse the probe liner with 0.1 N HNO3. While
rotating the probe so that all inside surfaces will be rinsed with 0.1 N

[[Page 352]]

HNO3, tilt the probe, and squirt 0.1 N HNO3 into
its upper end. Let the 0.1 N HNO3 drain from the lower end
into the sample container. A glass funnel may be used to aid in
transferring liquid washes to the container. Follow the rinse with a
probe brush. Hold the probe in an inclined position, squirt 0.1 N
HNO3 into the upper end of the probe as the probe brush is
being pushed with a twisting action through the probe; hold the sample
container underneath the lower end of the probe, and catch any 0.1 N
HNO3 and sample matter that is brushed from the probe. Run
the brush through the probe three times or more until no visible sample
matter is carried out with the 0.1 N HNO3 and none remains on
the probe liner on visual inspection. With stainless steel or other
metal probes, run the brush through in the above prescribed manner at
least six times, since metal probes have small crevices in which sample
matter can be entrapped. Rinse the brush with 0.1 N HNO3, and
quantitatively collect these washings in the sample container. After the
brushing, make a final rinse of the probe as described above.
8.7.1.5 It is recommended that two people clean the probe to
minimize loss of sample. Between sampling runs, keep brushes clean and
protected from contamination.
8.7.1.6 After ensuring that all joints are wiped clean of silicone
grease, brush and rinse with 0.1 N HNO3 the inside of the
from half of the filter holder. Brush and rinse each surface three times
or more, if needed, to remove visible sample matter. Make a final rinse
of the brush and filter holder. After all 0.1 N HNO3 washings
and sample matter are collected in the sample container, tighten the lid
on the sample container so that the fluid will not leak out when it is
shipped to the laboratory. Mark the height of the fluid level to
determine whether leakage occurs during transport. Label the container
to identify its contents clearly.
8.7.2 Container No. 3 (Silica Gel). Note the color of the
indicating silica gel to determine if it has been completely spent, and
make a notation of its condition. Transfer the silica gel from the
fourth impinger to the original container, and seal. A funnel may be
used to pour the silica gel from the impinger and a rubber policeman may
be used to remove the silica gel from the impinger. It is not necessary
to remove the small amount of particles that may adhere to the walls and
are difficult to remove. Since the gain in weight is to be used for
moisture calculations, do not use any water or other liquids to transfer
the silica gel. If a balance is available in the field, follow the
procedure for Container No. 3 in Section 11.4.2.
8.7.3 Container No. 4 (Impingers). Due to the large quantity of
liquid involved, the impinger solutions may be placed in several
containers. Clean each of the first three impingers and connecting
glassware in the following manner:
8.7.3.1. Wipe the impinger ball joints free of silicone grease, and
cap the joints.
8.7.3.2. Rotate and agitate each impinger, so that the impinger
contents might serve as a rinse solution.
8.7.3.3. Transfer the contents of the impingers to a 500-ml
graduated cylinder. Remove the outlet ball joint cap, and drain the
contents through this opening. Do not separate the impinger parts (inner
and outer tubes) while transferring their contents to the cylinder.
Measure the liquid volume to within 2 ml. Alternatively, determine the
weight of the liquid to within 0.5 g. Record in the log the volume or
weight of the liquid present, along with a notation of any color or film
observed in the impinger catch. The liquid volume or weight is needed,
along with the silica gel data, to calculate the stack gas moisture
content (see Method 5, Figure 5-6).
8.7.3.4. Transfer the contents to Container No. 4.

Note: In Sections 8.7.3.5 and 8.7.3.6, measure and record the total
amount of 0.1 N HNO3 used for rinsing.

8.7.3.5. Pour approximately 30 ml of 0.1 N HNO3 into
each of the first three impingers and agitate the impingers. Drain the
0.1 N HNO3 through the outlet arm of each impinger into
Container No. 4. Repeat this operation a second time; inspect the
impingers for any abnormal conditions.
8.7.3.6. Wipe the ball joints of the glassware connecting the
impingers free of silicone grease and rinse each piece of glassware
twice with 0.1 N HNO3; transfer this rinse into Container No.
4. Do not rinse or brush the glass-fritted filter support. Mark the
height of the fluid level to determine whether leakage occurs during
transport. Label the container to identify its contents clearly.
8.8 Blanks.
8.8.1 Nitric Acid. Save 200 ml of the 0.1 N HNO3 used
for sampling and cleanup as a blank. Take the solution directly from the
bottle being used and place into a glass sample container labeled ``0.1
N HNO3 blank.''
8.8.2 Filter. Save two filters from each lot of filters used in
sampling. Place these filters in a container labeled ``filter blank.''

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

[[Page 353]]

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.4, 10.1..................... Sampling Ensure accuracy and
equipment leak- precision of
checks and sampling
calibration. measurements.
10.2.......................... Spectrophotometer Ensure linearity of
calibration. spectrophotometer
response to
standards.
11.5.......................... Check for matrix Eliminate matrix
effects. effects.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardizations

Note: Maintain a laboratory log of all calibrations.
10.1 Sampling Equipment. Same as Method 5, Section 10.0.
10.2 Spectrophotometer.
10.2.1 Measure the absorbance of the standard solutions using the
instrument settings recommended by the spectrophotometer manufacturer.
Repeat until good agreement (3 percent) is obtained between
two consecutive readings. Plot the absorbance (y-axis) versus
concentration in g Pb/ml (x-axis). Draw or compute a straight
line through the linear portion of the curve. Do not force the
calibration curve through zero, but if the curve does not pass through
the origin or at least lie closer to the origin than 0.003
absorbance units, check for incorrectly prepared standards and for
curvature in the calibration curve.
10.2.2 To determine stability of the calibration curve, run a blank
and a standard after every five samples, and recalibrate as necessary.

11.0 Analytical Procedures

11.1 Sample Loss Check. Prior to analysis, check the liquid level
in Containers Number 2 and Number 4. Note on the analytical data sheet
whether leakage occurred during transport. If a noticeable amount of
leakage occurred, either void the sample or take steps, subject to the
approval of the Administrator, to adjust the final results.
11.2 Sample Preparation.
11.2.1 Container No. 1 (Filter). Cut the filter into strips and
transfer the strips and all loose particulate matter into a 125-ml
Erlenmeyer flask. Rinse the petri dish with 10 ml of 50 percent
HNO3 to ensure a quantitative transfer, and add to the flask.

Note: If the total volume required in Section 11.2.3 is expected to
exceed 80 ml, use a 250-ml flask in place of the 125-ml flask.
11.2.2 Containers No. 2 and No. 4 (Probe and Impingers). Combine
the contents of Containers No. 2 and No. 4, and evaporate to dryness on
a hot plate.
11.2.3 Sample Extraction for Lead.
11.2.3.1 Based on the approximate stack gas particulate
concentration and the total volume of stack gas sampled, estimate the
total weight of particulate sample collected. Next, transfer the residue
from Containers No. 2 and No. 4 to the 125-ml Erlenmeyer flask that
contains the sampling filter using a rubber policeman and 10 ml of 50
percent HNO3 for every 100 mg of sample collected in the
train or a minimum of 30 ml of 50 percent HNO3, whichever is
larger.
11.2.3.2 Place the Erlenmeyer flask on a hot plate, and heat with
periodic stirring for 30 minutes at a temperature just below boiling. If
the sample volume falls below 15 ml, add more 50 percent
HNO3. Add 10 ml of 3 percent H2O2, and
continue heating for 10 minutes. Add 50 ml of hot (80 deg.C, 176
deg.F) water, and heat for 20 minutes. Remove the flask from the hot
plate, and allow to cool. Filter the sample through a Millipore membrane
filter, or equivalent, and transfer the filtrate to a 250-ml volumetric
flask. Dilute to volume with water.
11.2.4 Filter Blank. Cut each filter into strips, and place each
filter in a separate 125-ml Erlenmeyer flask. Add 15 ml of 50 percent
HNO3, and treat as described in Section 11.2.3 using 10 ml of
3 percent H2O2 and 50 ml of hot water. Filter and
dilute to a total volume of 100 ml using water.
11.2.5 Nitric Acid Blank, 0.1 N. Take the entire 200 ml of 0.1 N
HNO3 to dryness on a steam bath, add 15 ml of 50 percent
HNO3, and treat as described in Section 11.2.3 using 10 ml of
3 percent H202 and 50 ml of hot water. Dilute to a
total volume of 100 ml using water.
11.3 Spectrophotometer Preparation. Turn on the power; set the
wavelength, slit width, and lamp current; and adjust the background
corrector as instructed by the manufacturer's manual for the particular
atomic absorption spectrophotometer. Adjust the burner and flame
characteristics as necessary.
11.4 Analysis.
11.4.1 Lead Determination. Calibrate the spectrophotometer as
outlined in Section 10.2, and determine the absorbance for each source
sample, the filter blank, and 0.1 N HNO3 blank. Analyze each
sample three times in this manner. Make appropriate dilutions, as
needed, to bring all sample Pb concentrations into the linear absorbance
range of the spectrophotometer. Because instruments vary between
manufacturers, no detailed operating instructions will be given here.
Instead, the instructions provided with the particular instrument should
be followed. If the Pb concentration of a sample is at the low end of
the calibration curve and

[[Page 354]]

high accuracy is required, the sample can be taken to dryness on a hot
plate and the residue dissolved in the appropriate volume of water to
bring it into the optimum range of the calibration curve.
11.4.2 Container No. 3 (Silica Gel). This step may be conducted in
the field. Weigh the spent silica gel (or silica gel plus impinger) to
the nearest 0.5 g; record this weight.
11.5 Check for Matrix Effects. Use the Method of Standard Additions
as follows to check at least one sample from each source for matrix
effects on the Pb results:
11.5.1 Add or spike an equal volume of standard solution to an
aliquot of the sample solution.
11.5.2 Measure the absorbance of the resulting solution and the
absorbance of an aliquot of unspiked sample.
11.5.3 Calculate the Pb concentration Cm in g/
ml of the sample solution using Equation 12-1 in Section 12.5.
Volume corrections will not be required if the solutions as analyzed
have been made to the same final volume. Therefore, Cm and
Ca represent Pb concentration before dilutions.
Method of Standard Additions procedures described on pages 9-4 and
9-5 of the section entitled ``General Information'' of the Perkin Elmer
Corporation Atomic Absorption Spectrophotometry Manual, Number 303-0152
(Reference 1 in Section 17.0) may also be used. In any event, if the
results of the Method of Standard Additions procedure used on the single
source sample do not agree to within 5 percent of the value
obtained by the routine atomic absorption analysis, then reanalyze all
samples from the source using the Method of Standard Additions
procedure.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Am = Absorbance of the sample solution.
An = Cross-sectional area of nozzle, m\2\ (ft\2\).
At = Absorbance of the spiked sample solution.
Bws = Water in the gas stream, proportion by volume.
Ca = Lead concentration in standard solution, g/ml.
Cm = Lead concentration in sample solution analyzed during
check for matrix effects, g/ml.
Cs = Lead concentration in stack gas, dry basis, converted to
standard conditions, mg/dscm (gr/dscf).
I = Percent of isokinetic sampling.
L1 = Individual leakage rate observed during the leak-check
conducted prior to the first component change, m\3\/min
(ft\3\/min)
La = Maximum acceptable leakage rate for either a pretest
leak-check or for a leak-check following a component change;
equal to 0.00057 m\3\/min (0.020 cfm) or 4 percent of the
average sampling rate, whichever is less.
Li = Individual leakage rate observed during the leak-check
conducted prior to the ``ith'' component change (i = 1, 2, 3 *
* * n), m\3\/min (cfm).
Lp = Leakage rate observed during the post-test leak-check,
m\3\/min (cfm).
mt = Total weight of lead collected in the sample,
g.
Mw = Molecular weight of water, 18.0 g/g-mole (18.0 lb/lb-
mole).
Pbar = Barometric pressure at the sampling site, mm Hg (in.
Hg).
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 [(mm Hg) (m\3\)]/[( deg.K) (g-mole)]
{21.85 [(in. Hg) (ft\3\)]/[( deg.R) (lb-mole)]}.
Tm = Absolute average dry gas meter temperature (see Figure
5-3 of Method 5), deg.K ( deg.R).
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
vs = Stack gas velocity, m/sec (ft/sec).
Vm = Volume of gas sample as measured by the dry gas meter,
dry basis, m\3\ (ft\3\).
Vm(std) = Volume of gas sample as measured by the dry gas
meter, corrected to standard conditions, m\3\ (ft\3\).
Vw(std) = Volume of water vapor collected in the sampling
train, corrected to standard conditions, m\3\ (ft\3\).
Y = Dry gas meter calibration factor.
H = Average pressure differential across the orifice meter (see
Figure 5-3 of Method 5), mm H2O (in.
H2O).
= Total sampling time, min.
l = Sampling time interval, from the beginning of a
run until the first component change, min.
i = Sampling time interval, between two successive
component changes, beginning with the interval between the
first and second changes, min.
p = Sampling time interval, from the final (n\th\)
component change until the end of the sampling run, min.
w = Density of water, 0.9982 g/ml (0.002201 lb/ml).
12.2 Average Dry Gas Meter Temperatures (Tm) and Average
Orifice Pressure Drop (H). See data sheet (Figure 5-3 of Method
5).
12.3 Dry Gas Volume, Volume of Water Vapor, and Moisture Content.
Using data obtained in this test, calculate Vm(std),
Vw(std), and Bws according to the procedures
outlined in Method 5, Sections 12.3 through 12.5.
12.4 Total Lead in Source Sample. For each source sample, correct
the average absorbance for the contribution of the filter blank and the
0.1 N HNO3 blank. Use the calibration curve and this
corrected absorbance to determine the Pb concentration in the

[[Page 355]]

sample aspirated into the spectrophotometer. Calculate the total Pb
content mt (in g) in the original source sample;
correct for all the dilutions that were made to bring the Pb
concentration of the sample into the linear range of the
spectrophotometer.
12.5 Sample Lead Concentration. Calculate the Pb concentration of
the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.244

12.6 Lead Concentration. Calculate the stack gas Pb concentration
Cs using Equation 12-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.245

Where:

K3 = 0.001 mg/g for metric units.
= 1.54 x 10^-\5\ gr/g for English units

12.7 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate using data obtained
in this method and the equations in Sections 12.2 and 12.3 of Method 2.
12.8 Isokinetic Variation. Same as Method 5, Section 12.11.

13.0 Method Performance

13.1 Precision. The within-laboratory precision, as measured by the
coefficient of variation, ranges from 0.2 to 9.5 percent relative to a
run-mean concentration. These values were based on tests conducted at a
gray iron foundry, a lead storage battery manufacturing plant, a
secondary lead smelter, and a lead recovery furnace of an alkyl lead
manufacturing plant. The concentrations encountered during these tests
ranged from 0.61 to 123.3 mg Pb/m\3\.
13.2 Analytical Range. For a minimum analytical accuracy of
10 percent, the lower limit of the range is 100 g.
The upper limit can be extended considerably by dilution.
13.3 Analytical Sensitivity. Typical sensitivities for a 1-percent
change in absorption (0.0044 absorbance units) are 0.2 and 0.5
g Pb/ml for the 217.0 and 283.3 nm lines, respectively.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 Simultaneous Determination of Particulate and Lead Emissions.
Method 5 may be used to simultaneously determine Pb provided: (1)
acetone is used to remove particulate from the probe and inside of the
filter holder as specified by Method 5, (2) 0.1 N HNO3 is
used in the impingers, (3) a glass fiber filter with a low Pb background
is used, and (4) the entire train contents, including the impingers, are
treated and analyzed for Pb as described in Sections 8.0 and 11.0 of
this method.
16.2 Filter Location. A filter may be used between the third and
fourth impingers provided the filter is included in the analysis for Pb.
16.3 In-Stack Filter. An in-stack filter may be used provided: (1)
A glass-lined probe and at least two impingers, each containing 100 ml
of 0.1 N HNO3 after the in-stack filter, are used and (2) the
probe and impinger contents are recovered and analyzed for Pb. Recover
sample from the nozzle with acetone if a particulate analysis is to be
made.

17.0 References

Same as Method 5, Section 17.0, References 2, 3, 4, 5, and 7, with
the addition of the following:

1. Perkin Elmer Corporation. Analytical Methods for Atomic
Absorption Spectrophotometry. Norwalk, Connecticut. September 1976.
2. American Society for Testing and Materials. Annual Book of ASTM
Standards, Part 31: Water, Atmospheric Analysis. Philadelphia, PA 1974.
p. 40-42.
3. Kelin, R., and C. Hach. Standard Additions--Uses and Limitations
in Spectrophotometric Analysis. Amer. Lab. 9:21-27. 1977.
4. Mitchell, W.J., and M.R. Midgett. Determining Inorganic and Alkyl
Lead Emissions from Stationary Sources. U.S. Environmental Protection
Agency. Emission Monitoring and Support Laboratory. Research Triangle
Park, NC. (Presented at National APCA Meeting, Houston. June 26, 1978).

[[Page 356]]

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.246

Method 13A--Determination of Total Fluoride Emissions From Stationary
Sources (Spadns Zirconium Lake Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3, and
Method 5.

[[Page 357]]

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine.... 7782-41-4 Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of fluoride (F^-) emissions from sources as specified in the
regulations. It does not measure fluorocarbons, such as Freons.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary

Gaseous and particulate F^- are withdrawn isokinetically
from the source and collected in water and on a filter. The total
F^- is then determined by the SPADNS Zirconium Lake
Colorimetric method.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Chloride. Large quantities of chloride will interfere with the
analysis, but this interference can be prevented by adding silver
sulfate into the distillation flask (see Section 11.3). If chloride ion
is present, it may be easier to use the specific ion electrode method of
analysis (Method 13B).
4.2 Grease. Grease on sample-exposed surfaces may cause low
F^- results due to adsorption.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. A schematic of the sampling train used in
performing this method is shown in Figure 13A-1; it is similar to the
Method 5 sampling train except that the filter position is
interchangeable. The sampling train consists of the following
components:
6.1.1 Probe Nozzle, Pitot Tube, Differential Pressure Gauge, Filter
Heating System, Temperature Sensor, Metering System, Barometer, and Gas
Density Determination Equipment. Same as Method 5, Sections 6.1.1.1,
6.1.1.3 through 6.1.1.7, 6.1.1.9, 6.1.2, and 6.1.3, respectively. The
filter heating system and temperature sensor are needed only when
moisture condensation is a problem.
6.1.2 Probe Liner. Borosilicate glass or 316 stainless steel. When
the filter is located immediately after the probe, a probe heating
system may be used to prevent filter plugging resulting from moisture
condensation, but the temperature in the probe shall not be allowed to
exceed 120 14 deg.C (248 25 deg.F).
6.1.3 Filter Holder. With positive seal against leakage from the
outside or around the filter. If the filter is located between the probe
and first impinger, use borosilicate glass or stainless steel with a 20-
mesh stainless steel screen filter support and a silicone rubber gasket;
do not use a glass frit or a sintered metal filter support. If the
filter is located between the third and fourth impingers, borosilicate
glass with a glass frit filter support and a silicone rubber gasket may
be used. Other materials of construction may be used, subject to the
approval of the Administrator.
6.1.4 Impingers. Four impingers connected as shown in Figure 13A-1
with ground-glass (or equivalent), vacuum-tight fittings. For the first,
third, and fourth impingers, use the

[[Page 358]]

Greenburg-Smith design, modified by replacing the tip with a 1.3-cm (\1/
2\ in.) ID glass tube extending to 1.3 cm (\1/2\ in.) from the bottom of
the flask. For the second impinger, use a Greenburg-Smith impinger with
the standard tip. Modifications (e.g., flexible connections between the
impingers or materials other than glass) may be used, subject to the
approval of the Administrator. Place a temperature sensor, capable of
measuring temperature to within 1 deg.C (2 deg.F), at the outlet of
the fourth impinger for monitoring purposes.
6.2 Sample Recovery. The following items are needed for sample
recovery:
6.2.1 Probe-liner and Probe-Nozzle Brushes, Wash Bottles, Graduated
Cylinder and/or Balance, Plastic Storage Containers, Funnel and Rubber
Policeman, and Funnel. Same as Method 5, Sections 6.2.1, 6.2.2 and 6.2.5
to 6.2.8, respectively.
6.2.2 Sample Storage Container. Wide-mouth, high-density
polyethylene bottles for impinger water samples, 1 liter.
6.3 Sample Preparation and Analysis. The following items are needed
for sample preparation and analysis:
6.3.1 Distillation Apparatus. Glass distillation apparatus
assembled as shown in Figure 13A-2.
6.3.2 Bunsen Burner.
6.3.3 Electric Muffle Furnace. Capable of heating to 600 deg.C
(1100 deg.F).
6.3.4 Crucibles. Nickel, 75- to 100-ml.
6.3.5 Beakers. 500-ml and 1500-ml.
6.3.6 Volumetric Flasks. 50-ml.
6.3.7 Erlenmeyer Flasks or Plastic Bottles. 500-ml.
6.3.8 Constant Temperature Bath. Capable of maintaining a constant
temperature of 1.0 deg.C at room temperature conditions.
6.3.9 Balance. 300-g capacity, to measure to 0.5 g.
6.3.10 Spectrophotometer. Instrument that measures absorbance at
570 nm and provides at least a 1-cm light path.
6.3.11 Spectrophotometer Cells. 1-cm path length.

7.0 Reagents and Standards

Unless otherwise indicated, all reagents are to conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society, where such specifications are available.
Otherwise, use the best available grade.
7.1 Sample Collection. The following reagents are needed for sample
collection:
7.1.1 Filters.
7.1.1.1 If the filter is located between the third and fourth
impingers, use a Whatman No. 1 filter, or equivalent, sized to fit the
filter holder.
7.1.1.2 If the filter is located between the probe and first
impinger, use any suitable medium (e.g., paper, organic membrane) that
can withstand prolonged exposure to temperatures up to 135 deg.C (275
deg.F), and has at least 95 percent collection efficiency (5 percent
penetration) for 0.3 m dioctyl phthalate smoke particles.
Conduct the filter efficiency test before the test series, using ASTM D
2986-71, 78, or 95a (incorporated by reference--see Sec. 60.17), or use
test data from the supplier's quality control program. The filter must
also have a low F^- blank value (0.015 mg F^-/cm\2\
of filter area). Before the test series, determine the average
F^- blank value of at least three filters (from the lot to be
used for sampling) using the applicable procedures described in Sections
8.3 and 8.4 of this method. In general, glass fiber filters have high
and/or variable F^- blank values, and will not be acceptable
for use.
7.1.2 Water. Deionized distilled, to conform to ASTM D 1193-77 or
91, Type 3 (incorporated by reference--see Sec. 60.17). If high
concentrations of organic matter are not expected to be present, the
potassium permanganate test for oxidizable organic matter may be
deleted.
7.1.3 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method
5, Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
7.2 Sample Recovery. Water, as described in Section 7.1.2, is
needed for sample recovery.
7.3 Sample Preparation and Analysis. The following reagents and
standards are needed for sample preparation and analysis:
7.3.1 Calcium Oxide (CaO). Certified grade containing 0.005 percent
F^- or less.
7.3.2 Phenolphthalein Indicator. Dissolve 0.1 g of phenolphthalein
in a mixture of 50 ml of 90 percent ethanol and 50 ml of water.
7.3.3 Silver Sulfate (Ag2SO4).
7.3.4 Sodium Hydroxide (NaOH), Pellets.
7.3.5 Sulfuric Acid (H2SO4), Concentrated.
7.3.6 Sulfuric Acid, 25 Percent (v/v). Mix 1 part of concentrated
H2SO4 with 3 parts of water.
7.3.7 Filters. Whatman No. 541, or equivalent.
7.3.8 Hydrochloric Acid (HCl), Concentrated.
7.3.9 Water. Same as in Section 7.1.2.
7.3.10 Fluoride Standard Solution, 0.01 mg F^-/ml. Dry
approximately 0.5 g of sodium fluoride (NaF) in an oven at 110 deg.C
(230 deg.F) for at least 2 hours. Dissolve 0.2210 g of NaF in 1 liter
of water. Dilute 100 ml of this solution to 1 liter with water.
7.3.11 SPADNS Solution [4,5 Dihydroxyl-3-(p-Sulfophenylazo)-2,7-
Naphthalene-Disulfonic Acid Trisodium Salt]. Dissolve 0.960
0.010 g of SPADNS reagent in 500 ml water. If stored in a well-sealed
bottle protected from the sunlight, this solution is stable for at least
1 month.
7.3.12 Spectrophotometer Zero Reference Solution. Add 10 ml of
SPADNS solution to 100 ml water, and acidify with a solution prepared by
diluting 7 ml of concentrated HCl to

[[Page 359]]

10 ml with deionized, distilled water. Prepare daily.
7.3.13 SPADNS Mixed Reagent. Dissolve 0.135 0.005 g of
zirconyl chloride octahydrate (ZrOCl2 8H2O) in 25
ml of water. Add 350 ml of concentrated HCl, and dilute to 500 ml with
deionized, distilled water. Mix equal volumes of this solution and
SPADNS solution to form a single reagent. This reagent is stable for at
least 2 months.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparation. Follow the general procedure given in
Method 5, Section 8.1, except that the filter need not be weighed.
8.2 Preliminary Determinations. Follow the general procedure given
in Method 5, Section 8.2, except that the nozzle size must be selected
such that isokinetic sampling rates below 28 liters/min (1.0 cfm) can be
maintained.
8.3 Preparation of Sampling Train. Follow the general procedure
given in Method 5, Section 8.3, except for the following variation:
Assemble the train as shown in Figure 13A-1 with the filter between the
third and fourth impingers. Alternatively, if a 20-mesh stainless steel
screen is used for the filter support, the filter may be placed between
the probe and first impinger. A filter heating system to prevent
moisture condensation may be used, but shall not allow the temperature
to exceed 120 14 deg.C (248 25 deg.F).
Record the filter location on the data sheet (see Section 8.5).
8.4 Leak-Check Procedures. Follow the leak-check procedures given
in Method 5, Section 8.4.
8.5 Sampling Train Operation. Follow the general procedure given in
Method 5, Section 8.5, keeping the filter and probe temperatures (if
applicable) at 120 14 deg.C (248 25 deg.F)
and isokinetic sampling rates below 28 liters/min (1.0 cfm). For each
run, record the data required on a data sheet such as the one shown in
Method 5, Figure 5-3.
8.6 Sample Recovery. Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the sampling period. Allow
the probe to cool.
8.6.1 When the probe can be safely handled, wipe off all external
particulate matter near the tip of the probe nozzle, and place a cap
over it to keep from losing part of the sample. Do not cap off the probe
tip tightly while the sampling train is cooling down as this would
create a vacuum in the filter holder, thus drawing water from the
impingers into the filter holder.
8.6.2 Before moving the sample train to the cleanup site, remove
the probe from the sample train, wipe off any silicone grease, and cap
the open outlet of the probe. Be careful not to lose any condensate that
might be present. Remove the filter assembly, wipe off any silicone
grease from the filter holder inlet, and cap this inlet. Remove the
umbilical cord from the last impinger, and cap the impinger. After
wiping off any silicone grease, cap off the filter holder outlet and any
open impinger inlets and outlets. Ground-glass stoppers, plastic caps,
or serum caps may be used to close these openings.
8.6.3 Transfer the probe and filter-impinger assembly to the
cleanup area. This area should be clean and protected from the wind so
that the chances of contaminating or losing the sample will be
minimized.
8.6.4 Inspect the train prior to and during disassembly, and note
any abnormal conditions. Treat the samples as follows:
8.6.4.1 Container No. 1 (Probe, Filter, and Impinger Catches).
8.6.4.1.1 Using a graduated cylinder, measure to the nearest ml,
and record the volume of the water in the first three impingers; include
any condensate in the probe in this determination. Transfer the impinger
water from the graduated cylinder into a polyethylene container. Add the
filter to this container. (The filter may be handled separately using
procedures subject to the Administrator's approval.) Taking care that
dust on the outside of the probe or other exterior surfaces does not get
into the sample, clean all sample-exposed surfaces (including the probe
nozzle, probe fitting, probe liner, first three impingers, impinger
connectors, and filter holder) with water. Use less than 500 ml for the
entire wash. Add the washings to the sample container. Perform the water
rinses as follows:
8.6.4.1.2 Carefully remove the probe nozzle and rinse the inside
surface with water from a wash bottle. Brush with a Nylon bristle brush,
and rinse until the rinse shows no visible particles, after which make a
final rinse of the inside surface. Brush and rinse the inside parts of
the Swagelok fitting with water in a similar way.
8.6.4.1.3 Rinse the probe liner with water. While squirting the
water into the upper end of the probe, tilt and rotate the probe so that
all inside surfaces will be wetted with water. Let the water drain from
the lower end into the sample container. A funnel (glass or
polyethylene) may be used to aid in transferring the liquid washes to
the container. Follow the rinse with a probe brush. Hold the probe in an
inclined position, and squirt water into the upper end as the probe
brush is being pushed with a twisting action through the probe. Hold the
sample container underneath the lower end of the probe, and catch any
water and particulate matter that is brushed from the probe. Run the
brush through the probe three times or more. With stainless steel or
other metal probes, run the brush through in the above prescribed manner
at least six times since metal probes have small crevices in which
particulate matter can be entrapped. Rinse the brush with water, and
quantitatively collect these washings in the

[[Page 360]]

sample container. After the brushing, make a final rinse of the probe as
described above.
8.6.4.1.4 It is recommended that two people clean the probe to
minimize sample losses. Between sampling runs, keep brushes clean and
protected from contamination.
8.6.4.1.5 Rinse the inside surface of each of the first three
impingers (and connecting glassware) three separate times. Use a small
portion of water for each rinse, and brush each sample-exposed surface
with a Nylon bristle brush, to ensure recovery of fine particulate
matter. Make a final rinse of each surface and of the brush.
8.6.4.1.6 After ensuring that all joints have been wiped clean of
the silicone grease, brush and rinse with water the inside of the filter
holder (front-half only, if filter is positioned between the third and
fourth impingers). Brush and rinse each surface three times or more if
needed. Make a final rinse of the brush and filter holder.
8.6.4.1.7 After all water washings and particulate matter have been
collected in the sample container, tighten the lid so that water will
not leak out when it is shipped to the laboratory. Mark the height of
the fluid level to transport. Label the container clearly to identify
its contents.
8.6.4.2 Container No. 2 (Sample Blank). Prepare a blank by placing
an unused filter in a polyethylene container and adding a volume of
water equal to the total volume in Container No. 1. Process the blank in
the same manner as for Container No. 1.
8.6.4.3 Container No. 3 (Silica Gel). Note the color of the
indicating silica gel to determine whether it has been completely spent,
and make a notation of its condition. Transfer the silica gel from the
fourth impinger to its original container, and seal. A funnel may be
used to pour the silica gel and a rubber policeman to remove the silica
gel from the impinger. It is not necessary to remove the small amount of
dust particles that may adhere to the impinger wall and are difficult to
remove. Since the gain in weight is to be used for moisture
calculations, do not use any water or other liquids to transfer the
silica gel. If a balance is available in the field, follow the
analytical procedure for Container No. 3 in Section 11.4.2.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Sampling Equipment. Calibrate the probe nozzle, pitot tube,
metering system, probe heater, temperature sensors, and barometer
according to the procedures outlined in Method 5, Sections 10.1 through
10.6. Conduct the leak-check of the metering system according to the
procedures outlined in Method 5, Section 8.4.1.
10.2 Spectrophotometer.
10.2.1 Prepare the blank standard by adding 10 ml of SPADNS mixed
reagent to 50 ml of water.
10.2.2 Accurately prepare a series of standards from the 0.01 mg
F^-/ml standard fluoride solution (Section 7.3.10) by diluting
0, 2, 4, 6, 8, 10, 12, and 14 ml to 100 ml with deionized, distilled
water. Pipet 50 ml from each solution, and transfer each to a separate
100-ml beaker. Then add 10 ml of SPADNS mixed reagent (Section 7.3.13)
to each. These standards will contain 0, 10, 20, 30, 40, 50, 60, and 70
g F^-(0 to 1.4 g/ml), respectively.
10.2.3 After mixing, place the blank and calibration standards in a
constant temperature bath for 30 minutes before reading the absorbance
with the spectrophotometer. Adjust all samples to this same temperature
before analyzing.
10.2.4 With the spectrophotometer at 570 nm, use the blank standard
to set the absorbance to zero. Determine the absorbance of the
standards.
10.2.5 Prepare a calibration curve by plotting g
F^-/50 ml versus absorbance on linear graph paper. Prepare the
standard curve initially and thereafter whenever the SPADNS mixed
reagent is newly made. Also, run a calibration standard with each set of
samples and, if it differs from the calibration curve by more than
2 percent, prepare a new standard curve.

11.0 Analytical Procedures

11.1 Sample Loss Check. Note the liquid levels in Containers No. 1
and No. 2, determine whether leakage occurred during transport, and note
this finding on the analytical

[[Page 361]]

data sheet. If noticeable leakage has occurred, either void the sample
or use methods, subject to the approval of the Administrator, to correct
the final results.
11.2 Sample Preparation. Treat the contents of each sample
container as described below:
11.2.1 Container No. 1 (Probe, Filter, and Impinger Catches).
Filter this container's contents, including the sampling filter, through
Whatman No. 541 filter paper, or equivalent, into a 1500-ml beaker.
11.2.1.1 If the filtrate volume exceeds 900 ml, make the filtrate
basic (red to phenolphthalein) with NaOH, and evaporate to less than 900
ml.
11.2.1.2 Place the filtered material (including sampling filter) in
a nickel crucible, add a few ml of water, and macerate the filters with
a glass rod.
11.2.1.2.1 Add 100 mg CaO to the crucible, and mix the contents
thoroughly to form a slurry. Add two drops of phenolphthalein indicator.
Place the crucible in a hood under infrared lamps or on a hot plate at
low heat. Evaporate the water completely. During the evaporation of the
water, keep the slurry basic (red to phenolphthalein) to avoid loss of
F^-. If the indicator turns colorless (acidic) during the
evaporation, add CaO until the color turns red again.
11.2.1.2.2 After evaporation of the water, place the crucible on a
hot plate under a hood, and slowly increase the temperature until the
Whatman No. 541 and sampling filters char. It may take several hours to
char the filters completely.
11.2.1.2.3 Place the crucible in a cold muffle furnace. Gradually
(to prevent smoking) increase the temperature to 600 deg.C (1100
deg.F), and maintain this temperature until the contents are reduced to
an ash. Remove the crucible from the furnace, and allow to cool.
11.2.1.2.4 Add approximately 4 g of crushed NaOH to the crucible,
and mix. Return the crucible to the muffle furnace, and fuse the sample
for 10 minutes at 600 deg.C.
11.2.1.2.5 Remove the sample from the furnace, and cool to ambient
temperature. Using several rinsings of warm water, transfer the contents
of the crucible to the beaker containing the filtrate. To ensure
complete sample removal, rinse finally with two 20-ml portions of 25
percent H2SO4, and carefully add to the beaker.
Mix well, and transfer to a 1-liter volumetric flask. Dilute to volume
with water, and mix thoroughly. Allow any undissolved solids to settle.
11.2.2 Container No. 2 (Sample Blank). Treat in the same manner as
described in Section 11.2.1 above.
11.2.3 Adjustment of Acid/Water Ratio in Distillation Flask. Place
400 ml of water in the distillation flask, and add 200 ml of
concentrated H2SO4. Add some soft glass beads and
several small pieces of broken glass tubing, and assemble the apparatus
as shown in Figure 13A-2. Heat the flask until it reaches a temperature
of 175 deg.C (347 deg.F) to adjust the acid/water ratio for subsequent
distillations. Discard the distillate.

Caution: Use a protective shield when carrying out this procedure.
Observe standard precautions when mixing H2SO4
with water. Slowly add the acid to the flask with constant swirling.

11.3 Distillation.
11.3.1 Cool the contents of the distillation flask to below 80
deg.C (180 deg.F). Pipet an aliquot of sample containing less than 10.0
mg F^- directly into the distillation flask, and add water to
make a total volume of 220 ml added to the distillation flask. (To
estimate the appropriate aliquot size, select an aliquot of the
solution, and treat as described in Section 11.4.1. This will be an
approximation of the F^- content because of possible
interfering ions.)

Note: If the sample contains chloride, add 5 mg of
Ag2SO4 to the flask for every mg of chloride.

11.3.2 Place a 250-ml volumetric flask at the condenser exit. Heat
the flask as rapidly as possible with a Bunsen burner, and collect all
the distillate up to 175 deg.C (347 deg.F). During heatup, play the
burner flame up and down the side of the flask to prevent bumping.
Conduct the distillation as rapidly as possible (15 minutes or less).
Slow distillations have been found to produce low F^-
recoveries. Be careful not to exceed 175 deg.C (347 deg.F) to avoid
causing H2SO4 to distill over. If F^-
distillation in the mg range is to be followed by a distillation in the
fractional mg range, add 220 ml of water and distill it over as in the
acid adjustment step to remove residual F^- from the
distillation system.
11.3.3 The acid in the distillation flask may be used until there
is carry-over of interferences or poor F^- recovery. Check for
interference and for recovery efficiency every tenth distillation using
a water blank and a standard solution. Change the acid whenever the
F^- recovery is less than 90 percent or the blank value
exceeds 0.1 g/ml.
11.4 Sample Analysis.
11.4.1 Containers No. 1 and No. 2.
11.4.1.1 After distilling suitable aliquots from Containers No. 1
and No. 2 according to Section 11.3, dilute the distillate in the
volumetric flasks to exactly 250 ml with water, and mix thoroughly.
Pipet a suitable aliquot of each sample distillate (containing 10 to 40
g F^-/ml) into a beaker, and dilute to 50 ml with
water. Use the same aliquot size for the blank. Add 10 ml of SPADNS
mixed reagent (Section 7.3.13), and mix thoroughly.
11.4.1.2 After mixing, place the sample in a constant-temperature
bath containing the standard solutions for 30 minutes before reading the
absorbance on the spectrophotometer.

[[Page 362]]

Note: After the sample and colorimetric reagent are mixed, the color
formed is stable for approximately 2 hours. Also, a 3 deg.C (5.4
deg.F) temperature difference between the sample and standard solutions
produces an error of approximately 0.005 mg F^-/liter. To
avoid this error, the absorbencies of the sample and standard solutions
must be measured at the same temperature.

11.4.1.3 Set the spectrophotometer to zero absorbance at 570 nm
with the zero reference solution (Section 7.3.12), and check the
spectrophotometer calibration with the standard solution (Section
7.3.10). Determine the absorbance of the samples, and determine the
concentration from the calibration curve. If the concentration does not
fall within the range of the calibration curve, repeat the procedure
using a different size aliquot.
11.4.2 Container No. 3 (Silica Gel). Weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g using a balance. This
step may be conducted in the field.

12.0 Data Analysis and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculation. Other forms of the equations may be used, provided that
they yield equivalent results.
12.1 Nomenclature.

Ad = Aliquot of distillate taken for color development, ml.
At = Aliquot of total sample added to still, ml.
Bws = Water vapor in the gas stream, portion by volume.
Cs = Concentration of F^- in stack gas, mg/dscm
(gr/dscf).
Fc = F^- concentration from the calibration curve,
g.
Ft = Total F^- in sample, mg.
Tm = Absolute average dry gas meter (DGM) temperature (see
Figure 5-3 of Method 5), deg.K ( deg.R).
Ts = Absolute average stack gas temperature (see Figure 5-3
of Method 5), deg.K ( deg.R).
Vd = Volume of distillate as diluted, ml.
Vm(std) = Volume of gas sample as measured by DGM at standard
conditions, dscm (dscf).
Vt = Total volume of F^- sample, after final
dilution, ml.
Vw(std) = Volume of water vapor in the gas sample at standard
conditions, scm (scf)

12.2 Average DGM Temperature and Average Orifice Pressure Drop (see
Figure 5-3 of Method 5).
12.3 Dry Gas Volume. Calculate Vm(std), and adjust for
leakage, if necessary, using Equation 5-1 of Method 5.
12.4 Volume of Water Vapor and Moisture Content. Calculate
Vw(std) and Bws from the data obtained in this
method. Use Equations 5-2 and 5-3 of Method 5.
12.5 Total Fluoride in Sample. Calculate the amount of
F^- in the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.247

Where:

K = 10^-3 mg/g (metric units)
= 1.54 x 10^-5 gr/g (English units)

12.6 Fluoride Concentration in Stack Gas. Determine the
F^- concentration in the stack gas using the following
equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.248

12.7 Isokinetic Variation. Same as Method 5, Section 12.11.

13.0 Method Performance

The following estimates are based on a collaborative test done at a
primary aluminum smelter. In the test, six laboratories each sampled the
stack simultaneously using two sampling trains for a total of 12 samples
per sampling run. Fluoride concentrations encountered during the test
ranged from 0.1 to 1.4 mg F^-/m\3\.
13.1 Precision. The intra- and inter-laboratory standard
deviations, which include sampling and analysis errors, were 0.044 mg
F^-/m\3\ with 60 degrees of freedom and 0.064 mg
F^-/m\3\ with five degrees of freedom, respectively.
13.2 Bias. The collaborative test did not find any bias in the
analytical method.
13.3 Range. The range of this method is 0 to 1.4 g
F-/ml.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 Compliance with ASTM D 3270-73T, 80, 91, or 95 (incorporated
by reference--see Sec. 60.17) ``Analysis of Fluoride Content of the
Atmosphere and Plant Tissues (Semiautomated Method) is an acceptable
alternative for the requirements specified in Sections 11.2, 11.3, and
11.4.1 when applied to suitable aliquots of Containers 1 and 2 samples.

17.0 References

1. Bellack, Ervin. Simplified Fluoride Distillation Method. J. of
the American Water Works Association. 50:5306. 1958.
2. Mitchell, W.J., J.C. Suggs, and F.J. Bergman. Collaborative Study
of EPA Method 13A and Method 13B. Publication No. EPA-300/4-77-050. U.S.
Environmental Protection Agency, Research Triangle Park, NC. December
1977.

[[Page 363]]

3. Mitchell, W.J., and M.R. Midgett. Adequacy of Sampling Trains and
Analytical Procedures Used for Fluoride. Atm. Environ. 10:865-872. 1976.

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.249

[[Page 364]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.250

Method 13B--Determination of Total Fluoride Emissions From Stationary
Sources (Specific Ion Electrode Method)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, and Method 13A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine.... 7782-41-4 Not determined.
------------------------------------------------------------------------

2.0 Summary

Gaseous and particulate F^- are withdrawn isokinetically
from the source and collected in water and on a filter. The total
F^- is then determined by the specific ion electrode method.

3.0 Definitions. [Reserved]

4.0 Interferences

Grease on sample-exposed surfaces may cause low F^-
results because of adsorption.

5.0 Safety

[[Page 365]]

user of this test method to establish appropriate safety and health
practices and to determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Corrosive Reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Sodium Hydroxide (NaOH). Causes severe damage to eye tissues
and to skin. Inhalation causes irritation to nose, throat, and lungs.
Reacts exothermically with limited amounts of water.
5.2.2 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 1 mg/m\3\ for 8 hours will cause lung damage or, in higher
concentrations, death. Provide ventilation to limit inhalation. Reacts
violently with metals and organics.

6.0 Equipment and Supplies

6.1 Sample Collection and Sample Recovery. Same as Method 13A,
Sections 6.1 and 6.2, respectively.
6.2 Sample Preparation and Analysis. The following items are
required for sample preparation and analysis:
6.2.1 Distillation Apparatus, Bunsen Burner, Electric Muffle
Furnace, Crucibles, Beakers, Volumetric Flasks, Erlenmeyer Flasks or
Plastic Bottles, Constant Temperature Bath, and Balance. Same as Method
13A, Sections 6.3.1 to 6.3.9, respectively.
6.2.2 Fluoride Ion Activity Sensing Electrode.
6.2.3 Reference Electrode. Single junction, sleeve type.
6.2.4 Electrometer. A pH meter with millivolt-scale capable of
0.1-mv resolution, or a specific ion meter made specifically
for specific ion electrode use.
6.2.5 Magnetic Stirrer and Tetrafluoroethylene (TFE) Fluorocarbon-
Coated Stirring Bars.
6.2.6 Beakers. Polyethylene, 100-ml.

7.0 Reagents and Standards

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 13A, Section 8.0.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

[[Page 366]]

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardizations

Note: Maintain a laboratory log of all calibrations.

10.1 Sampling Equipment. Same as Method 13A, Section 10.1.
10.2 Fluoride Electrode. Prepare fluoride standardizing solutions
by serial dilution of the 0.1 M fluoride standard solution. Pipet 10 ml
of 0.1 M fluoride standard solution into a 100-ml volumetric flask, and
make up to the mark with water for a 10^-\2\ M standard
solution. Use 10 ml of 10^-\2\ M solution to make a
10^-\3\ M solution in the same manner. Repeat the dilution
procedure, and make 10^-\4\ and 10^-\5\ M solutions.
10.2.1 Pipet 50 ml of each standard into a separate beaker. Add 50
ml of TISAB to each beaker. Place the electrode in the most dilute
standard solution. When a steady millivolt reading is obtained, plot the
value on the linear axis of semilog graph paper versus concentration on
the log axis. Plot the nominal value for concentration of the standard
on the log axis, (e.g., when 50 ml of 10^-\2\ M standard is
diluted with 50 ml of TISAB, the concentration is still designated
``10^-\2\ M'').
10.2.2 Between measurements, soak the fluoride sensing electrode in
water for 30 seconds, and then remove and blot dry. Analyze the
standards going from dilute to concentrated standards. A straight-line
calibration curve will be obtained, with nominal concentrations of
10^-\4\, 10^-\3\, 10^-\2\,
10^-\1\ fluoride molarity on the log axis plotted versus
electrode potential (in mv) on the linear scale. Some electrodes may be
slightly nonlinear between 10^-\5\ and 10^-\4\ M. If
this occurs, use additional standards between these two concentrations.
10.2.3 Calibrate the fluoride electrode daily, and check it hourly.
Prepare fresh fluoride standardizing solutions daily (10^-\2\
M or less). Store fluoride standardizing solutions in polyethylene or
polypropylene containers.
Note: Certain specific ion meters have been designed specifically
for fluoride electrode use and give a direct readout of fluoride ion
concentration. These meters may be used in lieu of calibration curves
for fluoride measurements over a narrow concentration ranges. Calibrate
the meter according to the manufacturer's instructions.

11.0 Analytical Procedures

11.1 Sample Loss Check, Sample Preparation, and Distillation. Same
as Method 13A, Sections 11.1 through 11.3, except that the Note
following Section 11.3.1 is not applicable.
11.2 Analysis.
11.2.1 Containers No. 1 and No. 2. Distill suitable aliquots from
Containers No. 1 and No. 2. Dilute the distillate in the volumetric
flasks to exactly 250 ml with water, and mix thoroughly. Pipet a 25-ml
aliquot from each of the distillate into separate beakers. Add an equal
volume of TISAB, and mix. The sample should be at the same temperature
as the calibration standards when measurements are made. If ambient
laboratory temperature fluctuates more than 2 deg.C from
the temperature at which the calibration standards were measured,
condition samples and standards in a constant-temperature bath before
measurement. Stir the sample with a magnetic stirrer during measurement
to minimize electrode response time. If the stirrer generates enough
heat to change solution temperature, place a piece of temperature
insulating material, such as cork, between the stirrer and the beaker.
Hold dilute samples (below 10^-\4\ M fluoride ion content) in
polyethylene beakers during measurement.
11.2.2 Insert the fluoride and reference electrodes into the
solution. When a steady millivolt reading is obtained, record it. This
may take several minutes. Determine concentration from the calibration
curve. Between electrode measurements, rinse the electrode with water.
11.2.3 Container No. 3 (Silica Gel). Same as in Method 13A, Section
11.4.2.

12.0 Data Analysis and Calculations

M = F^- concentration from calibration curve, molarity.

12.2 Average DGM Temperature and Average Orifice Pressure Drop, Dry
Gas Volume, Volume of Water Vapor and Moisture Content, Fluoride
Concentration in Stack Gas, and Isokinetic Variation. Same as Method
13A, Sections 12.2 to 12.4, 12.6, and 12.7, respectively.
12.3 Total Fluoride in Sample. Calculate the amount of
F^- in the sample using Equation 13B-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.251

Where:

K = 19 [(mgl)/(moleml)] (metric units)
= 0.292 [(grl)/(moleml)] (English units)

13.0 Method Performance

[[Page 367]]

sampling run. Fluoride concentrations encountered during the test ranged
from 0.1 to 1.4 mg F^-/m\3\.
13.1 Precision. The intra-laboratory and inter-laboratory standard
deviations, which include sampling and analysis errors, are 0.037 mg
F^-/m\3\ with 60 degrees of freedom and 0.056 mg
F^-/m\3\ with five degrees of freedom, respectively.
13.2 Bias. The collaborative test did not find any bias in the
analytical method.
13.3 Range. The range of this method is 0.02 to 2,000 g
F^-/ml; however, measurements of less than 0.1 g
F^-/ml require extra care.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 Compliance with ASTM D 3270-73T, 91, 95 ``Analysis for
Fluoride Content of the Atmosphere and Plant Tissues (Semiautomated
Method)'' is an acceptable alternative for the distillation and analysis
requirements specified in Sections 11.1 and 11.2 when applied to
suitable aliquots of Containers 1 and 2 samples.

17.0 References

Same as Method 13A, Section 16.0, References 1 and 2, with the
following addition:

1. MacLeod, Kathryn E., and Howard L. Crist. Comparison of the
SPADNS-Zirconium Lake and Specific Ion Electrode Methods of Fluoride
Determination in Stack Emission Samples. Analytical Chemistry. 45:1272-
1273. 1973.

18.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 14--Determination of Fluoride Emissions From Potroom Roof
Monitors for Primary Aluminum Plants

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5, Method 13A, and Method 13B.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total fluorides as Fluorine....... 7782-41-4 Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of fluoride emissions from roof monitors at primary aluminum reduction
plant potroom groups.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Gaseous and particulate fluoride roof monitor emissions are
drawn into a permanent sampling manifold through several large nozzles.
The sample is transported from the sampling manifold to ground level
through a duct. The fluoride content of the gas in the duct is
determined using either Method 13A or Method 13B. Effluent velocity and
volumetric flow rate are determined using anemometers located in the
roof monitor.

3.0 Definitions

Potroom means a building unit which houses a group of electrolytic
cells in which aluminum is produced.
Potroom group means an uncontrolled potroom, a potroom which is
controlled individually, or a group of potrooms or potroom segments
ducted to a common control system.
Roof monitor means that portion of the roof of a potroom where gases
not captured at the cell exit from the potroom.

4.0 Interferences

Same as Section 4.0 of either Method 13A or Method 13B, with the
addition of the following:
4.1 Magnetic Field Effects. Anemometer readings can be affected by
potroom magnetic field effects. Section 6.1 provides for minimization of
this interference through proper shielding or encasement of anemometer
components.

5.0 Safety

[[Page 368]]

5.2 Corrosive Reagents. Same as Section 5.2 of either Method 13A or
Method 13B.

6.0 Equipment and Supplies

Same as Section 6.0 of either Method 13A or Method 13B, as
applicable, with the addition of the following:
6.1 Velocity Measurement Apparatus.
6.1.1 Anemometer Specifications. Propeller anemometers, or
equivalent. Each anemometer shall meet the following specifications:
6.1.1.1 Its propeller shall be made of polystyrene, or similar
material of uniform density. To ensure uniformity of performance among
propellers, it is desirable that all propellers be made from the same
mold.
6.1.1.2 The propeller shall be properly balanced, to optimize
performance.
6.1.1.3 When the anemometer is mounted horizontally, its threshold
velocity shall not exceed 15 m/min (50 ft/min).
6.1.1.4 The measurement range of the anemometer shall extend to at
least 600 m/min (2,000 ft/min).
6.1.1.5 The anemometer shall be able to withstand prolonged
exposure to dusty and corrosive environments; one way of achieving this
is to purge the bearings of the anemometer continuously with filtered
air during operation.
6.1.1.6 All anemometer components shall be properly shielded or
encased, such that the performance of the anemometer is uninfluenced by
potroom magnetic field effects.
6.1.1.7 A known relationship shall exist between the electrical
output signal from the anemometer generator and the propeller shaft rpm
(see Section 10.2.1). Anemometers having other types of output signals
(e.g., optical) may be used, subject to the approval of the
Administrator. If other types of anemometers are used, there must be a
known relationship between output signal and shaft rpm (see Section
10.2.2).
6.1.1.8 Each anemometer shall be equipped with a suitable readout
system (see Section 6.1.3).
6.1.2 Anemometer Installation Requirements.
6.1.2.1 Single, Isolated Potroom. If the affected facility consists
of a single, isolated potroom (or potroom segment), install at least one
anemometer for every 85 m (280 ft) of roof monitor length. If the length
of the roof monitor divided by 85 m (280 ft) is not a whole number,
round the fraction to the nearest whole number to determine the number
of anemometers needed. For monitors that are less than 130 m (430 ft) in
length, use at least two anemometers. Divide the monitor cross-section
into as many equal areas as anemometers, and locate an anemometer at the
centroid of each equal area. See exception in Section 6.1.2.3.
6.1.2.2 Two or More Potrooms. If the affected facility consists of
two or more potrooms (or potroom segments) ducted to a common control
device, install anemometers in each potroom (or segment) that contains a
sampling manifold. Install at least one anemometer for every 85 m (280
ft) of roof monitor length of the potroom (or segment). If the potroom
(or segment) length divided by 85 m (280 ft) is not a whole number,
round the fraction to the nearest whole number to determine the number
of anemometers needed. If the potroom (or segment) length is less than
130 m (430 ft), use at least two anemometers. Divide the potroom (or
segment) monitor cross-section into as many equal areas as anemometers,
and locate an anemometer at the centroid of each equal area. See
exception in Section 6.1.2.3.
6.1.2.3 Placement of Anemometer at the Center of Manifold. At least
one anemometer shall be installed in the immediate vicinity (i.e.,
within 10 m (33 ft)) of the center of the manifold (see Section 6.2.1).
For its placement in relation to the width of the monitor, there are two
alternatives. The first is to make a velocity traverse of the width of
the roof monitor where an anemometer is to be placed and install the
anemometer at a point of average velocity along this traverse. The
traverse may be made with any suitable low velocity measuring device,
and shall be made during normal process operating conditions. The second
alternative is to install the anemometer half-way across the width of
the roof monitor. In this latter case, the velocity traverse need not be
conducted.
6.1.3 Recorders. Recorders that are equipped with suitable
auxiliary equipment (e.g., transducers) for converting the output signal
from each anemometer to a continuous recording of air flow velocity or
to an integrated measure of volumetric flowrate shall be used. A
suitable recorder is one that allows the output signal from the
propeller anemometer to be read to within 1 percent when the velocity is
between 100 and 120 m/min (330 and 390 ft/min). For the purpose of
recording velocity, ``continuous'' shall mean one readout per 15-minute
or shorter time interval. A constant amount of time shall elapse between
readings. Volumetric flow rate may be determined by an electrical count
of anemometer revolutions. The recorders or counters shall permit
identification of the velocities or flowrates measured by each
individual anemometer.
6.1.4 Pitot Tube. Standard-type pitot tube, as described in Section
6.7 of Method 2, and having a coefficient of 0.99 0.01.
6.1.5 Pitot Tube (Optional). Isolated, Type S pitot, as described
in Section 6.1 of Method 2, and having a known coefficient, determined
as outlined in Section 4.1 of Method 2.
6.1.6 Differential Pressure Gauge. Inclined manometer, or
equivalent, as described in Section 6.1.2 of Method 2.

[[Page 369]]

6.2 Roof Monitor Air Sampling System.
6.2.1 Manifold System and Ductwork. A minimum of one manifold
system shall be installed for each potroom group. The manifold system
and ductwork shall meet the following specifications:
6.2.1.1 The manifold system and connecting duct shall be
permanently installed to draw an air sample from the roof monitor to
ground level. A typical installation of a duct for drawing a sample from
a roof monitor to ground level is shown in Figure 14-1 in Section 17.0.
A plan of a manifold system that is located in a roof monitor is shown
in Figure 14-2. These drawings represent a typical installation for a
generalized roof monitor. The dimensions on these figures may be altered
slightly to make the manifold system fit into a particular roof monitor,
but the general configuration shall be followed.
6.2.1.2 There shall be eight nozzles, each having a diameter of
0.40 to 0.50 m.
6.2.1.3 The length of the manifold system from the first nozzle to
the eighth shall be 35 m (115 ft) or eight percent of the length of the
potroom (or potroom segment) roof monitor, whichever is greater.
Deviation from this requirement is subject to the approval of the
Administrator.
6.2.1.4 The duct leading from the roof monitor manifold system
shall be round with a diameter of 0.30 to 0.40 m (1.0 to 1.3 ft). All
connections in the ductwork shall be leak-free.
6.2.1.5 As shown in Figure 14-2, each of the sample legs of the
manifold shall have a device, such as a blast gate or valve, to enable
adjustment of the flow into each sample nozzle.
6.2.1.6 The manifold system shall be located in the immediate
vicinity of one of the propeller anemometers (see Section 8.1.1.4) and
as close as possible to the midsection of the potroom (or potroom
segment). Avoid locating the manifold system near the end of a potroom
or in a section where the aluminum reduction pot arrangement is not
typical of the rest of the potroom (or potroom segment). The sample
nozzles shall be centered in the throat of the roof monitor (see Figure
14-1).
6.2.1.7 All sample-exposed surfaces within the nozzles, manifold,
and sample duct shall be constructed with 316 stainless steel.
Alternatively, aluminum may be used if a new ductwork is conditioned
with fluoride-laden roof monitor air for a period of six weeks before
initial testing. Other materials of construction may be used if it is
demonstrated through comparative testing, to the satisfaction of the
Administrator, that there is no loss of fluorides in the system.
6.2.1.8 Two sample ports shall be located in a vertical section of
the duct between the roof monitor and the exhaust fan (see Section
6.2.2). The sample ports shall be at least 10 duct diameters downstream
and three diameters upstream from any flow disturbance such as a bend or
contraction. The two sample ports shall be situated 90 deg. apart. One
of the sample ports shall be situated so that the duct can be traversed
in the plane of the nearest upstream duct bend.
6.2.2 Exhaust Fan. An industrial fan or blower shall be attached to
the sample duct at ground level (see Figure 14-1). This exhaust fan
shall have a capacity such that a large enough volume of air can be
pulled through the ductwork to maintain an isokinetic sampling rate in
all the sample nozzles for all flow rates normally encountered in the
roof monitor. The exhaust fan volumetric flow rate shall be adjustable
so that the roof monitor gases can be drawn isokinetically into the
sample nozzles. This control of flow may be achieved by a damper on the
inlet to the exhauster or by any other workable method.
6.3 Temperature Measurement Apparatus. To monitor and record the
temperature of the roof monitor effluent gas, and consisting of the
following:
6.3.1 Temperature Sensor. A temperature sensor shall be installed
in the roof monitor near the sample duct. The temperature sensor shall
conform to the specifications outlined in Method 2, Section 6.3.
6.3.2 Signal Transducer. Transducer, to change the temperature
sensor voltage output to a temperature readout.
6.3.3 Thermocouple Wire. To reach from roof monitor to signal
transducer and recorder.
6.3.4 Recorder. Suitable recorder to monitor the output from the
thermocouple signal transducer.

7.0 Reagents and Standards

Same as Section 7.0 of either Method 13A or Method 13B, as
applicable.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Roof Monitor Velocity Determination.
8.1.1 Velocity Estimate(s) for Setting Isokinetic Flow. To assist
in setting isokinetic flow in the manifold sample nozzles, the
anticipated average velocity in the section of the roof monitor
containing the sampling manifold shall be estimated before each test
run. Any convenient means to make this estimate may be used (e.g., the
velocity indicated by the anemometer in the section of the roof monitor
containing the sampling manifold may be continuously monitored during
the 24-hour period before the test run). If there is question as to
whether a single estimate of average velocity is adequate for an entire
test run (e.g., if velocities are anticipated to be significantly
different during different potroom operations), the test run may be
divided into two

[[Page 370]]

or more ``sub-runs,'' and a different estimated average velocity may be
used for each sub-run (see Section 8.4.2).
8.1.2 Velocity Determination During a Test Run. During the actual
test run, record the velocity or volumetric flowrate readings of each
propeller anemometer in the roof monitor. Readings shall be taken from
each anemometer at equal time intervals of 15 minutes or less (or
continuously).
8.2 Temperature Recording. Record the temperature of the roof
monitor effluent gases at least once every 2 hours during the test run.
8.3 Pretest Ductwork Conditioning. During the 24-hour period
immediately preceding the test run, turn on the exhaust fan, and draw
roof monitor air through the manifold system and ductwork. Adjust the
fan to draw a volumetric flow through the duct such that the velocity of
gas entering the manifold nozzles approximates the average velocity of
the air exiting the roof monitor in the vicinity of the sampling
manifold.
8.4 Manifold Isokinetic Sample Rate Adjustment(s).
8.4.1 Initial Adjustment. Before the test run (or first sub-run, if
applicable; see Sections 8.1.1 and 8.4.2), adjust the fan such that air
enters the manifold sample nozzles at a velocity equal to the
appropriate estimated average velocity determined under Section 8.1.1.
Use Equation 14-1 (Section 12.2.2) to determine the correct stream
velocity needed in the duct at the sampling location, in order for
sample gas to be drawn isokinetically into the manifold nozzles. Next,
verify that the correct stream velocity has been achieved, by performing
a pitot tube traverse of the sample duct (using either a standard or
Type S pitot tube); use the procedure outlined in Method 2.
8.4.2 Adjustments During Run. If the test run is divided into two
or more ``sub-runs'' (see Section 8.1.1), additional isokinetic rate
adjustment(s) may become necessary during the run. Any such adjustment
shall be made just before the start of a sub-run, using the procedure
outlined in Section 8.4.1 above.

Note: Isokinetic rate adjustments are not permissible during a sub-
run.

8.5 Pretest Preparation, Preliminary Determinations, Preparation of
Sampling Train, Leak-Check Procedures, Sampling Train Operation, and
Sample Recovery. Same as Method 13A, Sections 8.1 through 8.6, with the
exception of the following:
8.5.1 A single train shall be used for the entire sampling run.
Alternatively, if two or more sub-runs are performed, a separate train
may be used for each sub-run; note, however, that if this option is
chosen, the area of the sampling nozzle shall be the same (2
percent) for each train. If the test run is divided into sub-runs, a
complete traverse of the duct shall be performed during each sub-run.
8.5.2 Time Per Run. Each test run shall last 8 hours or more; if
more than one run is to be performed, all runs shall be of approximately
the same (10 percent) length. If questions exist as to the
representativeness of an 8-hour test, a longer period should be
selected. Conduct each run during a period when all normal operations
are performed underneath the sampling manifold. For most recently-
constructed plants, 24 hours are required for all potroom operations and
events to occur in the area beneath the sampling manifold. During the
test period, all pots in the potroom group shall be operated such that
emissions are representative of normal operating conditions in the
potroom group.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality Control
Section Measure Effect
------------------------------------------------------------------------
8.0, 10.0..................... Sampling Ensure accurate
equipment leak- measurement of gas
check and flow rate in duct
calibration. and of sample
volume.
10.3, 10.4.................... Initial and Ensure accurate and
periodic precise measurement
performance of roof monitor
checks of roof effluent gas
monitor effluent temperature and flow
gas rate.
characterization
apparatus.
11.0.......................... Interference/ Minimize negative
recovery effects of used
efficiency check acid.
during
distillation.
------------------------------------------------------------------------

9.2 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Same as Section 10.0 of either Method 13A or Method 13B, as
applicable, with the addition of the following:
10.1 Manifold Intake Nozzles. The manifold intake nozzles shall be
calibrated when the manifold system is installed or, alternatively, the
manifold may be preassembled and the nozzles calibrated on the ground
prior to installation. The following procedures shall be observed:
10.1.1 Adjust the exhaust fan to draw a volumetric flow rate (refer
to Equation 14-1) such that the entrance velocity into each manifold
nozzle approximates the average effluent velocity in the roof monitor.
10.1.2 Measure the velocity of the air entering each nozzle by
inserting a standard pitot tube into a 2.5 cm or less diameter hole

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(see Figure 14-2) located in the manifold between each blast gate (or
valve) and nozzle. Note that a standard pitot tube is used, rather than
a type S, to eliminate possible velocity measurement errors due to
cross-section blockage in the small (0.13 m diameter) manifold leg
ducts. The pitot tube tip shall be positioned at the center of each
manifold leg duct. Take care to ensure that there is no leakage around
the pitot tube, which could affect the indicated velocity in the
manifold leg.
10.1.3 If the velocity of air being drawn into each nozzle is not
the same, open or close each blast gate (or valve) until the velocity in
each nozzle is the same. Fasten each blast gate (or valve) so that it
will remain in position, and close the pitot port holes.
10.2 Initial Calibration of Propeller Anemometers.
10.2.1 Anemometers that meet the specifications outlined in Section
6.1.1 need not be calibrated, provided that a reference performance
curve relating anemometer signal output to air velocity (covering the
velocity range of interest) is available from the manufacturer. If a
reference performance curve is not available from the manufacturer, such
a curve shall be generated.
For the purpose of this method, a ``reference'' performance curve is
defined as one that has been derived from primary standard calibration
data, with the anemometer mounted vertically. ``Primary standard'' data
are obtainable by: (a) direct calibration of one or more of the
anemometers by the National Institute of Standards and Technology
(NIST); (b) NIST-traceable calibration; or (c) Calibration by direct
measurement of fundamental parameters such as length and time (e.g., by
moving the anemometers through still air at measured rates of speed, and
recording the output signals).
10.2.2 Anemometers having output signals other than electrical
(e.g., optical) may be used, subject to the approval of the
Administrator. If other types of anemometers are used, a reference
performance curve shall be generated, using procedures subject to the
approval of the Administrator.
10.2.3 The reference performance curve shall be derived from at
least the following three points: 60 15, 900
100, and 1800 100 rpm.
10.3 Initial Performance Checks. Conduct these checks within 60
days before the first performance test.
10.3.1 Anemometers. A performance-check shall be conducted as
outlined in Sections 10.3.1.1 through 10.3.1.3. Alternatively, any other
suitable method that takes into account the signal output, propeller
condition, and threshold velocity of the anemometer may be used, subject
to the approval of the Administrator.
10.3.1.1 Check the signal output of the anemometer by using an
accurate rpm generator (see Figure 14-3) or synchronous motors to spin
the propeller shaft at each of the three rpm settings described in
Section 10.2.3, and measuring the output signal at each setting. If, at
each setting, the output signal is within 5 percent of the
manufacturer's value, the anemometer can be used. If the anemometer
performance is unsatisfactory, the anemometer shall either be replaced
or repaired.
10.3.1.2 Check the propeller condition, by visually inspecting the
propeller, making note of any significant damage or warpage; damaged or
deformed propellers shall be replaced.
10.3.1.3 Check the anemometer threshold velocity as follows: With
the anemometer mounted as shown in Figure 14-4(A), fasten a known weight
(a straight-pin will suffice) to the anemometer propeller at a fixed
distance from the center of the propeller shaft. This will generate a
known torque; for example, a 0.1-g weight, placed 10 cm from the center
of the shaft, will generate a torque of 1.0 g-cm. If the known torque
causes the propeller to rotate downward, approximately 90 deg. [see
Figure 14-4(B)], then the known torque is greater than or equal to the
starting torque; if the propeller fails to rotate approximately 90 deg.,
the known torque is less than the starting torque. By trying different
combinations of weight and distance, the starting torque of a particular
anemometer can be satisfactorily estimated. Once an estimate of the
starting torque has been obtained, the threshold velocity of the
anemometer (for horizontal mounting) can be estimated from a graph such
as Figure 14-5 (obtained from the manufacturer). If the horizontal
threshold velocity is acceptable [15 m/min (50 ft/min), when this
technique is used], the anemometer can be used. If the threshold
velocity of an anemometer is found to be unacceptably high, the
anemometer shall either be replaced or repaired.
10.3.2 Recorders and Counters. Check the calibration of each
recorder and counter (see Section 6.1.2) at a minimum of three points,
approximately spanning the expected range of velocities. Use the
calibration procedures recommended by the manufacturer, or other
suitable procedures (subject to the approval of the Administrator). If a
recorder or counter is found to be out of calibration by an average
amount greater than 5 percent for the three calibration points, replace
or repair the system; otherwise, the system can be used.
10.3.3 Temperature Measurement Apparatus. Check the calibration of
the Temperature Measurement Apparatus, using the procedures outlined in
Section 10.3 of Method 2, at temperatures of 0, 100, and 150 deg.C (32,
212, and 302 deg.F). If the calibration is off by more than 5 deg.C (9
deg.F) at any of the temperatures,

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repair or replace the apparatus; otherwise, the apparatus can be used.
10.4 Periodic Performance Checks. Repeat the procedures outlined in
Section 10.3 no more than 12 months after the initial performance
checks. If the above systems pass the performance checks (i.e., if no
repair or replacement of any component is necessary), continue with the
performance checks on a 12-month interval basis. However, if any of the
above systems fail the performance checks, repair or replace the
system(s) that failed, and conduct the periodic performance checks on a
3-month interval basis, until sufficient information (to the
satisfaction of the Administrator) is obtained to establish a modified
performance check schedule and calculation procedure.
Note: If any of the above systems fails the 12-month periodic
performance checks, the data for the past year need not be recalculated.

11.0 Analytical Procedures

Same as Section 11.0 of either Method 13A or Method 13B.

12.0 Data Analysis and Calculations

Same as Section 12.0 of either Method 13A or Method 13B, as
applicable, with the following additions and exceptions:
12.1 Nomenclature.

A = Roof monitor open area, m\2\ (ft\2\).
Bws = Water vapor in the gas stream, portion by volume.
Cs = Average fluoride concentration in roof monitor air, mg
F/dscm (gr/dscf).
Dd = Diameter of duct at sampling location, m (ft).
Dn = Diameter of a roof monitor manifold nozzle, m (ft).
F = Emission Rate multiplication factor, dimensionless.
Ft = Total fluoride mass collected during a particular sub-
run (from Equation 13A-1 of Method 13A or Equation 13B-1 of
Method 13B), mg F^- (gr F^-).
Md = Mole fraction of dry gas, dimensionless.
Prm = Pressure in the roof monitor; equal to barometric
pressure for this application.
Qsd = Average volumetric flow from roof monitor at standard
conditions on a dry basis, m\3\/min.
Trm = Average roof monitor temperature (from Section 8.2),
deg.C ( deg.F).
Vd = Desired velocity in duct at sampling location, m/sec.
Vm = Anticipated average velocity (from Section 8.1.1) in
sampling duct, m/sec.
Vmt = Arithmetic mean roof monitor effluent gas velocity, m/
sec.
Vs = Actual average velocity in the sampling duct (from
Equation 2-9 of Method 2 and data obtained from Method 13A or
13B), m/sec.

12.2 Isokinetic Sampling Check.
12.2.1 Calculate the arithmetic mean of the roof monitor effluent
gas velocity readings (vm) as measured by the anemometer in
the section of the roof monitor containing the sampling manifold. If two
or more sub-runs have been performed, the average velocity for each sub-
run may be calculated separately.
12.2.2 Calculate the expected average velocity (vd) in
the duct, corresponding to each value of vm obtained under
Section 12.2.1, using Equation 14-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.252

Where:

8 = number of required manifold nozzles.
60 = sec/min.

12.2.3 Calculate the actual average velocity (vs) in the
sampling duct for each run or sub-run according to Equation 2-9 of
Method 2, using data obtained during sampling (Section 8.0 of Method
13A).
12.2.4 Express each vs value from Section 12.2.3 as a percentage of
the corresponding vd value from Section 12.2.2.
12.2.4.1 If vs is less than or equal to 120 percent of
vd, the results are acceptable (note that in cases where the
above calculations have been performed for each sub-run, the results are
acceptable if the average percentage for all sub-runs is less than or
equal to 120 percent).
12.2.4.2 If vs is more than 120 percent of
vd, multiply the reported emission rate by the following
factor:
[GRAPHIC] [TIFF OMITTED] TR17OC00.253

12.3 Average Velocity of Roof Monitor Effluent Gas. Calculate the
arithmetic mean roof monitor effluent gas velocity (vmt)
using all the velocity or volumetric flow readings from Section 8.1.2.
12.4 Average Temperature of Roof Monitor Effluent Gas. Calculate
the arithmetic mean roof monitor effluent gas temperature
(Tm) using all the temperature readings recorded in Section
8.2.
12.5 Concentration of Fluorides in Roof Monitor Effluent Gas.
12.5.1 If a single sampling train was used throughout the run,
calculate the average fluoride concentration for the roof monitor using
Equation 13A-2 of Method 13A.
12.5.2 If two or more sampling trains were used (i.e., one per sub-
run), calculate the average fluoride concentration for the run using
Equation 14-3:

[[Page 373]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.254

Where:

n = Total number of sub-runs.
12.6 Mole Fraction of Dry Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.255

12.7 Average Volumetric Flow Rate of Roof Monitor Effluent Gas.
Calculate the arithmetic mean volumetric flow rate of the roof monitor
effluent gases using Equation 14-5.
[GRAPHIC] [TIFF OMITTED] TR17OC00.256

Where:

K1 = 0.3858 K/mm Hg for metric units,
= 17.64 deg.R/in. Hg for English units.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Section 16.0 of either Method 13A or Method 13B, as
applicable, with the addition of the following:

1. Shigehara, R.T. A Guideline for Evaluating Compliance Test
Results (Isokinetic Sampling Rate Criterion). U.S. Environmental
Protection Agency, Emission Measurement Branch, Research Triangle Park,
NC. August 1977.

[[Page 374]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.257

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[GRAPHIC] [TIFF OMITTED] TR17OC00.258

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[GRAPHIC] [TIFF OMITTED] TR17OC00.259

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[GRAPHIC] [TIFF OMITTED] TR17OC00.260

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[GRAPHIC] [TIFF OMITTED] TR17OC00.261

Method 14A--Determination of Total Fluoride Emissions from Selected
Sources at Primary Aluminum Production Facilities

[[Page 379]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total fluorides................. None assigned..... Not determined.
Includes hydrogen fluoride...... 007664-39-3....... Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total fluorides (TF) emissions from sources specified in the
applicable regulation. This method was developed by consensus with the
Aluminum Association and the U.S. Environmental Protection Agency (EPA).
2.0 Summary of Method
2.1 Total fluorides, in the form of solid and gaseous fluorides,
are withdrawn from the ascending air stream inside of an aluminum
reduction potroom and, prior to exiting the potroom roof monitor, into a
specific cassette arrangement. The cassettes are connected by tubing to
flowmeters and a manifold system that allows for the equal distribution
of volume pulled through each cassette, and finally to a dry gas meter.
The cassettes have a specific internal arrangement of one unaltered
cellulose filter and support pad in the first section of the cassette
for solid fluoride retention and two cellulose filters with support pads
that are impregnated with sodium formate for the chemical absorption of
gaseous fluorides in the following two sections of the cassette. A
minimum of eight cassettes shall be used for a potline and shall be
strategically located at equal intervals across the potroom roof so as
to encompass a minimum of 8 percent of the total length of the potroom.
A greater number of cassettes may be used should the regulated facility
choose to do so. The mass flow rate of pollutants is determined with
anemometers and temperature sensing devices located immediately below
the opening of the roof monitor and spaced evenly within the cassette
group.
3.0 Definitions
3.1 Cassette. A segmented, styrene acrylonitrile cassette
configuration with three separate segments and a base, for the purpose
of this method, to capture and retain fluoride from potroom gases.
3.2 Cassette arrangement. The cassettes, tubing, manifold system,
flowmeters, dry gas meter, and any other related equipment associated
with the actual extraction of the sample gas stream.
3.3 Cassette group. That section of the potroom roof monitor where
a distinct group of cassettes is located.
3.4 Potline. A single, discrete group of electrolytic reduction
cells electrically connected in series, in which alumina is reduced to
form aluminum.
3.5 Potroom. A building unit that houses a group of electrolytic
reduction cells in which aluminum is produced.
3.6 Potroom group. An uncontrolled potroom, a potroom that is
controlled individually, or a group of potrooms or potroom segments
ducted to a common primary control system.
3.7 Primary control system. The equipment used to capture the gases
and particulate matter generated during the reduction process and the
emission control device(s) used to remove pollutants prior to discharge
of the cleaned gas to the atmosphere.
3.8 Roof monitor. That portion of the roof of a potroom building
where gases, not captured at the cell, exit from the potroom.
3.9 Total fluorides (TF). Elemental fluorine and all fluoride
compounds as measured by Methods 13A or 13B of this appendix or by an
approved alternative method.
4.0 Interferences and Known Limitations
4.1 There are two principal categories of limitations that must be
addressed when using this method. The first category is sampling bias
and the second is analytical bias. Biases in sampling can occur when
there is an insufficient number of cassettes located along the roof
monitor of a potroom or if the distribution of those cassettes is
spatially unequal. Known sampling biases also can occur when there are
leaks within the cassette arrangement and if anemometers and temperature
devices are not providing accurate data. Applicable instruments must be
properly calibrated to avoid sampling bias. Analytical biases can occur
when instrumentation is not calibrated or fails calibration and the
instrument is used out of proper calibration. Additionally, biases can
occur in the laboratory if fusion crucibles retain residual fluorides
over lengthy periods of use. This condition could result in falsely
elevated fluoride values. Maintaining a clean work environment in the
laboratory is crucial to producing accurate values.
4.2 Biases during sampling can be avoided by properly spacing the
appropriate number of cassettes along the roof monitor, conducting leak
checks of the cassette arrangement, calibrating the dry gas meter every
30 days, verifying the accuracy of individual flowmeters (so that there
is no more than 5 percent difference in the volume pulled between any
two flowmeters), and calibrating or replacing anemometers and
temperature sensing devices as necessary to maintain true data
generation.
4.3 Analytical biases can be avoided by calibrating instruments
according to the manufacturer's specifications prior to conducting any
analyses, by performing internal and external audits of up to 10 percent
of all samples analyzed, and by rotating individual crucibles as the
``blank'' crucible to detect any potential residual fluoride carry-over
to samples. Should any contamination be discovered in the blank
crucible, the crucible shall be thoroughly cleaned to remove any
detected residual fluorides and a ``blank'' analysis conducted again to
evaluate the effectiveness of the cleaning. The crucible

[[Page 380]]

shall remain in service as long as no detectable residual fluorides are
present.
5.0 Safety
5.1 This method may involve the handling of hazardous materials in
the analytical phase. This method does not purport to address all of the
potential safety hazards associated with its use. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Corrosive reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water for at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.3 Sodium Hydroxide (NaOH). Causes severe damage to eyes and skin.
Inhalation causes irritation to nose, throat, and lungs. Reacts
exothermically with limited amounts of water.
5.4 Perchloric Acid (HClO4). Corrosive to eyes, skin,
nose, and throat. Provide ventilation to limit exposure. Very strong
oxidizer. Keep separate from water and oxidizable materials to prevent
vigorous evolution of heat, spontaneous combustion, or explosion. Heat
solutions containing HClO4 only in hoods specifically designed for
HClO4.
6.0 Equipment and Supplies
6.1 Sampling.
6.1.1 Cassette arrangement. The cassette itself is a three-piece,
styrene acrylonitrile cassette unit (a Gelman Sciences product), 37
millimeter (mm), with plastic connectors. In the first section (the
intake section), an untreated Gelman Sciences 37 mm, 0.8 micrometer
(m) DM-800 metricel membrane filter and cellulose support pad,
or equivalent, is situated. In the second and third segments of the
cassette there is placed one each of Gelman Sciences 37 mm, 5 m
GLA-5000 low-ash PVC filter with a cellulose support pad or equivalent
product. Each of these two filters and support pads shall have been
immersed in a solution of 10 percent sodium formate (volume/volume in an
ethyl alcohol solution). The impregnated pads shall be placed in the
cassette segments while still wet and heated at 50 deg.C (122 deg.F)
until the pad is completely dry. It is important to check for a proper
fit of the filter and support pad to the cassette segment to ensure that
there are no areas where gases could bypass the filter. Once all of the
cassette segments have been prepared, the cassette shall be assembled
and a plastic plug shall be inserted into the exhaust hole of the
cassette. Prior to placing the cassette into service, the space between
each segment shall be taped with an appropriately durable tape to
prevent the infiltration of gases through the points of connection, and
an aluminum nozzle shall be inserted into the intake hole of the
cassette. The aluminum nozzle shall have a short section of tubing
placed over the opening of the nozzle, with the tubing plugged to
prevent dust from entering the nozzle and to prepare the nozzle for the
cassette arrangement leak check. An alternate nozzle type can be used if
historical results or scientific demonstration of applicability can be
shown.
6.1.2 Anemometers and temperature sensing devices. To calculate the
mass flow rate of TF from the roof monitor under standard conditions,
anemometers that meet the specifications in section 2.1.1 in Method 14
of this appendix or an equivalent device yielding equivalent information
shall be used. A recording mechanism capable of accurately recording the
exit gas temperature at least every 2 hours shall be used.
6.1.3 Barometer. To correct the volumetric flow from the potline
roof monitor to standard conditions, a mercury (Hg), aneroid, or other
barometer capable of measuring atmospheric pressure to within 2.5 mm
[0.1 inch (in)] Hg shall be used.

Note: The barometric reading may be obtained from a nearby National
Weather Service Station. In this case, the station value (which is
absolute barometric pressure) shall be requested and an adjustment for
elevation differences between the weather station and the sampling point
shall be made at a rate of minus 2.5 mm (0.1 in) Hg per 30 meters (m)
[100 feet (ft)] elevation increase or plus 2.5 mm (0.1 in) Hg per 30 m
(100 ft) elevation decrease.
6.2 Sample recovery.
6.2.1 Hot plate.
6.2.2 Muffle furnace.
6.2.3 Nickel crucible.
6.2.4 Stirring rod. Teflon'.
6.2.5 Volumetric flask. 50-milliliter (ml).
6.2.6 Plastic vial. 50-ml.
6.3 Analysis.
6.3.1 Primary analytical method. An automated analyzer having the
following components or equivalent: a multichannel proportioning pump,
multiposition sampler, voltage stabilizer, colorimeter, instrument
recording device, microdistillation apparatus, flexible Teflon
heating bath, vacuum pump, pulse suppressers and an air flow system.
6.3.2 Secondary analytical method. Specific Ion Electrode (SIE).
7.0 Reagents and Standards
7.1 Water. Deionized distilled to conform to ASTM Specification D
1193-77, Type 3 (incorporated by reference in Sec. 60.17(a)(22) of this
part). The KMnO4 test for oxidizable organic matter may be
omitted when high concentrations of organic matter are not expected to
be present.
7.2 Calcium oxide.
7.3 Sodium hydroxide (NaOH). Pellets.

[[Page 381]]

7.4 Perchloric acid (HClO4). Mix 1:1 with water.
Sulfuric acid (H2SO4) may be used in place of
HClO4.
7.5 Audit samples. The audit samples discussed in section 9.1 shall
be prepared from reagent grade, water soluble stock reagents, or
purchased as an aqueous solution from a commercial supplier. If the
audit stock solution is purchased from a commercial supplier, the
standard solution must be accompanied by a certificate of analysis or an
equivalent proof of fluoride concentration.
8.0 Sample Collection and Analysis
8.1 Preparing cassette arrangement for sampling. The cassettes are
initially connected to flexible tubing. The tubing is connected to
flowmeters and a manifold system. The manifold system is connected to a
dry gas meter (Research Appliance Company model 201009 or equivalent).
The length of tubing is managed by pneumatically or electrically
operated hoists located in the roof monitor, and the travel of the
tubing is controlled by encasing the tubing in aluminum conduit. The
tubing is lowered for cassette insertion by operating a control box at
floor level. Once the cassette has been securely inserted into the
tubing and the leak check performed, the tubing and cassette are raised
to the roof monitor level using the floor level control box.
Arrangements similar to the one described are acceptable if the
scientific sample collection principles are followed.
8.2 Test run sampling period. A test run shall comprise a minimum
of a 24-hour sampling event encompassing at least eight cassettes per
potline (or four cassettes per potroom group). Monthly compliance shall
be based on three test runs during the month. Test runs of greater than
24 hours are allowed; however, three such runs shall be conducted during
the month.
8.3 Leak-check procedures.
8.3.1 Pretest leak check. A pretest leak-check is recommended;
however, it is not required. To perform a pretest leak-check after the
cassettes have been inserted into the tubing, isolate the cassette to be
leak-checked by turning the valves on the manifold to stop all flows to
the other sampling points connected to the manifold and meter. The
cassette, with the plugged tubing section securing the intake of the
nozzle, is subjected to the highest vacuum expected during the run. If
no leaks are detected, the tubing plug can be briefly removed as the dry
gas meter is rapidly turned off.
8.3.2 Post-test leak check. A leak check is required at the
conclusion of each test run for each cassette. The leak check shall be
performed in accordance with the procedure outlined in section 8.3.1 of
this method except that it shall be performed at a vacuum greater than
the maximum vacuum reached during the test run. If the leakage rate is
found to be no greater than 4 percent of the average sampling rate, the
results are acceptable. If the leakage rate is greater than 4 percent of
the average sampling rate, either record the leakage rate and correct
the sampling volume as discussed in section 12.4 of this method or void
the test run if the minimum number of cassettes were used. If the number
of cassettes used was greater than the minimum required, discard the
leaking cassette and use the remaining cassettes for the emission
determination.
8.3.3 Anemometers and temperature sensing device placement. Install
the recording mechanism to record the exit gas temperature. Anemometers
shall be installed as required in section 6.1.2 of Method 14 of this
appendix, except replace the word ``manifold'' with ``cassette group''
in section 6.1.2.3. These two different instruments shall be located
near each other along the roof monitor. See conceptual configurations in
Figures 14A-1, 14A-2, and 14A-3 of this method. Fewer temperature
devices than anemometers may be used if at least one temperature device
is located within the span of the cassette group. Other anemometer
location siting scenarios may be acceptable as long as the exit velocity
of the roof monitor gases is representative of the entire section of the
potline being sampled.
8.4 Sampling. The actual sample run shall begin with the removal of
the tubing and plug from the cassette nozzle. Each cassette is then
raised to the roof monitor area, the dry gas meter is turned on, and the
flowmeters are set to the calibration point, which allows an equal
volume of sampled gas to enter each cassette. The dry gas meter shall be
set to a range suitable for the specific potroom type being sampled that
will yield valid data known from previous experience or a range
determined by the use of the calculation in section 12 of this method.
Parameters related to the test run that shall be recorded, either during
the test run or after the test run if recording devices are used,
include: anemometer data, roof monitor exit gas temperature, dry gas
meter temperature, dry gas meter volume, and barometric pressure. At the
conclusion of the test run, the cassettes shall be lowered, the dry gas
meter turned off, and the volume registered on the dry gas meter
recorded. The post-test leak check procedures described in section 8.3.2
of this method shall be performed. All data relevant to the test shall
be recorded on a field data sheet and maintained on file.
8.5 Sample recovery.
8.5.1 The cassettes shall be brought to the laboratory with the
intake nozzle contents protected with the section of plugged tubing
previously described. The exterior of cassettes shall carefully be wiped
free of any dust or debris, making sure that any falling dust or debris
does not present a potential laboratory contamination problem.

[[Page 382]]

8.5.2 Carefully remove all tape from the cassettes and remove the
initial filter, support pad, and all loose solids from the first
(intake) section of the cassette. Fold the filter and support pad
several times and, along with all loose solids removed from the interior
of the first section of the cassette, place them into a nickel crucible.
Using water, wash the interior of the nozzle into the same nickel
crucible. Add 0.1 gram (g) [0.1 milligram (mg)] of calcium
oxide and a sufficient amount of water to make a loose slurry. Mix the
contents of the crucible thoroughly with a Teflon'' stirring rod. After
rinsing any adhering residue from the stirring rod back into the
crucible, place the crucible on a hot plate or in a muffle furnace until
all liquid is evaporated and allow the mixture to gradually char for 1
hour.
8.5.3 Transfer the crucible to a cold muffle furnace and ash at 600
deg.C (1,112 deg.F). Remove the crucible after the ashing phase and,
after the crucible cools, add 3.0 g (0.1 g) of NaOH pellets.
Place this mixture in a muffle furnace at 600 deg.C (1,112 deg.F) for
3 minutes. Remove the crucible and roll the melt so as to reach all of
the ash with the molten NaOH. Let the melt cool to room temperature. Add
10 to 15 ml of water to the crucible and place it on a hot plate at a
low temperature setting until the melt is soft or suspended. Transfer
the contents of the crucible to a 50-ml volumetric flask. Rinse the
crucible with 20 ml of 1:1 perchloric acid or 20 ml of 1:1 sulfuric acid
in two (2) 10 ml portions. Pour the acid rinse slowly into the
volumetric flask and swirl the flask after each addition. Cool to room
temperature. The product of this procedure is particulate fluorides.
8.5.4 Gaseous fluorides can be isolated for analysis by folding
the gaseous fluoride filters and support pads to approximately \1/4\ of
their original size and placing them in a 50-ml plastic vial. To the
vial add exactly 10 ml of water and leach the sample for a minimum of 1
hour. The leachate from this process yields the gaseous fluorides for
analysis.
9.0 Quality Control
9.1 Laboratory auditing. Laboratory audits of specific and known
concentrations of fluoride shall be submitted to the laboratory with
each group of samples submitted for analysis. An auditor shall prepare
and present the audit samples as a ``blind'' evaluation of laboratory
performance with each group of samples submitted to the laboratory. The
audits shall be prepared to represent concentrations of fluoride that
could be expected to be in the low, medium and high range of actual
results. Average recoveries of all three audits must equal 90 to 110
percent for acceptable results; otherwise, the laboratory must
investigate procedures and instruments for potential problems.

Note: The analytical procedure allows for the analysis of individual
or combined filters and pads from the cassettes provided that equal
volumes (10 percent) are sampled through each cassette.
10.0 Calibrations
10.1 Equipment evaluations. To ensure the integrity of this method,
periodic calibrations and equipment replacements are necessary.
10.1.1 Metering system. At 30-day intervals the metering system
shall be calibrated. Connect the metering system inlet to the outlet of
a wet test meter that is accurate to 1 percent. Refer to Figure 5-4 of
Method 5 of this appendix. The wet-test meter shall have a capacity of
30 liters/revolution [1 cubic foot (ft\3\)/revolution]. A spirometer of
400 liters (14 ft\3\) or more capacity, or equivalent, may be used for
calibration; however, a wet-test meter is usually more practical. The
wet-test meter shall be periodically tested with a spirometer or a
liquid displacement meter to ensure the accuracy. Spirometers or wet-
test meters of other sizes may be used, provided that the specified
accuracies of the procedure are maintained. Run the metering system pump
for about 15 min. with the orifice manometer indicating a median reading
as expected in field use to allow the pump to warm up and to thoroughly
wet the interior of the wet-test meter. Then, at each of a minimum of
three orifice manometer settings, pass an exact quantity of gas through
the wet-test meter and record the volume indicated by the dry gas meter.
Also record the barometric pressure, the temperatures of the wet test
meter, the inlet temperatures of the dry gas meter, and the temperatures
of the outlet of the dry gas meter. Record all calibration data on a
form similar to the one shown in Figure 5-5 of Method 5 of this appendix
and calculate Y, the dry gas meter calibration factor, and H@,
the orifice calibration factor at each orifice setting. Allowable
tolerances for Y and H@ are given in Figure 5-6 of Method 5 of
this appendix.
10.1.2 Estimating volumes for initial test runs. For a facility's
initial test runs, the regulated facility must have a target or desired
volume of gases to be sampled and a target range of volumes to use
during the calibration of the dry gas meter. Use Equations 14A-1 and
14A-2 in section 12 of this method to derive the target dry gas meter
volume (Fv) for these purposes.
10.1.3 Calibration of anemometers and temperature sensing devices.
If the standard anemometers in Method 14 of this appendix are used, the
calibration and integrity evaluations in sections 10.3.1.1 through
10.3.1.3 of Method 14 of this appendix shall be used as well as the
recording device described in section 2.1.3 of Method 14. The
calibrations or complete change-outs of anemometers shall take place at
a minimum of once per year. The temperature sensing and recording
devices shall be calibrated according to the manufacturer's
specifications.

[[Page 383]]

10.1.4 Calibration of flowmeters. The calibration of flowmeters is
necessary to ensure that an equal volume of sampled gas is entering each
of the individual cassettes and that no large differences, which could
possibly bias the sample, exist between the cassettes.
10.1.4.1 Variable area, 65 mm flowmeters or equivalent shall be
used. These flowmeters can be mounted on a common base for convenience.
These flowmeters shall be calibrated by attaching a prepared cassette,
complete with filters and pads, to the flowmeter and then to the system
manifold. This manifold is an aluminum cylinder with valved inlets for
connections to the flowmeters/cassettes and one outlet to a dry gas
meter. The connection is then made to the wet-test meter and finally to
a dry gas meter. All connections are made with tubing.
10.1.4.2 Turn the dry gas meter on for 15 min. in preparation for
the calibration. Turn the dry gas meter off and plug the intake hole of
the cassette. Turn the dry gas meter back on to evaluate the entire
system for leaks. If the dry gas meter shows a leakage rate of less than
0.02 ft³/min at 10 in. of Hg vacuum as noted on the dry gas
meter, the system is acceptable to further calibration.
10.1.4.3 With the dry gas meter turned on and the flow indicator
ball at a selected flow rate, record the exact amount of gas pulled
through the flowmeter by taking measurements from the wet test meter
after exactly 10 min. Record the room temperature and barometric
pressure. Conduct this test for all flowmeters in the system with all
flowmeters set at the same indicator ball reading. When all flowmeters
have gone through the procedure above, correct the volume pulled through
each flowmeter to standard conditions. The acceptable difference between
the highest and lowest flowmeter rate is 5 percent. Should one or more
flowmeters be outside of the acceptable limit of 5 percent, repeat the
calibration procedure at a lower or higher indicator ball reading until
all flowmeters show no more than 5 percent difference among them.
10.1.4.4 This flowmeter calibration shall be conducted at least
once per year.
10.1.5 Miscellaneous equipment calibrations. Miscellaneous
equipment used such as an automatic recorder/ printer used to measure
dry gas meter temperatures shall be calibrated according to the
manufacturer's specifications in order to maintain the accuracy of the
equipment.
11.0 Analytical Procedure
11.1 The preferred primary analytical determination of the
individual isolated samples or the combined particulate and gaseous
samples shall be performed by an automated methodology. The analytical
method for this technology shall be based on the manufacturer's
instructions for equipment operation and shall also include the analysis
of five standards with concentrations in the expected range of the
actual samples. The results of the analysis of the five standards shall
have a coefficient of correlation of at least 0.99. A check standard
shall be analyzed as the last sample of the group to determine if
instrument drift has occurred. The acceptable result for the check
standard is 95 to 105 percent of the standard's true value.
11.2 The secondary analytical method shall be by specific ion
electrode if the samples are distilled or if a TISAB IV buffer is used
to eliminate aluminum interferences. Five standards with concentrations
in the expected range of the actual samples shall be analyzed, and a
coefficient of correlation of at least 0.99 is the minimum acceptable
limit for linearity. An exception for this limit for linearity is a
condition when low-level standards in the range of 0.01 to 0.48
g fluoride/ml are analyzed. In this situation, a minimum
coefficient of correlation of 0.97 is required. TISAB II shall be used
for low-level analyses.
12.0 Data Analysis and Calculations
12.1 Carry out calculations, retaining at least one extra decimal
point beyond that of the acquired data. Round off values after the final
calculation. Other forms of calculations may be used as long as they
give equivalent results.
12.2 Estimating volumes for initial test runs.
[GRAPHIC] [TIFF OMITTED] TR07OC97.000

Where

Fv = Desired volume of dry gas to be sampled, ft\3\.
Fd = Desired or analytically optimum mass of TF per cassette,
micrograms of TF per cassette (g/cassette).
X = Number of cassettes used.
Fe = Typical concentration of TF in emissions to be sampled,
g/ft \3\, calculated from Equation 14A-2.

[[Page 384]]

[GRAPHIC] [TIFF OMITTED] TR07OC97.001

Where

Re = Typical emission rate from the facility, pounds of TF
per ton (lb/ton) of aluminum.
Rp = Typical production rate of the facility, tons of
aluminum per minute (ton/min).
Vr = Typical exit velocity of the roof monitor gases, feet
per minute (ft/min).
Ar=Open area of the roof monitor, square feet
(ft²).

12.2.1 Example calculation. Assume that the typical emission rate
(Re) is 1.0 lb TF/ton of aluminum, the typical roof vent gas
exit velocity (Vr) is 250 ft/min, the typical production rate
(Rp) is 0.10 ton/min, the known open area for the roof
monitor (Ar) is 8,700 ft², and the desired
(analytically optimum) mass of TF per cassette is 1,500 g.
First calculate the concentration of TF per cassette (Fe) in
g/ft³ using Equation 14A-2. Then calculate the
desired volume of gas to be sampled (Fv) using Equation 14A-
1.
[GRAPHIC] [TIFF OMITTED] TR07OC97.002

[GRAPHIC] [TIFF OMITTED] TR07OC97.003

This is a total of 575.40 ft³ for eight cassettes or
71.925 ft³/cassette.
12.3 Calculations of TF emissions from field and laboratory data
that would yield a production related emission rate can be calculated as
follows:
12.3.1 Obtain a standard cubic feet (scf) value for the volume
pulled through the dry gas meter for all cassettes by using the field
and calibration data and Equation 5-1 of Method 5 of this appendix.
12.3.2 Derive the average quantity of TF per cassette (in
g TF/cassette) by adding all laboratory data for all cassettes
and dividing this value by the total number of cassettes used. Divide
this average TF value by the corrected dry gas meter volume for each
cassette; this value then becomes TFstd (g/
ft³).
12.3.3 Calculate the production-based emission rate (Re)
in lb/ton using Equation 14A-5.
[GRAPHIC] [TIFF OMITTED] TR07OC97.004

12.3.4 As an example calculation, assume eight cassettes located in
a potline were used to sample for 72 hours during the run. The analysis
of all eight cassettes yielded a total of 3,000 g of TF. The
dry gas meter volume was corrected to yield a total of 75 scf per
cassette, which yields a value for TFstd of 3,000/75=5
g/ft³. The open area of the roof monitor for the
potline (Ar) is 17,400 ft². The exit velocity of
the roof monitor gases (Vr) is 250 ft/min. The production
rate of aluminum over the previous 720 hours was 5,000 tons, which is
6.94 tons/hr or 0.116 ton/min (Rp). Substituting these values
into Equation 14A-5 yields:

[[Page 385]]

[GRAPHIC] [TIFF OMITTED] TR07OC97.005

12.4 Corrections to volumes due to leakage. Should the post-test
leak check leakage rate exceed 4 percent as described in section 8.3.2
of this method, correct the volume as detailed in Case I in section 6.3
of Method 5 of this appendix.
[GRAPHIC] [TIFF OMITTED] TR07OC97.020

[[Page 386]]

[GRAPHIC] [TIFF OMITTED] TR07OC97.021

[[Page 387]]

[GRAPHIC] [TIFF OMITTED] TR07OC97.022

[[Page 388]]

Method 15--Determination of Hydrogen Sulfide, Carbonyl Sulfide, and
Carbon Disulfide Emissions From Stationary Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Sensitivity (See Sec
Analyte CAS No. 13.2)
------------------------------------------------------------------------
Carbon disulfide [CS2]......... 75-15-0 0.5 ppmv
Carbonyl sulfide [COS]......... 463-58-1 0.5 ppmv
Hydrogen sulfide [H2S]......... 7783-06-4 0.5 ppmv
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This method applies to the determination of emissions of
reduced sulfur compounds from tail gas control units of sulfur recovery
plants, H2S in fuel gas for fuel gas combustion devices, and
where specified in other applicable subparts of the regulations.
1.2.2 The method described below uses the principle of gas
chromatographic (GC) separation and flame photometric detection (FPD).
Since there are many systems or sets of operating conditions that
represent useable methods for determining sulfur emissions, all systems
which employ this principle, but differ only in details of equipment and
operation, may be used as alternative methods, provided that the
calibration precision and sample-line loss criteria are met.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the emission source and diluted
with clean dry air (if necessary). An aliquot of the diluted sample is
then analyzed for CS2, COS, and H2S by GC/FPD.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Moisture Condensation. Moisture condensation in the sample
delivery system, the analytical column, or the FPD burner block can
cause losses or interferences. This potential is eliminated by heating
the probe, filter box, and connections, and by maintaining the
SO2 scrubber in an ice water bath. Moisture is removed in the
SO2 scrubber and heating the sample beyond this point is not
necessary provided the ambient temperature is above 0 deg.C (32
deg.F). Alternatively, moisture may be eliminated by heating the sample
line, and by conditioning the sample with dry dilution air to lower its
dew point below the operating temperature of the GC/FPD analytical
system prior to analysis.
4.2 Carbon Monoxide (CO) and Carbon Dioxide (CO2). CO
and CO2 have substantial desensitizing effects on the FPD
even after 9:1 dilution. (Acceptable systems must demonstrate that they
have eliminated this interference by some procedure such as eluting CO
and CO2 before any of the sulfur compounds to be measured.)
Compliance with this requirement can be demonstrated by submitting
chromatograms of calibration gases with and without CO2 in
the diluent gas. The CO2 level should be approximately 10
percent for the case with CO2 present. The two chromatograms
should show agreement within the precision limits of Section 13.3.
4.3 Elemental Sulfur. The condensation of sulfur vapor in the
sampling system can lead to blockage of the particulate filter. This
problem can be minimized by observing the filter for buildup and
changing as needed.
4.4 Sulfur Dioxide (SO2). SO2 is not a
specific interferent but may be present in such large amounts that it
cannot be effectively separated from the other compounds of interest.
The SO2 scrubber described in Section 6.1.3 will effectively
remove SO2 from the sample.
4.5 Alkali Mist. Alkali mist in the emissions of some control
devices may cause a rapid increase in the SO2 scrubber pH,
resulting in low sample recoveries. Replacing the SO2
scrubber contents after each run will minimize the chances of
interference in these cases.

5.0 Safety

[[Page 389]]

6.0 Equipment and Supplies

6.1 Sample Collection. See Figure 15-1. The sampling train
component parts are discussed in the following sections:
6.1.1 Probe. The probe shall be made of Teflon or Teflon-lined
stainless steel and heated to prevent moisture condensation. It shall be
designed to allow calibration gas to enter the probe at or near the
sample point entry. Any portion of the probe that contacts the stack gas
must be heated to prevent moisture condensation. The probe described in
Section 6.1.1 of Method 16A having a nozzle directed away from the gas
stream is recommended for sources having particulate or mist emissions.
Where very high stack temperatures prohibit the use of Teflon probe
components, glass or quartz-lined probes may serve as substitutes.
6.1.2 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
micron porosity Teflon filter (available through Savillex Corporation,
5325 Highway 101, Minnetonka, Minnesota 55343). The filter holder must
be maintained in a hot box at a temperature of at least 120 deg.C (248
deg.F).
6.1.3 SO2 Scrubber. Three 300-ml Teflon segment
impingers connected in series with flexible, thick-walled, Teflon
tubing. (Impinger parts and tubing available through Savillex.) The
first two impingers contain 100 ml of citrate buffer, and the third
impinger is initially dry. The tip of the tube inserted into the
solution should be constricted to less than 3-mm (\1/8\-in.) ID and
should be immersed to a depth of at least 50 cm (2 in.). Immerse the
impingers in an ice water bath and maintain near 0 deg.C. The scrubber
solution will normally last for a 3-hour run before needing replacement.
This will depend upon the effects of moisture and particulate matter on
the solution strength and pH. Connections between the probe, particulate
filter, and SO2 scrubber shall be made of Teflon and as short
in length as possible. All portions of the probe, particulate filter,
and connections prior to the SO2 scrubber (or alternative
point of moisture removal) shall be maintained at a temperature of at
least 120 deg.C (248 deg.F).
6.1.4 Sample Line. Teflon, no greater than 13-mm (\1/2\-in.) ID.
Alternative materials, such as virgin Nylon, may be used provided the
line-loss test is acceptable.
6.1.5 Sample Pump. The sample pump shall be a leakless Teflon-
coated diaphragm type or equivalent.
6.2 Analysis. The following items are needed for sample analysis:
6.2.1 Dilution System. The dilution system must be constructed such
that all sample contacts are made of Teflon, glass, or stainless steel.
It must be capable of approximately a 9:1 dilution of the sample.
6.2.2 Gas Chromatograph (see Figure 15-2). The gas chromatograph
must have at least the following components:
6.2.2.1 Oven. Capable of maintaining the separation column at the
proper operating temperature 1 deg.C.
6.2.2.2 Temperature Gauge. To monitor column oven, detector, and
exhaust temperature 1 deg.C.
6.2.2.3 Flow System. Gas metering system to measure sample, fuel,
combustion gas, and carrier gas flows.
6.2.2.4 Flame Photometric Detector.
6.2.2.4.1 Electrometer. Capable of full scale amplification of
linear ranges of 10^-9 to 10^-4 amperes full scale.
6.2.2.4.2 Power Supply. Capable of delivering up to 750 volts.
6.2.2.5 Recorder. Compatible with the output voltage range of the
electrometer.
6.2.2.6 Rotary Gas Valves. Multiport Teflon-lined valves equipped
with sample loop. Sample loop volumes shall be chosen to provide the
needed analytical range. Teflon tubing and fittings shall be used
throughout to present an inert surface for sample gas. The GC shall be
calibrated with the sample loop used for sample analysis.
6.2.2.7 GC Columns. The column system must be demonstrated to be
capable of resolving three major reduced sulfur compounds:
H2S, COS, and CS2. To demonstrate that adequate
resolution has been achieved, a chromatogram of a calibration gas
containing all three reduced sulfur compounds in the concentration range
of the applicable standard must be submitted. Adequate resolution will
be defined as base line separation of adjacent peaks when the amplifier
attenuation is set so that the smaller peak is at least 50 percent of
full scale. Base line separation is defined as a return to zero
(5 percent) in the interval between peaks. Systems not
meeting this criteria may be considered alternate methods subject to the
approval of the Administrator.
6.3 Calibration System (See Figure 15-3). The calibration system
must contain the following components:
6.3.1 Flow System. To measure air flow over permeation tubes within
2 percent. Each flowmeter shall be calibrated after each complete test
series with a wet-test meter. If the flow measuring device differs from
the wet-test meter by more than 5 percent, the completed test shall be
discarded. Alternatively, use the flow data that will yield the lowest
flow measurement. Calibration with a wet-test meter before a test is
optional. Flow over the permeation device may also be determined using a
soap bubble flowmeter.
6.3.2 Constant Temperature Bath. Device capable of maintaining the
permeation tubes at the calibration temperature within 0.1 deg.C.

[[Page 390]]

6.3.3 Temperature Sensor. Thermometer or equivalent to monitor bath
temperature within 0.1 deg.C.

7.0 Reagents and Standards

7.1 Fuel. Hydrogen gas (H2). Prepurified grade or
better.
7.2 Combustion Gas. Oxygen (O2) or air, research purity
or better.
7.3 Carrier Gas. Prepurified grade or better.
7.4 Diluent. Air containing less than 0.5 ppmv total sulfur
compounds and less than 10 ppmv each of moisture and total hydrocarbons.
7.5 Calibration Gases.
7.5.1 Permeation Devices. One each of H2S, COS, and
CS2, gravimetrically calibrated and certified at some
convenient operating temperature. These tubes consist of hermetically
sealed FEP Teflon tubing in which a liquified gaseous substance is
enclosed. The enclosed gas permeates through the tubing wall at a
constant rate. When the temperature is constant, calibration gases
covering a wide range of known concentrations can be generated by
varying and accurately measuring the flow rate of diluent gas passing
over the tubes. These calibration gases are used to calibrate the GC/FPD
system and the dilution system.
7.5.2 Cylinder Gases. Cylinder gases may be used as alternatives to
permeation devices. The gases must be traceable to a primary standard
(such as permeation tubes) and not used beyond the certification
expiration date.
7.6 Citrate Buffer. Dissolve 300 g of potassium citrate and 41 g of
anhydrous citric acid in 1 liter of water. Alternatively, 284 g of
sodium citrate may be substituted for the potassium citrate. Adjust the
pH to between 5.4 and 5.6 with potassium citrate or citric acid, as
required.
8.0 Sample Collection, Preservation, Transport, and Storage
8.1 Pretest Procedures. After the complete measurement system has
been set up at the site and deemed to be operational, the following
procedures should be completed before sampling is initiated. These
procedures are not required, but would be helpful in preventing any
problem which might occur later to invalidate the entire test.
8.1.1 Leak-Check. Appropriate leak-check procedures should be
employed to verify the integrity of all components, sample lines, and
connections. The following procedure is suggested: For components
upstream of the sample pump, attach the probe end of the sample line to
a manometer or vacuum gauge, start the pump and pull a vacuum greater
than 50 mm (2 in.) Hg, close off the pump outlet, and then stop the pump
and ascertain that there is no leak for 1 minute. For components after
the pump, apply a slight positive pressure and check for leaks by
applying a liquid (detergent in water, for example) at each joint.
Bubbling indicates the presence of a leak. As an alternative to the
initial leak-test, the sample line loss test described in Section 8.3.1
may be performed to verify the integrity of components.
8.1.2 System Performance. Since the complete system is calibrated
at the beginning and end of each day of testing, the precise calibration
of each component is not critical. However, these components should be
verified to operate properly. This verification can be performed by
observing the response of flowmeters or of the GC output to changes in
flow rates or calibration gas concentrations, respectively, and
ascertaining the response to be within predicted limits. If any
component or the complete system fails to respond in a normal and
predictable manner, the source of the discrepancy should be identified
and corrected before proceeding.

8.2 Sample Collection and Analysis

8.2.1 After performing the calibration procedures outlined in
Section 10.0, insert the sampling probe into the test port ensuring that
no dilution air enters the stack through the port. Begin sampling and
dilute the sample approximately 9:1 using the dilution system. Note that
the precise dilution factor is the one determined in Section 10.4.
Condition the entire system with sample for a minimum of 15 minutes
before beginning the analysis. Inject aliquots of the sample into the
GC/FPD analyzer for analysis. Determine the concentration of each
reduced sulfur compound directly from the calibration curves or from the
equation for the least-squares line.
8.2.2 If reductions in sample concentrations are observed during a
sample run that cannot be explained by process conditions, the sampling
must be interrupted to determine if the probe or filter is clogged with
particulate matter. If either is found to be clogged, the test must be
stopped and the results up to that point discarded. Testing may resume
after cleaning or replacing the probe and filter. After each run, the
probe and filter shall be inspected and, if necessary, replaced.
8.2.3 A sample run is composed of 16 individual analyses (injects)
performed over a period of not less than 3 hours or more than 6 hours.
8.3 Post-Test Procedures.
8.3.1 Sample Line Loss. A known concentration of H2S at
the level of the applicable standard, 20 percent, must be
introduced into the sampling system at the opening of the probe in
sufficient quantities to ensure that there is an excess of sample which
must be vented to the atmosphere. The sample must be transported through
the entire sampling system to the measurement system in

[[Page 391]]

the same manner as the emission samples. The resulting measured
concentration is compared to the known value to determine the sampling
system loss. For sampling losses greater than 20 percent, the previous
sample run is not valid. Sampling losses of 0-20 percent must be
corrected by dividing the resulting sample concentration by the fraction
of recovery. The known gas sample may be calibration gas as described in
Section 7.5. Alternatively, cylinder gas containing H2S mixed
in nitrogen and verified according to Section 7.1.4 of Method 16A may be
used. The optional pretest procedures provide a good guideline for
determining if there are leaks in the sampling system.
8.3.2 Determination of Calibration Drift. After each run, or after
a series of runs made within a 24-hour period, perform a partial
recalibration using the procedures in Section 10.0. Only H2S
(or other permeant) need be used to recalibrate the GC/FPD analysis
system and the dilution system. Compare the calibration curves obtained
after the runs to the calibration curves obtained under Section 10.3.
The calibration drift should not exceed the limits set forth in Section
13.4. If the drift exceeds this limit, the intervening run or runs
should be considered invalid. As an option, the calibration data set
which gives the highest sample values may be chosen by the tester.

9.0 Quality Control

10.0 Calibration and Standardization

Prior to any sampling run, calibrate the system using the following
procedures. (If more than one run is performed during any 24-hour
period, a calibration need not be performed prior to the second and any
subsequent runs. However, the calibration drift must be determined as
prescribed in Section 8.3.2 after the last run is made within the 24-
hour period.)

Note: This section outlines steps to be followed for use of the GC/
FPD and the dilution system. The calibration procedure does not include
detailed instructions because the operation of these systems is complex,
and it requires an understanding of the individual system being used.
Each system should include a written operating manual describing in
detail the operating procedures associated with each component in the
measurement system. In addition, the operator should be familiar with
the operating principles of the components, particularly the GC/FPD. The
references in Section 16.0 are recommended for review for this purpose.
10.1 Calibration Gas Permeation Tube Preparation.
10.1.1 Insert the permeation tubes into the tube chamber. Check the
bath temperature to assure agreement with the calibration temperature of
the tubes within 0.1 deg.C. Allow 24 hours for the tubes to
equilibrate. Alternatively, equilibration may be verified by injecting
samples of calibration gas at 1-hour intervals. The permeation tubes can
be assumed to have reached equilibrium when consecutive hourly samples
agree within 5 percent of their mean.
10.1.2 Vary the amount of air flowing over the tubes to produce the
desired concentrations for calibrating the analytical and dilution
systems. The air flow across the tubes must at all times exceed the flow
requirement of the analytical systems. The concentration in ppmv
generated by a tube containing a specific permeant can be calculated
using Equation 15-1 in Section 12.2.
10.2 Calibration of Analytical System. Generate a series of three
or more known concentrations spanning the linear range of the FPD
(approximately 0.5 to 10 ppmv for a 1-ml sample) for each of the three
major sulfur compounds. Bypassing the dilution system, inject these
standards into the GC/FPD and monitor the responses until three
consecutive injections for each concentration agree within 5 percent of
their mean. Failure to attain this precision indicates a problem in the
calibration or analytical system. Any such problem must be identified
and corrected before proceeding.
10.3 Calibration Curves. Plot the GC/FPD response in current
(amperes) versus their causative concentrations in ppmv on log-log
coordinate graph paper for each sulfur compound. Alternatively, a least-
squares equation may be generated from the calibration data using
concentrations versus the appropriate instrument response units.
10.4 Calibration of Dilution System. Generate a known concentration
of H2S using the permeation tube system. Adjust the flow rate
of diluent air for the first dilution stage

[[Page 392]]

so that the desired level of dilution is approximated. Inject the
diluted calibration gas into the GC/FPD system until the results of
three consecutive injections for each dilution agree within 5 percent of
their mean. Failure to attain this precision in this step is an
indication of a problem in the dilution system. Any such problem must be
identified and corrected before proceeding. Using the calibration data
for H2S (developed under Section 10.3), determine the diluted
calibration gas concentration in ppmv. Then calculate the dilution
factor as the ratio of the calibration gas concentration before dilution
to the diluted calibration gas concentration determined under this
section. Repeat this procedure for each stage of dilution required.
Alternatively, the GC/FPD system may be calibrated by generating a
series of three or more concentrations of each sulfur compound and
diluting these samples before injecting them into the GC/FPD system.
These data will then serve as the calibration data for the unknown
samples and a separate determination of the dilution factor will not be
necessary. However, the precision requirements are still applicable.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
Section 8.0).

12.0 Data Analysis and Calculations

12.1 Nomenclature.

C = Concentration of permeant produced, ppmv.
COS = Carbonyl sulfide concentration, ppmv.
CS2 = Carbon disulfide concentration, ppmv.
d = Dilution factor, dimensionless.
H2S = Hydrogen sulfide concentration, ppmv.
K = 24.04 L/g mole. (Gas constant at 20 deg.C and 760 mm Hg)
L = Flow rate, L/min, of air over permeant 20 deg.C, 760 mm Hg.
M = Molecular weight of the permeant, g/g-mole.
N = Number of analyses performed.
Pr = Permeation rate of the tube, g/min.
12.2 Permeant Concentration. Calculate the concentration generated
by a tube containing a specific permeant (see Section 10.1) using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.262

12.3 Calculation of SO2 Equivalent. SO2
equivalent will be determined for each analysis made by summing the
concentrations of each reduced sulfur compound resolved during the given
analysis. The SO2 equivalent is expressed as SO2
in ppmv.
[GRAPHIC] [TIFF OMITTED] TR17OC00.263

12.4 Average SO2 Equivalent. This is determined using the
following equation. Systems that do not remove moisture from the sample
but condition the gas to prevent condensation must correct the average
SO2 equivalent for the fraction of water vapor present. This
is not done under applications where the emission standard is not
specified on a dry basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.264

Where:

Avg SO2 equivalent = Average SO2 equivalent in
ppmv, dry basis.
Average SO2 equivalent i = SO2 in ppmv
as determined by Equation 15-2.

13.0 Method Performance

13.1 Range. Coupled with a GC system using a 1-ml sample size, the
maximum limit of the FPD for each sulfur compound is approximately 10
ppmv. It may be necessary to dilute samples from sulfur recovery plants
a hundredfold (99:1), resulting in an upper limit of about 1000 ppmv for
each compound.
13.2 Sensitivity. The minimum detectable concentration of the FPD
is also dependent on sample size and would be about 0.5 ppmv for a 1-ml
sample.

[[Page 393]]

13.3 Calibration Precision. A series of three consecutive
injections of the same calibration gas, at any dilution, shall produce
results which do not vary by more than 5 percent from the mean of the
three injections.
13.4 Calibration Drift. The calibration drift determined from the
mean of three injections made at the beginning and end of any run or
series of runs within a 24-hour period shall not exceed 5 percent.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References.

1. O'Keeffe, A.E., and G.C. Ortman. ``Primary Standards for Trace
Gas Analysis.'' Anal. Chem. 38,760. 1966.
2. Stevens, R.K., A.E. O'Keeffe, and G.C. Ortman. ``Absolute
Calibration of a Flame Photometric Detector to Volatile Sulfur Compounds
at Sub-Part-Per-Million Levels.'' Environmental Science and Technology
3:7. July 1969.
3. Mulik, J.D., R.K. Stevens, and R. Baumgardner. ``An Analytical
System Designed to Measure Multiple Malodorous Compounds Related to
Kraft Mill Activities.'' Presented at the 12th Conference on Methods in
Air Pollution and Industrial Hygiene Studies, University of Southern
California, Los Angeles, CA, April 6-8, 1971.
4. Devonald, R.H., R.S. Serenius, and A.D. McIntyre. ``Evaluation of
the Flame Photometric Detector for Analysis of Sulfur Compounds.'' Pulp
and Paper Magazine of Canada, 73,3. March 1972.
5. Grimley, K.W., W.S. Smith, and R.M. Martin. ``The Use of a
Dynamic Dilution System in the Conditioning of Stack Gases for Automated
Analysis by a Mobile Sampling Van.'' Presented at the 63rd Annual APCA
Meeting in St. Louis, MO. June 14-19, 1970.
6. General Reference. Standard Methods of Chemical Analysis Volume
III-A and III-B: Instrumental Analysis. Sixth Edition. Van Nostrand
Reinhold Co.

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17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.265

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[GRAPHIC] [TIFF OMITTED] TR17OC00.266

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[GRAPHIC] [TIFF OMITTED] TR17OC00.267

Method 15A--Determination of Total Reduced Sulfur Emissions From Sulfur
Recovery Plants in Petroleum Refineries

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 6, Method 15,
and Method 16A.

1.0 Scope and Application

1.1 Analytes.

[[Page 397]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Reduced sulfur compounds...... None assigned... Not determined.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of emissions of reduced sulfur compounds from sulfur recovery plants
where the emissions are in a reducing atmosphere, such as in Stretford
units.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the stack, and
combustion air is added to the oxygen (O2)-deficient gas at a
known rate. The reduced sulfur compounds [including carbon disulfide
(CS2), carbonyl sulfide (COS), and hydrogen sulfide
(H2S)] are thermally oxidized to sulfur dioxide
(SO2), which is then collected in hydrogen peroxide as
sulfate ion and analyzed according to the Method 6 barium-thorin
titration procedure.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Reduced sulfur compounds, other than CS2, COS, and
H2S, that are present in the emissions will also be oxidized
to SO2, causing a positive bias relative to emission
standards that limit only the three compounds listed above. For example,
thiophene has been identified in emissions from a Stretford unit and
produced a positive bias of 30 percent in the Method 15A result.
However, these biases may not affect the outcome of the test at units
where emissions are low relative to the standard.
4.2 Calcium and aluminum have been shown to interfere in the Method
6 titration procedure. Since these metals have been identified in
particulate matter emissions from Stretford units, a Teflon filter is
required to minimize this interference.
4.3 Dilution of the hydrogen peroxide (H2O2)
absorbing solution can potentially reduce collection efficiency, causing
a negative bias. When used to sample emissions containing 7 percent
moisture or less, the midget impingers have sufficient volume to contain
the condensate collected during sampling. Dilution of the
H2O2 does not affect the collection of
SO2. At higher moisture contents, the potassium citrate-
citric acid buffer system used with Method 16A should be used to collect
the condensate.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train used in performing this
method is shown in Figure 15A-1, and component parts are discussed
below. Modifications to this sampling train are acceptable provided that
the system performance check is met.
6.1.1 Probe. 6.4-mm (\1/4\-in.) OD Teflon tubing sequentially
wrapped with heat-resistant fiber strips, a rubberized heating tape
(with a plug at one end), and heat-resistant adhesive tape. A flexible
thermocouple or some other suitable temperature-measuring device shall
be placed between the Teflon tubing and the fiber strips so that the
temperature can be monitored. The probe should be sheathed in stainless
steel to provide in-stack rigidity. A series of bored-out stainless
steel fittings placed at the front of the sheath will prevent flue gas
from entering between the probe and sheath. The sampling probe is
depicted in Figure 15A-2.
6.1.2 Particulate Filter. A 50-mm Teflon filter holder and a 1- to
2-mm porosity Teflon filter (available through Savillex Corporation,
5325 Highway 101, Minnetonka, Minnesota 55345). The filter holder must
be

[[Page 398]]

maintained in a hot box at a temperature high enough to prevent
condensation.
6.1.3 Combustion Air Delivery System. As shown in the schematic
diagram in Figure 15A-3. The rate meter should be selected to measure an
air flow rate of 0.5 liter/min (0.02 ft\3\/min).
6.1.4 Combustion Tube. Quartz glass tubing with an expanded
combustion chamber 2.54 cm (1 in.) in diameter and at least 30.5 cm (12
in.) long. The tube ends should have an outside diameter of 0.6 cm (\1/
4\ in.) and be at least 15.3 cm (6 in.) long. This length is necessary
to maintain the quartz-glass connector near ambient temperature and
thereby avoid leaks. Alternatively, the outlet may be constructed with a
90 degree glass elbow and socket that would fit directly onto the inlet
of the first peroxide impinger.
6.1.5 Furnace. Of sufficient size to enclose the combustion tube.
The furnace must have a temperature regulator capable of maintaining the
temperature at 1100 50 deg.C (2,012 90
deg.F). The furnace operating temperature must be checked with a
thermocouple to ensure accuracy. Lindberg furnaces have been found to be
satisfactory.
6.1.6 Peroxide Impingers, Stopcock Grease, Temperature Sensor,
Drying Tube, Valve, Pump, and Barometer. Same as in Method 6, Sections
6.1.1.2, 6.1.1.4, 6.1.1.5, 6.1.1.6, 6.1.1.7, 6.1.1.8, and 6.1.2,
respectively, except that the midget bubbler of Method 6, Section
6.1.1.2 is not required.
6.1.7 Vacuum Gauge and Rate Meter. At least 760 mm Hg (30 in. Hg)
gauge and rotameter, or equivalent, capable of measuring flow rate to
5 percent of the selected flow rate and calibrated as in
Section 10.2.
6.1.8 Volume Meter. Dry gas meter capable of measuring the sample
volume under the particular sampling conditions with an accuracy of 2
percent.
6.1.9 U-tube manometer. To measure the pressure at the exit of the
combustion gas dry gas meter.
6.2 Sample Recovery and Analysis. Same as Method 6, Sections 6.2
and 6.3, except a 10-ml buret with 0.05-ml graduations is required for
titrant volumes of less than 10.0 ml, and the spectrophotometer is not
needed.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents and standards are
required for sample analysis:
7.1.1 Water. Same as Method 6, Section 7.1.1.
7.1.2 Hydrogen Peroxide (H2O2), 3 Percent by
Volume. Same as Method 6, Section 7.1.3 (40 ml is needed per sample).
7.1.3 Recovery Check Gas. Carbonyl sulfide in nitrogen [100 parts
per million by volume (ppmv) or greater, if necessary] in an aluminum
cylinder. Concentration certified by the manufacturer with an accuracy
of 2 percent or better, or verified by gas chromatography
where the instrument is calibrated with a COS permeation tube.
7.1.4 Combustion Gas. Air, contained in a gas cylinder equipped
with a two-stage regulator. The gas shall contain less than 50 ppb of
reduced sulfur compounds and less than 10 ppm total hydrocarbons.
7.2 Sample Recovery and Analysis. Same as Method 6, Sections 7.2
and 7.3.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Preparation of Sampling Train. For the Method 6 part of the
train, measure 20 ml of 3 percent H2O2 into the
first and second midget impingers. Leave the third midget impinger empty
and add silica gel to the fourth impinger. Alternatively, a silica gel
drying tube may be used in place of the fourth impinger. Place crushed
ice and water around all impingers. Maintain the oxidation furnace at
1100 50 deg.C (2,012 90 deg.F) to ensure 100
percent oxidation of COS. Maintain the probe and filter temperatures at
a high enough level (no visible condensation) to prevent moisture
condensation and monitor the temperatures with a thermocouple.
8.2 Leak-Check Procedure. Assemble the sampling train and leak-
check as described in Method 6, Section 8.2. Include the combustion air
delivery system from the needle valve forward in the leak-check.
8.3 Sample Collection. Adjust the pressure on the second stage of
the regulator on the combustion air cylinder to 10 psig. Adjust the
combustion air flow rate to 0.5 0.05 L/min (1.1
0.1 ft\3\/hr) before injecting combustion air into the
sampling train. Then inject combustion air into the sampling train,
start the sample pump, and open the stack sample gas valve. Carry out
these three operations within 15 to 30 seconds to avoid pressurizing the
sampling train. Adjust the total sample flow rate to 2.0
0.2 L/min (4.2 0.4 ft\3\/hr). These flow rates produce an
O2 concentration of 5.0 percent in the stack gas, which must
be maintained constantly to allow oxidation of reduced sulfur compounds
to SO2. Adjust these flow rates during sampling as necessary.
Monitor and record the combustion air manometer reading at regular
intervals during the sampling period. Sample for 1 or 3 hours. At the
end of sampling, turn off the sample pump and combustion air
simultaneously (within 30 seconds of each other). All other procedures
are the same as in Method 6, Section 8.3, except that the sampling train
should not be purged. After collecting the

[[Page 399]]

sample, remove the probe from the stack and conduct a leak-check
according to the procedures outlined in Section 8.2 of Method 6
(mandatory). After each 3-hour test run (or after three 1-hour samples),
conduct one system performance check (see Section 8.5). After this
system performance check and before the next test run, it is recommended
that the probe be rinsed and brushed and the filter replaced.

Note: In Method 15, a test run is composed of 16 individual analyses
(injects) performed over a period of not less than 3 hours or more than
6 hours. For Method 15A to be consistent with Method 15, the following
may be used to obtain a test run: (1) Collect three 60-minute samples or
(2) collect one 3-hour sample. (Three test runs constitute a test.)

8.4 Sample Recovery. Recover the hydrogen peroxide-containing
impingers as detailed in Method 6, Section 8.4.
8.5 System Performance Check.
8.5.1 A system performance check is done (1) to validate the
sampling train components and procedure (before testing, optional) and
(2) to validate a test run (after a run, mandatory). Perform a check in
the field before testing consisting of at least two samples (optional),
and perform an additional check after each 3-hour run or after three 1-
hour samples (mandatory).
8.5.2 The checks involve sampling a known concentration of COS and
comparing the analyzed concentration with the known concentration. Mix
the recovery gas with N2 as shown in Figure 15A-4 if dilution
is required. Adjust the flow rates to generate a COS concentration in
the range of the stack gas or within 20 percent of the applicable
standard at a total flow rate of at least 2.5 L/min (5.3 ft\3\/hr). Use
Equation 15A-4 (see Section 12.5) to calculate the concentration of
recovery gas generated. Calibrate the flow rate from both sources with a
soap bubble flow tube so that the diluted concentration of COS can be
accurately calculated. Collect 30-minute samples, and analyze in the
same manner as the emission samples. Collect the samples through the
probe of the sampling train using a manifold or some other suitable
device that will ensure extraction of a representative sample.
8.5.3 The recovery check must be performed in the field before
replacing the particulate filter and before cleaning the probe. A sample
recovery of 100 20 percent must be obtained for the data to
be valid and should be reported with the emission data, but should not
be used to correct the data. However, if the performance check results
do not affect the compliance or noncompliance status of the affected
facility, the Administrator may decide to accept the results of the
compliance test. Use Equation 15A-5 (see Section 12.6) to calculate the
recovery efficiency.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.5........................... System Ensures validity of
performance sampling train
check. components and
analytical
procedure.
8.2, 10.0..................... Sampling Ensures accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume
10.0.......................... Barium standard Ensures precision of
solution normality
standardization. determination.
11.1.......................... Replicate Ensures precision of
titrations. titration
determinations.
11.2.......................... Audit sample Evaluates analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Metering System, Temperature Sensors, Barometer, and Barium
Perchlorate Solution. Same as Method 6, Sections 10.1, 10.2, 10.4, and
10.5, respectively.
10.2 Rate Meter. Calibrate with a bubble flow tube.

11.0 Analytical Procedure

11.1 Sample Loss Check and Sample Analysis. Same as Method 6,
Sections 11.1 and 11.2.
11.2 Audit Sample Analysis. Same as Method 6, Section 11.3.

12.0 Data Analysis and Calculations

In the calculations, retain at least one extra decimal figure beyond
that of the acquired data. Round off figures after final calculations.
12.1 Nomenclature.

CCOS = Concentration of COS recovery gas, ppm.
CRG(act) = Actual concentration of recovery check gas (after
dilution), ppm.
CRG(m) = Measured concentration of recovery check gas
generated, ppm.
CRS = Concentration of reduced sulfur compounds as
SO2, dry basis, corrected to standard conditions,
ppm.
N = Normality of barium perchlorate titrant, milliequivalents/ml.
Pbar = Barometric pressure at exit orifice of the dry gas
meter, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
QCOS = Flow rate of COS recovery gas, liters/min.
QN = Flow rate of diluent N2, liters/min.
R = Recovery efficiency for the system performance check, percent.

[[Page 400]]

Tm = Average dry gas meter absolute temperature, deg.K.
Tstd = Standard absolute temperature, 293 deg.K.
Va = Volume of sample aliquot titrated, ml.
Vms = Dry gas volume as measured by the sample train dry gas
meter, liters.
Vmc = Dry gas volume as measured by the combustion air dry
gas meter, liters.
Vms(std) = Dry gas volume measured by the sample train dry
gas meter, corrected to standard conditions, liters.
Vmc(std) = Dry gas volume measured by the combustion air dry
gas meter, corrected to standard conditions, liters.
Vsoln = Total volume of solution in which the sulfur dioxide
sample is contained, 100 ml.
Vt = Volume of barium perchlorate titrant used for the sample
(average of replicate titrations), ml.
Vtb = Volume of barium perchlorate titrant used for the
blank, ml.
Y = Calibration factor for sampling train dry gas meter.
Yc = Calibration factor for combustion air dry gas meter.
32.03 = Equivalent weight of sulfur dioxide, mg/meq.
[GRAPHIC] [TIFF OMITTED] TR17OC00.411

12.2 Dry Sample Gas Volume, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.268

Where:

K1 = 0.3855 deg.K/mm Hg for metric units,
= 17.65 deg.R/in. Hg for English units.

12.3 Combustion Air Gas Volume, corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.269

Note: Correct Pbar for the average pressure of the manometer
during the sampling period.
12.4 Concentration of reduced sulfur compounds as ppm SO2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.270

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.271

[[Page 401]]

12.5 Concentration of Generated Recovery Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.272

12.6 Recovery Efficiency for the System Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.273

13.0 Method Performance

13.1 Analytical Range. The lower detectable limit is 0.1 ppmv when
sampling at 2 lpm for 3 hours or 0.3 ppmv when sampling at 2 lpm for 1
hour. The upper concentration limit of the method exceeds concentrations
of reduced sulfur compounds generally encountered in sulfur recovery
plants.
13.2 Precision. Relative standard deviations of 2.8 and 6.9 percent
have been obtained when sampling a stream with a reduced sulfur compound
concentration of 41 ppmv as SO2 for 1 and 3 hours,
respectively.
13.3 Bias. No analytical bias has been identified. However, results
obtained with this method are likely to contain a positive bias relative
to emission regulations due to the presence of nonregulated sulfur
compounds (that are present in petroleum) in the emissions. The
magnitude of this bias varies accordingly, and has not been quantified.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. American Society for Testing and Materials Annual Book of ASTM
Standards. Part 31: Water, Atmospheric Analysis. Philadelphia,
Pennsylvania. 1974. pp. 40-42.
2. Blosser, R.O., H.S. Oglesby, and A.K. Jain. A Study of Alternate
SO2 Scrubber Designs Used for TRS Monitoring. National
Council of the Paper Industry for Air and Stream Improvement, Inc., New
York, New York. Special Report 77-05. July 1977.
3. Curtis, F., and G.D. McAlister. Development and Evaluation of an
Oxidation/Method 6 TRS Emission Sampling Procedure. Emission Measurement
Branch, Emission Standards and Engineering Division, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina. February
1980.
4. Gellman, I. A Laboratory and Field Study of Reduced Sulfur
Sampling and Monitoring Systems. National Council of the Paper Industry
for Air and Stream Improvement, Inc., New York, New York. Atmospheric
Quality Improvement Technical Bulletin No. 81. October 1975.
5. Margeson, J.H., et al. A Manual Method for TRS Determination.
Journal of Air Pollution Control Association. 35:1280-1286. December
1985.

[[Page 402]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.274

[[Page 403]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.275

[[Page 404]]

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[GRAPHIC] [TIFF OMITTED] TR17OC00.277

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A see the List of CFR Sections Affected, which appears in the
Finding Aids section of the printed volume and on GPO Access.

[[Page 406]]

Appendix A-6 to Part 60--Test Methods 16 through 18

Method 16--Semicontinuous determination of sulfur emissions from
stationary sources
Method 16A--Determination of total reduced sulfur emissions from
stationary sources (impinger technique)
Method 16B--Determination of total reduced sulfur emissions from
stationary sources
Method 17--Determination of particulate emissions from stationary
sources (in-stack filtration method)
Method 18--Measurement of gaseous organic compound emissions by gas
chromatography
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the the degree of detail should be similar to the detail contained
in the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 16--Semicontinuous Determination of Sulfur Emissions From
Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 4, Method 15,
and Method 16A.

[[Page 407]]

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Dimethyl disulfide [(CH3)2S2].. 62-49-20 50 ppb.
Dimethyl sulfide [(CH3)2S]..... 75-18-3 50 ppb.
Hydrogen sulfide [H2S]......... 7783-06-4 50 ppb.
Methyl mercaptan [CH4S]........ 74-93-1 50 ppb.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total reduced sulfur (TRS) compounds from recovery furnaces, lime
kilns, and smelt dissolving tanks at kraft pulp mills and fuel gas
combustion devices at petroleum refineries.

Note: The method described below uses the principle of gas
chromatographic (GC) separation and flame photometric detection (FPD).
Since there are many systems or sets of operating conditions that
represent useable methods of determining sulfur emissions, all systems
which employ this principle, but differ only in details of equipment and
operation, may be used as alternative methods, provided that the
calibration precision and sample line loss criteria are met.

1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the emission source and an
aliquot is analyzed for hydrogen sulfide (H2S), methyl
mercaptan (MeSH), dimethyl sulfide (DMS), and dimethyl disulfide (DMDS)
by GC/FPD. These four compounds are known collectively as TRS.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Moisture. Moisture condensation in the sample delivery system,
the analytical column, or the FPD burner block can cause losses or
interferences. This is prevented by maintaining the probe, filter box,
and connections at a temperature of at least 120 deg.C (248 deg.F).
Moisture is removed in the SO2 scrubber and heating the
sample beyond this point is not necessary when the ambient temperature
is above 0 deg.C (32 deg.F). Alternatively, moisture may be eliminated
by heating the sample line, and by conditioning the sample with dry
dilution air to lower its dew point below the operating temperature of
the GC/FPD analytical system prior to analysis.
4.2 Carbon Monoxide (CO) and Carbon Dioxide (CO2). CO
and CO2 have a substantial desensitizing effect on the flame
photometric detector even after dilution. Acceptable systems must
demonstrate that they have eliminated this interference by some
procedure such as eluting these compounds before any of the compounds to
be measured. Compliance with this requirement can be demonstrated by
submitting chromatograms of calibration gases with and without
CO2 in the diluent gas. The CO2 level should be
approximately 10 percent for the case with CO2 present. The
two chromatograms should show agreement within the precision limits of
Section 10.2.
4.3 Particulate Matter. Particulate matter in gas samples can cause
interference by eventual clogging of the analytical system. This
interference is eliminated by using the Teflon filter after the probe.
4.4 Sulfur Dioxide (SO2). Sulfur dioxide is not a
specific interferant but may be present in such large amounts that it
cannot effectively be separated from the other compounds of interest.
The SO2 scrubber described in Section 6.1.3 will effectively
remove SO2 from the sample.

5.0 Safety

6.0 Equipment and Supplies

6.1. Sample Collection. The following items are needed for sample
collection.
6.1.1 Probe. Teflon or Teflon-lined stainless steel. The probe must
be heated to prevent moisture condensation. It must be designed to allow
calibration gas to enter the probe at or near the sample point entry.
Any portion of the probe that contacts the stack gas must be heated to
prevent moisture condensation. Figure 16-1 illustrates the probe used in
lime kilns and other sources where

[[Page 408]]

significant amounts of particulate matter are present. The probe is
designed with the deflector shield placed between the sample and the gas
inlet holes to reduce clogging of the filter and possible adsorption of
sample gas. As an alternative, the probe described in Section 6.1.1 of
Method 16A having a nozzle directed away from the gas stream may be used
at sources having significant amounts of particulate matter.
6.1.2 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
micron porosity Teflon filter (available through Savillex Corporation,
5325 Highway 101, Minnetonka, Minnesota 55343). The filter holder must
be maintained in a hot box at a temperature of at least 120 deg.C (248
deg.F).
6.1.3 SO2 Scrubber. Three 300-ml Teflon segmented
impingers connected in series with flexible, thick-walled, Teflon
tubing. (Impinger parts and tubing available through Savillex.) The
first two impingers contain 100 ml of citrate buffer and the third
impinger is initially dry. The tip of the tube inserted into the
solution should be constricted to less than 3 mm (\1/8\ in.) ID and
should be immersed to a depth of at least 5 cm (2 in.). Immerse the
impingers in an ice water bath and maintain near 0 deg.C (32 deg.F).
The scrubber solution will normally last for a 3-hour run before needing
replacement. This will depend upon the effects of moisture and
particulate matter on the solution strength and pH. Connections between
the probe, particulate filter, and SO2 scrubber must be made
of Teflon and as short in length as possible. All portions of the probe,
particulate filter, and connections prior to the SO2 scrubber
(or alternative point of moisture removal) must be maintained at a
temperature of at least 120 deg.C (248 deg.F).
6.1.4 Sample Line. Teflon, no greater than 1.3 cm (\1/2\ in.) ID.
Alternative materials, such as virgin Nylon, may be used provided the
line loss test is acceptable.
6.1.5 Sample Pump. The sample pump must be a leakless Teflon-coated
diaphragm type or equivalent.
6.2 Analysis. The following items are needed for sample analysis:
6.2.1 Dilution System. Needed only for high sample concentrations.
The dilution system must be constructed such that all sample contacts
are made of Teflon, glass, or stainless steel.
6.2.2 Gas Chromatograph. The gas chromatograph must have at least
the following components:
6.2.2.1 Oven. Capable of maintaining the separation column at the
proper operating temperature 1 deg.C (2 deg.F).
6.2.2.2 Temperature Gauge. To monitor column oven, detector, and
exhaust temperature 1 deg.C (2 deg.F).
6.2.2.3 Flow System. Gas metering system to measure sample, fuel,
combustion gas, and carrier gas flows.
6.2.2.4 Flame Photometric Detector.
6.2.2.4.1 Electrometer. Capable of full scale amplification of
linear ranges of 10^-\9\ to 10^-\4\ amperes full
scale.
6.2.2.4.2 Power Supply. Capable of delivering up to 750 volts.
6.2.2.4.3 Recorder. Compatible with the output voltage range of the
electrometer.
6.2.2.4.4 Rotary Gas Valves. Multiport Teflon-lined valves equipped
with sample loop. Sample loop volumes must be chosen to provide the
needed analytical range. Teflon tubing and fittings must be used
throughout to present an inert surface for sample gas. The gas
chromatograph must be calibrated with the sample loop used for sample
analysis.
6.2.3 Gas Chromatogram Columns. The column system must be
demonstrated to be capable of resolving the four major reduced sulfur
compounds: H2S, MeSH, DMS, and DMDS. It must also demonstrate
freedom from known interferences. To demonstrate that adequate
resolution has been achieved, submit a chromatogram of a calibration gas
containing all four of the TRS compounds in the concentration range of
the applicable standard. Adequate resolution will be defined as base
line separation of adjacent peaks when the amplifier attenuation is set
so that the smaller peak is at least 50 percent of full scale. Baseline
separation is defined as a return to zero 5 percent in the
interval between peaks. Systems not meeting this criteria may be
considered alternate methods subject to the approval of the
Administrator.
6.3 Calibration. A calibration system, containing the following
components, is required (see Figure 16-2).
6.3.1 Tube Chamber. Chamber of glass or Teflon of sufficient
dimensions to house permeation tubes.
6.3.2 Flow System. To measure air flow over permeation tubes at
2 percent. Flow over the permeation device may also be
determined using a soap bubble flowmeter.
6.3.3 Constant Temperature Bath. Device capable of maintaining the
permeation tubes at the calibration temperature within 0.1 deg.C (0.2
deg.F).
6.3.4 Temperature Gauge. Thermometer or equivalent to monitor bath
temperature within 1 deg.C (2 deg.F).

7.0 Reagents and Standards

7.1 Fuel. Hydrogen (H2), prepurified grade or better.
7.2 Combustion Gas. Oxygen (O2) or air, research purity
or better.
7.3 Carrier Gas. Prepurified grade or better.
7.4 Diluent (if required). Air containing less than 50 ppb total
sulfur compounds and less than 10 ppmv each of moisture and total
hydrocarbons.

[[Page 409]]

7.5 Calibration Gases

7.5.1 Permeation tubes, one each of H2S, MeSH, DMS, and
DMDS, gravimetrically calibrated and certified at some convenient
operating temperature. These tubes consist of hermetically sealed FEP
Teflon tubing in which a liquified gaseous substance is enclosed. The
enclosed gas permeates through the tubing wall at a constant rate. When
the temperature is constant, calibration gases covering a wide range of
known concentrations can be generated by varying and accurately
measuring the flow rate of diluent gas passing over the tubes. These
calibration gases are used to calibrate the GC/FPD system and the
dilution system.
7.5.2 Cylinder Gases. Cylinder gases may be used as alternatives to
permeation devices. The gases must be traceable to a primary standard
(such as permeation tubes) and not used beyond the certification
expiration date.
7.6 Citrate Buffer and Sample Line Loss Gas. Same as Method 15,
Sections 7.6 and 7.7.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 15, Section 8.0, except that the references to the
dilution system may not be applicable.

9.0 Quality Control

10.0 Calibration and Standardization

Same as Method 15, Section 10.0, with the following addition and
exceptions:
10.1 Use the four compounds that comprise TRS instead of the three
reduced sulfur compounds measured by Method 15.
10.2 Flow Meter. Calibration before each test run is recommended,
but not required; calibration following each test series is mandatory.
Calibrate each flow meter after each complete test series with a wet-
test meter. If the flow measuring device differs from the wet-test meter
by 5 percent or more, the completed test runs must be voided.
Alternatively, the flow data that yield the lower flow measurement may
be used. Flow over the permeation device may also be determined using a
soap bubble flowmeter.

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this method (see
Section 8.0).

12.0 Data Analysis and Calculations

12.1 Concentration of Reduced Sulfur Compounds. Calculate the
average concentration of each of the four analytes (i.e., DMDS, DMS,
H2S, and MeSH) over the sample run (specified in Section 8.2
of Method 15 as 16 injections).
[GRAPHIC] [TIFF OMITTED] TR17OC00.278

Where:

Si = Concentration of any reduced sulfur compound from the
i^th sample injection, ppm.
C = Average concentration of any one of the reduced sulfur compounds for
the entire run, ppm.
N = Number of injections in any run period.
12.2 TRS Concentration. Using Equation 16-2, calculate the TRS
concentration for each sample run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.279

Where:

CTRS = TRS concentration, ppmv.
CH2S = Hydrogen sulfide concentration, ppmv.
CMeSH = Methyl mercaptan concentration, ppmv.
CDMS = Dimethyl sulfide concentration, ppmv.
CDMDS = Dimethyl disulfide concentration, ppmv.
d = Dilution factor, dimensionless.

[[Page 410]]

12.3 Average TRS Concentration. Calculate the average TRS
concentration for all sample runs performed.
[GRAPHIC] [TIFF OMITTED] TR17OC00.280

Where:

Average TRS = Average total reduced sulfur in ppm.
TRSi = Total reduced sulfur in ppm as determined by Equation
16-2.
N = Number of samples.
Bwo = Fraction of volume of water vapor in the gas stream as
determined by Method 4--Determination of Moisture in Stack
Gases.

13.0 Method Performance

13.1 Analytical Range. The analytical range will vary with the
sample loop size. Typically, the analytical range may extend from 0.1 to
100 ppmv using 10- to 0.1-ml sample loop sizes. This eliminates the need
for sample dilution in most cases.
13.2 Sensitivity. Using the 10-ml sample size, the minimum
detectable concentration is approximately 50 ppb.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. O'Keeffe, A.E., and G.C. Ortman. ``Primary Standards for Trace
Gas Analysis.'' Analytical Chemical Journal, 38,76. 1966.
2. Stevens, R.K., A.E. O'Keeffe, and G.C. Ortman. ``Absolute
Calibration of a Flame Photometric Detector to Volatile Sulfur Compounds
at Sub-Part-Per-Million Levels.'' Environmental Science and Technology,
3:7. July 1969.
3. Mulik, J.D., R.K. Stevens, and R. Baumgardner. ``An Analytical
System Designed to Measure Multiple Malodorous Compounds Related to
Kraft Mill Activities.'' Presented at the 12th Conference on Methods in
Air Pollution and Industrial Hygiene Studies, University of Southern
California, Los Angeles, CA. April 6-8, 1971.
4. Devonald, R.H., R.S. Serenius, and A.D. McIntyre. ``Evaluation of
the Flame Photometric Detector for Analysis of Sulfur Compounds.'' Pulp
and Paper Magazine of Canada, 73,3. March 1972.
5. Grimley, K.W., W.S. Smith, and R.M. Martin. ``The Use of a
Dynamic Dilution System in the Conditioning of Stack Gases for Automated
Analysis by a Mobile Sampling Van.'' Presented at the 63rd Annual APCA
Meeting, St. Louis, MO. June 14-19, 1970.
6. General Reference. Standard Methods of Chemical Analysis, Volumes
III-A and III-B Instrumental Methods. Sixth Edition. Van Nostrand
Reinhold Co.

[[Page 411]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.281

[[Page 412]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.282

Method 16A--Determination of Total Reduced Sulfur Emissions From
Stationary Sources (Impinger Technique)

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 6, and Method
16.

1.0 Scope and Application

1.1 Analytes.

[[Page 413]]

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total reduced sulfur (TRS) N/A See Section 13.1.
including:
Dimethyl disulfide [(CH3)2S2]. 62-49-20
Dimethyl sulfide [(CH3)2S].... 75-18-3
Hydrogen sulfide [H2S]........ 7783-06-4
Methyl mercaptan [CH4S]....... 74-93-1
Reduced sulfur (RS) including: N/A
H2S........................... 7783-06-4
Carbonyl sulfide [COS]........ 463-58-1
Carbon disulfide [CS2]........ 75-15-0
Reported as: Sulfur dioxide (SO2). 7449-09-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of TRS emissions from recovery boilers, lime kilns, and smelt dissolving
tanks at kraft pulp mills, reduced sulfur compounds (H2S,
carbonyl sulfide, and carbon disulfide from sulfur recovery units at
onshore natural gas processing facilities, and from other sources when
specified in an applicable subpart of the regulations. The flue gas must
contain at least 1 percent oxygen for complete oxidation of all TRS to
SO2.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the stack.
SO2 is removed selectively from the sample using a citrate
buffer solution. TRS compounds are then thermally oxidized to
SO2, collected in hydrogen peroxide as sulfate, and analyzed
by the Method 6 barium-thorin titration procedure.

3.0 Definitions. [Reserved]

4.0 Interferences

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train is shown in Figure 16A-1
and component parts are discussed below. Modifications to this sampling
train are acceptable provided the system performance check is met (see
Section 8.5).
6.1.1 Probe. Teflon tubing, 6.4-mm (\1/4\-in.) diameter,
sequentially wrapped with heat-resistant fiber strips, a rubberized heat
tape (plug at one end), and heat-resistant adhesive tape. A flexible
thermocouple or other suitable temperature measuring device

[[Page 414]]

should be placed between the Teflon tubing and the fiber strips so that
the temperature can be monitored to prevent softening of the probe. The
probe should be sheathed in stainless steel to provide in-stack
rigidity. A series of bored-out stainless steel fittings placed at the
front of the sheath will prevent moisture and particulate from entering
between the probe and sheath. A 6.4-mm (\1/4\-in.) Teflon elbow (bored
out) should be attached to the inlet of the probe, and a 2.54 cm (1 in.)
piece of Teflon tubing should be attached at the open end of the elbow
to permit the opening of the probe to be turned away from the
particulate stream; this will reduce the amount of particulate drawn
into the sampling train. The probe is depicted in Figure 16A-2.
6.1.2 Probe Brush. Nylon bristle brush with handle inserted into a
3.2-mm (\1/8\-in.) Teflon tubing. The Teflon tubing should be long
enough to pass the brush through the length of the probe.
6.1.3 Particulate Filter. 50-mm Teflon filter holder and a 1- to 2-
m porosity, Teflon filter (available through Savillex
Corporation, 5325 Highway 101, Minnetonka, Minnesota 55343). The filter
holder must be maintained in a hot box at a temperature sufficient to
prevent moisture condensation. A temperature of 121 deg.C (250 deg.F)
was found to be sufficient when testing a lime kiln under sub-freezing
ambient conditions.
6.1.4 SO2 Scrubber. Three 300-ml Teflon segmented
impingers connected in series with flexible, thick-walled, Teflon
tubing. (Impinger parts and tubing available through Savillex.) The
first two impingers contain 100 ml of citrate buffer and the third
impinger is initially dry. The tip of the tube inserted into the
solution should be constricted to less than 3 mm (\1/8\-in.) ID and
should be immersed to a depth of at least 5 cm (2 in.).
6.1.5 Combustion Tube. Quartz glass tubing with an expanded
combustion chamber 2.54 cm (1 in.) in diameter and at least 30.5 cm (12
in.) long. The tube ends should have an outside diameter of 0.6 cm (\1/
4\ in.) and be at least 15.3 cm (6 in.) long. This length is necessary
to maintain the quartz-glass connector near ambient temperature and
thereby avoid leaks. Alternatively, the outlet may be constructed with a
90-degree glass elbow and socket that would fit directly onto the inlet
of the first peroxide impinger.
6.1.6 Furnace. A furnace of sufficient size to enclose the
combustion chamber of the combustion tube with a temperature regulator
capable of maintaining the temperature at 800 100 deg.C
(1472 180 deg.F). The furnace operating temperature should
be checked with a thermocouple to ensure accuracy.
6.1.7 Peroxide Impingers, Stopcock Grease, Temperature Sensor,
Drying Tube, Valve, Pump, and Barometer. Same as Method 6, Sections
6.1.1.2, 6.1.1.4, 6.1.1.5, 6.1.1.6, 6.1.1.7, 6.1.1.8, and 6.1.2,
respectively, except that the midget bubbler of Method 6, Section
6.1.1.2 is not required.
6.1.8 Vacuum Gauge. At least 760 mm Hg (30 in. Hg) gauge.
6.1.9 Rate Meter. Rotameter, or equivalent, accurate to within 5
percent at the selected flow rate of approximately 2 liters/min (4.2
ft\3\/hr).
6.1.10 Volume Meter. Dry gas meter capable of measuring the sample
volume under the sampling conditions of 2 liters/min (4.2 ft\3\/hr) with
an accuracy of 2 percent.
6.2 Sample Recovery. Polyethylene Bottles, 250-ml (one per sample).
6.3 Sample Preparation and Analysis. Same as Method 6, Section 6.3,
except a 10-ml buret with 0.05-ml graduations is required, and the
spectrophotometer is not needed.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents must conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society. When such specifications are not
available, the best available grade must be used.
7.1 Sample Collection. The following reagents are required for
sample analysis:
7.1.1 Water. Same as in Method 6, Section 7.1.1.
7.1.2 Citrate Buffer. Dissolve 300 g of potassium citrate (or 284 g
of sodium citrate) and 41 g of anhydrous citric acid in 1 liter of water
(200 ml is needed per test). Adjust the pH to between 5.4 and 5.6 with
potassium citrate or citric acid, as required.
7.1.3 Hydrogen Peroxide, 3 percent. Same as in Method 6, Section
7.1.3 (40 ml is needed per sample).
7.1.4 Recovery Check Gas. Hydrogen sulfide (100 ppmv or less) in
nitrogen, stored in aluminum cylinders. Verify the concentration by
Method 11 or by gas chromatography where the instrument is calibrated
with an H2S permeation tube as described below. For Method
11, the relative standard deviation should not exceed 5 percent on at
least three 20-minute runs.
Note: Alternatively, hydrogen sulfide recovery gas generated from a
permeation device gravimetrically calibrated and certified at some
convenient operating temperature may be used. The permeation rate of the
device must be such that at a dilution gas flow rate of 3 liters/min
(6.4 ft\3\/hr), an H2S concentration in the range of the
stack gas or within 20 percent of the standard can be generated.
7.1.5 Combustion Gas. Gas containing less than 50 ppb reduced
sulfur compounds and less than 10 ppmv total hydrocarbons. The gas may
be generated from a clean-air system that purifies ambient air and
consists of the following components: Diaphragm pump, silica gel drying
tube, activated charcoal tube, and flow rate measuring device. Flow

[[Page 415]]

from a compressed air cylinder is also acceptable.
7.2 Sample Recovery and Analysis. Same as Method 6, Sections 7.2.1
and 7.3, respectively.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Preparation of Sampling Train.
8.1.1 For the SO2 scrubber, measure 100 ml of citrate
buffer into the first and second impingers; leave the third impinger
empty. Immerse the impingers in an ice bath, and locate them as close as
possible to the filter heat box. The connecting tubing should be free of
loops. Maintain the probe and filter temperatures sufficiently high to
prevent moisture condensation, and monitor with a suitable temperature
sensor.
8.1.2 For the Method 6 part of the train, measure 20 ml of 3
percent hydrogen peroxide into the first and second midget impingers.
Leave the third midget impinger empty, and place silica gel in the
fourth midget impinger. Alternatively, a silica gel drying tube may be
used in place of the fourth impinger. Maintain the oxidation furnace at
800 100 deg.C (1472 180 deg.F). Place
crushed ice and water around all impingers.
8.2 Citrate Scrubber Conditioning Procedure. Condition the citrate
buffer scrubbing solution by pulling stack gas through the Teflon
impingers and bypassing all other sampling train components. A purge
rate of 2 liters/min for 10 minutes has been found to be sufficient to
obtain equilibrium. After the citrate scrubber has been conditioned,
assemble the sampling train, and conduct (optional) a leak-check as
described in Method 6, Section 8.2.
8.3 Sample Collection. Same as in Method 6, Section 8.3, except the
sampling rate is 2 liters/min (10 percent) for 1 or 3 hours.
After the sample is collected, remove the probe from the stack, and
conduct (mandatory) a post-test leak-check as described in Method 6,
Section 8.2. The 15-minute purge of the train following collection
should not be performed. After each 3-hour test run (or after three 1-
hour samples), conduct one system performance check (see Section 8.5) to
determine the reduced sulfur recovery efficiency through the sampling
train. After this system performance check and before the next test run,
rinse and brush the probe with water, replace the filter, and change the
citrate scrubber (optional but recommended).

Note: In Method 16, a test run is composed of 16 individual analyses
(injects) performed over a period of not less than 3 hours or more than
6 hours. For Method 16A to be consistent with Method 16, the following
may be used to obtain a test run: (1) collect three 60-minute samples or
(2) collect one 3-hour sample. (Three test runs constitute a test.)
8.4 Sample Recovery. Disconnect the impingers. Quantitatively
transfer the contents of the midget impingers of the Method 6 part of
the train into a leak-free polyethylene bottle for shipment. Rinse the
three midget impingers and the connecting tubes with water and add the
washings to the same storage container. Mark the fluid level. Seal and
identify the sample container.
8.5 System Performance Check.
8.5.1 A system performance check is done (1) to validate the
sampling train components and procedure (prior to testing; optional) and
(2) to validate a test run (after a run). Perform a check in the field
prior to testing consisting of at least two samples (optional), and
perform an additional check after each 3 hour run or after three 1-hour
samples (mandatory).
8.5.2 The checks involve sampling a known concentration of
H2S and comparing the analyzed concentration with the known
concentration. Mix the H2S recovery check gas (Section 7.1.4)
and combustion gas in a dilution system such as that shown in Figure
16A-3. Adjust the flow rates to generate an H2S concentration
in the range of the stack gas or within 20 percent of the applicable
standard and an oxygen concentration greater than 1 percent at a total
flow rate of at least 2.5 liters/min (5.3 ft\3\/hr). Use Equation 16A-3
to calculate the concentration of recovery gas generated. Calibrate the
flow rate from both sources with a soap bubble flow meter so that the
diluted concentration of H2S can be accurately calculated.
8.5.3 Collect 30-minute samples, and analyze in the same manner as
the emission samples. Collect the sample through the probe of the
sampling train using a manifold or some other suitable device that will
ensure extraction of a representative sample.
8.5.4 The recovery check must be performed in the field prior to
replacing the SO2 scrubber and particulate filter and before
the probe is cleaned. Use Equation 16A-4 (see Section 12.5) to calculate
the recovery efficiency. Report the recovery efficiency with the
emission data; do not correct the emission data for the recovery
efficiency. A sample recovery of 100 20 percent must be
obtained for the emission data to be valid. However, if the recovery
efficiency is not in the 100 20 percent range but the
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may decide to accept the results of
the compliance test.

9.0 Quality Control

[[Page 416]]

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.5........................... System Ensure validity of
performance sampling train
check. components and
analytical
procedure.
8.2, 10.0..................... Sampling equipme Ensure accurate
nt leak-check measurement of stack
and calibration. gas flow rate,
sample volume.
10.0.......................... Barium standard Ensure precision of
solution normality
standardization. determination.
11.1.......................... Replicate Ensure precision of
titrations. titration
determinations.
11.2.......................... Audit sample Evaluate analyst's
analysis. technique and
standards
preparation.
------------------------------------------------------------------------

10.0 Calibration

Same as Method 6, Section 10.0.

11.0 Analytical Procedure

11.1 Sample Loss Check and Sample Analysis. Same as Method 6,
Sections 11.1 and 11.2, respectively, with the following exception: for
1-hour sampling, take a 40-ml aliquot, add 160 ml of 100 percent
isopropanol and four drops of thorin.
11.2 Audit Sample Analysis. Same as Method 6, Section 11.3.

12.0 Data Analysis and Calculations

In the calculations, at least one extra decimal figure should be
retained beyond that of the acquired data. Figures should be rounded off
after final calculations.
12.1 Nomenclature.

CTRS = Concentration of TRS as SO2, dry basis
corrected to standard conditions, ppmv.
CRG(act) = Actual concentration of recovery check gas (after
dilution), ppm.
CRG(m) = Measured concentration of recovery check gas
generated, ppm.
CH2S = Verified concentration of H2S recovery gas.
N = Normality of barium perchlorate titrant, milliequivalents/ml.
Pbar = Barometric pressure at exit orifice of the dry gas
meter, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
QH2S = Calibrated flow rate of H2S recovery gas,
liters/min.
QCG = Calibrated flow rate of combustion gas, liters/min.
R = Recovery efficiency for the system performance check, percent.
Tm = Average dry gas meter absolute temperature, deg.K
( deg.R).
Tstd = Standard absolute temperature, 293 deg.K (528
deg.R).
Va = Volume of sample aliquot titrated, ml.
Vm = Dry gas volume as measured by the dry gas meter, liters
(dcf).
Vm(std) = Dry gas volume measured by the dry gas meter,
corrected to standard conditions, liters (dscf).
Vsoln = Total volume of solution in which the sulfur dioxide
sample is contained, 100 ml.
Vt = Volume of barium perchlorate titrant used for the
sample, ml (average of replicate titrations).
Vtb = Volume of barium perchlorate titrant used for the
blank, ml.
Y = Dry gas meter calibration factor.
32.03 = Equivalent weight of sulfur dioxide, mg/meq.

12.2 Dry Sample Gas Volume, Corrected to Standard Conditions.
[GRAPHIC] [TIFF OMITTED] TR17OC00.283

Where:

K1 = 0.3855 deg.K/mm Hg for metric units,
= 17.65 deg.R/in. Hg for English units.

12.3 Concentration of TRS as ppm SO2.
[GRAPHIC] [TIFF OMITTED] TR17OC00.284

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.285

[[Page 417]]

12.4 Concentration of Recovery Gas Generated in the System
Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.286

12.5 Recovery Efficiency for the System Performance Check.
[GRAPHIC] [TIFF OMITTED] TR17OC00.287

13.0 Method Performance

13.1 Analytical Range. The lower detectable limit is 0.1 ppmv
SO2 when sampling at 2 liters/min (4.2 ft\3\/hr) for 3 hours
or 0.3 ppmv when sampling at 2 liters/min (4.2 ft\3\/hr) for 1 hour. The
upper concentration limit of the method exceeds the TRS levels generally
encountered at kraft pulp mills.
13.2 Precision. Relative standard deviations of 2.0 and 2.6 percent
were obtained when sampling a recovery boiler for 1 and 3 hours,
respectively.
13.3 Bias.
13.3.1 No bias was found in Method 16A relative to Method 16 in a
separate study at a recovery boiler.
13.3.2 Comparison of Method 16A with Method 16 at a lime kiln
indicated that there was no bias in Method 16A. However, instability of
the source emissions adversely affected the comparison. The precision of
Method 16A at the lime kiln was similar to that obtained at the recovery
boiler (Section 13.2.1).
13.3.3 Relative standard deviations of 2.7 and 7.7 percent have
been obtained for system performance checks.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

As an alternative to the procedures specified in Section 7.1.4, the
following procedure may be used to verify the H2S
concentration of the recovery check gas.
16.1 Summary. The H2S is collected from the calibration
gas cylinder and is absorbed in zinc acetate solution to form zinc
sulfide. The latter compound is then measured iodometrically.
16.2 Range. The procedure has been examined in the range of 5 to
1500 ppmv.
16.3 Interferences. There are no known interferences to this
procedure when used to analyze cylinder gases containing H2S
in nitrogen.
16.4 Precision and Bias. Laboratory tests have shown a relative
standard deviation of less than 3 percent. The procedure showed no bias
when compared to a gas chromatographic method that used gravimetrically
certified permeation tubes for calibration.
16.5 Equipment and Supplies.
16.5.1 Sampling Apparatus. The sampling train is shown in Figure
16A-4. Its component parts are discussed in Sections 16.5.1.1 through
16.5.2.
16.5.1.1 Sampling Line. Teflon tubing (\1/4\-in.) to connect the
cylinder regulator to the sampling valve.
16.5.1.2 Needle Valve. Stainless steel or Teflon needle valve to
control the flow rate of gases to the impingers.
16.5.1.3 Impingers. Three impingers of approximately 100-ml
capacity, constructed to permit the addition of reagents through the gas
inlet stem. The impingers shall be connected in series with leak-free
glass or Teflon connectors. The impinger bottoms have a standard 24/25
ground-glass fitting. The stems are from standard 6.4-mm (\1/4\-in.)
ball joint midget impingers, custom lengthened by about 1 in. When
fitted together, the stem end should be approximately 1.27 cm (\1/2\
in.) from the bottom (Southern Scientific, Inc., Micanopy, Florida: Set
Number S6962-048). The third in-line impinger acts as a drop-out bottle.
16.5.1.4 Drying Tube, Rate Meter, and Barometer. Same as Method 11,
Sections 6.1.5, 6.1.8, and 6.1.10, respectively.
16.5.1.5 Cylinder Gas Regulator. Stainless steel, to reduce the
pressure of the gas stream entering the Teflon sampling line to a safe
level.
16.5.1.6 Soap Bubble Meter. Calibrated for 100 and 500 ml, or two
separate bubble meters.
16.5.1.7 Critical Orifice. For volume and rate measurements. The
critical orifice may be fabricated according to Section 16.7.3 and must
be calibrated as specified in Section 16.12.4.
16.5.1.8 Graduated Cylinder. 50-ml size.
16.5.1.9 Volumetric Flask. 1-liter size.
16.5.1.10 Volumetric Pipette. 15-ml size.
16.5.1.11 Vacuum Gauge. Minimum 20 in. Hg capacity.
16.5.1.12 Stopwatch.
16.5.2 Sample Recovery and Analysis.
16.5.2.1 Erlenmeyer Flasks. 125- and 250-ml sizes.
16.5.2.2 Pipettes. 2-, 10-, 20-, and 100-ml volumetric.
16.5.2.3 Burette. 50-ml size.
16.5.2.4 Volumetric Flask. 1-liter size.
16.5.2.5 Graduated Cylinder. 50-ml size.
16.5.2.6 Wash Bottle.
16.5.2.7 Stirring Plate and Bars.
16.6 Reagents and Standards. Unless otherwise indicated, all
reagents must conform to the specifications established by the Committee
on Analytical Reagents of the American Chemical Society, where such
specifications are available. Otherwise, use the best available grade.

[[Page 418]]

16.6.1 Water. Same as Method 11, Section 7.1.3.
16.6.2 Zinc Acetate Absorbing Solution. Dissolve 20 g zinc acetate
in water, and dilute to 1 liter.
16.6.3 Potassium Bi-iodate [KH(IO3)2]
Solution, Standard 0.100 N. Dissolve 3.249 g anhydrous
KH(IO3)2 in water, and dilute to 1 liter.
16.6.4 Sodium Thiosulfate
(Na2S2O3) Solution, Standard 0.1 N.
Same as Method 11, Section 7.3.2. Standardize according to Section
16.12.2.
16.6.5 Na2S2O3 Solution, Standard
0.01 N. Pipette 100.0 ml of 0.1 N
Na2S2O3 solution into a 1-liter
volumetric flask, and dilute to the mark with water.
16.6.6 Iodine Solution, 0.1 N. Same as Method 11, Section 7.2.3.
16.6.7 Standard Iodine Solution, 0.01 N. Same as in Method 11,
Section 7.2.4. Standardize according to Section 16.12.3.
16.6.8 Hydrochloric Acid (HCl) Solution, 10 Percent by Weight. Add
230 ml concentrated HCl (specific gravity 1.19) to 770 ml water.
16.6.9 Starch Indicator Solution. To 5 g starch (potato, arrowroot,
or soluble), add a little cold water, and grind in a mortar to a thin
paste. Pour into 1 liter of boiling water, stir, and let settle
overnight. Use the clear supernatant. Preserve with 1.25 g salicylic
acid, 4 g zinc chloride, or a combination of 4 g sodium propionate and 2
g sodium azide per liter of starch solution. Some commercial starch
substitutes are satisfactory.
16.7 Pre-test Procedures.
16.7.1 Selection of Gas Sample Volumes. This procedure has been
validated for estimating the volume of cylinder gas sample needed when
the H2S concentration is in the range of 5 to 1500 ppmv. The
sample volume ranges were selected in order to ensure a 35 to 60 percent
consumption of the 20 ml of 0.01 N iodine (thus ensuring a 0.01 N
Na2S2O3 titer of approximately 7 to 12
ml). The sample volumes for various H2S concentrations can be
estimated by dividing the approximate ppm-liters desired for a given
concentration range by the H2S concentration stated by the
manufacturer. For example, for analyzing a cylinder gas containing
approximately 10 ppmv H2S, the optimum sample volume is 65
liters (650 ppm-liters/10 ppmv). For analyzing a cylinder gas containing
approximately 1000 ppmv H2S, the optimum sample volume is 1
liter (1000 ppm-liters/1000 ppmv).

------------------------------------------------------------------------
Approximate
Approximate cylinder gas H2S concentration (ppmv) ppm-liters
desired
------------------------------------------------------------------------
5 to 30................................................. 650
30 to 500............................................... 800
500 to 1500............................................. 1000
------------------------------------------------------------------------

16.7.2 Critical Orifice Flow Rate Selection. The following table
shows the ranges of sample flow rates that are desirable in order to
ensure capture of H2S in the impinger solution. Slight
deviations from these ranges will not have an impact on measured
concentrations.

------------------------------------------------------------------------
Critical orifice flow rate
Cylinder gas H2S concentration (ppmv) (ml/min)
------------------------------------------------------------------------
5 to 50 ppmv............................. 1500 500
50 to 250 ppmv........................... 500 250
250 to 1000 ppmv......................... 200 50
>1000 ppmv............................... 75 25
------------------------------------------------------------------------

16.7.3 Critical Orifice Fabrication. Critical orifice of desired
flow rates may be fabricated by selecting an orifice tube of desired
length and connecting \1/16\-in. x \1/4\-in. (0.16 cm x 0.64 cm)
reducing fittings to both ends. The inside diameters and lengths of
orifice tubes needed to obtain specific flow rates are shown below.

----------------------------------------------------------------------------------------------------------------
Flowrate (ml/ Altech
Tube (in. OD) Tube (in. ID) Length (in.) min) Catalog No.
----------------------------------------------------------------------------------------------------------------
\1/16\.......................................... 0.007 1.2 85 301430
\1/16\.......................................... 0.01 3.2 215 300530
\1/16\.......................................... 0.01 1.2 350 300530
\1/16\.......................................... 0.02 1.2 1400 300230
----------------------------------------------------------------------------------------------------------------

16.7.4 Determination of Critical Orifice Approximate Flow Rate.
Connect the critical orifice to the sampling system as shown in Figure
16A-4 but without the H2S cylinder. Connect a rotameter in
the line to the first impinger. Turn on the pump, and adjust the valve
to give a reading of about half atmospheric pressure. Observe the
rotameter reading. Slowly increase the vacuum until a stable flow rate
is reached, and record this as the critical vacuum. The measured flow
rate indicates the expected critical flow rate of the orifice. If this
flow rate is in the range shown in Section 16.7.2, proceed with the
critical orifice calibration according to Section 16.12.4.
16.7.5 Determination of Approximate Sampling Time. Determine the
approximate sampling time for a cylinder of known concentration. Use the
optimum sample volume obtained in Section 16.7.1.

[[Page 419]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.288

16.8 Sample Collection.
16.8.1 Connect the Teflon tubing, Teflon tee, and rotameter to the
flow control needle valve as shown in Figure 16A-4. Vent the rotameter
to an exhaust hood. Plug the open end of the tee. Five to 10 minutes
prior to sampling, open the cylinder valve while keeping the flow
control needle valve closed. Adjust the delivery pressure to 20 psi.
Open the needle valve slowly until the rotameter shows a flow rate
approximately 50 to 100 ml above the flow rate of the critical orifice
being used in the system.
16.8.2 Place 50 ml of zinc acetate solution in two of the
impingers, connect them and the empty third impinger (dropout bottle)
and the rest of the equipment as shown in Figure 16A-4. Make sure the
ground-glass fittings are tight. The impingers can be easily stabilized
by using a small cardboard box in which three holes have been cut, to
act as a holder. Connect the Teflon sample line to the first impinger.
Cover the impingers with a dark cloth or piece of plastic to protect the
absorbing solution from light during sampling.
16.8.3 Record the temperature and barometric pressure. Note the gas
flow rate through the rotameter. Open the closed end of the tee. Connect
the sampling tube to the tee, ensuring a tight connection. Start the
sampling pump and stopwatch simultaneously. Note the decrease in flow
rate through the excess flow rotameter. This decrease should equal the
known flow rate of the critical orifice being used. Continue sampling
for the period determined in Section 16.7.5.
16.8.4 When sampling is complete, turn off the pump and stopwatch.
Disconnect the sampling line from the tee and plug it. Close the needle
valve followed by the cylinder valve. Record the sampling time.
16.9 Blank Analysis. While the sample is being collected, run a
blank as follows: To a 250-ml Erlenmeyer flask, add 100 ml of zinc
acetate solution, 20.0 ml of 0.01 N iodine solution, and 2 ml HCl
solution. Titrate, while stirring, with 0.01 N
Na2S2O3 until the solution is light
yellow. Add starch, and continue titrating until the blue color
disappears. Analyze a blank with each sample, as the blank titer has
been observed to change over the course of a day.

Note: Iodine titration of zinc acetate solutions is difficult to
perform because the solution turns slightly white in color near the end
point, and the disappearance of the blue color is hard to recognize. In
addition, a blue color may reappear in the solution about 30 to 45
seconds after the titration endpoint is reached. This should not be
taken to mean the original endpoint was in error. It is recommended that
persons conducting this test perform several titrations to be able to
correctly identify the endpoint. The importance of this should be
recognized because the results of this analytical procedure are
extremely sensitive to errors in titration.

16.10 Sample Analysis. Sample treatment is similar to the blank
treatment. Before detaching the stems from the bottoms of the impingers,
add 20.0 ml of 0.01 N iodine solution through the stems of the impingers
holding the zinc acetate solution, dividing it between the two (add
about 15 ml to the first impinger and the rest to the second). Add 2 ml
HCl solution through the stems, dividing it as with the iodine.
Disconnect the sampling line, and store the impingers for 30 minutes. At
the end of 30 minutes, rinse the impinger stems into the impinger
bottoms. Titrate the impinger contents with 0.01 N
Na2S2O3. Do not transfer the contents
of the impinger to a flask because this may result in a loss of iodine
and cause a positive bias.
16.11 Post-test Orifice Calibration. Conduct a post-test critical
orifice calibration run using the calibration procedures outlined in
Section 16.12.4. If the Qstd obtained before and after the
test differs by more than 5 percent, void the sample; if not, proceed to
perform the calculations.
16.12 Calibrations and Standardizations.
16.12.1 Rotameter and Barometer. Same as Method 11, Sections 10.1.3
and 10.1.4.
16.12.2 Na2S2O3 Solution, 0.1 N.
Standardize the 0.1 N Na2S2O3 solution
as follows: To 80 ml water, stirring constantly, add 1 ml concentrated
H2SO4, 10.0 ml of 0.100 N
KH(IO3)2 and 1 g potassium iodide. Titrate
immediately with 0.1 N Na2S2O3 until
the solution is light yellow. Add 3 ml starch solution, and titrate
until the blue color just disappears. Repeat the titration until
replicate analyses agree within 0.05 ml. Take the average volume of
Na2S2O3 consumed to calculate the
normality to three decimal figures using Equation 16A-5.
16.12.3 Iodine Solution, 0.01 N. Standardize the 0.01 N iodine
solution as follows: Pipet 20.0 ml of 0.01 N iodine solution into a 125-
ml Erlenmeyer flask. Titrate with standard 0.01 N
Na2S2O3 solution until the solution is
light yellow. Add 3 ml starch solution, and continue titrating until the
blue color just disappears. If the normality of the iodine tested is not
0.010, add a few ml of 0.1 N iodine solution if it is low, or a few ml
of water if it is high, and standardize again. Repeat

[[Page 420]]

the titration until replicate values agree within 0.05 ml. Take the
average volume to calculate the normality to three decimal figures using
Equation 16A-6.
16.12.4 Critical Orifice. Calibrate the critical orifice using the
sampling train shown in Figure 16A-4 but without the H2S
cylinder and vent rotameter. Connect the soap bubble meter to the Teflon
line that is connected to the first impinger. Turn on the pump, and
adjust the needle valve until the vacuum is higher than the critical
vacuum determined in Section 16.7.4. Record the time required for gas
flow to equal the soap bubble meter volume (use the 100-ml soap bubble
meter for gas flow rates below 100 ml/min, otherwise use the 500-ml soap
bubble meter). Make three runs, and record the data listed in Table 16A-
1. Use these data to calculate the volumetric flow rate of the orifice.
16.13 Calculations.
16.13.1 Nomenclature.

Bwa = Fraction of water vapor in ambient air during orifice
calibration.
CH2S = H2S concentration in cylinder
gas, ppmv.
[GRAPHIC] [TIFF OMITTED] TR17OC00.289

Ma = Molecular weight of ambient air saturated at impinger
temperature, g/g-mole.
Ms = Molecular weight of sample gas (nitrogen) saturated at
impinger temperature, g/g-mole.

Note: (For tests carried out in a laboratory where the impinger
temperature is 25 deg.C, Ma = 28.5 g/g-mole and
Ms = 27.7 g/g-mole.)

NI = Normality of standard iodine solution (0.01 N), g-eq/
liter.
NT = Normality of standard
Na2S2O3 solution (0.01 N), g-
eq/liter.
Pbar = Barometric pressure, mm Hg.
Pstd = Standard absolute pressure, 760 mm Hg.
Qstd = Average volumetric flow rate through critical orifice,
liters/min.
Tamb = Absolute ambient temperature, deg.K.
Tstd = Standard absolute temperature, 293 deg.K.
s = Sampling time, min.
sb = Time for soap bubble meter flow rate
measurement, min.
Vm(std) = Sample gas volume measured by the critical orifice,
corrected to standard conditions, liters.
Vsb = Volume of gas as measured by the soap bubble meter, ml.
Vsb(std) = Volume of gas as measured by the soap bubble
meter, corrected to standard conditions, liters.
VI = Volume of standard iodine solution (0.01 N) used, ml.
VT = Volume of standard
Na2S2O3 solution (0.01 N) used,
ml.
VTB = Volume of standard
Na2S2O3 solution (0.01 N) used
for the blank, ml.

16.13.2 Normality of Standard Na2S2O3
Solution (0.1 N).
[GRAPHIC] [TIFF OMITTED] TR17OC00.290

16.13.3 Normality of Standard Iodine Solution (0.01 N).
[GRAPHIC] [TIFF OMITTED] TR17OC00.291

16.13.4 Sample Gas Volume.
[GRAPHIC] [TIFF OMITTED] TR17OC00.292

[[Page 421]]

16.13.5 Concentration of H2S in the Gas Cylinder.

17.0 References
[GRAPHIC] [TIFF OMITTED] TR17OC00.293

1. American Public Health Association, American Water Works
Association, and Water Pollution Control Federation. Standard Methods
for the Examination of Water and Wastewater. Washington, DC. American
Public Health Association. 1975. pp. 316-317.
2. American Society for Testing and Materials. Annual Book of ASTM
Standards. Part 31: Water, Atmospheric Analysis. Philadelphia, PA. 1974.
pp. 40-42.
3. Blosser, R.O. A Study of TRS Measurement Methods. National
Council of the Paper Industry for Air and Stream Improvement, Inc., New
York, NY. Technical Bulletin No. 434. May 1984. 14 pp.
4. Blosser, R.O., H.S. Oglesby, and A.K. Jain. A Study of Alternate
SO2 Scrubber Designs Used for TRS Monitoring. A Special
Report by the National Council of the Paper Industry for Air and Stream
Improvement, Inc., New York, NY. July 1977.
5. Curtis, F., and G.D. McAlister. Development and Evaluation of an
Oxidation/Method 6 TRS Emission Sampling Procedure. Emission Measurement
Branch, Emission Standards and Engineering Division, U.S. Environmental
Protection Agency, Research Triangle Park, NC 27711. February 1980.
6. Gellman, I. A Laboratory and Field Study of Reduced Sulfur
Sampling and Monitoring Systems. National Council of the Paper Industry
for Air and Stream Improvement, Inc., New York, NY. Atmospheric Quality
Improvement Technical Bulletin No. 81. October 1975.
7. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method for
TRS Determination. Source Branch, Quality Assurance Division, U.S.
Environmental Protection Agency, Research Triangle Park, NC 27711.
8. National Council of the Paper Industry for Air and Stream
Improvement. An Investigation of H2S and SO2.
Calibration Cylinder Gas Stability and Their Standardization Using Wet
Chemical Techniques. Special Report 76-06. New York, NY. August 1976.
9. National Council of the Paper Industry for Air and Stream
Improvement. Wet Chemical Method for Determining the H2S
Concentration of Calibration Cylinder Gases. Technical Bulletin Number
450. New York, NY. January 1985. 23 pp.
10. National Council of the Paper Industry for Air and Stream
Improvement. Modified Wet Chemical Method for Determining the
H2S Concentration of Calibration Cylinder Gases. Draft
Report. New York, NY. March 1987. 29 pp.

[[Page 422]]

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.294

[[Page 423]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.295

[[Page 424]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.296

[[Page 425]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.297

[[Page 426]]

Date

Critical orifice ID

Soap bubble meter volume, Vsb____ liters
Time, sb
Run no. 1 ____ min ____ sec
Run no. 2 ____ min ____ sec
Run no. 3 ____ min ____ sec
Average ____ min ____ sec
Covert the seconds to fraction of minute:
Time = ____ min + ____ Sec/60 = ____ min
Barometric pressure, Pbar = ____ mm Hg
Ambient temperature, t amb = 273 + ____ deg.C = ____ deg.K
= ____ mm Hg. (This should be approximately 0.4 times barometric
pressure.)
[GRAPHIC] [TIFF OMITTED] TR17OC00.298

Table 16A-1. Critical Orifice Calibration Data

Method 16B--Determination of Total Reduced Sulfur Emissions From
Stationary Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a knowledge of at least the
following additional test methods: Method 6C, Method 16, and Method 16A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Total reduced sulfur (TRS) including: N/A
Dimethyl disulfide (DMDS), [(CH3)2S2]............... 62-49-20
Dimethyl sulfide (DMS), [(CH3)2S]................... 75-18-3
Hydrogen sulfide (H2S).............................. 7783-06-4
Methyl mercaptan (MeSH), [CH4S]..................... 74-93-1
Reported as: Sulfur dioxide (SO2)....................... 7449-09-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for determining TRS
emissions from recovery furnaces (boilers), lime kilns, and smelt
dissolving tanks at kraft pulp mills, and from other sources when
specified in an applicable subpart of the regulations. The flue gas must
contain at least 1 percent oxygen for complete oxidation of all TRS to
SO2.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

[[Page 427]]

2.0 Summary of Method

2.1 An integrated gas sample is extracted from the stack. The
SO2 is removed selectively from the sample using a citrate
buffer solution. The TRS compounds are then thermally oxidized to
SO2 and analyzed as SO2 by gas chromatography (GC)
using flame photometric detection (FPD).

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Reduced sulfur compounds other than those regulated by the
emission standards, if present, may be measured by this method.
Therefore, carbonyl sulfide, which is partially oxidized to
SO2 and may be present in a lime kiln exit stack, would be a
positive interferant.
4.2 Particulate matter from the lime kiln stack gas (primarily
calcium carbonate) can cause a negative bias if it is allowed to enter
the citrate scrubber; the particulate matter will cause the pH to rise
and H2S to be absorbed before oxidation. Proper use of the
particulate filter, described in Section 6.1.3 of Method 16A, will
eliminate this interference.
4.3 Carbon monoxide (CO) and carbon dioxide (CO2) have
substantial desensitizing effects on the FPD even after dilution.
Acceptable systems must demonstrate that they have eliminated this
interference by some procedure such as eluting these compounds before
the SO2. Compliance with this requirement can be demonstrated
by submitting chromatograms of calibration gases with and without
CO2 in diluent gas. The CO2 level should be
approximately 10 percent for the case with CO2 present. The
two chromatograms should show agreement within the precision limits of
Section 13.0.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling train is shown in Figure 16B-1.
Modifications to the apparatus are accepted provided the system
performance check in Section 8.4.1 is met.
6.1.1 Probe, Probe Brush, Particulate Filter, SO2
Scrubber, Combustion Tube, and Furnace. Same as in Method 16A, Sections
6.1.1 to 6.1.6.
6.1.2 Sampling Pump. Leakless Teflon-coated diaphragm type or
equivalent.
6.2 Analysis.
6.2.1 Dilution System (optional), Gas Chromatograph, Oven,
Temperature Gauges, Flow System, Flame Photometric Detector,
Electrometer, Power Supply, Recorder, Calibration System, Tube Chamber,
Flow System, and Constant Temperature Bath. Same as in Method 16,
Sections 6.2.1, 6.2.2, and 6.3.
6.2.2 Gas Chromatograph Columns. Same as in Method 16, Section
6.2.3. Other columns with demonstrated ability to resolve SO2
and be free from known interferences are acceptable alternatives. Single
column systems such as a 7-ft Carbsorb B HT 100 column have been found
satisfactory in resolving SO2 from CO2.

7.0 Reagents and Standards

Same as in Method 16, Section 7.0, except for the following:
7.1 Calibration Gas. SO2 permeation tube gravimetrically
calibrated and certified at some convenient operating temperature. These
tubes consist of hermetically sealed FEP Teflon tubing in which a
liquefied gaseous substance is enclosed. The enclosed gas permeates
through the tubing wall at a constant rate. When the temperature is
constant, calibration gases covering a wide range of known
concentrations can be generated by varying and accurately measuring the
flow rate of diluent gas passing over the tubes. In place of
SO2 permeation tubes, cylinder gases containing
SO2 in nitrogen may be used for calibration. The cylinder gas
concentration must be verified according to Section 8.2.1 of Method 6C.
The calibration gas is used to calibrate the GC/FPD system and the
dilution system.
7.2 Recovery Check Gas.
7.2.1 Hydrogen sulfide [100 parts per million by volume (ppmv) or
less] in nitrogen, stored in aluminum cylinders. Verify the
concentration by Method 11, the procedure discussed in Section 16.0 of
Method 16A, or gas chromatography where the instrument is calibrated
with an H2S permeation tube as described below. For the wet-
chemical methods, the standard deviation should not exceed 5 percent on
at least three 20-minute runs.
7.2.2 Hydrogen sulfide recovery gas generated from a permeation
device gravimetrically calibrated and certified at some convenient
operation temperature may be used. The permeation rate of the device
must be such that at a dilution gas flow rate of 3 liters/min (64 ft\3\/
hr), an H2S concentration in

[[Page 428]]

the range of the stack gas or within 20 percent of the emission standard
can be generated.
7.3 Combustion Gas. Gas containing less than 50 ppbv reduced sulfur
compounds and less than 10 ppmv total hydrocarbons. The gas may be
generated from a clean-air system that purifies ambient air and consists
of the following components: diaphragm pump, silica gel drying tube,
activated charcoal tube, and flow rate measuring device. Gas from a
compressed air cylinder is also acceptable.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Procedures. Same as in Method 15, Section 8.1.
8.2 Sample Collection. Before any source sampling is performed,
conduct a system performance check as detailed in Section 8.4.1 to
validate the sampling train components and procedures. Although this
test is optional, it would significantly reduce the possibility of
rejecting tests as a result of failing the post-test performance check.
At the completion of the pretest system performance check, insert the
sampling probe into the test port making certain that no dilution air
enters the stack though the port. Condition the entire system with
sample for a minimum of 15 minutes before beginning analysis. If the
sample is diluted, determine the dilution factor as in Section 10.4 of
Method 15.
8.3 Analysis. Inject aliquots of the sample into the GC/FPD
analyzer for analysis. Determine the concentration of SO2
directly from the calibration curves or from the equation for the least-
squares line.
8.4. Post-Test Procedures
8.4.1 System Performance Check. Same as in Method 16A, Section 8.5.
A sufficient number of sample injections should be made so that the
precision requirements of Section 13.2 are satisfied.
8.4.2 Determination of Calibration Drift. Same as in Method 15,
Section 8.3.2.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.2, 8.3...................... System Ensure validity of
performance sampling train
check. components and
analytical
procedure.
8.1........................... Sampling Ensure accurate
equipment leak- measurement of stack
check and gas flow rate,
calibration. sample volume.
10.0.......................... Analytical Ensure precision of
calibration. analytical results
within 5 percent.
------------------------------------------------------------------------

10.0 Calibration

Same as in Method 16, Section 10, except SO2 is used instead
of H2S.

11.0 Analytical Procedure

11.1 Sample collection and analysis are concurrent for this method (see
section 8.3).
12.0 Data Analysis and Calculations
12.1 Nomenclature.

CSO2 = Sulfur dioxide concentration,
ppmv.
CTRS = Total reduced sulfur
concentration as determined by Equation 16B-1, ppmv.
d = Dilution factor, dimensionless.
N = Number of samples.

12.2 SO2 Concentration. Determine the concentration of
SO2, CSO2, directly from the
calibration curves. Alternatively, the concentration may be calculated
using the equation for the least-squares line.
12.3 TRS Concentration.
[GRAPHIC] [TIFF OMITTED] TR17OC00.299

12.4 Average TRS Concentration
[GRAPHIC] [TIFF OMITTED] TR17OC00.300

13.0 Method Performance.

13.1 Range and Sensitivity. Coupled with a GC using a 1-ml sample
size, the maximum limit of the FPD for SO2 is approximately
10 ppmv. This limit is extended by diluting the sample gas before
analysis or by reducing the sample aliquot size. For sources with
emission levels between 10 and 100 ppm, the measuring range can be best
extended by reducing the sample size.
13.2 GC/FPD Calibration and Precision. A series of three
consecutive injections of the

[[Page 429]]

sample calibration gas, at any dilution, must produce results which do
not vary by more than 5 percent from the mean of the three injections.
13.3 Calibration Drift. The calibration drift determined from the
mean of the three injections made at the beginning and end of any run or
series of runs within a 24-hour period must not exceed 5 percent.
13.4 System Calibration Accuracy. Losses through the sample
transport system must be measured and a correction factor developed to
adjust the calibration accuracy to 100 percent.
13.5 Field tests between this method and Method 16A showed an
average difference of less than 4.0 percent. This difference was not
determined to be significant.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Same as in Method 16, Section 16.0.
2. National Council of the Paper Industry for Air and Stream
Improvement, Inc, A Study of TRS Measurement Methods. Technical Bulletin
No. 434. New York, NY. May 1984. 12p.
3. Margeson, J.H., J.E. Knoll, and M.R. Midgett. A Manual Method for
TRS Determination. Draft available from the authors. Source Branch,
Quality Assurance Division, U.S. Environmental Protection Agency,
Research Triangle Park, NC 27711.

[[Page 430]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.301

Method 17--Determination of Particulate Matter Emissions From Stationary
Sources

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 5.

[[Page 431]]

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
Note: Particulate matter is not an absolute quantity. It is a
function of temperature and pressure. Therefore, to prevent variability
in PM emission regulations and/or associated test methods, the
temperature and pressure at which PM is to be measured must be carefully
defined. Of the two variables (i.e., temperature and pressure),
temperature has the greater effect upon the amount of PM in an effluent
gas stream; in most stationary source categories, the effect of pressure
appears to be negligible. In Method 5, 120 deg.C (248 deg.F) is
established as a nominal reference temperature. Thus, where Method 5 is
specified in an applicable subpart of the standard, PM is defined with
respect to temperature. In order to maintain a collection temperature of
120 deg.C (248 deg.F), Method 5 employs a heated glass sample probe
and a heated filter holder. This equipment is somewhat cumbersome and
requires care in its operation. Therefore, where PM concentrations (over
the normal range of temperature associated with a specified source
category) are known to be independent of temperature, it is desirable to
eliminate the glass probe and the heating systems, and to sample at
stack temperature.
1.2 Applicability. This method is applicable for the determination
of PM emissions, where PM concentrations are known to be independent of
temperature over the normal range of temperatures characteristic of
emissions from a specified source category. It is intended to be used
only when specified by an applicable subpart of the standards, and only
within the applicable temperature limits (if specified), or when
otherwise approved by the Administrator. This method is not applicable
to stacks that contain liquid droplets or are saturated with water
vapor. In addition, this method shall not be used as written if the
projected cross-sectional area of the probe extension-filter holder
assembly covers more than 5 percent of the stack cross-sectional area
(see Section 8.1.2).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter is withdrawn isokinetically from the source
and collected on a glass fiber filter maintained at stack temperature.
The PM mass is determined gravimetrically after the removal of
uncombined water.

3.0 Definitions

Same as Method 5, Section 3.0.

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Sampling Train. A schematic of the sampling train used in this
method is shown in Figure 17-1. The sampling train components and
operation and maintenance are very similar to Method 5, which should be
consulted for details.
6.1.1 Probe Nozzle, Differential Pressure Gauge, Metering System,
Barometer, Gas Density Determination Equipment. Same as in Method 5,
Sections 6.1.1, 6.1.4, 6.1.8, 6.1.9, and 6.1.10, respectively.
6.1.2 Filter Holder. The in-stack filter holder shall be
constructed of borosilicate or quartz glass, or stainless steel. If a
gasket is used, it shall be made of silicone rubber, Teflon, or
stainless steel. Other holder and gasket materials may be used, subject
to the approval of the Administrator. The filter holder shall be
designed to provide a positive seal against leakage from the outside or
around the filter.
6.1.3 Probe Extension. Any suitable rigid probe extension may be
used after the filter holder.
6.1.4 Pitot Tube. Same as in Method 5, Section 6.1.3.
6.1.4.1 It is recommended (1) that the pitot tube have a known
baseline coefficient, determined as outlined in Section 10 of Method 2;
and (2) that this known coefficient be preserved by placing the pitot
tube in an interference-free arrangement with respect to the sampling
nozzle, filter holder, and temperature sensor (see Figure 17-1). Note
that the 1.9 cm (\3/4\-in.) free-space between the nozzle and pitot tube
shown in Figure 17-1, is based on a 1.3 cm (\1/2\-in.) ID nozzle. If the
sampling train is designed for sampling at higher flow rates than that
described in APTD-0581, thus necessitating the use of larger sized
nozzles, the free-space shall be 1.9 cm (\3/4\-in.) with the largest
sized nozzle in place.
6.1.4.2 Source-sampling assemblies that do not meet the minimum
spacing requirements of Figure 17-1 (or the equivalent of these
requirements, e.g., Figure 2-4 of Method 2) may be used; however, the
pitot tube coefficients of such assemblies shall be determined by
calibration, using methods subject to the approval of the Administrator.

[[Page 432]]

6.1.5 Condenser. It is recommended that the impinger system or
alternatives described in Method 5 be used to determine the moisture
content of the stack gas. Flexible tubing may be used between the probe
extension and condenser. Long tubing lengths may affect the moisture
determination.
6.2 Sample Recovery. Probe-liner and probe-nozzle brushes, wash
bottles, glass sample storage containers, petri dishes, graduated
cylinder and/or balance, plastic storage containers, funnel and rubber
policeman, funnel. Same as in Method 5, Sections 6.2.1 through 6.2.8,
respectively.
6.3 Sample Analysis. Glass weighing dishes, desiccator, analytical
balance, balance, beakers, hygrometer, temperature sensor. Same as in
Method 5, Sections 6.3.1 through 6.3.7, respectively.

7.0 Reagents and Standards

7.1 Sampling. Filters, silica gel, water, crushed ice, stopcock
grease. Same as in Method 5, Sections 7.1.1, 7.1.2, 7.1.3, 7.1.4, and
7.1.5, respectively. Thimble glass fiber filters may also be used.
7.2 Sample Recovery. Acetone (reagent grade). Same as in Method 5,
Section 7.2.
7.3 Sample Analysis. Acetone and Desiccant. Same as in Method 5,
Sections 7.3.1 and 7.3.2, respectively.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling.
8.1.1 Pretest Preparation. Same as in Method 5, Section 8.1.1.
8.1.2 Preliminary Determinations. Same as in Method 5, Section
8.1.2, except as follows: Make a projected-area model of the probe
extension-filter holder assembly, with the pitot tube face openings
positioned along the centerline of the stack, as shown in Figure 17-2.
Calculate the estimated cross-section blockage, as shown in Figure 17-2.
If the blockage exceeds 5 percent of the duct cross sectional area, the
tester has the following options exist: (1) a suitable out-of-stack
filtration method may be used instead of in-stack filtration; or (2) a
special in-stack arrangement, in which the sampling and velocity
measurement sites are separate, may be used; for details concerning this
approach, consult with the Administrator (see also Reference 1 in
Section 17.0). Select a probe extension length such that all traverse
points can be sampled. For large stacks, consider sampling from opposite
sides of the stack to reduce the length of probes.
8.1.3 Preparation of Sampling Train. Same as in Method 5, Section
8.1.3, except the following: Using a tweezer or clean disposable
surgical gloves, place a labeled (identified) and weighed filter in the
filter holder. Be sure that the filter is properly centered and the
gasket properly placed so as not to allow the sample gas stream to
circumvent the filter. Check filter for tears after assembly is
completed. Mark the probe extension with heat resistant tape or by some
other method to denote the proper distance into the stack or duct for
each sampling point. Assemble the train as in Figure 17-1, using a very
light coat of silicone grease on all ground glass joints and greasing
only the outer portion (see APTD-0576) to avoid possibility of
contamination by the silicone grease. Place crushed ice around the
impingers.
8.1.4 Leak-Check Procedures. Same as in Method 5, Section 8.1.4,
except that the filter holder is inserted into the stack during the
sampling train leak-check. To do this, plug the inlet to the probe
nozzle with a material that will be able to withstand the stack
temperature. Insert the filter holder into the stack and wait
approximately 5 minutes (or longer, if necessary) to allow the system to
come to equilibrium with the temperature of the stack gas stream.
8.1.5 Sampling Train Operation. The operation is the same as in
Method 5. Use a data sheet such as the one shown in Figure 5-3 of Method
5, except that the filter holder temperature is not recorded.
8.1.6 Calculation of Percent Isokinetic. Same as in Method 5,
Section 12.11.
8.2 Sample Recovery.
8.2.1 Proper cleanup procedure begins as soon as the probe
extension assembly is removed from the stack at the end of the sampling
period. Allow the assembly to cool.
8.2.2 When the assembly can be safely handled, wipe off all
external particulate matter near the tip of the probe nozzle and place a
cap over it to prevent losing or gaining particulate matter. Do not cap
off the probe tip tightly while the sampling train is cooling down as
this would create a vacuum in the filter holder, forcing condenser water
backward.
8.2.3 Before moving the sample train to the cleanup site,
disconnect the filter holder-probe nozzle assembly from the probe
extension; cap the open inlet of the probe extension. Be careful not to
lose any condensate, if present. Remove the umbilical cord from the
condenser outlet and cap the outlet. If a flexible line is used between
the first impinger (or condenser) and the probe extension, disconnect
the line at the probe extension and let any condensed water or liquid
drain into the impingers or condenser. Disconnect the probe extension
from the condenser; cap the probe extension outlet. After wiping off the
silicone grease, cap off the condenser inlet. Ground glass stoppers,
plastic caps, or serum caps (whichever are appropriate) may be used to
close these openings.
8.2.4 Transfer both the filter holder-probe nozzle assembly and the
condenser to the cleanup area. This area should be clean and protected
from the wind so that the chances

[[Page 433]]

of contaminating or losing the sample will be minimized.
8.2.5 Save a portion of the acetone used for cleanup as a blank.
Take 200 ml of this acetone from the wash bottle being used and place it
in a glass sample container labeled ``acetone blank.'' Inspect the train
prior to and during disassembly and not any abnormal conditions. Treat
the sample as discussed in Method 5, Section 8.2.

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardization

The calibrations of the probe nozzle, pitot tube, metering system,
temperature sensors, and barometer are the same as in Method 5, Sections
10.1 through 10.3, 10.5, and 10.6, respectively.

11.0 Analytical Procedure

Same as in Method 5, Section 11.0. Analytical data should be
recorded on a form similar to that shown in Figure 5-6 of Method 5.

12.0 Data Analysis and Calculations.

Same as in Method 5, Section 12.0.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

Same as in Method 5, Section 16.0.

17.0 References

Same as in Method 5, Section 17.0, with the addition of the
following:

1. Vollaro, R.F. Recommended Procedure for Sample Traverses in Ducts
Smaller than 12 Inches in Diameter. U.S. Environmental Protection
Agency, Emission Measurement Branch. Research Triangle Park, NC.
November 1976.

[[Page 434]]

18.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.302

[[Page 435]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.303

Method 18--Measurement of Gaseous Organic Compound Emissions By Gas
Chromatography

[[Page 436]]

should be exercised in the area of safety concerning choice of equipment
and operation in potentially explosive atmospheres.

1.0 Scope and Application

1.1 Analyte. Total gaseous organic compounds.
1.2 Applicability.
1.2.1 This method is designed to measure gaseous organics emitted
from an industrial source. While designed for ppm level sources, some
detectors are quite capable of detecting compounds at ambient levels,
e.g., ECD, ELCD, and helium ionization detectors. Some other types of
detectors are evolving such that the sensitivity and applicability may
well be in the ppb range in only a few years.
1.2.2 This method will not determine compounds that (1) are
polymeric (high molecular weight), (2) can polymerize before analysis,
or (3) have very low vapor pressures at stack or instrument conditions.
1.3 Range. The lower range of this method is determined by the
sampling system; adsorbents may be used to concentrate the sample, thus
lowering the limit of detection below the 1 part per million (ppm)
typically achievable with direct interface or bag sampling. The upper
limit is governed by GC detector saturation or column overloading; the
upper range can be extended by dilution of sample with an inert gas or
by using smaller volume gas sampling loops. The upper limit can also be
governed by condensation of higher boiling compounds.
1.4 Sensitivity. The sensitivity limit for a compound is defined as
the minimum detectable concentration of that compound, or the
concentration that produces a signal-to-noise ratio of three to one. The
minimum detectable concentration is determined during the presurvey
calibration for each compound.

2.0 Summary of Method

The major organic components of a gas mixture are separated by gas
chromatography (GC) and individually quantified by flame ionization,
photoionization, electron capture, or other appropriate detection
principles. The retention times of each separated component are compared
with those of known compounds under identical conditions. Therefore, the
analyst confirms the identity and approximate concentrations of the
organic emission components beforehand. With this information, the
analyst then prepares or purchases commercially available standard
mixtures to calibrate the GC under conditions identical to those of the
samples. The analyst also determines the need for sample dilution to
avoid detector saturation, gas stream filtration to eliminate
particulate matter, and prevention of moisture condensation.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Resolution interferences that may occur can be eliminated by
appropriate GC column and detector choice or by shifting the retention
times through changes in the column flow rate and the use of temperature
programming.
4.2 The analytical system is demonstrated to be essentially free
from contaminants by periodically analyzing blanks that consist of
hydrocarbon-free air or nitrogen.
4.3 Sample cross-contamination that occurs when high-level and low-
level samples or standards are analyzed alternately is best dealt with
by thorough purging of the GC sample loop between samples.
4.4 To assure consistent detector response, calibration gases are
contained in dry air. To adjust gaseous organic concentrations when
water vapor is present in the sample, water vapor concentrations are
determined for those samples, and a correction factor is applied.
4.5 The gas chromatograph run time must be sufficient to clear all
eluting peaks from the column before proceeding to the next run (in
order to prevent sample carryover).

5.0 Safety

6.0 Equipment and Supplies

6.1 Equipment needed for the presurvey sampling procedure can be
found in Section 16.1.1.
6.2 Equipment needed for the integrated bag sampling and analysis
procedure can be found in Section 8.2.1.1.1.
6.3 Equipment needed for direct interface sampling and analysis can
be found in Section 8.2.2.1.
6.4 Equipment needed for the dilution interface sampling and
analysis can be found in Section 8.2.3.1.
6.5 Equipment needed for adsorbent tube sampling and analysis can
be found in Section 8.2.4.1.

7.0 Reagents and Standards

7.1 Reagents needed for the presurvey sampling procedure can be
found in Section 16.1.2.

[[Page 437]]

7.2 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, an audit sample may be obtained
from the appropriate EPA Regional Office or from the responsible
enforcement authority.
Note: The responsible enforcement autority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Storage, and Transport

8.2 Final Sampling and Analysis Procedure. Considering safety
(flame hazards) and the source conditions, select an appropriate
sampling and analysis procedure (Section 8.2.1, 8.2.2, 8.2.3 or 8.2.4).
In situations where a hydrogen flame is a hazard and no intrinsically
safe GC is suitable, use the flexible bag collection technique or an
adsorption technique.
8.2.1 Integrated Bag Sampling and Analysis.
8.2.1.1 Evacuated Container Sampling Procedure. In this procedure,
the bags are filled by evacuating the rigid air-tight container holding
the bags. Use a field sample data sheet as shown in Figure 18-10.
Collect triplicate samples from each sample location.
8.2.1.1.1 Apparatus.
8.2.1.1.1.1 Probe. Stainless steel, Pyrex glass, or Teflon tubing
probe, according to the duct temperature, with Teflon tubing of
sufficient length to connect to the sample bag. Use stainless steel or
Teflon unions to connect probe and sample line.
8.2.1.1.1.2 Quick Connects. Male (2) and female (2) of stainless
steel construction.
8.2.1.1.1.3 Needle Valve. To control gas flow.
8.2.1.1.1.4 Pump. Leakless Teflon-coated diaphragm-type pump or
equivalent. To deliver at least 1 liter/min.
8.2.1.1.1.5 Charcoal Adsorption Tube. Tube filled with activated
charcoal, with glass wool plugs at each end, to adsorb organic vapors.
8.2.1.1.1.6 Flowmeter. 0 to 500-ml flow range; with manufacturer's
calibration curve.
8.2.1.1.2 Sampling Procedure. To obtain a sample, assemble the
sample train as shown in Figure 18-9. Leak-check both the bag and the
container. Connect the vacuum line from the needle valve to the Teflon
sample line from the probe. Place the end of the probe at the centroid
of the stack or at a point no closer to the walls than 1 m, and start
the pump. Set the flow rate so that the final volume of the sample is
approximately 80 percent of the bag capacity. After allowing sufficient
time to purge the line several times, connect the vacuum line to the
bag, and evacuate until the rotameter indicates no flow. Then position
the sample and vacuum lines for sampling, and begin the actual sampling,
keeping the rate proportional to the stack velocity. As a precaution,
direct the gas exiting the rotameter away from sampling personnel. At
the end of the sample period, shut off the pump, disconnect the sample
line from the bag, and disconnect the vacuum line from the bag
container. Record the source temperature, barometric pressure, ambient
temperature, sampling flow rate, and initial and final sampling time on
the data sheet shown in Figure 18-10. Protect the Tedlar bag and its
container from sunlight. Record the time lapsed between sample
collection and analysis, and then conduct the recovery procedure in
Section 8.4.2.
8.2.1.2 Direct Pump Sampling Procedure. Follow 8.2.1.1, except
place the pump and needle valve between the probe and the bag. Use a
pump and needle valve constructed of inert material not affected by the
stack gas. Leak-check the system, and then purge with stack gas before
connecting to the previously evacuated bag.
8.2.1.3 Explosion Risk Area Bag Sampling Procedure. Follow 8.2.1.1
except replace the pump with another evacuated can (see Figure 18-9a).
Use this method whenever there is a possibility of an explosion due to
pumps, heated probes, or other flame producing equipment.
8.2.1.4 Other Modified Bag Sampling Procedures. In the event that
condensation is observed in the bag while collecting the sample and a
direct interface system cannot be used, heat the bag during collection,
and maintain it at a suitably elevated temperature during all subsequent
operations. (Note: Take care to leak-check the system prior to the
dilutions so as not to create a potentially explosive atmosphere.) As an
alternative, collect the sample gas, and simultaneously dilute it in the
Tedlar bag.
8.2.1.4.1 First Alternative Procedure. Heat the box containing the
sample bag to 120 deg.C (5 deg.C). Then transport the bag
as rapidly as possible to the analytical area while maintaining the
heating, or cover the box with an insulating blanket. In the analytical
area, keep the box heated to 120 deg.C (5 deg.C) until
analysis. Be sure that the method of heating the box and the control for
the heating circuit are compatible with the safety restrictions required
in each area.
8.2.1.4.2 Second Alternative Procedure. Prefill the Tedlar bag with
a known quantity of inert gas. Meter the inert gas into the bag
according to the procedure for the preparation of gas concentration
standards of volatile liquid materials (Section 10.1.2.2), but eliminate
the midget impinger section. Take the partly filled bag to the source,
and meter the source gas into the bag through heated sampling lines and
a heated flowmeter, or Teflon positive displacement pump. Verify the
dilution factors before sampling each bag

[[Page 438]]

through dilution and analysis of gases of known concentration.
8.2.1.5 Analysis of Bag Samples.
8.2.1.5.1 Apparatus. Same as Section 8.1. A minimum of three gas
standards are required.
8.2.1.5.2 Procedure.
8.2.1.5.2.1 Establish proper GC operating conditions as described
in Section 10.2, and record all data listed in Figure 18-7. Prepare the
GC so that gas can be drawn through the sample valve. Flush the sample
loop with calibration gas mixture, and activate the valve (sample
pressure at the inlet to the GC introduction valve should be similar
during calibration as during actual sample analysis). Obtain at least
three chromatograms for the mixture. The results are acceptable when the
peak areas for the three injections agree to within 5 percent of their
average. If they do not agree, run additional samples or correct the
analytical techniques until this requirement is met. Then analyze the
other two calibration mixtures in the same manner. Prepare a calibration
curve as described in Section 10.2.
8.2.1.5.2.2 Analyze the two field audit samples as described in
Section 9.2 by connecting each Tedlar bag containing an audit gas
mixture to the sampling valve. Calculate the results; record and report
the data to the audit supervisor.
8.2.1.5.2.3 Analyze the three source gas samples by connecting each
bag to the sampling valve with a piece of Teflon tubing identified with
that bag. Analyze each bag sample three times. Record the data in Figure
18-11. If certain items do not apply, use the notation ``N.A.'' If the
bag has been maintained at an elevated temperature as described in
Section 8.2.1.4, determine the stack gas water content by Method 4.
After all samples have been analyzed, repeat the analysis of the mid-
level calibration gas for each compound. Compare the average response
factor of the pre- and post-test analysis for each compound. If they
differ by >5percent, analyze the other calibration gas levels for that
compound, and prepare a calibration curve using all the pre- and post-
test calibration gas mixture values. If the two response factor averages
(pre-and post-test) differ by less than 5 percent from their mean value,
the tester has the option of using only the pre-test calibration curve
to generate the concentration values.
8.2.1.6 Determination of Bag Water Vapor Content. Measure the
ambient temperature and barometric pressure near the bag. From a water
saturation vapor pressure table, determine and record the water vapor
content of the bag as a decimal figure. (Assume the relative humidity to
be 100 percent unless a lesser value is known.) If the bag has been
maintained at an elevated temperature as described in Section 8.2.1.4,
determine the stack gas water content by Method 4.
8.2.1.7 Audit Gas Analysis. Immediately prior to the analysis of
the stack gas samples, perform audit analyses as described in Section
9.2.
8.2.1.8 Emission Calculations. From the calibration curve described
in Section 8.2.1.5, select the value of Cs that corresponds
to the peak area. Calculate the concentration Cc in ppm, dry
basis, of each organic in the sample using Equation 18-5 in Section
12.6.
8.2.2 Direct Interface Sampling and Analysis Procedure. The direct
interface procedure can be used provided that the moisture content of
the gas does not interfere with the analysis procedure, the physical
requirements of the equipment can be met at the site, and the source gas
concentration falls within the linear range of the detector. Adhere to
all safety requirements with this method.
8.2.2.1 Apparatus.
8.2.2.1.1 Probe. Constructed of stainless steel, Pyrex glass, or
Teflon tubing as dictated by duct temperature and reactivity of target
compounds. A filter or glass wool plug may be needed if particulate is
present in the stack gas. If necessary, heat the probe with heating tape
or a special heating unit capable of maintaining a temperature greater
than 110 deg.C.
8.2.2.1.2 Sample Lines. 6.4-mm OD (or other diameter as needed)
Teflon lines, heat-traced to prevent condensation of material (greater
than 110 deg.C).
8.2.2.1.3 Quick Connects. To connect sample line to gas sampling
valve on GC instrument and to pump unit used to withdraw source gas. Use
a quick connect or equivalent on the cylinder or bag containing
calibration gas to allow connection of the calibration gas to the gas
sampling valve.
8.2.2.1.4 Thermocouple Readout Device. Potentiometer or digital
thermometer, to measure source temperature and probe temperature.
8.2.2.1.5 Heated Gas Sampling Valve. Of two-position, six-port
design, to allow sample loop to be purged with source gas or to direct
source gas into the GC instrument.
8.2.2.1.6 Needle Valve. To control gas sampling rate from the
source.
8.2.2.1.7 Pump. Leakless Teflon-coated diaphragm-type pump or
equivalent, capable of at least 1 liter/minute sampling rate.
8.2.2.1.8 Flowmeter. Of suitable range to measure sampling rate.
8.2.2.1.9 Charcoal Adsorber. To adsorb organic vapor vented from
the source to prevent exposure of personnel to source gas.
8.2.2.1.10 Gas Cylinders. Carrier gas, oxygen and fuel as needed to
run GC and detector.
8.2.2.1.11 Gas Chromatograph. Capable of being moved into the
field, with detector, heated gas sampling valve, column required

[[Page 439]]

to complete separation of desired components, and option for temperature
programming.
8.2.2.1.12 Recorder/Integrator. To record results.
8.2.2.2 Procedure. Calibrate the GC using the procedures in Section
8.2.1.5.2.1. To obtain a stack gas sample, assemble the sampling system
as shown in Figure 18-12. Make sure all connections are tight. Turn on
the probe and sample line heaters. As the temperature of the probe and
heated line approaches the target temperature as indicated on the
thermocouple readout device, control the heating to maintain a
temperature greater than 110 deg.C. Conduct a 3-point calibration of
the GC by analyzing each gas mixture in triplicate. Generate a
calibration curve. Place the inlet of the probe at the centroid of the
duct, or at a point no closer to the walls than 1 m, and draw source gas
into the probe, heated line, and sample loop. After thorough flushing,
analyze the stack gas sample using the same conditions as for the
calibration gas mixture. For each run, sample, analyze, and record five
consecutive samples. A test consists of three runs (five samples per run
times three runs, for a total of fifteen samples). After all samples
have been analyzed, repeat the analysis of the mid-level calibration gas
for each compound. For each calibration standard, compare the pre- and
post-test average response factors (RF) for each compound. If the two
calibration RF values (pre- and post-analysis) differ by more than 5
percent from their mean value, then analyze the other calibration gas
levels for that compound and determine the stack gas sample
concentrations by comparison to both calibration curves (this is done by
preparing a calibration curve using all the pre and post-test
calibration gas mixture values). If the two calibration RF values differ
by less than 5 percent from their mean value, the tester has the option
of using only the pre-test calibration curve to generate the
concentration values. Record this calibration data and the other
required data on the data sheet shown in Figure 18-11, deleting the
dilution gas information.

Note: Take care to draw all samples, calibration mixtures, and
audits through the sample loop at the same pressure.

8.2.2.3 Determination of Stack Gas Moisture Content. Use Method 4
to measure the stack gas moisture content.
8.2.2.4 Quality Assurance. Same as Section 8.2.1.7. Introduce the
audit gases in the sample line immediately following the probe.
8.2.2.5 Emission Calculations. Same as Section 8.2.1.8.
8.2.3 Dilution Interface Sampling and Analysis Procedure. Source
samples that contain a high concentration of organic materials may
require dilution prior to analysis to prevent saturating the GC
detector. The apparatus required for this direct interface procedure is
basically the same as that described in the Section 8.2.2, except a
dilution system is added between the heated sample line and the gas
sampling valve. The apparatus is arranged so that either a 10:1 or 100:1
dilution of the source gas can be directed to the chromatograph. A pump
of larger capacity is also required, and this pump must be heated and
placed in the system between the sample line and the dilution apparatus.
8.2.3.1 Apparatus. The equipment required in addition to that
specified for the direct interface system is as follows:
8.2.3.1.1 Sample Pump. Leakless Teflon-coated diaphragm-type that
can withstand being heated to 120 deg.C and deliver 1.5 liters/minute.
8.2.3.1.2 Dilution Pumps. Two Model A-150 Komhyr Teflon positive
displacement type delivering 150 cc/minute, or equivalent. As an option,
calibrated flowmeters can be used in conjunction with Teflon-coated
diaphragm pumps.
8.2.3.1.3 Valves. Two Teflon three-way valves, suitable for
connecting to Teflon tubing.
8.2.3.1.4 Flowmeters. Two, for measurement of diluent gas.
8.2.3.1.5 Diluent Gas with Cylinders and Regulators. Gas can be
nitrogen or clean dry air, depending on the nature of the source gases.
8.2.3.1.6 Heated Box. Suitable for being heated to 120 deg.C, to
contain the three pumps, three-way valves, and associated connections.
The box should be equipped with quick connect fittings to facilitate
connection of: (1) the heated sample line from the probe, (2) the gas
sampling valve, (3) the calibration gas mixtures, and (4) diluent gas
lines. A schematic diagram of the components and connections is shown in
Figure 18-13. The heated box shown in Figure 18-13 is designed to
receive a heated line from the probe. An optional design is to build a
probe unit that attaches directly to the heated box. In this way, the
heated box contains the controls for the probe heaters, or, if the box
is placed against the duct being sampled, it may be possible to
eliminate the probe heaters. In either case, a heated Teflon line is
used to connect the heated box to the gas sampling valve on the
chromatograph.
Note: Care must be taken to leak-check the system prior to the
dilutions so as not to create a potentially explosive atmosphere.
8.2.3.2 Procedure.
8.2.3.2.1 Assemble the apparatus by connecting the heated box,
shown in Figure 18-13, between the heated sample line from the probe and
the gas sampling valve on the chromatograph. Vent the source gas from
the gas sampling valve directly to the charcoal filter, eliminating the
pump and rotameter. Heat the sample probe, sample line, and

[[Page 440]]

heated box. Insert the probe and source thermocouple at the centroid of
the duct, or to a point no closer to the walls than 1 m. Measure the
source temperature, and adjust all heating units to a temperature 0 to 3
deg.C above this temperature. If this temperature is above the safe
operating temperature of the Teflon components, adjust the heating to
maintain a temperature high enough to prevent condensation of water and
organic compounds (greater than 110 deg.C). Calibrate the GC through
the dilution system by following the procedures in Section 8.2.1.5.2.1.
Determine the concentration of the diluted calibration gas using the
dilution factor and the certified concentration of the calibration gas.
Record the pertinent data on the data sheet shown in Figure 18-11.
8.2.3.2.2 Once the dilution system and GC operations are
satisfactory, proceed with the analysis of source gas, maintaining the
same dilution settings as used for the standards.
8.2.3.2.3 Analyze the audit samples using either the dilution
system, or directly connect to the gas sampling valve as required.
Record all data and report the results to the audit supervisor.
8.2.3.3 Determination of Stack Gas Moisture Content. Same as
Section 8.2.2.3.
8.2.3.4 Quality Assurance. Same as Section 8.2.2.4.
8.2.3.5 Emission Calculations. Same as section 8.2.2.5, with the
dilution factor applied.
8.2.4 Adsorption Tube Procedure. Any commercially available
adsorbent is allowed for the purposes of this method, as long as the
recovery study criteria in Section 8.4.3 are met. Help in choosing the
adsorbent may be found by calling the distributor, or the tester may
refer to National Institute for Occupational Safety and Health (NIOSH)
methods for the particular organics to be sampled. For some adsorbents,
the principal interferent will be water vapor. If water vapor is thought
to be a problem, the tester may place a midget impinger in an ice bath
before the adsorbent tubes. If this option is chosen, the water catch in
the midget impinger shall be analyzed for the target compounds. Also,
the spike for the recovery study (in Section 8.4.3) shall be conducted
in both the midget impinger and the adsorbent tubes. The combined
recovery (add the recovered amount in the impinger and the adsorbent
tubes to calculate R) shall then meet the criteria in Section 8.4.3.
Note: Post-test leak-checks are not allowed for this technique since
this can result in sample contamination.
8.2.4.1 Additional Apparatus. The following items (or equivalent)
are suggested.
8.2.4.1.1 Probe. Borosilicate glass or stainless steel,
approximately 6-mm ID, with a heating system if water condensation is a
problem, and a filter (either in-stack or out-of-stack, heated to stack
temperature) to remove particulate matter. In most instances, a plug of
glass wool is a satisfactory filter.
8.2.4.1.2 Flexible Tubing. To connect probe to adsorption tubes.
Use a material that exhibits minimal sample adsorption.
8.2.4.1.3 Leakless Sample Pump. Flow controlled, constant rate
pump, with a set of limiting (sonic) orifices.
8.2.4.1.4 Bubble-Tube Flowmeter. Volume accuracy within 1 percent,
to calibrate pump.
8.2.4.1.5 Stopwatch. To time sampling and pump rate calibration.
8.2.4.1.6 Adsorption Tubes. Precleaned adsorbent, with mass of
adsorbent to be determined by calculating breakthrough volume and
expected concentration in the stack.
8.2.4.1.7 Barometer. Accurate to 5 mm Hg, to measure atmospheric
pressure during sampling and pump calibration.
8.2.4.1.8 Rotameter. O to 100 cc/min, to detect changes in flow
rate during sampling.
8.2.4.2 Sampling and Analysis.
8.2.4.2.1 Calibrate the pump and limiting orifice flow rate through
adsorption tubes with the bubble tube flowmeter before sampling. The
sample system can be operated as a ``recirculating loop'' for this
operation. Record the ambient temperature and barometric pressure. Then,
during sampling, use the rotameter to verify that the pump and orifice
sampling rate remains constant.
8.2.4.2.2 Use a sample probe, if required, to obtain the sample at
the centroid of the duct, or at a point no closer to the walls than 1 m.
Minimize the length of flexible tubing between the probe and adsorption
tubes. Several adsorption tubes can be connected in series, if the extra
adsorptive capacity is needed. Adsorption tubes should be maintained
vertically during the test in order to prevent channeling. Provide the
gas sample to the sample system at a pressure sufficient for the
limiting orifice to function as a sonic orifice. Record the total time
and sample flow rate (or the number of pump strokes), the barometric
pressure, and ambient temperature. Obtain a total sample volume
commensurate with the expected concentration(s) of the volatile
organic(s) present, and recommended sample loading factors (weight
sample per weight adsorption media). Laboratory tests prior to actual
sampling may be necessary to predetermine this volume. If water vapor is
present in the sample at concentrations above 2 to 3 percent, the
adsorptive capacity may be severely reduced. Operate the gas
chromatograph according to the manufacturer's instructions. After
establishing optimum conditions, verify and document these conditions
during all operations. Calibrate the instrument. Analyze the audit
samples (see Section 16.1.4.3), then the emission samples.
8.2.4.3 Standards and Calibration. If using thermal desorption,
obtain calibration gases using the procedures in Section 10.1. If using

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solvent extraction, prepare liquid standards in the desorption solvent.
Use a minimum of three different standards; select the concentrations to
bracket the expected average sample concentration. Perform the
calibration before and after each day's sample analyses using the
procedures in Section 8.2.1.5.2.1.
8.2.4.4 Quality Assurance.
8.2.4.4.1 Determine the recovery efficiency of the pollutants of
interest according to Section 8.4.3.
8.2.4.4.2 Determination of Sample Collection Efficiency (Optional).
If sample breakthrough is thought to be a problem, a routine procedure
for determining breakthrough is to analyze the primary and backup
portions of the adsorption tubes separately. If the backup portion
exceeds 10 percent of the total amount (primary and back-up), it is
usually a sign of sample breakthrough. For the purposes of this method,
only the recovery efficiency value (Section 8.4.3) is used to determine
the appropriateness of the sampling and analytical procedure.
8.2.4.4.3 Volume Flow Rate Checks. Perform this check immediately
after sampling with all sampling train components in place. Use the
bubble-tube flowmeter to measure the pump volume flow rate with the
orifice used in the test sampling, and record the result. If it has
changed by more than 5 but less than 20 percent, calculate an average
flow rate for the test. If the flow rate has changed by more than 20
percent, recalibrate the pump and repeat the sampling.
8.2.4.4.4 Calculations. Correct all sample volumes to standard
conditions. If a sample dilution system has been used, multiply the
results by the appropriate dilution ratio. Correct all results according
to the applicable procedure in Section 8.4.3. Report results as ppm by
volume, dry basis.
8.3 Reporting of Results. At the completion of the field analysis
portion of the study, ensure that the data sheets shown in Figure 18-11
have been completed. Summarize this data on the data sheets shown in
Figure 18-15.
8.4 Recovery Study. After conducting the presurvey and identifying
all of the pollutants of interest, conduct the appropriate recovery
study during the test based on the sampling system chosen for the
compounds of interest.
8.4.1 Recovery Study for Direct Interface or Dilution Interface
Sampling. If the procedures in Section 8.2.2 or 8.2.3 are to be used to
analyze the stack gas, conduct the calibration procedure as stated in
Section 8.2.2.2 or 8.2.3.2, as appropriate. Upon successful completion
of the appropriate calibration procedure, attach the mid-level
calibration gas for at least one target compound to the inlet of the
probe or as close as possible to the inlet of the probe, but before the
filter. Repeat the calibration procedure by sampling and analyzing the
mid-level calibration gas through the entire sampling and analytical
system in triplicate. The mean of the calibration gas response sampled
through the probe shall be within 10 percent of the analyzer response.
If the difference in the two means is greater than 10 percent, check for
leaks throughout the sampling system and repeat the analysis of the
standard through the sampling system until this criterion is met.
8.4.2 Recovery Study for Bag Sampling.
8.4.2.1 Follow the procedures for the bag sampling and analysis in
Section 8.2.1. After analyzing all three bag samples, choose one of the
bag samples and tag this bag as the spiked bag. Spike the chosen bag
sample with a known mixture (gaseous or liquid) of all of the target
pollutants. The theoretical concentration, in ppm, of each spiked
compound in the bag shall be 40 to 60 percent of the average
concentration measured in the three bag samples. If a target compound
was not detected in the bag samples, the concentration of that compound
to be spiked shall be 5 times the limit of detection for that compound.
Store the spiked bag for the same period of time as the bag samples
collected in the field. After the appropriate storage time has passed,
analyze the spiked bag three times. Calculate the average fraction
recovered (R) of each spiked target compound with the equation in
Section 12.7.
8.4.2.2 For the bag sampling technique to be considered valid for a
compound, 0.70 R 1.30. If the R value does not
meet this criterion for a target compound, the sampling technique is not
acceptable for that compound, and therefore another sampling technique
shall be evaluated for acceptance (by repeating the recovery study with
another sampling technique). Report the R value in the test report and
correct all field measurements with the calculated R value for that
compound by using the equation in Section 12.8.
8.4.3 Recovery Study for Adsorption Tube Sampling. If following the
adsorption tube procedure in Section 8.2.4, conduct a recovery study of
the compounds of interest during the actual field test. Set up two
identical sampling trains. Collocate the two sampling probes in the
stack. The probes shall be placed in the same horizontal plane, where
the first probe tip is 2.5 cm from the outside edge of the other. One of
the sampling trains shall be designated the spiked train and the other
the unspiked train. Spike all of the compounds of interest (in gaseous
or liquid form) onto the adsorbent tube(s) in the spiked train before
sampling. The mass of each spiked compound shall be 40 to 60 percent of
the mass expected to be collected with the unspiked train. Sample the
stack

[[Page 442]]

gas into the two trains simultaneously. Analyze the adsorbents from the
two trains utilizing identical analytical procedures and
instrumentation. Determine the fraction of spiked compound recovered (R)
using the equations in Section 12.9.
8.4.3.1 Repeat the procedure in Section 8.4.3 twice more, for a
total of three runs. In order for the adsorbent tube sampling and
analytical procedure to be acceptable for a compound,
0.70R1.30 (R in this case is the average of three
runs). If the average R value does not meet this criterion for a target
compound, the sampling technique is not acceptable for that compound,
and therefore another sampling technique shall be evaluated for
acceptance (by repeating the recovery study with another sampling
technique). Report the R value in the test report and correct all field
measurements with the calculated R value for that compound by using the
equation in Section 12.8.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures

9.2 Quality Assurance for Laboratory Procedures. Immediately after
the preparation of the calibration curves, the analysis audit described
in 40 CFR Part 61, Appendix C, Procedure 2: ``Procedure for Field
Auditing GC Analysis,'' should be performed if audit materials are
available. The information required to document the analysis of the
audit samples has been included on the example data sheets shown in
Figures 18-3 and 18-7. The audit analyses should agree with the
certified audit concentrations within 10 percent. Audit sample results
shall be submitted according to directions provided with the audit
samples.

10.0 Calibration and Standardization.

10.1 Calibration Standards. Obtain calibration gas standards for
each target compound to be analyzed. Commercial cylinder gases certified
by the manufacturer to be accurate to within 1 percent of the certified
label value are preferable, although cylinder gases certified by the
manufacturer to 2 percent accuracy are allowed. Another option allowed
by this method is for the tester to obtain high concentration certified
cylinder gases and then use a dilution system meeting the requirements
of Test Method 205, 40 CFR Part 51, Appendix M to make multi-level
calibration gas standards. Prepare or obtain enough calibration
standards so that there are three different concentrations of each
organic compound expected to be measured in the source sample. For each
organic compound, select those concentrations that bracket the
concentrations expected in the source samples. A calibration standard
may contain more than one organic compound. If samples are collected in
adsorbent tubes and extracted using solvent extraction, prepare or
obtain standards in the same solvent used for the sample extraction
procedure. Verify the stability of all standards for the time periods
they are used.
10.2 Preparation of Calibration Curves.
10.2.1 Establish proper GC conditions, then flush the sampling loop
for 30 seconds. Allow the sample loop pressure to equilibrate to
atmospheric pressure, and activate the injection valve. Record the
standard concentration, attenuator factor, injection time, chart speed,
retention time, peak area, sample loop temperature, column temperature,
and carrier gas flow rate. Analyze each standard in triplicate.
10.2.2 Repeat this procedure for each standard. Prepare a graphical
plot of concentration (Cs) versus the calibration area
values. Perform a regression analysis, and draw the least square line.

11.0 Analytical Procedures

11.1 Analysis Development
11.1.1 Selection of GC Parameters
11.1.1.1 Column Choice. Based on the initial contact with plant
personnel concerning the plant process and the anticipated emissions,
choose a column that provides good resolution and rapid analysis time.
The choice of an appropriate column can be aided by a literature search,
contact with manufacturers of GC columns, and discussion with personnel
at the emission source.
Note: Most column manufacturers keep excellent records on their
products. Their technical service departments may be able to recommend
appropriate columns and detector type for separating the anticipated
compounds, and they may be able to provide information on interferences,
optimum operating conditions, and column limitations. Plants with
analytical laboratories may be

[[Page 443]]

able to provide information on their analytical procedures.
11.1.1.2 Preliminary GC Adjustment. Using the standards and column
obtained in Section 11.1.1.1, perform initial tests to determine
appropriate GC conditions that provide good resolution and minimum
analysis time for the compounds of interest.
11.1.1.3 Preparation of Presurvey Samples. If the samples were
collected on an adsorbent, extract the sample as recommended by the
manufacturer for removal of the compounds with a solvent suitable to the
type of GC analysis. Prepare other samples in an appropriate manner.
11.1.1.4 Presurvey Sample Analysis.
11.1.1.4.1 Before analysis, heat the presurvey sample to the duct
temperature to vaporize any condensed material. Analyze the samples by
the GC procedure, and compare the retention times against those of the
calibration samples that contain the components expected to be in the
stream. If any compounds cannot be identified with certainty by this
procedure, identify them by other means such as GC/mass spectroscopy
(GC/MS) or GC/infrared techniques. A GC/MS system is recommended.
11.1.1.4.2 Use the GC conditions determined by the procedure of
Section 11.1.1.2 for the first injection. Vary the GC parameters during
subsequent injections to determine the optimum settings. Once the
optimum settings have been determined, perform repeat injections of the
sample to determine the retention time of each compound. To inject a
sample, draw sample through the loop at a constant rate (100 ml/min for
30 seconds). Be careful not to pressurize the gas in the loop. Turn off
the pump and allow the gas in the sample loop to come to ambient
pressure. Activate the sample valve, and record injection time, loop
temperature, column temperature, carrier flow rate, chart speed, and
attenuator setting. Calculate the retention time of each peak using the
distance from injection to the peak maximum divided by the chart speed.
Retention times should be repeatable within 0.5 seconds.
11.1.1.4.3 If the concentrations are too high for appropriate
detector response, a smaller sample loop or dilutions may be used for
gas samples, and, for liquid samples, dilution with solvent is
appropriate. Use the standard curves (Section 10.2) to obtain an
estimate of the concentrations.
11.1.1.4.4 Identify all peaks by comparing the known retention
times of compounds expected to be in the retention times of peaks in the
sample. Identify any remaining unidentified peaks which have areas
larger than 5 percent of the total using a GC/MS, or estimation of
possible compounds by their retention times compared to known compounds,
with confirmation by further GC analysis.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Bws = Water vapor content of the bag sample or stack gas,
proportion by volume.
Cs = Concentration of the organic from the calibration curve,
ppm.
Gv = Gas volume or organic compound injected, ml.
Lv = Liquid volume of organic injected, l.
M = Molecular weight of organic, g/g-mole.
ms = Total mass of compound measured on adsorbent with spiked
train (g).
mu = Total mass of compound measured on adsorbent with
unspiked train (g).
mv = Mass per volume of spiked compound measured (g/
L).
Pi = Barometric or absolute sample loop pressure at time of
sample analysis, mm Hg.
Pm = Absolute pressure of dry gas meter, mm Hg.
Pr = Reference pressure, the barometric pressure or absolute
sample loop pressure recorded during calibration, mm Hg.
Ps = Absolute pressure of syringe before injection, mm Hg.
qc = Flow rate of the calibration gas to be diluted.
qc1 = Flow rate of the calibration gas to be diluted in stage
1.
qc2 = Flow rate of the calibration gas to be diluted in stage
2.
qd = Diluent gas flow rate.
qd1 = Flow rate of diluent gas in stage 1.
qd2 = Flow rate of diluent gas in stage 2.
s = Theoretical concentration (ppm) of spiked target compound in the
bag.
S = Theoretical mass of compound spiked onto adsorbent in spiked train
(g).
t = Measured average concentration (ppm) of target compound and source
sample (analysis results subsequent to bag spiking)
Ti = Sample loop temperature at the time of sample analysis,
deg.K.
Tm = Absolute temperature of dry gas meter, deg.K.
Ts = Absolute temperature of syringe before injection,
deg.K.
u = Source sample average concentration (ppm) of target compound in the
bag (analysis results before bag spiking).
Vm = Gas volume indicated by dry gas meter, liters.
vs = volume of stack gas sampled with spiked train (L).
vu = volume of stack gas sampled with unspiked train (L).
X = Mole or volume fraction of the organic in the calibration gas to be
diluted.
Y = Dry gas meter calibration factor, dimensionless.
l = Liquid organic density as determined, g/ml.

24.055 = Ideal gas molar volume at 293 deg.K and 760 mm Hg, liters/g-
mole.

[[Page 444]]

1000 = Conversion factor, ml/liter.
10\6\ = Conversion to ppm.

12.2 Calculate the concentration, Cs, in ppm using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.304

12.3 Calculate the concentration, Cs, in ppm of the organic
in the final gas mixture using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.305

12.4 Calculate each organic standard concentration, Cs, in
ppm using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.306

12.5 Calculate each organic standard concentration, Cs, in
ppm using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.307

12.6 Calculate the concentration, Cc, in ppm, dry basis, of
each organic is the sample using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.308

12.7 Calculate the average fraction recovered (R) of each spiked target
compound using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.309

12.8 Correct all field measurements with the calculated R value for
that compound using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.310

12.9 Determine the mass per volume of spiked compound measured
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.311

12.10 Calculate the fraction of spiked compound recovered, R, using
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.312

[[Page 445]]

13.0 Method Performance

13.1 Since a potential sample may contain a variety of compounds
from various sources, a specific precision limit for the analysis of
field samples is impractical. Precision in the range of 5 to 10 percent
relative standard deviation (RSD) is typical for gas chromatographic
techniques, but an experienced GC operator with a reliable instrument
can readily achieve 5 percent RSD. For this method, the following
combined GC/operator values are required.
(a) Precision. Triplicate analyses of calibration standards fall
within 5 percent of their mean value.
(b) Accuracy. Analysis results of prepared audit samples are within
10 percent of preparation values.
(c) Recovery. After developing an appropriate sampling and
analytical system for the pollutants of interest, conduct the procedure
in Section 8.4. Conduct the appropriate recovery study in Section 8.4 at
each sampling point where the method is being applied. Submit the data
and results of the recovery procedure with the reporting of results
under Section 8.3.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures

16.1 Optional Presurvey and Presurvey Sampling.
Note: Presurvey screening is optional. Presurvey sampling should be
conducted for sources where the target pollutants are not known from
previous tests and/or process knowledge.
Perform a presurvey for each source to be tested. Refer to Figure
18-1. Some of the information can be collected from literature surveys
and source personnel. Collect gas samples that can be analyzed to
confirm the identities and approximate concentrations of the organic
emissions.
16.1.1 Apparatus. This apparatus list also applies to Sections 8.2
and 11.
16.1.1.1 Teflon Tubing. (Mention of trade names or specific
products does not constitute endorsement by the U.S. Environmental
Protection Agency.) Diameter and length determined by connection
requirements of cylinder regulators and the GC. Additional tubing is
necessary to connect the GC sample loop to the sample.
16.1.1.2 Gas Chromatograph. GC with suitable detector, columns,
temperature-controlled sample loop and valve assembly, and temperature
programmable oven, if necessary. The GC shall achieve sensitivity
requirements for the compounds under study.
16.1.1.3 Pump. Capable of pumping 100 ml/min. For flushing sample
loop.
16.1.1.4 Flow Meter. To measure flow rates.
16.1.1.5 Regulators. Used on gas cylinders for GC and for cylinder
standards.
16.1.1.6 Recorder. Recorder with linear strip chart is minimum
acceptable. Integrator (optional) is recommended.
16.1.1.7 Syringes. 0.5-ml, 1.0- and 10-microliter size, calibrated,
maximum accuracy (gas tight) for preparing calibration standards. Other
appropriate sizes can be used.
16.1.1.8 Tubing Fittings. To plumb GC and gas cylinders.
16.1.1.9 Septa. For syringe injections.
16.1.1.10 Glass Jars. If necessary, clean, colored glass jars with
Teflon-lined lids for condensate sample collection. Size depends on
volume of condensate.
16.1.1.11 Soap Film Flowmeter. To determine flow rates.
16.1.1.12 Tedlar Bags. 10- and 50-liter capacity, for preparation
of standards.
16.1.1.13 Dry Gas Meter with Temperature and Pressure Gauges.
Accurate to 2 percent, for preparation of gas standards.
16.1.1.14 Midget Impinger/Hot Plate Assembly. For preparation of
gas standards.
16.1.1.15 Sample Flasks. For presurvey samples, must have gas-tight
seals.
16.1.1.16 Adsorption Tubes. If necessary, blank tubes filled with
necessary adsorbent (charcoal, Tenax, XAD-2, etc.) for presurvey
samples.
16.1.1.17 Personnel Sampling Pump. Calibrated, for collecting
adsorbent tube presurvey samples.
16.1.1.18 Dilution System. Calibrated, the dilution system is to be
constructed following the specifications of an acceptable method.
16.1.1.19 Sample Probes. Pyrex or stainless steel, of sufficient
length to reach centroid of stack, or a point no closer to the walls
than 1 m.
16.1.1.20 Barometer. To measure barometric pressure.
16.1.2 Reagents.
16.1.2.1 Water. Deionized distilled.
16.1.2.2 Methylene chloride.
16.1.2.3 Calibration Gases. A series of standards prepared for
every compound of interest.
16.1.2.4 Organic Compound Solutions. Pure (99.9 percent), or as
pure as can reasonably be obtained, liquid samples of all the organic
compounds needed to prepare calibration standards.
16.1.2.5 Extraction Solvents. For extraction of adsorbent tube
samples in preparation for analysis.
16.1.2.6 Fuel. As recommended by the manufacturer for operation of
the GC.
16.1.2.7 Carrier Gas. Hydrocarbon free, as recommended by the
manufacturer for operation of the detector and compatibility with the
column.

[[Page 446]]

16.1.2.8 Zero Gas. Hydrocarbon free air or nitrogen, to be used for
dilutions, blank preparation, and standard preparation.
16.1.3 Sampling.
16.1.3.1 Collection of Samples with Glass Sampling Flasks.
Presurvey samples may be collected in precleaned 250-ml double-ended
glass sampling flasks. Teflon stopcocks, without grease, are preferred.
Flasks should be cleaned as follows: Remove the stopcocks from both ends
of the flasks, and wipe the parts to remove any grease. Clean the
stopcocks, barrels, and receivers with methylene chloride (or other non-
target pollutant solvent, or heat and humidified air). Clean all glass
ports with a soap solution, then rinse with tap and deionized distilled
water. Place the flask in a cool glass annealing furnace, and apply heat
up to 500 deg.C. Maintain at this temperature for 1 hour. After this
time period, shut off and open the furnace to allow the flask to cool.
Return the stopcocks to the flask receivers. Purge the assembly with
high-purity nitrogen for 2 to 5 minutes. Close off the stopcocks after
purging to maintain a slight positive nitrogen pressure. Secure the
stopcocks with tape. Presurvey samples can be obtained either by drawing
the gases into the previously evacuated flask or by drawing the gases
into and purging the flask with a rubber suction bulb.
16.1.3.1.1 Evacuated Flask Procedure. Use a high-vacuum pump to
evacuate the flask to the capacity of the pump; then close off the
stopcock leading to the pump. Attach a 6-mm outside diameter (OD) glass
tee to the flask inlet with a short piece of Teflon tubing. Select a 6-
mm OD borosilicate sampling probe, enlarged at one end to a 12-mm OD and
of sufficient length to reach the centroid of the duct to be sampled.
Insert a glass wool plug in the enlarged end of the probe to remove
particulate matter. Attach the other end of the probe to the tee with a
short piece of Teflon tubing. Connect a rubber suction bulb to the third
leg of the tee. Place the filter end of the probe at the centroid of the
duct, and purge the probe with the rubber suction bulb. After the probe
is completely purged and filled with duct gases, open the stopcock to
the grab flask until the pressure in the flask reaches duct pressure.
Close off the stopcock, and remove the probe from the duct. Remove the
tee from the flask and tape the stopcocks to prevent leaks during
shipment. Measure and record the duct temperature and pressure.
16.1.3.1.2 Purged Flask Procedure. Attach one end of the sampling
flask to a rubber suction bulb. Attach the other end to a 6-mm OD glass
probe as described in Section 8.3.3.1.1. Place the filter end of the
probe at the centroid of the duct, or at a point no closer to the walls
than 1 m, and apply suction with the bulb to completely purge the probe
and flask. After the flask has been purged, close off the stopcock near
the suction bulb, and then close off the stopcock near the probe. Remove
the probe from the duct, and disconnect both the probe and suction bulb.
Tape the stopcocks to prevent leakage during shipment. Measure and
record the duct temperature and pressure.
16.1.3.2 Flexible Bag Procedure. Tedlar or aluminized Mylar bags
can also be used to obtain the presurvey sample. Use new bags, and leak-
check them before field use. In addition, check the bag before use for
contamination by filling it with nitrogen or air, and analyzing the gas
by GC at high sensitivity. Experience indicates that it is desirable to
allow the inert gas to remain in the bag about 24 hours or longer to
check for desorption of organics from the bag. Follow the leak-check and
sample collection procedures given in Section 8.2.1.
16.1.3.3 Determination of Moisture Content. For combustion or
water-controlled processes, obtain the moisture content from plant
personnel or by measurement during the presurvey. If the source is below
59 deg.C, measure the wet bulb and dry bulb temperatures, and calculate
the moisture content using a psychrometric chart. At higher
temperatures, use Method 4 to determine the moisture content.
16.1.4 Determination of Static Pressure. Obtain the static pressure
from the plant personnel or measurement. If a type S pitot tube and an
inclined manometer are used, take care to align the pitot tube 90 deg.
from the direction of the flow. Disconnect one of the tubes to the
manometer, and read the static pressure; note whether the reading is
positive or negative.
16.1.5 Collection of Presurvey Samples with Adsorption Tube. Follow
Section 8.2.4 for presurvey sampling.

17.0 References

1. American Society for Testing and Materials. C1 Through C5
Hydrocarbons in the Atmosphere by Gas Chromatography. ASTM D 2820-72,
Part 23. Philadelphia, Pa. 23:950-958. 1973.
2. Corazon, V.V. Methodology for Collecting and Analyzing Organic
Air Pollutants. U.S. Environmental Protection Agency. Research Triangle
Park, N.C. Publication No. EPA-600/2-79-042. February 1979.
3. Dravnieks, A., B.K. Krotoszynski, J. Whitfield, A. O'Donnell, and
T. Burgwald. Environmental Science and Technology. 5(12):1200-1222.
1971.
4. Eggertsen, F.T., and F.M. Nelsen. Gas Chromatographic Analysis of
Engine Exhaust and Atmosphere. Analytical Chemistry. 30(6): 1040-1043.
1958.
5. Feairheller, W.R., P.J. Marn, D.H. Harris, and D.L. Harris.
Technical Manual for Process Sampling Strategies for Organic Materials.
U.S. Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA 600/2-76-122. April 1976. 172 p.

[[Page 447]]

6. Federal Register, 39 FR 9319-9323. 1974.
7. Federal Register, 39 FR 32857-32860. 1974.
8. Federal Register, 23069-23072 and 23076-23090. 1976.
9. Federal Register, 46569-46571. 1976.
10. Federal Register, 41771-41776. 1977.
11. Fishbein, L. Chromatography of Environmental Hazards, Volume II.
Elesevier Scientific Publishing Company. New York, N.Y. 1973.
12. Hamersma, J.W., S.L. Reynolds, and R.F. Maddalone. EPA/IERL-RTP
Procedures Manual: Level 1 Environmental Assessment. U.S. Environmental
Protection Agency. Research Triangle Park, N.C. Publication No. EPA 600/
276-160a. June 1976. 130 p.
13. Harris, J.C., M.J. Hayes, P.L. Levins, and D.B. Lindsay. EPA/
IERL-RTP Procedures for Level 2 Sampling and Analysis of Organic
Materials. U.S. Environmental Protection Agency. Research Triangle Park,
N.C. Publication No. EPA 600/7-79-033. February 1979. 154 p.
14. Harris, W.E., H.W. Habgood. Programmed Temperature Gas
Chromatography. John Wiley and Sons, Inc. New York. 1966.
15. Intersociety Committee. Methods of Air Sampling and Analysis.
American Health Association. Washington, D.C. 1972.
16. Jones, P.W., R.D. Grammer, P.E. Strup, and T.B. Stanford.
Environmental Science and Technology. 10:806-810. 1976.
17. McNair Han Bunelli, E.J. Basic Gas Chromatography. Consolidated
Printers. Berkeley. 1969.
18. Nelson, G.O. Controlled Test Atmospheres, Principles and
Techniques. Ann Arbor. Ann Arbor Science Publishers. 1971. 247 p.
19. NIOSH Manual of Analytical Methods, Volumes 1, 2, 3, 4, 5, 6, 7.
U.S. Department of Health and Human Services, National Institute for
Occupational Safety and Health. Center for Disease Control. 4676
Columbia Parkway, Cincinnati, Ohio 45226. April 1977--August 1981. May
be available from the Superintendent of Documents, Government Printing
Office, Washington, D.C. 20402. Stock Number/Price:

Volume 1--O17-033-00267-3/$13
Volume 2--O17-033-00260-6/$11
Volume 3--O17-033-00261-4/$14
Volume 4--O17-033-00317-3/$7.25
Volume 5--O17-033-00349-1/$10
Volume 6--O17-033-00369-6/$9
Volume 7--O17-033-00396-5/$7

Prices subject to change. Foreign orders add 25 percent.
20. Schuetzle, D., T.J. Prater, and S.R. Ruddell. Sampling and
Analysis of Emissions from Stationary Sources; I. Odor and Total
Hydrocarbons. Journal of the Air Pollution Control Association. 25(9):
925-932. 1975.
21. Snyder, A.D., F.N. Hodgson, M.A. Kemmer and J.R. McKendree.
Utility of Solid Sorbents for Sampling Organic Emissions from Stationary
Sources. U.S. Environmental Protection Agency. Research Triangle Park,
N.C. Publication No. EPA 600/2-76-201. July 1976. 71 p.
22. Tentative Method for Continuous Analysis of Total Hydrocarbons
in the Atmosphere. Intersociety Committee, American Public Health
Association. Washington, D.C. 1972. p. 184-186.
23. Zwerg, G. CRC Handbook of Chromatography, Volumes I and II.
Sherma, Joseph (ed.). CRC Press. Cleveland. 1972.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

I. Name of company

Date

Address

Contracts

Phone

Process to be sampled

Duct or vent to be sampled

II. Process description

Raw material

Products

[[Page 448]]

Timing of batch or cycle

Best time to test

III. Sampling site

A. Description

Site decription

Duct shape and size

Material

Size of port

Size of access area

Location to set up GC

Special hazards to be considered

Power available at duct

Power available for GC

Plant safety requirements

Vehicle traffic rules

Plant entry requirements

Security agreements

Potential problems

Figure 18-1. Preliminary Survey Data Sheet

[[Page 449]]

Suggested chromatographic column

Figure 18-2. Chromatographic Conditions Data Sheet

Figure 18-3. Preparation of Standards in Tedlar Bags and Calibration Curve
----------------------------------------------------------------------------------------------------------------
Standards
-----------------------------------------------------
Mixture 1 Mixture 2 Mixture 3
----------------------------------------------------------------------------------------------------------------
Standards Preparation Data:
Organic:
Bag number or identification......................
Dry gas meter calibration factor..................
Final meter reading (liters)......................
Initial meter reading (liters)....................
Metered volume (liters)...........................
Average meter temperature ( deg.K)................
Average meter pressure, gauge (mm Hg).............
Average atmospheric perssure (mm Hg)..............
Average meter pressure, absolute (mm Hg)..........
Syringe temperature ( deg.K) (see Section
10.1.2.1)........................................
Syringe pressure, absolute (mm Hg) (see Section
10.1.2.1)........................................
Volume of gas in syringe (ml) (Section 10.1.2.1)..
Density of liquid organic (g/ml) (Section
10.1.2.1)........................................
Volume of liquid in syringe (ml) (Section
10.1.2.1)........................................
GC Operating Conditions:
Sample loop volume (ml)...............................
Sample loop temperature ( deg.C).....................
Carrier gas flow rate (ml/min)........................
Column temperature:
Initial ( deg.C).....................................
Rate change ( deg.C/min).............................
Final ( deg.C).......................................
Organic Peak Identification and Calculated Concentrations:
Injection time (24 hour clock)........................
Distance to peak (cm).................................
Chart speed (cm/min)..................................
Organic retention time (min)..........................
Attenuation factor....................................
Peak height (mm)......................................
Peak area (mm2).......................................
Peak area * attenuation factor (mm2)..................
Calculated concentration (ppm) (Equation 18-3 or 18-4)
----------------------------------------------------------------------------------------------------------------
Plot peak area * attenuation factor against calculated concentration to obtain calibration curve.

Flowmeter number or identification

Flowmeter Type

[[Page 450]]

Flowmeter
----------------------------------------------------------------------------------------------------------------
Reading (as marked) Temp. ( deg.K) Pressure (absolute)
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

Calibration Device
----------------------------------------------------------------------------------------------------------------
Time (min) Gas volume ^a Flow rate ^b
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------
^a Vol. of gas may be measured in milliliters, liters or cubic feet.
^b Convert to standard conditions (20 deg.C and 760 mm Hg). Plot flowmeter reading against flow rate (standard
conditions), and draw a smooth curve. If the flowmeter being calibrated is a rotameter or other flow device
that is viscosity dependent, it may be necessary to generate a ``family'' of calibration curves that cover the
operating pressure and temperature ranges of the flowmeter. While the following technique should be verified
before application, it may be possible to calculate flow rate reading for rotameters at standard conditions
Qstd as follows:

[GRAPHIC] [TIFF OMITTED] TR17OC00.313

------------------------------------------------------------------------
Flow rate (laboratory conditions) Flow rate (STD conditions)
------------------------------------------------------------------------

------------------------------------------------------------------------

Figure 18-4. Flowmeter Calibration

[[Page 451]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.314

[[Page 452]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.315

Preparation of Standards by Dilution of Cylinder Standard
[Cylinder Standard: Organic -------- Certified Concentration -------- ppm]
----------------------------------------------------------------------------------------------------------------
Date:
Standards preparation data: --------------------------------------------------------------------------
Mixture 1 Mixture 2 Mixture 3
----------------------------------------------------------------------------------------------------------------
Stage 1:
Standard gas flowmeter reading...
Diluent gas flowmeter reading
Laboratory temperature ( deg.K)
Barometric pressure (mm Hg)
Flowmeter gage pressure (mm Hg)
Flow rate cylinder gas at
standard conditions (ml/min)
Flow rate diluent gas at standard
conditions (ml/min)
Calculated concentration (ppm)
Stage 2 (if used):
Standard gas flowmeter reading
Diluent gas flowmeter reading
Flow rate Stage 1 gas at standard
conditions (ml/min)
Flow rate diluent gas at standard
conditions
Calculated concentration (ppm)
GC Operating Conditions:
Sample loop volume (ml)
Sample loop temperature ( deg.C)
Carrier gas flow rate (ml/min)
Column temperature:
Initial ( deg.C)
Program rate ( deg.C/min)
Final ( deg.C)
Organic Peak Identification and
Calculated Concentrations:

[[Page 453]]

Injection time (24-hour clock)
Distance to peak (cm)
Chart speed (cm/min)
Retention time (min)
Attenuation factor
Peak area (mm \2\)
Peak area *attenuation factor
----------------------------------------------------------------------------------------------------------------
Plot peak area *attenuation factor against calculated concentration to obtain calibration curve.

Figure 18-7. Standards Prepared by Dilution of Cylinder Standard
[GRAPHIC] [TIFF OMITTED] TR17OC00.316

[[Page 454]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.317

[[Page 455]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.318

Plant________ Date________ Site________
----------------------------------------------------------------------------------------------------------------
Sample 1 Sample 2 Sample 3
----------------------------------------------------------------------------------------------------------------
Source temperature ( deg.C).................................... .............. .............. ..............
Barometric pressure (mm Hg)..................................... .............. .............. ..............
Ambient temperature ( deg.C)................................... .............. .............. ..............
Sample flow rate (appr.)........................................ .............. .............. ..............
Bag number...................................................... .............. .............. ..............
Start time...................................................... .............. .............. ..............
Finish time..................................................... .............. .............. ..............
----------------------------------------------------------------------------------------------------------------

Figure 18-10. Field Sample Data Sheet--Tedlar Bag Collection Method

Plant -------- Date -------- Location --------

1. General information:
Source temperature ( deg.C)...................... ................
Probe temperature ( deg.C)....................... ................
Ambient temperature ( deg.C)..................... ................
Atmospheric pressure (mm)......................... ................
Source pressure ('Hg)............................. ................
Absolute source pressure (mm)..................... ................
Sampling rate (liter/min)......................... ................
Sample loop volume (ml)........................... ................
Sample loop temperature ( deg.C)................. ................
Columnar temperature:
Initial ( deg.C) time (min).................. ................

[[Page 456]]

Program rate ( deg.C/min).................... ................
Final ( deg.C)/time (min).................... ................
Carrier gas flow rate (ml/min).................... ................
Detector temperature ( deg.C).................... ................
Injection time (24-hour basis).................... ................
Chart Speed (mm/min).............................. ................
Dilution gas flow rate (ml/min)................... ................
Dilution gas used (symbol)........................ ................
Dilution ratio.................................... ................

2. Field Analysis Data--Calibration Gas
2. [Run No.________ Time________]
----------------------------------------------------------------------------------------------------------------
Components Area Attenuation A x A Factor Conc.__ (ppm)
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------
............... ...................... ...................... ......................
----------------------------------------------------------------------------------------------------------------

Figure 18-11. Field Analysis Data Sheets

[[Page 457]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.319

[[Page 458]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.320

Gaseous Organic Sampling and Analysis Check List
[Respond with initials or number as appropriate]

Date

1. Presurvey data:
A. Grab sample collected........................ {time} ______
B. Grab sample analyzed for composition..... {time} ______
Method GC................................... {time} ______
GC/MS................................... {time} ______
Other................................... {time} ______
C. GC-FID analysis performed.................... {time} ______
2. Laboratory calibration data:
A. Calibration curves prepared.................. {time} ______
Number of components........................ {time} ______
Number of concentrations/component (3 {time} ______
required).
B. Audit samples (optional):
Analysis completed.............................. {time} ______
Verified for concentration...................... {time} ______
OK obtained for field work...................... {time} ______
3. Sampling procedures:
A. Method:
Bag sample.................................. {time} ______
Direct interface............................ {time} ______
Dilution interface.......................... {time} ______
B. Number of samples collected.................. {time} ______
4. Field Analysis:
A. Total hydrocarbon analysis performed......... {time} ______
B. Calibration curve prepared................... {time} ______
Number of components........................ {time} ______
Number of concentrations per component (3 {time} ______
required).

Gaseous Organic Sampling and Analysis Data

Plant

Date

Location

[[Page 459]]

----------------------------------------------------------------------------------------------------------------
Source sample 1 Source sample 2 Source sample 3
---------------------------------------------------------------------------------------------------------------
1. General information:
Source temperature ( deg.C)...... .................................. ..................................
Probe temperature ( deg.C)....... .................................. ..................................
Ambient temperature ( deg.C)..... .................................. ..................................
Atmospheric pressure (mm Hg)...... .................................. ..................................
Source pressure (mm Hg)........... .................................. ..................................
Sampling rate (ml/min)............ .................................. ..................................
Sample loop volume (ml)........... .................................. ..................................
Sample loop temperature ( deg.C). .................................. ..................................
Sample collection time (24-hr .................................. ..................................
basis).
Column temperature:
Initial ( deg.C)............. .................................. ..................................
Program rate ( deg.C/min).... .................................. ..................................
Final ( deg.C)............... .................................. ..................................
Carrier gas flow rate (ml/min).... .................................. ..................................
Detector temperature ( deg.C).... .................................. ..................................
Chart speed (cm/min).............. .................................. ..................................
Dilution gas flow rate (ml/min)... .................................. ..................................
Diluent gas used (symbol)......... .................................. ..................................
Dilution ratio.................... .................................. ..................................
Performed by: (signature):________________________ Date:________________________
----------------------------------------------------------------------------------------------------------------

Figure 18-14. Sampling and Analysis Sheet

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A see the List of CFR Sections Affected, which appears in the
Finding Aids section of the printed volume and on GPO Access.

Appendix A-7 to Part 60--Test Methods 19 through 25E

Method 19--Determination of sulfur dioxide removal efficiency and
particulate, sulfur dioxide and nitrogen oxides emission rates
Method 20--Determination of nitrogen oxides, sulfur dioxide, and diluent
emissions from stationary gas turbines
Method 21--Determination of volatile organic compound leaks
Method 22--Visual determination of fugitive emissions from material
sources and smoke emissions from flares
Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans From Stationary Sources
Method 24--Determination of volatile matter content, water content,
density, volume solids, and weight solids of surface coatings
Method 24A--Determination of volatile matter content and density of
printing inks and related coatings
Method 25--Determination of total gaseous nonmethane organic emissions
as carbon
Method 25A--Determination of total gaseous organic concentration using a
flame ionization analyzer
Method 25B--Determination of total gaseous organic concentration using a
nondispersive infrared analyzer
Method 25C--Determination of nonmethane organic compounds (NMOC) in MSW
landfill gases
Method 25D--Determination of the Volatile Organic Concentration of Waste
Samples
Method 25E--Determination of Vapor Phase Organic Concentration in Waste
Samples
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The

[[Page 460]]

methods are potentially applicable to other sources; however,
applicability should be confirmed by careful and appropriate evaluation
of the conditions prevalent at such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the the degree of detail should be similar to the detail contained
in the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 19--Determination of Sulfur Dioxide Removal Efficiency and
Particulate Matter, Sulfur Dioxide, and Nitrogen Oxide Emission Rates

1.0 Scope and Application

1.1 Analytes. This method provides data reduction procedures relating
to the following pollutants, but does not include any sample collection
or analysis procedures.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Nitrogen oxides (NOX),
including:
Nitric oxide (NO)......... 10102-43-9....... N/A
Nitrogen dioxide (NO2).... 10102-44-0.......
Particulate matter (PM)....... None assigned.... N/A
Sulfur dioxide (SO2).......... 7499-09-05....... N/A
------------------------------------------------------------------------

1.2 Applicability. Where specified by an applicable subpart of the
regulations, this method is applicable for the determination of (a) PM,
SO2, and NOX emission rates; (b) sulfur removal
efficiencies of fuel pretreatment and SO2 control devices;
and (c) overall reduction of potential SO2 emissions.

2.0 Summary of Method

2.1 Emission Rates. Oxygen (O2) or carbon dioxide
(CO2) concentrations and appropriate F factors (ratios of
combustion gas volumes to heat inputs) are used to calculate pollutant
emission rates from pollutant concentrations.
2.2 Sulfur Reduction Efficiency and SO2 Removal
Efficiency. An overall SO2 emission

[[Page 461]]

reduction efficiency is computed from the efficiency of fuel
pretreatment systems, where applicable, and the efficiency of
SO2 control devices.
2.2.1 The sulfur removal efficiency of a fuel pretreatment system
is determined by fuel sampling and analysis of the sulfur and heat
contents of the fuel before and after the pretreatment system.
2.2.2 The SO2 removal efficiency of a control device is
determined by measuring the SO2 rates before and after the
control device.
2.2.2.1 The inlet rates to SO2 control systems (or, when
SO2 control systems are not used, SO2 emission
rates to the atmosphere) are determined by fuel sampling and analysis.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety [Reserved]

6.0 Equipment and Supplies [Reserved]

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedures [Reserved]

12.0 Data Analysis and Calculations

12.1 Nomenclature

Bwa = Moisture fraction of ambient air, percent.
Bws = Moisture fraction of effluent gas, percent.
%C = Concentration of carbon from an ultimate analysis of fuel, weight
percent.
Cd = Pollutant concentration, dry basis, ng/scm (lb/scf)
%CO2d,%CO2w = Concentration of carbon dioxide on a
dry and wet basis, respectively, percent.
Cw = Pollutant concentration, wet basis, ng/scm (lb/scf).
D = Number of sampling periods during the performance test period.
E = Pollutant emission rate, ng/J (lb/million Btu).
Ea = Average pollutant rate for the specified performance
test period, ng/J (lb/million Btu).
Eao, Eai = Average pollutant rate of the control
device, outlet and inlet, respectively, for the performance
test period, ng/J (lb/million Btu).
Ebi = Pollutant rate from the steam generating unit, ng/J
(lb/million Btu)
Ebo = Pollutant emission rate from the steam generating unit,
ng/J (lb/million Btu).
Eci = Pollutant rate in combined effluent, ng/J (lb/million
Btu).
Eco = Pollutant emission rate in combined effluent, ng/J (lb/
million Btu).
Ed = Average pollutant rate for each sampling period (e.g.,
24-hr Method 6B sample or 24-hr fuel sample) or for each fuel
lot (e.g., amount of fuel bunkered), ng/J (lb/million Btu).
Edi = Average inlet SO2 rate for each sampling
period d, ng/J (lb/million Btu)
Eg = Pollutant rate from gas turbine, ng/J (lb/million Btu).
Ega = Daily geometric average pollutant rate, ng/J (lbs/
million Btu) or ppm corrected to 7 percent O2.
Ejo,Eji = Matched pair hourly arithmetic average
pollutant rate, outlet and inlet, respectively, ng/J (lb/
million Btu) or ppm corrected to 7 percent O2.
Eh = Hourly average pollutant, ng/J (lb/million Btu).
Ehj = Hourly arithmetic average pollutant rate for hour
``j,'' ng/J (lb/million Btu) or ppm corrected to 7 percent
O2.
EXP = Natural logarithmic base (2.718) raised to the value enclosed by
brackets.
Fd, Fw, Fc = Volumes of combustion
components per unit of heat content, scm/J (scf/million Btu).
GCV = Gross calorific value of the fuel consistent with the ultimate
analysis, kJ/kg (Btu/lb).
GCVp, GCVr = Gross calorific value for the product
and raw fuel lots, respectively, dry basis, kJ/kg (Btu/lb).
%H = Concentration of hydrogen from an ultimate analysis of fuel, weight
percent.
H = Total number of operating hours for which pollutant rates are
determined in the performance test period.
Hb = Heat input rate to the steam generating unit from fuels
fired in the steam generating unit, J/hr (million Btu/hr).
Hg = Heat input rate to gas turbine from all fuels fired in
the gas turbine, J/hr (million Btu/hr).
%H2O = Concentration of water from an ultimate analysis of
fuel, weight percent.
Hr = Total numbers of hours in the performance test period
(e.g., 720 hours for 30-day performance test period).
K = Conversion factor, 10^-\5\ (kJ/J)/(%) [10⁶ Btu/
million Btu].
Kc = (9.57 scm/kg)/% [(1.53 scf/lb)/%].
Kcc = (2.0 scm/kg)/% [(0.321 scf/lb)/%].
Khd = (22.7 scm/kg)/% [(3.64 scf/lb)/%].
Khw = (34.74 scm/kg)/% [(5.57 scf/lb)/%].
Kn = (0.86 scm/kg)/% [(0.14 scf/lb)/%].
Ko = (2.85 scm/kg)/% [(0.46 scf/lb)/%].
Ks = (3.54 scm/kg)/% [(0.57 scf/lb)/%].
Kw = (1.30 scm/kg)/% [(0.21 scf/lb)/%].
ln = Natural log of indicated value.
Lp,Lr = Weight of the product and raw fuel lots,
respectively, metric ton (ton).
%N = Concentration of nitrogen from an ultimate analysis of fuel, weight
percent.

[[Page 462]]

N = Number of fuel lots during the averaging period.
n = Number of fuels being burned in combination.
nd = Number of operating hours of the affected facility
within the performance test period for each Ed
determined.
nt = Total number of hourly averages for which paired inlet
and outlet pollutant rates are available within the 24-hr
midnight to midnight daily period.
%O = Concentration of oxygen from an ultimate analysis of fuel, weight
percent.
%O2d, %O2w = Concentration of oxygen on a dry and
wet basis, respectively, percent.
Ps = Potential SO2 emissions, percent.
%Rf = SO2 removal efficiency from fuel
pretreatment, percent.
%Rg = SO2 removal efficiency of the control
device, percent.
%Rga = Daily geometric average percent reduction.
%Ro = Overall SO2 reduction, percent.
%S = Sulfur content of as-fired fuel lot, dry basis, weight percent.
Se = Standard deviation of the hourly average pollutant rates
for each performance test period, ng/J (lb/million Btu).
%Sf = Concentration of sulfur from an ultimate analysis of
fuel, weight percent.
Si = Standard deviation of the hourly average inlet pollutant
rates for each performance test period, ng/J (lb/million Btu).
So = Standard deviation of the hourly average emission rates
for each performance test period, ng/J (lb/million Btu).
%Sp, %Sr = Sulfur content of the product and raw
fuel lots respectively, dry basis, weight percent.
t0.95 = Values shown in Table 19-3 for the indicated number
of data points n.
Xk = Fraction of total heat input from each type of fuel k.

12.2 Emission Rates of PM, SO2, and NOx.
Select from the following sections the applicable procedure to compute
the PM, SO2, or NOx emission rate (E) in ng/J (lb/
million Btu). The pollutant concentration must be in ng/scm (lb/scf) and
the F factor must be in scm/J (scf/million Btu). If the pollutant
concentration (C) is not in the appropriate units, use Table 19-1 in
Section 17.0 to make the proper conversion. An F factor is the ratio of
the gas volume of the products of combustion to the heat content of the
fuel. The dry F factor (Fd) includes all components of
combustion less water, the wet F factor (Fw) includes all
components of combustion, and the carbon F factor (Fc)
includes only carbon dioxide.
Note: Since Fw factors include water resulting only from
the combustion of hydrogen in the fuel, the procedures using
Fw factors are not applicable for computing E from steam
generating units with wet scrubbers or with other processes that add
water (e.g., steam injection).
12.2.1 Oxygen-Based F Factor, Dry Basis. When measurements are on a
dry basis for both O (%O2d) and pollutant (Cd)
concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.321

12.2.2 Oxygen-Based F Factor, Wet Basis. When measurements are on a wet
basis for both O2 (%O2w) and pollutant
(Cw) concentrations, use either of the following:
12.2.2.1 If the moisture fraction of ambient air (Bwa) is
measured:
[GRAPHIC] [TIFF OMITTED] TR17OC00.322

Instead of actual measurement, Bwa may be estimated according
to the procedure below.
Note: The estimates are selected to ensure that negative errors will not
be larger than -1.5 percent. However, positive errors, or over-
estimation of emissions by as much as 5 percent may be introduced
depending upon the geographic location of the facility and the
associated range of ambient moisture.
12.2.2.1.1 Bwa = 0.027. This value may be used at any
location at all times.
12.2.2.1.2 Bwa = Highest monthly average of Bwa
that occurred within the previous calendar year at the nearest Weather
Service Station. This value shall be determined annually and may be used
as an estimate for the entire current calendar year.
12.2.2.1.3 Bwa = Highest daily average of Bwa that occurred
within a calendar month at the nearest Weather Service Station,
calculated from the data from the

[[Page 463]]

past 3 years. This value shall be computed for each month and may be
used as an estimate for the current respective calendar month.
12.2.2.2 If the moisture fraction (Bws) of the effluent gas
is measured:
[GRAPHIC] [TIFF OMITTED] TR17OC00.323

12.2.3 Oxygen-Based F Factor, Dry/Wet Basis.
12.2.3.1 When the pollutant concentration is measured on a wet
basis (Cw) and O2 concentration is measured on a
dry basis (%O2d), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.324

12.2.3.2 When the pollutant concentration is measured on a dry
basis (Cd) and the O2 concentration is measured on
a wet basis (%O2w), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.325

12.2.4 Carbon Dioxide-Based F Factor, Dry Basis. When measurements
are on a dry basis for both CO2 (%CO2d) and
pollutant (Cd) concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.326

12.2.5 Carbon Dioxide-Based F Factor, Wet Basis. When measurements
are on a wet basis for both CO2 (%CO2w) and
pollutant (Cw) concentrations, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.327

12.2.6 Carbon Dioxide-Based F Factor, Dry/Wet Basis.
12.2.6.1 When the pollutant concentration is measured on a wet
basis (Cw) and CO2 concentration is measured on a
dry basis (%CO2d), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.328

12.2.6.2 When the pollutant concentration is measured on a dry
basis (Cd) and CO2 concentration is measured on a
wet basis (%CO2w), use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.329

12.2.7 Direct-Fired Reheat Fuel Burning. The effect of direct-fired
reheat fuel burning (for the purpose of raising the temperature of the
exhaust effluent from wet scrubbers to above the moisture dew-point) on
emission rates will be less than 1.0 percent and, therefore, may be
ignored.
12.2.8 Combined Cycle-Gas Turbine Systems. For gas turbine-steam
generator combined cycle systems, determine the emissions from the steam
generating unit or the percent reduction in potential SO2
emissions as follows:
12.2.8.1 Compute the emission rate from the steam generating unit
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.330

12.2.8.1.1 Use the test methods and procedures section of 40 CFR
Part 60, Subpart GG to obtain Eco and Eg. Do not
use Fw factors for determining Eg or
Eco. If an SO2 control device is used, measure
Eco after the control device.
12.2.8.1.2 Suitable methods shall be used to determine the heat
input rates to the steam generating units (Hb) and the gas
turbine (Hg).
12.2.8.2 If a control device is used, compute the percent of
potential SO2 emissions (Ps) using the following
equations:
[GRAPHIC] [TIFF OMITTED] TR17OC00.331

[GRAPHIC] [TIFF OMITTED] TR17OC00.332

Note: Use the test methods and procedures section of Subpart GG to
obtain Eci and Eg. Do not use Fw
factors for determining Eg or Eci.

[[Page 464]]

12.3 F Factors. Use an average F factor according to Section 12.3.1 or
determine an applicable F factor according to Section 12.3.2. If
combined fuels are fired, prorate the applicable F factors using the
procedure in Section 12.3.3.
12.3.1 Average F Factors. Average F factors (Fd,
Fw, or Fc) from Table 19-2 in Section 17.0 may be
used.
12.3.2 Determined F Factors. If the fuel burned is not listed in Table
19-2 or if the owner or operator chooses to determine an F factor rather
than use the values in Table 19-2, use the procedure below:
12.3.2.1 Equations. Use the equations below, as appropriate, to compute
the F factors:
[GRAPHIC] [TIFF OMITTED] TR17OC00.333

[GRAPHIC] [TIFF OMITTED] TR17OC00.334

[GRAPHIC] [TIFF OMITTED] TR17OC00.335

Note: Omit the %H2O term in the equations for
Fw if %H and %O include the unavailable hydrogen and oxygen
in the form of H2O.)
12.3.2.2 Use applicable sampling procedures in Section 12.5.2.1 or
12.5.2.2 to obtain samples for analyses.
12.3.2.3 Use ASTM D 3176-74 or 89 (all cited ASTM standards are
incorporated by reference--see Sec. 60.17) for ultimate analysis of the
fuel.
12.3.2.4 Use applicable methods in Section 12.5.2.1 or 12.5.2.2 to
determine the heat content of solid or liquid fuels. For gaseous fuels,
use ASTM D 1826-77 or 94 (incorporated by reference--see Sec. 60.17) to
determine the heat content.
12.3.3 F Factors for Combination of Fuels. If combinations of fuels
are burned, use the following equations, as applicable unless otherwise
specified in an applicable subpart:
[GRAPHIC] [TIFF OMITTED] TR17OC00.336

[GRAPHIC] [TIFF OMITTED] TR17OC00.337

[GRAPHIC] [TIFF OMITTED] TR17OC00.338

12.4 Determination of Average Pollutant Rates.
12.4.1 Average Pollutant Rates from Hourly Values. When hourly
average pollutant rates (Eh), inlet or outlet, are obtained
(e.g., CEMS values), compute the average pollutant rate (Ea)
for the performance test period (e.g., 30 days) specified in the
applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.339

12.4.2 Average Pollutant Rates from Other than Hourly Averages.
When pollutant rates are determined from measured values representing
longer than 1-hour periods (e.g., daily fuel sampling and analyses or
Method 6B values), or when pollutant rates are determined from
combinations of 1-hour and longer than 1-hour periods (e.g., CEMS and
Method 6B values), compute the average pollutant rate (Ea)
for the performance test period (e.g., 30 days) specified in the
applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.340

12.4.3 Daily Geometric Average Pollutant Rates from Hourly Values.
The geometric average pollutant rate (Ega) is computed using
the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.341

12.5 Determination of Overall Reduction in Potential Sulfur Dioxide
Emission.
12.5.1 Overall Percent Reduction. Compute the overall percent
SO2 reduction (%Ro) using the following equation:

[[Page 465]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.342

12.5.2 Pretreatment Removal Efficiency (Optional). Compute the
SO2 removal efficiency from fuel pretreatment
(%Rf) for the averaging period (e.g., 90 days) as specified
in the applicable regulation using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.343

Note: In calculating %Rf, include %S and GCV values for
all fuel lots that are not pretreated and are used during the averaging
period.
12.5.2.1 Solid Fossil (Including Waste) Fuel/Sampling and Analysis.
Note: For the purposes of this method, raw fuel (coal or oil) is the
fuel delivered to the desulfurization (pretreatment) facility. For oil,
the input oil to the oil desulfurization process (e.g., hydrotreatment)
is considered to be the raw fuel.
12.5.2.1.1 Sample Increment Collection. Use ASTM D 2234-76, 96,
97a, or 98 (incorporated by reference--see Sec. 60.17), Type I,
Conditions A, B, or C, and systematic spacing. As used in this method,
systematic spacing is intended to include evenly spaced increments in
time or increments based on equal weights of coal passing the collection
area. As a minimum, determine the number and weight of increments
required per gross sample representing each coal lot according to Table
2 or Paragraph 7.1.5.2 of ASTM D 2234. Collect one gross sample for each
lot of raw coal and one gross sample for each lot of product coal.
12.5.2.1.2 ASTM Lot Size. For the purpose of Section 12.5.2 (fuel
pretreatment), the lot size of product coal is the weight of product
coal from one type of raw coal. The lot size of raw coal is the weight
of raw coal used to produce one lot of product coal. Typically, the lot
size is the weight of coal processed in a 1-day (24-hour) period. If
more than one type of coal is treated and produced in 1 day, then gross
samples must be collected and analyzed for each type of coal. A coal lot
size equaling the 90-day quarterly fuel quantity for a steam generating
unit may be used if representative sampling can be conducted for each
raw coal and product coal.
Note: Alternative definitions of lot sizes may be used, subject to
prior approval of the Administrator.
12.5.2.1.3 Gross Sample Analysis. Use ASTM D 2013-72 or 86 to
prepare the sample, ASTM D 3177-75 or 89 or ASTM D 4239-85, 94, or 97 to
determine sulfur content (%S), ASTM D 3173-73 or 87 to determine
moisture content, and ASTM D 2015-77 (Reapproved 1978) or 96, D 3286-85
or 96, or D 5865-98 to determine gross calorific value (GCV) (all
standards cited are incorporated by reference--see Sec. 60.17 for
acceptable versions of the standards) on a dry basis for each gross
sample.
12.5.2.2 Liquid Fossil Fuel-Sampling and Analysis. See Note under
Section 12.5.2.1.
12.5.2.2.1 Sample Collection. Follow the procedures for continuous
sampling in ASTM D 270 or D 4177-95 (incorporated by reference--see
Sec. 60.17) for each gross sample from each fuel lot.
12.5.2.2.2 Lot Size. For the purpose of Section 12.5.2 (fuel
pretreatment), the lot size of a product oil is the weight of product
oil from one pretreatment facility and intended as one shipment (ship
load, barge load, etc.). The lot size of raw oil is the weight of each
crude liquid fuel type used to produce a lot of product oil.
Note: Alternative definitions of lot sizes may be used, subject to
prior approval of the Administrator.
12.5.2.2.3 Sample Analysis. Use ASTM D 129-64, 78, or 95, ASTM D
1552-83 or 95, or ASTM D 4057-81 or 95 to determine the sulfur content
(%S) and ASTM D 240-76 or 92 (all standards cited are incorporated by
reference--see Sec. 60.17) to determine the GCV of each gross sample.
These values may be assumed to be on a dry basis. The owner or operator
of an affected facility may elect to determine the GCV by sampling the
oil combusted on the first steam generating unit operating day of each
calendar month and then using the lowest GCV value of the three GCV
values per quarter for the GCV of all oil combusted in that calendar
quarter.
12.5.2.3 Use appropriate procedures, subject to the approval of the
Administrator, to determine the fraction of total mass input derived
from each type of fuel.

[[Page 466]]

12.5.3 Control Device Removal Efficiency. Compute the percent
removal efficiency (%Rg) of the control device using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.344

12.5.3.1 Use continuous emission monitoring systems or test
methods, as appropriate, to determine the outlet SO2 rates
and, if appropriate, the inlet SO2 rates. The rates may be
determined as hourly (Eh) or other sampling period averages
(Ed). Then, compute the average pollutant rates for the
performance test period (Eao and Eai) using the
procedures in Section 12.4.
12.5.3.2 As an alternative, as-fired fuel sampling and analysis may
be used to determine inlet SO2 rates as follows:
12.5.3.2.1 Compute the average inlet SO2 rate
(Edi) for each sampling period using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.345

Where:
[GRAPHIC] [TIFF OMITTED] TR17OC00.346

After calculating Edi, use the procedures in Section 12.4 to
determine the average inlet SO2 rate for the performance test
period (Eai).
12.5.3.2.2 Collect the fuel samples from a location in the fuel
handling system that provides a sample representative of the fuel
bunkered or consumed during a steam generating unit operating day. For
the purpose of as-fired fuel sampling under Section 12.5.3.2 or Section
12.6, the lot size for coal is the weight of coal bunkered or consumed
during each steam generating unit operating day. The lot size for oil is
the weight of oil supplied to the ``day'' tank or consumed during each
steam generating unit operating day. For reporting and calculation
purposes, the gross sample shall be identified with the calendar day on
which sampling began. For steam generating unit operating days when a
coal-fired steam generating unit is operated without coal being added to
the bunkers, the coal analysis from the previous ``as bunkered'' coal
sample shall be used until coal is bunkered again. For steam generating
unit operating days when an oil-fired steam generating unit is operated
without oil being added to the oil ``day'' tank, the oil analysis from
the previous day shall be used until the ``day'' tank is filled again.
Alternative definitions of fuel lot size may be used, subject to prior
approval of the Administrator.
12.5.3.2.3 Use ASTM procedures specified in Section 12.5.2.1 or
12.5.2.2 to determine %S and GCV.
12.5.4 Daily Geometric Average Percent Reduction from Hourly
Values. The geometric average percent reduction (%Rga) is
computed using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.347

Note: The calculation includes only paired data sets (hourly average)
for the inlet and outlet pollutant measurements.
12.6 Sulfur Retention Credit for Compliance Fuel. If fuel sampling and
analysis procedures in Section 12.5.2.1 are being used to determine
average SO2 emission rates (Eas) to the atmosphere
from a coal-fired steam generating unit when there is no SO2
control device, the following equation may be used to adjust the
emission rate for sulfur retention credits (no credits are allowed for
oil-fired systems) (Edi) for each sampling period using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.348

Where:

[[Page 467]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.349

After calculating Edi, use the procedures in Section
12.4.2 to determine the average SO2 emission rate to the
atmosphere for the performance test period (Eao).
12.7 Determination of Compliance When Minimum Data Requirement Is
Not Met.
12.7.1 Adjusted Emission Rates and Control Device Removal
Efficiency. When the minimum data requirement is not met, the
Administrator may use the following adjusted emission rates or control
device removal efficiencies to determine compliance with the applicable
standards.
12.7.1.1 Emission Rate. Compliance with the emission rate standard
may be determined by using the lower confidence limit of the emission
rate (Eao*) as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.350

12.7.1.2 Control Device Removal Efficiency. Compliance with the
overall emission reduction (%Ro) may be determined by using
the lower confidence limit of the emission rate (Eao*) and
the upper confidence limit of the inlet pollutant rate (Eai*)
in calculating the control device removal efficiency (%Rg) as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.351

[GRAPHIC] [TIFF OMITTED] TR17OC00.352

12.7.2 Standard Deviation of Hourly Average Pollutant Rates.
Compute the standard deviation (Se) of the hourly average
pollutant rates using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.353

Equation 19-19 through 19-31 may be used to compute the standard
deviation for both the outlet (So) and, if applicable, inlet
(Si) pollutant rates.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References [Reserved]

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 19-1.--Conversion Factors for Concentration
----------------------------------------------------------------------------------------------------------------
From To Multiply by
----------------------------------------------------------------------------------------------------------------
g/scm................................... ng/scm......................... 10\9\
mg/scm.................................. ng/scm......................... 10\6\
lb/scf.................................. ng/scm......................... 1.602 x 10\13\
ppm SO2................................. ng/scm......................... 2.66 x 10\6\
ppm NOx................................. ng/scm......................... 1.912 x 10\6\
ppm SO2................................. lb/scf......................... 1.660 x 10^-\7\
ppm NOx................................. lb/scf......................... 1.194 x 10^-7
----------------------------------------------------------------------------------------------------------------

[[Page 468]]

Table 19-2.--F Factors for Various Fuels\1\
--------------------------------------------------------------------------------------------------------------------------------------------------------
Fd Fw Fc
Fuel Type -----------------------------------------------------------------------------------------------
dscm/J dscf/10\6\ Btu wscm/J wscf/10\6\ Btu scm/J scf/10\6\ Btu
--------------------------------------------------------------------------------------------------------------------------------------------------------
Coal:
Anthracite ²........................................ 2.71 x 10^-7 10,100 2.83 x 10^-7 10,540 0.530 x 10^-7 1,970
Bituminus ²......................................... 2.63 x 10^-7 9,780 2.86 x 10^-7 10,640 0.484 x 10^-7 1,800
Lignite............................................. 2.65 x 10^-7 9,860 3.21 x 10^-7 11,950 0.513 x 10^-7 1,910
Oil \3\............................................. 2.47 x 10^-7 9,190 2.77 x 10^-7 10,320 0.383 x 10^-7 1,420
Gas:....................................................
Natural............................................. 2.34 x 10^-7 8,710 2.85 x 10^-7 10,610 0.287 x 10^-7 1,040
Propane............................................. 2.34 x 10^-7 8,710 2.74 x 10^-7 10,200 0.321 x 10^-7 1,190
Butane.............................................. 2.34 x 10^-7 8,710 2.79 x 10^-7 10,390 0.337 x 10^-7 1,250
Wood.................................................... 2.48 x 10^-7 9,240 .............. .............. 0.492 x 10^-7 1,830
Wood Bark............................................... 2.58 x 10^-7 9,600 .............. .............. 0.516 x 10^-7 1,920
Municipal............................................... 2.57 x 10^-7 9,570 .............. .............. 0.488 x 10^-7 1,820
Solid Waste............................................. .............. .............. .............. .............. .............. ..............
--------------------------------------------------------------------------------------------------------------------------------------------------------
\1\ Determined at standard conditions: 20 deg.C (68 deg.F) and 760 mm Hg (29.92 in Hg)
\2\ As classified according to ASTM D 388.
\3\ Crude, residual, or distillate.

Table 19-3.--Values for T0.95*
----------------------------------------------------------------------------------------------------------------
n\1\ t0.95 n\1\ t0.95 n\1\ t0.95
----------------------------------------------------------------------------------------------------------------
2................................................. 6.31 8 1.89 22-26 1.71
3................................................. 2.42 9 1.86 27-31 1.70
4................................................. 2.35 10 1.83 32-51 1.68
5................................................. 2.13 11 1.81 52-91 1.67
6................................................. 2.02 12-16 1.77 92-151 1.66
7................................................. 1.94 17-21 1.73 152 or more 1.65
----------------------------------------------------------------------------------------------------------------
\1\The values of this table are corrected for n-1 degrees of freedom. Use n equal to the number (H) of hourly
average data points.

Method 20--Determination of Nitrogen Oxides, Sulfur Dioxide, and Diluent
Emissions from Stationary Gas Turbines

1. Principle and Applicability

1.1 Applicability. This method is applicable for the determination
of nitrogen oxides (NOx), sulfur dioxide (SO2),
and a diluent gas, either oxygen (O2) or carbon dioxide
(CO2), emissions from stationary gas turbines. For the
NOx and diluent concentration determinations, this method
includes: (1) Measurement system design criteria; (2) Analyzer
performance specifications and performance test procedures; and (3)
Procedures for emission testing.

1.2 Principle. A gas sample is continuously extracted from the
exhaust stream of a stationary gas turbine; a portion of the sample
stream is conveyed to instrumental analyzers for determination of
NOx and diluent content. During each NOx and
diluent determination, a separate measurement of SO2
emissions is made, using Method 6, or its equivalent. The diluent
determination is used to adjust the NOx and SO2
concentrations to a reference condition.

2. Definitions

2.1 Measurement System. The total equipment required for the
determination of a gas concentration or a gas emission rate. The system
consists of the following major subsystems:
2.1.1 Sample Interface. That portion of a system that is used for
one or more of the following: sample acquisition, sample transportation,
sample conditioning, or protection of the analyzers from the effects of
the stack effluent.
2.1.2 NOx Analyzer. That portion of the system that
senses NOx and generates an output proportional to the gas
concentration.
2.1.3 O2 Analyzer. That portion of the system that
senses O2 and generates an output proportional to the gas
concentration.
2.1.4 CO2 Analyzer. That portion of the system that
senses CO2 and generates an output proportional to the gas
concentration.
2.1.5 Data Recorder. That portion of the measurement system that
provides a permanent record of the analyzer(s) output. The data recorder
may include automatic data reduction capabilities.
2.2 Span Value. The upper limit of a gas concentration measurement
range that is specified for affected source categories in the applicable
part of the regulations.
2.3 Calibration Gas. A known concentration of a gas in an
appropriate diluent gas.
2.4 Calibration Error. The difference between the gas concentration
indicated by the measurement system and the known concentration of the
calibration gas.

[[Page 469]]

2.5 Zero Drift. The difference in the measurement system output
readings from zero after a stated period of operation during which no
unscheduled maintenance, repair, or adjustment took place and the input
concentration at the time of the measurements was zero.
2.6 Calibration Drift. The difference in the measurement system
output readings from the known concentration of the calibration gas
after a stated period of operation during which no unscheduled
maintenance, repair, or adjustment took place and the input at the time
of the measurements was a high-level value.
2.7 Response Time. The amount of time required for the measurement
system to display on the data output 95 percent of a step change in
pollutant concentration.
2.8 Interference Response. The output response of the measurement
system to a component in the sample gas, other than the gas component
being measured.

3. Measurement System Performance Specifications

3.1 NO2 to NO Converter. Greater than 90 percent
conversion efficiency of NO2 to NO.
3.2 Interference Response. Less than ^plus-minus2 percent
of the span value.
3.3 Response Time. No greater than 30 seconds.
3.4 Zero Drift. Less than ^plus-minus2 percent of the
span value over the period of each test run.
3.5 Calibration Drift. Less than ^plus-minus2 percent of
the span value over the period of each test run.

4. Apparatus and Reagents

4.1 Measurement System. Use any measurement system for NOx
and diluent that is expected to meet the specifications in this method.
A schematic of an acceptable measurement system is shown in Figure 20-1.
The essential components of the measurement system are described below:
[GRAPHIC] [TIFF OMITTED] TC01JN92.246

[[Page 470]]

4.1.1 Sample Probe. Heated stainless steel, or equivalent, open-
ended, straight tube of sufficient length to traverse the sample points.
4.1.2 Sample Line. Heated (>95 deg.C) stainless steel or Teflon
tubing to transport the sample gas to the sample conditioners and
analyzers.
4.1.3 Calibration Valve Assembly. A three-way valve assembly to
direct the zero and calibration gases to the sample conditioners and to
the analyzers. The calibration valve assembly shall be capable of
blocking the sample gas flow and of introducing calibration gases to the
measurement system when in the calibration mode.
4.1.4 NO2 to NO Converter. That portion of the system
that converts the nitrogen dioxide (NO2) in the sample gas to
nitrogen oxide (NO). Some analyzers are designed to measure NOx
as NO2 on a wet basis and can be used without an NO2
to NO converter or a moisture removal trap provided the sample line to
the analyzer is heated (>95 deg.C) to the inlet of the analyzer. In
addition, an NO2 to NO converter is not necessary if the
NO2 portion of the exhaust gas is less than 5 percent of the
total NOx concentration. As a guideline, an NO2 to
NO converter is not necessary if the gas turbine is operated at 90
percent or more of peak load capacity. A converter is necessary under
lower load conditions.
4.1.5 Moisture Removal Trap. A refrigerator-type condenser or other
type device designed to continuously remove condensate from the sample
gas while maintaining minimal contact between any condensate and the
sample gas. The moisture removal trap is not necessary for analyzers
that can measure NOx concentrations on a wet basis; for these
analyzers, (a) heat the sample line up to the inlet of the analyzers,
(b) determine the moisture content using methods subject to the approval
of the Administrator, and (c) correct the NOx and diluent
concentrations to a dry basis.
4.1.6 Particulate Filter. An in-stack or an out-of-stack glass
fiber filter, of the type specified in EPA Method 5; however, an out-of-
stack filter is recommended when the stack gas temperature exceeds 250
to 300 deg.C.
4.1.7 Sample Pump. A nonreactive leak-free sample pump to pull the
sample gas through the system at a flow rate sufficient to minimize
transport delay. The pump shall be made from stainless steel or coated
with Teflon or equivalent.
4.1.8 Sample Gas Manifold. A sample gas manifold to divert portions
of the sample gas stream to the analyzers. The manifold may be
constructed of glass, Teflon, stainless steel, or equivalent.
4.1.9 Diluent Gas Analyzer. An analyzer to determine the percent
O2 or CO2 concentration of the sample gas.
4.1.10 Nitrogen Oxides Analyzer. An analyzer to determine the ppm
NOx concentration in the sample gas stream.
4.1.11 Data Recorder. A strip-chart recorder, analog computer, or
digital recorder for recording measurement data.
4.2 Sulfur Dioxide Analysis. EPA Method 6 apparatus and reagents.
4.3 NOx Calibration Gases. The calibration gases for the
NOx analyzer shall be NO in N2. Use four
calibration gas mixtures as specified below:
4.3.1 High-level Gas. A gas concentration that is equivalent to 80
to 90 percent of the span value.
4.3.2 Mid-level Gas. A gas concentration that is equivalent to 45
to 55 percent of the span value.
4.3.3 Low-level Gas. A gas concentration that is equivalent to 20
to 30 percent of the span value.
4.3.4 Zero Gas. A gas concentration of less than 0.25 percent of
the span value. Ambient air may be used for the NOx zero gas.
4.4 Diluent Calibration Gases.
4.4.1 For O2 calibration gases, use purified air at 20.9
percent O2 as the high-level O2 gas. Use a gas
concentration between 11 and 15 percent O2 in nitrogen for
the mid-level gas, and use purified nitrogen for the zero gas.
4.4.2 For CO2 calibration gases, use a gas concentration
between 8 and 12 percent CO2 in air for the high-level
calibration gas. Use a gas concentration between 2 and 5 percent
CO2 in air for the mid-level calibration gas, and use
purified air (<100 ppm CO2) as the zero level calibration
gas.

5. Measurement System Performance Test Procedures

Perform the following procedures prior to measurement of emissions
(Section 6) and only once for each test program, i.e., the series of all
test runs for a given gas turbine engine.
5.1 Calibration Gas Checks. There are two alternatives for checking
the concentrations of the calibration gases. (a) The first is to use
calibration gases that are documented traceable to National Bureau of
Standards Reference Materials. Use Traceability Protocol for
Establishing True Concentrations of Gases Used for Calibrations and
Audits of Continuous Source Emission Monitors (Protocol Number 1) that
is available from the Environmental Monitoring Systems Laboratory,
Quality Assurance Branch, Mail Drop 77, Environmental Protection Agency,
Research Triangle Park, NC 27711. Obtain a certification from the gas
manufacturer that the protocol was followed. These calibration gases are
not to be analyzed with the Reference Methods. (b) The second
alternative is to use calibration gases not prepared according to the
protocol. If this alternative is chosen, within 1 month prior to the
emission test, analyze

[[Page 471]]

each of the calibration gas mixtures in triplicate using Method 7 or the
procedure outlined in Citation 1 for NOx and use Method 3 for
O2 or CO2. Record the results on a data sheet
(example is shown in Figure 20-2). For the low-level, mid-level, or
high-level gas mixtures, each of the individual NOx
analytical results must be within 10 percent (or 10 ppm, whichever is
greater) of the triplicate set average (O2 or CO2
test results must be within 0.5 percent O2 or
CO2); otherwise, discard the entire set and repeat the
triplicate analyses. If the average of the triplicate reference method
test results is within 5 percent for NOx gas or 0.5 percent
O2 or CO2 for the O2 or CO2
gas of the calibration gas manufacturer's tag value, use the tag value;
otherwise, conduct at least three additional reference method test
analyses until the results of six individual NOx runs (the
three original plus three additional) agree within 10 percent (or 10
ppm, whichever is greater) of the average (O2 or
CO2 test results must be within 0.5 percent O2 or
CO2). Then use this average for the cylinder value.
5.2 Measurement System Preparation. Prior to the emission test,
assemble the measurement system following the manufacturer's written
instructions in preparing and operating the NO2 to NO
converter, the NOx analyzer, the diluent analyzer, and other
components.

Figure 20-2--Analysis of Calibration Gases

Date __________ (Must be within 1 month prior to the test period)
Reference method used___________________________________________________

----------------------------------------------------------------------------------------------------------------
Gas concentration, ppm
Sample run --------------------------------------------------------------------------
Low level\a\ Mid level\b\ High level\c\
----------------------------------------------------------------------------------------------------------------
1
----------------------------------------------------------------------------------------------------------------
2
----------------------------------------------------------------------------------------------------------------
3
----------------------------------------------------------------------------------------------------------------
Average
----------------------------------------------------------------------------------------------------------------
Maximum % deviation\d\...............
----------------------------------------------------------------------------------------------------------------
\a\ Average must be 20 to 30% of span value.
\b\ Average must be 45 to 55% of span value.
\c\ Average must be 80 to 90% of span value.
\d\ Must be >^plus-minus10% of applicable average or 10 ppm, whichever is greater.

5.3 Calibration Check. Conduct the calibration checks for both the
NOx and the diluent analyzers as follows:
5.3.1 After the measurement system has been prepared for use
(Section 5.2), introduce zero gases and the mid-level calibration gases;
set the analyzer output responses to the appropriate levels. Then
introduce each of the remainder of the calibration gases described in
Sections 4.3 or 4.4, one at a time, to the measurement system. Record
the responses on a form similar to Figure 20-3.
5.3.2 If the linear curve determined from the zero and mid-level
calibration gas responses does not predict the actual response of the
low-level (not applicable for the diluent analyzer) and high-level gases
within 2 percent of the span value, the calibration shall be considered
invalid. Take corrective measures on the measurement system before
proceeding with the test.
5.4 Interference Response. Introduce the gaseous components listed
in Table 20-1 into the measurement system separately, or as gas
mixtures. Determine the total interference output response of the system
to these components in concentration units; record the values on a form
similar to Figure 20-4. If the sum of the interference responses of the
test gases for either the NOx or diluent analyzers is greater
than 2 percent of the applicable span value, take corrective measure on
the measurement system.

Figure 20-3--Zero and Calibration Data
Turbine type......................... Identification number....
Date................................. Test number..............
Analyzer type........................ Identification number....

----------------------------------------------------------------------------------------------------------------
Cylinder value, ppm Initial analyzer Final analyzer Difference: initial-
or % response, ppm or % responses, ppm or % final, ppm or %
----------------------------------------------------------------------------------------------------------------
Zero gas.................
----------------------------------------------------------------------------------------------------------------

Low-level gas............
----------------------------------------------------------------------------------------------------------------

Mid-level gas............
----------------------------------------------------------------------------------------------------------------

High-level gas...........
----------------------------------------------------------------------------------------------------------------

[[Page 472]]

[GRAPHIC] [TIFF OMITTED] TC16NO91.209

Table 20-1--Interference Test Gas Concentration

----------------------------------------------------------------------------------------------------------------
CO................................... 50050 ppm.. CO2.................... 101
percent.
SO2.................................. 20020 ppm.. O2..................... 20.91
percent.
----------------------------------------------------------------------------------------------------------------

Figure 20-4--Interference Response

Date of test __________
Analyzer type___________________________________________________________
Serial No.______________________________________________________________

----------------------------------------------------------------------------------------------------------------
Analyzer output
Test gas type Concentration, ppm response % of span
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

[GRAPHIC] [TIFF OMITTED] TC16NO91.210

Conduct an interference response test of each analyzer prior to its
initial use in the field. Thereafter, recheck the measurement system if
changes are made in the instrumentation that could alter the
interference response, e.g., changes in the type of gas detector.
In lieu of conducting the interference response test, instrument
vendor data, which demonstrate that for the test gases of Table 20-1 the
interference performance specification is not exceeded, are acceptable.
5.5 Response Time. To determine response time, first introduce zero
gas into the system at the calibration valve until all readings are
stable; then, switch to monitor the stack effluent until a stable
reading can be obtained. Record the upscale response time. Next,
introduce high-level calibration gas into the system. Once the system
has stabilized at the high-level concentration, switch to monitor the
stack effluent and wait until a stable value is reached. Record the
downscale response time. Repeat the procedure three times. A stable
value is equivalent to a change of less than 1 percent of span value for
30 seconds or less than 5 percent of the measured average concentration
for 2 minutes. Record the response time data on a form similar to Figure
20-5, the readings of the upscale or downscale reponse time, and report
the greater time as the ``response time'' for the analyzer. Conduct a
response time test prior to the initial field use of the measurement
system, and repeat if changes are made in the measurement system.

Figure 20-5--Response Time

Date of test __________

Analyzer type___________________________________________________________

S/N_____________________________________________________________________

Span gas concentration: ________ ppm.
Analyzer span setting: ________ ppm.
Upscale:
1 ________ seconds.
2 ________ seconds.
3 ________ seconds.
Average upscale response ____ seconds.

Downscale:
1 ________ seconds.
2 ________ seconds.
3 ________ seconds.
Average downscale response ____ seconds.

System response time=
slower average time=
________ seconds.

5.6 NO2 to NO Conversion Efficiency.
5.6.1 Add gas from the mid-level NO in N2 calibration
gas cylinder to a clean, evacuated, leak-tight Tedlar bag. Dilute this
gas approximately 1:1 with 20.9 percent O2, purified air.
Immediately attach the bag outlet to the calibration valve assembly and
begin operation of the sampling system. Operate the sampling system,
recording the NOx response, for at least 30 minutes. If the
NO2 to NO conversion is 100 percent, the instrument response
will be stable at the highest peak value observed. If the response at
the end of 30 minutes decreases more than 2.0 percent of the highest
peak value, the system is not acceptable and corrections must be made
before repeating the check.
5.6.2 Alternatively, the NO2 to NO converter check
described in Title 40, Part 86: Certification and Test Procedures for
Heavy-duty Engines for 1979 and Later Model Years may be used. Other
alternative procedures may be used with approval of the Administrator.

6. Emission Measurement Test Procedure

6.1 Preliminaries.
6.1.1 Selection of a Sampling Site. Select a sampling site as close
as practical to the exhaust of the turbine. Turbine geometry, stack
configuration, internal baffling, and point of introduction of dilution
air will vary for different turbine designs. Thus, each of these factors
must be given special consideration in order to obtain a representative
sample. Whenever possible, the sampling site

[[Page 473]]

shall be located upstream of the point of introduction of dilution air
into the duct. Sample ports may be located before or after the upturn
elbow, in order to accommodate the configuration of the turning vanes
and baffles and to permit a complete, unobstructed traverse of the
stack. The sample ports shall not be located within 5 feet or 2
diameters (whichever is less) of the gas discharge to atmosphere. For
supplementary-fired, combined-cycle plants, the sampling site shall be
located between the gas turbine and the boiler. The diameter of the
sample ports shall be sufficient to allow entry of the sample probe.
6.1.2 A preliminary O2 or CO2 traverse is
made for the purpose of selecting sampling points of low O2
or high CO2 concentrations, as appropriate for the
measurement system. Conduct this test at the turbine operating condition
that is the lowest percentage of peak load operation included in the
test program. Follow the procedure below, or use an alternative
procedure subject to the approval of the Administrator.
6.1.2.1 Minimum Number of Points. Select a minimum number of points
as follows: (1) Eight, for stacks having cross-sectional areas less than
1.5 m\2\ (16.1 ft\2\); (2) eight plus one additional sample point for
each 0.2 m\2\ (2.2 ft\2\ of areas, for stacks of 1.5 m\2\ to 10.0 m\2\
(16.1-107.6 ft\2\) in cross-sectional area; and (3) 49 sample points (48
for circular stacks) for stacks greater than 10.0 m \2\ (107.6 ft \2\)
in cross-sectional area. Note that for circular ducts, the number of
sample points must be a multiple of 4, and for rectangular ducts, the
number of points must be one of those listed in Table 20-2; therefore,
round off the number of points (upward), when appropriate.
6.1.2.2 Cross-sectional Layout and Location of Traverse Points.
After the number of traverse points for the preliminary diluent sampling
has been determined, use Method 1 to located the traverse points.
6.1.2.3 Preliminary Diluent Measurement. While the gas turbine is
operating at the lowest percent of peak load, conduct a preliminary
diluent measurement as follows: Position the probe at the first traverse
point and begin sampling. The minimum sampling time at each point shall
be 1 minute plus the average system response time. Determine the average
steady-state concentration of diluent at each point and record the data
on Figure 20-6.
6.1.2.4 Selection of Emission Test Sampling Points. Select the
eight sampling points at which the lowest O2 concentrations
or highest CO2 concentrations were obtained. Sample at each
of these selected points during each run at the different turbine load
conditions. More than eight points may be used, if desired, providing
that the points selected as described above are included.

Table 20-2--Cross-sectional Layout for Rectangular Stacks
------------------------------------------------------------------------
Matrix
layout
------------------------------------------------------------------------
No. of traverse points:
9......................................................... 3 x 3
12........................................................ 4 x 3
16........................................................ 4 x 4
20........................................................ 5 x 4
25........................................................ 5 x 5
30........................................................ 6 x 5
36........................................................ 6 x 6
42........................................................ 7 x 6
49........................................................ 7 x 7
------------------------------------------------------------------------

Figure 20-6--Preliminary Diluent Traverse

Date __________

Location:
Plant___________________________________________________________________
City, State_____________________________________________________________

Turbine identification:
Manufacturer____________________________________________________________
Model, serial number____________________________________________________

------------------------------------------------------------------------
Sample point Diluent concentration, ppm
------------------------------------------------------------------------

------------------------------------------------------------------------

6.2 NOx and Diluent Measurement. This test is to be
conducted at each of the specified load conditions. Three test runs at
each load condition constitute a complete test.
6.2.1 At the beginning of each NOx test run and, as
applicable, during the run, record turbine data as indicated in Figure
20-7. Also, record the location and number of the traverse points on a
diagram.
6.2.2 Position the probe at the first point determined in the
preceding section and begin sampling. The minimum sampling time at each
point shall be at least 1 minute plus the average system response time.
Determine the average steady-state concentration of diluent and NOx
at each point and record the data on Figure 20-8.

Figure 20-7--Stationary Gas Turbine Data

turbine operation record

Test operator ____________________ Date_________________________________

Turbine identification:
Type____________________________________________________________________
Serial No.______________________________________________________________

Location:
Plant___________________________________________________________________
City____________________________________________________________________

Ambient temperature_____________________________________________________
Ambient humidity________________________________________________________
Test time start_________________________________________________________
Test time finish________________________________________________________
Fuel flow rate\a\_______________________________________________________
Water or steam flow rate\a\_____________________________________________
Ambient pressure________________________________________________________

[[Page 474]]

Ultimate fuel analysis:
C_______________________________________________________________________
H_______________________________________________________________________
O_______________________________________________________________________
N_______________________________________________________________________
S_______________________________________________________________________
Ash_____________________________________________________________________
H20__________________________________________________________

Trace metals:
Na______________________________________________________________________
Va______________________________________________________________________
K_______________________________________________________________________
etc\b\__________________________________________________________________

Operating load__________________________________________________________
\a\Describe measurement method, i.e., continuous flow meter, start
finish volumes, etc.
\b\i.e., additional elements added for smoke suppression.

Figure 20-8--Stationary Gas Turbine Sample Point Record

Turbine identification:
Manufacturer____________________________________________________________
Model, serial No._______________________________________________________

Location:
Plant___________________________________________________________________
City, State_____________________________________________________________

Ambient temperature_____________________________________________________
Ambient pressure________________________________________________________
Date __________
Test time: start________________________________________________________
Test time: finish_______________________________________________________
Test operator name______________________________________________________

Diluent instrument type_________________________________________________
Serial No_______________________________________________________________

NOx instrument type__________________________________________
Serial No.______________________________________________________________

----------------------------------------------------------------------------------------------------------------
Sample point Time, min Diluent\a\, % NOx a, ppm
----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------

----------------------------------------------------------------------------------------------------------------
\a\Average steady-state value from recorder or instrument readout.

6.2.3 After sampling the last point, conclude the test run by
recording the final turbine operating parameters and by determining the
zero and calibration drift, as follows:
Immediately following the test run at each load condition, or if
adjustments are necessary for the measurement system during the tests,
reintroduce the zero and mid-level calibration gases as described in
Sections 4.3 and 4.4, one at a time, to the measurement system at the
calibration valve assembly. (Make no adjustments to the measurement
system until after the drift checks are made). Record the analyzers'
responses on a form similar to Figure 20-3. If the drift values exceed
the specified limits, the test run preceding the check is considered
invalid and will be repeated following corrections to the measurement
system. Alternatively, recalibrate the measurement system and
recalculate the measurement data. Report the test results based on both
the initial calibration and the recalibration data.
6.3 SO2 Measurement. This test is conducted only at the
100 percent peak load condition. Determine SO2 using Method
6, or equivalent, during the test. Select a minimum of six total points
from those required for the NOx measurements; use two points
for each sample run. The sample time at each point shall be at least 10
minutes. Average the diluent readings taken during the NOx
test runs at sample points corresponding to the SO2 traverse
points (see Section 6.2.2) and use this average diluent concentration to
correct the integrated SO2 concentration obtained by Method 6
to 15 percent diluent (see Equation 20-1).
If the applicable regulation allows fuel sampling and analysis for
fuel sulfur content to demonstrate compliance with sulfur emission unit,
emission sampling with Method 6 is not required, provided the fuel
sulfur content meets the limits of the regulation.

7. Emission Calculations
7.1 Moisture Correction. Measurement data used in most of these
calculations must be on a dry basis. If measurements must be corrected
to dry conditions, use the following equation:
[GRAPHIC] [TIFF OMITTED] TC16NO91.211

where:
Cd=Pollutant or diluent concentration adjusted to dry
conditions, ppm or percent.
Cw=Pollutant or diluent concentration measured under moist
sample conditions, ppm or percent.
Bws=Moisture content of sample gas as measured with Method 4,
reference method, or other approved method, percent/100.

7.2 CO2 Correction Factor. If pollutant concentrations
are to be corrected to 15 percent O2 and CO2
concentration is measured in lieu of O2 concentration
measurement, a CO2 correction factor is needed. Calculate the
CO2 correction factor as follows:
7.2.1 Calculate the fuel-specific F0 value for the fuel
burned during the test using values obtained from Method 19, Section
5.2, and the following equation.

[[Page 475]]

[GRAPHIC] [TIFF OMITTED] TC16NO91.212

where:

FO=Fuel factor based on the ratio of oxygen volume to the
ultimate CO2 volume produced by the fuel at zero
percent excess air, dimensionless.
0.209=Fraction of air that is oxygen, percent/100.
Fd=Ratio of the volume of dry effluent gas to the gross
calorific value of the fuel from Method 19, dsm\3\/J (dscf/
10\6\ Btu).
Fc=Ratio of the volume of carbon dioxide produced to the
gross calorific value of the fuel from Method 19, dsm\3\/J
(dscf\6\ Btu).
7.2.2. Calculate the CO2 correction factor for
correcting measurement data to 15 percent oxygen, as follows:
[GRAPHIC] [TIFF OMITTED] TC16NO91.213

where:
XCO2=CO2 Correction factor, percent.
5.9=20.9 percent O2-15 percent O2, the defined
O2 correction value, percent.

7.3 Correction of Pollutant Concentrations to 15 percent
O2. Calculate the NOx and SO2 gas
concentrations adjusted to 15 percent O2 using Equation 20-4
or 20-5, as appropriate. The correction to 15 percent O2 is
very sensitive to the accuracy of the O2 or CO2
concentration measurement. At the level of the analyzer drift specified
in Section 3, the O2 or CO2 correction can exceed
5 percent at the concentration levels expected in gas turbine exhaust
gases. Therefore, O2 or CO2 analyzer stability and
careful calibration are necessary.
7.3.1 Correction of Pollutant Concentration Using O2
Concentration. Calculate the O2 corrected pollutant
concentration, as follows:
[GRAPHIC] [TIFF OMITTED] TC16NO91.214

where:

Cadj=Pollutant concentration corrected to 15 percent
O2 ppm.
Cd=Pollutant concentration measured, dry basis, ppm.
%O2=Measured O2 concentration dry basis, percent.
7.3.2 Correction of Pollutant Concentration Using CO2
Concentration. Calculate the CO2 corrected pollutant
concentration, as follows:
[GRAPHIC] [TIFF OMITTED] TC16NO91.215

where:

%CO2=Measured CO2 concentration measured, dry
basis, percent.
7.4 Average Adjusted NOx Concentration. Calculate the
average adjusted NOx concentration by summing the adjusted
values for each sample point and dividing by the number of points for
each run.
7.5 NOx and SO2 Emission Rate Calculations.
The emission rates for NOx and SO2 in units of
pollutant mass per quantity of heat input can be calculated using the
pollutant and diluent concentrations and fuel-specific F-factors based
on the fuel combustion characteristics. The measured concentrations of
pollutant in units of parts per million by volume (ppm) must be
converted to mass per unit volume concentration units for these
calculations. Use the following table for such conversions:

Conversion Factors for Concentration
------------------------------------------------------------------------
From To Multiply by
------------------------------------------------------------------------
g/sm\3\......................... ng/sm\3\.......... 10\9\
mg/sm\3\........................ ng/sm\3\.......... 10\6\
lb/scf.......................... ng/sm\3\.......... 1.602 x 10\1\\3\
ppm (SO2)....................... ng/sm\3\.......... 2.660 x 10\6\
ppm (NOx)....................... ng/sm\3\.......... 1.912 x 10\6\
ppm (SO2)....................... lb/scf............ 1.660 x 10-\7\
ppm (NOx)....................... lb/scf............ 1.194 x 10-\7\
------------------------------------------------------------------------

7.5.1 Calculation of Emission Rate Using Oxygen Correction. Both
the O2 concentration and the pollutant concentration must be
on a dry basis. Calculate the pollutant emission rate, as follows:
[GRAPHIC] [TIFF OMITTED] TC16NO91.216

where:

E=Mass emission rate of pollutant, ng/J (lb/10\6\ Btu).
7.5.2 Calculation of Emission Rate Using Carbon Dioxide Correction.
The CO2 concentration and the pollutant concentration may be
on either a dry basis or a wet basis, but both concentrations must be on
the same basis for the calculations. Calculate the pollutant emission
rate using Equation 20-7 or 20-8:
[GRAPHIC] [TIFF OMITTED] TC16NO91.217

[GRAPHIC] [TIFF OMITTED] TC16NO91.218

where:

Cw=Pollutant concentration measured on a moist sample basis,
ng/sm\3\ (lb/scf).
%CO2w=Measured CO2 concentration measured on a
moist sample basis, percent.

[[Page 476]]

8. Bibliography

1. Curtis, F. A Method for Analyzing NOx Cylinder Gases-
Specific Ion Electrode Procedure, Monograph available from Emission
Measurement Laboratory, ESED, Research Triangle Park, NC 27711, October
1978.
2. Sigsby, John E., F. M. Black, T. A. Bellar, and D. L. Klosterman.
Chemiluminescent Method for Analysis of Nitrogen Compounds in Mobile
Source Emissions (NO, NO2, and NH3 ).
``Environmental Science and Technology,'' 7:51-54. January 1973.
3. Shigehara, R.T., R.M. Neulicht, and W.S. Smith. Validating Orsat
Analysis Data from Fossil Fuel-Fired Units. Emission Measurement Branch,
Emission Standards and Engineering Division, Office of Air Quality
Planning and Standards, U.S. Environmental Protection Agency, Research
Triangle Park, NC 27711. June 1975.

Method 21--Determination of Volatile Organic Compound Leaks

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile Organic Compounds (VOC).......... No CAS number assigned.
------------------------------------------------------------------------

1.2 Scope. This method is applicable for the determination of VOC
leaks from process equipment. These sources include, but are not limited
to, valves, flanges and other connections, pumps and compressors,
pressure relief devices, process drains, open-ended valves, pump and
compressor seal system degassing vents, accumulator vessel vents,
agitator seals, and access door seals.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A portable instrument is used to detect VOC leaks from
individual sources. The instrument detector type is not specified, but
it must meet the specifications and performance criteria contained in
Section 6.0. A leak definition concentration based on a reference
compound is specified in each applicable regulation. This method is
intended to locate and classify leaks only, and is not to be used as a
direct measure of mass emission rate from individual sources.

3.0 Definitions

3.1 Calibration gas means the VOC compound used to adjust the
instrument meter reading to a known value. The calibration gas is
usually the reference compound at a known concentration approximately
equal to the leak definition concentration.
3.2 Calibration precision means the degree of agreement between
measurements of the same known value, expressed as the relative
percentage of the average difference between the meter readings and the
known concentration to the known concentration.
3.3 Leak definition concentration means the local VOC concentration
at the surface of a leak source that indicates that a VOC emission
(leak) is present. The leak definition is an instrument meter reading
based on a reference compound.
3.4 No detectable emission means a local VOC concentration at the
surface of a leak source, adjusted for local VOC ambient concentration,
that is less than 2.5 percent of the specified leak definition
concentration. that indicates that a VOC emission (leak) is not present.
3.5 Reference compound means the VOC species selected as the
instrument calibration basis for specification of the leak definition
concentration. (For example, if a leak definition concentration is
10,000 ppm as methane, then any source emission that results in a local
concentration that yields a meter reading of 10,000 on an instrument
meter calibrated with methane would be classified as a leak. In this
example, the leak definition concentration is 10,000 ppm and the
reference compound is methane.)
3.6 Response factor means the ratio of the known concentration of a
VOC compound to the observed meter reading when measured using an
instrument calibrated with the reference compound specified in the
applicable regulation.
3.7 Response time means the time interval from a step change in VOC
concentration at the input of the sampling system to the time at which
90 percent of the corresponding final value is reached as displayed on
the instrument readout meter.

4.0 Interferences. [Reserved]

5.0 Safety

[[Page 477]]

6.0 Equipment and Supplies

A VOC monitoring instrument meeting the following specifications is
required:
6.1 The VOC instrument detector shall respond to the compounds
being processed. Detector types that may meet this requirement include,
but are not limited to, catalytic oxidation, flame ionization, infrared
absorption, and photoionization.
6.2 The instrument shall be capable of measuring the leak
definition concentration specified in the regulation.
6.3 The scale of the instrument meter shall be readable to
2.5 percent of the specified leak definition concentration.
6.4 The instrument shall be equipped with an electrically driven
pump to ensure that a sample is provided to the detector at a constant
flow rate. The nominal sample flow rate, as measured at the sample probe
tip, shall be 0.10 to 3.0 l/min (0.004 to 0.1 ft\3\/min) when the probe
is fitted with a glass wool plug or filter that may be used to prevent
plugging of the instrument.
6.5 The instrument shall be equipped with a probe or probe
extension or sampling not to exceed 6.4 mm (\1/4\ in) in outside
diameter, with a single end opening for admission of sample.
6.6 The instrument shall be intrinsically safe for operation in
explosive atmospheres as defined by the National Electrical Code by the
National Fire Prevention Association or other applicable regulatory code
for operation in any explosive atmospheres that may be encountered in
its use. The instrument shall, at a minimum, be intrinsically safe for
Class 1, Division 1 conditions, and/or Class 2, Division 1 conditions,
as appropriate, as defined by the example code. The instrument shall not
be operated with any safety device, such as an exhaust flame arrestor,
removed.

7.0 Reagents and Standards

7.1 Two gas mixtures are required for instrument calibration and
performance evaluation:
7.1.1 Zero Gas. Air, less than 10 parts per million by volume
(ppmv) VOC.
7.1.2 Calibration Gas. For each organic species that is to be
measured during individual source surveys, obtain or prepare a known
standard in air at a concentration approximately equal to the applicable
leak definition specified in the regulation.
7.2 Cylinder Gases. If cylinder calibration gas mixtures are used,
they must be analyzed and certified by the manufacturer to be within 2
percent accuracy, and a shelf life must be specified. Cylinder standards
must be either reanalyzed or replaced at the end of the specified shelf
life.
7.3 Prepared Gases. Calibration gases may be prepared by the user
according to any accepted gaseous preparation procedure that will yield
a mixture accurate to within 2 percent. Prepared standards must be
replaced each day of use unless it is demonstrated that degradation does
not occur during storage.
7.4 Mixtures with non-Reference Compound Gases. Calibrations may be
performed using a compound other than the reference compound. In this
case, a conversion factor must be determined for the alternative
compound such that the resulting meter readings during source surveys
can be converted to reference compound results.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Instrument Performance Evaluation. Assemble and start up the
instrument according to the manufacturer's instructions for recommended
warmup period and preliminary adjustments.
8.1.1 Response Factor. A response factor must be determined for
each compound that is to be measured, either by testing or from
reference sources. The response factor tests are required before placing
the analyzer into service, but do not have to be repeated at subsequent
intervals.
8.1.1.1 Calibrate the instrument with the reference compound as
specified in the applicable regulation. Introduce the calibration gas
mixture to the analyzer and record the observed meter reading. Introduce
zero gas until a stable reading is obtained. Make a total of three
measurements by alternating between the calibration gas and zero gas.
Calculate the response factor for each repetition and the average
response factor.
8.1.1.2 The instrument response factors for each of the individual
VOC to be measured shall be less than 10 unless otherwise specified in
the applicable regulation. When no instrument is available that meets
this specification when calibrated with the reference VOC specified in
the applicable regulation, the available instrument may be calibrated
with one of the VOC to be measured, or any other VOC, so long as the
instrument then has a response factor of less than 10 for each of the
individual VOC to be measured.
8.1.1.3 Alternatively, if response factors have been published for
the compounds of interest for the instrument or detector type, the
response factor determination is not required, and existing results may
be referenced. Examples of published response factors for flame
ionization and catalytic oxidation detectors are included in References
1-3 of Section 17.0.
8.1.2 Calibration Precision. The calibration precision test must be
completed prior to placing the analyzer into service and at subsequent
3-month intervals or at the next use, whichever is later.
8.1.2.1 Make a total of three measurements by alternately using
zero gas and the specified calibration gas. Record the meter

[[Page 478]]

readings. Calculate the average algebraic difference between the meter
readings and the known value. Divide this average difference by the
known calibration value and multiply by 100 to express the resulting
calibration precision as a percentage.
8.1.2.2 The calibration precision shall be equal to or less than 10
percent of the calibration gas value.
8.1.3 Response Time. The response time test is required before
placing the instrument into service. If a modification to the sample
pumping system or flow configuration is made that would change the
response time, a new test is required before further use.
8.1.3.1 Introduce zero gas into the instrument sample probe. When
the meter reading has stabilized, switch quickly to the specified
calibration gas. After switching, measure the time required to attain 90
percent of the final stable reading. Perform this test sequence three
times and record the results. Calculate the average response time.
8.1.3.2 The instrument response time shall be equal to or less than
30 seconds. The instrument pump, dilution probe (if any), sample probe,
and probe filter that will be used during testing shall all be in place
during the response time determination.
8.2 Instrument Calibration. Calibrate the VOC monitoring instrument
according to Section 10.0.
8.3 Individual Source Surveys.
8.3.1 Type I--Leak Definition Based on Concentration. Place the
probe inlet at the surface of the component interface where leakage
could occur. Move the probe along the interface periphery while
observing the instrument readout. If an increased meter reading is
observed, slowly sample the interface where leakage is indicated until
the maximum meter reading is obtained. Leave the probe inlet at this
maximum reading location for approximately two times the instrument
response time. If the maximum observed meter reading is greater than the
leak definition in the applicable regulation, record and report the
results as specified in the regulation reporting requirements. Examples
of the application of this general technique to specific equipment types
are:
8.3.1.1 Valves. The most common source of leaks from valves is the
seal between the stem and housing. Place the probe at the interface
where the stem exits the packing gland and sample the stem
circumference. Also, place the probe at the interface of the packing
gland take-up flange seat and sample the periphery. In addition, survey
valve housings of multipart assembly at the surface of all interfaces
where a leak could occur.
8.3.1.2 Flanges and Other Connections. For welded flanges, place
the probe at the outer edge of the flange-gasket interface and sample
the circumference of the flange. Sample other types of nonpermanent
joints (such as threaded connections) with a similar traverse.
8.3.1.3 Pumps and Compressors. Conduct a circumferential traverse
at the outer surface of the pump or compressor shaft and seal interface.
If the source is a rotating shaft, position the probe inlet within 1 cm
of the shaft-seal interface for the survey. If the housing configuration
prevents a complete traverse of the shaft periphery, sample all
accessible portions. Sample all other joints on the pump or compressor
housing where leakage could occur.
8.3.1.4 Pressure Relief Devices. The configuration of most pressure
relief devices prevents sampling at the sealing seat interface. For
those devices equipped with an enclosed extension, or horn, place the
probe inlet at approximately the center of the exhaust area to the
atmosphere.
8.3.1.5 Process Drains. For open drains, place the probe inlet at
approximately the center of the area open to the atmosphere. For covered
drains, place the probe at the surface of the cover interface and
conduct a peripheral traverse.
8.3.1.6 Open-ended Lines or Valves. Place the probe inlet at
approximately the center of the opening to the atmosphere.
8.3.1.7 Seal System Degassing Vents and Accumulator Vents. Place
the probe inlet at approximately the center of the opening to the
atmosphere.
8.3.1.8 Access door seals. Place the probe inlet at the surface of
the door seal interface and conduct a peripheral traverse.
8.3.2 Type II--``No Detectable Emission''. Determine the local
ambient VOC concentration around the source by moving the probe randomly
upwind and downwind at a distance of one to two meters from the source.
If an interference exists with this determination due to a nearby
emission or leak, the local ambient concentration may be determined at
distances closer to the source, but in no case shall the distance be
less than 25 centimeters. Then move the probe inlet to the surface of
the source and determine the concentration as outlined in Section 8.3.1.
The difference between these concentrations determines whether there are
no detectable emissions. Record and report the results as specified by
the regulation. For those cases where the regulation requires a specific
device installation, or that specified vents be ducted or piped to a
control device, the existence of these conditions shall be visually
confirmed. When the regulation also requires that no detectable
emissions exist, visual observations and sampling surveys are required.
Examples of this technique are:
8.3.2.1 Pump or Compressor Seals. If applicable, determine the type
of shaft seal. Perform a survey of the local area ambient VOC
concentration and determine if detectable emissions exist as described
in Section 8.3.2.

[[Page 479]]

8.3.2.2 Seal System Degassing Vents, Accumulator Vessel Vents,
Pressure Relief Devices. If applicable, observe whether or not the
applicable ducting or piping exists. Also, determine if any sources
exist in the ducting or piping where emissions could occur upstream of
the control device. If the required ducting or piping exists and there
are no sources where the emissions could be vented to the atmosphere
upstream of the control device, then it is presumed that no detectable
emissions are present. If there are sources in the ducting or piping
where emissions could be vented or sources where leaks could occur, the
sampling surveys described in Section 8.3.2 shall be used to determine
if detectable emissions exist.
8.3.3 Alternative Screening Procedure.
8.3.3.1 A screening procedure based on the formation of bubbles in
a soap solution that is sprayed on a potential leak source may be used
for those sources that do not have continuously moving parts, that do
not have surface temperatures greater than the boiling point or less
than the freezing point of the soap solution, that do not have open
areas to the atmosphere that the soap solution cannot bridge, or that do
not exhibit evidence of liquid leakage. Sources that have these
conditions present must be surveyed using the instrument technique of
Section 8.3.1 or 8.3.2.
8.3.3.2 Spray a soap solution over all potential leak sources. The
soap solution may be a commercially available leak detection solution or
may be prepared using concentrated detergent and water. A pressure
sprayer or squeeze bottle may be used to dispense the solution. Observe
the potential leak sites to determine if any bubbles are formed. If no
bubbles are observed, the source is presumed to have no detectable
emissions or leaks as applicable. If any bubbles are observed, the
instrument techniques of Section 8.3.1 or 8.3.2 shall be used to
determine if a leak exists, or if the source has detectable emissions,
as applicable.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.1.2......................... Instrument Ensure precision and
calibration accuracy,
precision check. respectively, of
instrument response
to standard.
10.0.......................... Instrument
calibration.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 Calibrate the VOC monitoring instrument as follows. After the
appropriate warmup period and zero internal calibration procedure,
introduce the calibration gas into the instrument sample probe. Adjust
the instrument meter readout to correspond to the calibration gas value.
Note: If the meter readout cannot be adjusted to the proper value, a
malfunction of the analyzer is indicated and corrective actions are
necessary before use.

11.0 Analytical Procedures. [Reserved]

12.0 Data Analyses and Calculations. [Reserved]

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Dubose, D.A., and G.E. Harris. Response Factors of VOC Analyzers
at a Meter Reading of 10,000 ppmv for Selected Organic Compounds. U.S.
Environmental Protection Agency, Research Triangle Park, NC. Publication
No. EPA 600/2-81051. September 1981.
2. Brown, G.E., et al. Response Factors of VOC Analyzers Calibrated
with Methane for Selected Organic Compounds. U.S. Environmental
Protection Agency, Research Triangle Park, NC. Publication No. EPA 600/
2-81-022. May 1981.
3. DuBose, D.A. et al. Response of Portable VOC Analyzers to
Chemical Mixtures. U.S. Environmental Protection Agency, Research
Triangle Park, NC. Publication No. EPA 600/2-81-110. September 1981.
4. Handbook of Hazardous Materials: Fire, Safety, Health. Alliance
of American Insurers. Schaumberg, IL. 1983.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 22--Visual Determination of Fugitive Emissions From Material
Sources and Smoke Emissions From Flares

Note: This method is not inclusive with respect to observer
certification. Some material is incorporated by reference from Method 9.

1.0 Scope and Application

This method is applicable for the determination of the frequency of
fugitive emissions from stationary sources, only as specified in an
applicable subpart of the regulations. This method also is applicable
for the determination of the frequency of visible smoke emissions from
flares.

[[Page 480]]

2.0 Summary of Method

2.1 Fugitive emissions produced during material processing,
handling, and transfer operations or smoke emissions from flares are
visually determined by an observer without the aid of instruments.
2.2 This method is used also to determine visible smoke emissions
from flares used for combustion of waste process materials.
2.3 This method determines the amount of time that visible
emissions occur during the observation period (i.e., the accumulated
emission time). This method does not require that the opacity of
emissions be determined. Since this procedure requires only the
determination of whether visible emissions occur and does not require
the determination of opacity levels, observer certification according to
the procedures of Method 9 is not required. However, it is necessary
that the observer is knowledgeable with respect to the general
procedures for determining the presence of visible emissions. At a
minimum, the observer must be trained and knowledgeable regarding the
effects of background contrast, ambient lighting, observer position
relative to lighting, wind, and the presence of uncombined water
(condensing water vapor) on the visibility of emissions. This training
is to be obtained from written materials found in References 1 and 2 or
from the lecture portion of the Method 9 certification course.

3.0 Definitions

3.1 Emission frequency means the percentage of time that emissions
are visible during the observation period.
3.2 Emission time means the accumulated amount of time that
emissions are visible during the observation period.
3.3 Fugitive emissions means emissions generated by an affected
facility which is not collected by a capture system and is released to
the atmosphere. This includes emissions that (1) escape capture by
process equipment exhaust hoods; (2) are emitted during material
transfer; (3) are emitted from buildings housing material processing or
handling equipment; or (4) are emitted directly from process equipment.
3.4 Observation period means the accumulated time period during
which observations are conducted, not to be less than the period
specified in the applicable regulation.
3.5 Smoke emissions means a pollutant generated by combustion in a
flare and occurring immediately downstream of the flame. Smoke occurring
within the flame, but not downstream of the flame, is not considered a
smoke emission.

4.0 Interferences

4.1 Occasionally, fugitive emissions from sources other than the
affected facility (e.g., road dust) may prevent a clear view of the
affected facility. This may particularly be a problem during periods of
high wind. If the view of the potential emission points is obscured to
such a degree that the observer questions the validity of continuing
observations, then the observations shall be terminated, and the
observer shall clearly note this fact on the data form.

5.0 Safety

6.0 Equipment

6.1 Stopwatches (two). Accumulative type with unit divisions of at
least 0.5 seconds.
6.2 Light Meter. Light meter capable of measuring illuminance in
the 50 to 200 lux range, required for indoor observations only.

7.0 Reagents and Supplies. [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transfer. [Reserved]

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardization. [Reserved]

11.0 Analytical Procedure

11.1 Selection of Observation Location. Survey the affected
facility, or the building or structure housing the process to be
observed, and determine the locations of potential emissions. If the
affected facility is located inside a building, determine an observation
location that is consistent with the requirements of the applicable
regulation (i.e., outside observation of emissions escaping the
building/structure or inside observation of emissions directly emitted
from the affected facility process unit). Then select a position that
enables a clear view of the potential emission point(s) of the affected
facility or of the building or structure housing the affected facility,
as appropriate for the applicable subpart. A position at least 4.6 m (15
feet), but not more than 400 m (0.25 miles), from the emission source is
recommended. For outdoor locations, select a position where the sunlight
is not shining directly in the observer's eyes.
11.2 Field Records.
11.2.1 Outdoor Location. Record the following information on the
field data sheet (Figure 22-1): Company name, industry, process unit,
observer's name, observer's affiliation, and date. Record also the
estimated

[[Page 481]]

wind speed, wind direction, and sky condition. Sketch the process unit
being observed, and note the observer location relative to the source
and the sun. Indicate the potential and actual emission points on the
sketch.
11.2.2 Indoor Location. Record the following information on the
field data sheet (Figure 22-2): Company name, industry, process unit,
observer's name, observer's affiliation, and date. Record as appropriate
the type, location, and intensity of lighting on the data sheet. Sketch
the process unit being observed, and note the observer location relative
to the source. Indicate the potential and actual fugitive emission
points on the sketch.
11.3 Indoor Lighting Requirements. For indoor locations, use a
light meter to measure the level of illumination at a location as close
to the emission source(s) as is feasible. An illumination of greater
than 100 lux (10 foot candles) is considered necessary for proper
application of this method.
11.4 Observations.
11.4.1 Procedure. Record the clock time when observations begin.
Use one stopwatch to monitor the duration of the observation period.
Start this stopwatch when the observation period begins. If the
observation period is divided into two or more segments by process
shutdowns or observer rest breaks (see Section 11.4.3), stop the
stopwatch when a break begins and restart the stopwatch without
resetting it when the break ends. Stop the stopwatch at the end of the
observation period. The accumulated time indicated by this stopwatch is
the duration of observation period. When the observation period is
completed, record the clock time. During the observation period,
continuously watch the emission source. Upon observing an emission
(condensed water vapor is not considered an emission), start the second
accumulative stopwatch; stop the watch when the emission stops. Continue
this procedure for the entire observation period. The accumulated
elapsed time on this stopwatch is the total time emissions were visible
during the observation period (i.e., the emission time.)
11.4.2 Observation Period. Choose an observation period of
sufficient length to meet the requirements for determining compliance
with the emission standard in the applicable subpart of the regulations.
When the length of the observation period is specifically stated in the
applicable subpart, it may not be necessary to observe the source for
this entire period if the emission time required to indicate
noncompliance (based on the specified observation period) is observed in
a shorter time period. In other words, if the regulation prohibits
emissions for more than 6 minutes in any hour, then observations may
(optional) be stopped after an emission time of 6 minutes is exceeded.
Similarly, when the regulation is expressed as an emission frequency and
the regulation prohibits emissions for greater than 10 percent of the
time in any hour, then observations may (optional) be terminated after 6
minutes of emission are observed since 6 minutes is 10 percent of an
hour. In any case, the observation period shall not be less than 6
minutes in duration. In some cases, the process operation may be
intermittent or cyclic. In such cases, it may be convenient for the
observation period to coincide with the length of the process cycle.
11.4.3 Observer Rest Breaks. Do not observe emissions continuously
for a period of more than 15 to 20 minutes without taking a rest break.
For sources requiring observation periods of greater than 20 minutes,
the observer shall take a break of not less than 5 minutes and not more
than 10 minutes after every 15 to 20 minutes of observation. If
continuous observations are desired for extended time periods, two
observers can alternate between making observations and taking breaks.
11.5 Recording Observations. Record the accumulated time of the
observation period on the data sheet as the observation period duration.
Record the accumulated time emissions were observed on the data sheet as
the emission time. Record the clock time the observation period began
and ended, as well as the clock time any observer breaks began and
ended.

12.0 Data Analysis and Calculations

If the applicable subpart requires that the emission rate be
expressed as an emission frequency (in percent), determine this value as
follows: Divide the accumulated emission time (in seconds) by the
duration of the observation period (in seconds) or by any minimum
observation period required in the applicable subpart, if the actual
observation period is less than the required period, and multiply this
quotient by 100.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Missan, R., and A. Stein. Guidelines for Evaluation of Visible
Emissions Certification, Field Procedures, Legal Aspects, and Background
Material. EPA Publication No. EPA-340/1-75-007. April 1975.
2. Wohlschlegel, P., and D.E. Wagoner. Guideline for Development of
a Quality Assurance Program: Volume IX-- Visual Determination of Opacity
Emissions from Stationary Sources. EPA Publication No. EPA-650/4-74-
005i. November 1975.

[[Page 482]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.354

[[Page 483]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.355

Method 23--Determination of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans From Stationary Sources

1. Applicability and Principle

1.1 Applicability. This method is applicable to the determination
of polychlorinated dibenzo-p-dioxins (PCDD's) and polychlorinated
dibenzofurans (PCDF's) from stationary sources.
1.2 Principle. A sample is withdrawn from the gas stream
isokinetically and collected in the sample probe, on a glass fiber
filter, and on a packed column of adsorbent material. The sample cannot
be separated into a particle vapor fraction. The PCDD's and

[[Page 484]]

PCDF's are extracted from the sample, separated by high resolution gas
chromatography, and measured by high resolution mass spectrometry.

2. Apparatus

2.1 Sampling. A schematic of the sampling train used in this method
is shown in Figure 23-1. Sealing greases may not be used in assembling
the train. The train is identical to that described in section 2.1 of
Method 5 of this appendix with the following additions:
[GRAPHIC] [TIFF OMITTED] TC01JN92.249

[[Page 485]]

2.1.1 Nozzle. The nozzle shall be made of nickel, nickel-plated
stainless steel, quartz, or borosilicate glass.
2.1.2 Sample Transfer Lines. The sample transfer lines, if needed,
shall be heat traced, heavy walled TFE (\1/2\ in. OD with \1/8\ in.
wall) with connecting fittings that are capable of forming leak-free,
vacuum-tight connections without using sealing greases. The line shall
be as short as possible and must be maintained at 120 deg.C.
2.1.1 Filter Support. Teflon or Teflon-coated wire.
2.1.2 Condenser. Glass, coil type with compatible fittings. A
schematic diagram is shown in Figure 23-2.
2.1.3 Water Bath. Thermostatically controlled to maintain the gas
temperature exiting the condenser at <20 deg.C (68 deg.F).
2.1.4 Adsorbent Module. Glass container to hold the solid
adsorbent. A shematic diagram is shown in Figure 23-2. Other physical
configurations of the resin trap/condenser assembly are acceptable. The
connecting fittings shall form leak-free, vacuum tight seals. No sealant
greases shall be used in the sampling train. A coarse glass frit is
included to retain the adsorbent.
2.2 Sample Recovery.
2.2.1 Fitting Caps. Ground glass, Teflon tape, or aluminum foil
(Section 2.2.6) to cap off the sample exposed sections of the train.
2.2.2 Wash Bottles. Teflon, 500-ml.
2.2.3 Probe-Liner Probe-Nozzle, and Filter-Holder Brushes. Inert
bristle brushes with precleaned stainless steel or Teflon handles. The
probe brush shall have extensions of stainless steel or Teflon, at least
as long as the probe. The brushes shall be properly sized and shaped to
brush out the nozzle, probe liner, and transfer line, if used.

[[Page 486]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.250

2.2.4 Filter Storage Container. Sealed filter holder, wide-mouth
amber glass jar with Teflon-lined cap, or glass petri dish.
2.2.5 Balance. Triple beam.
2.2.6 Aluminum Foil. Heavy duty, hexane-rinsed.
2.2.7 Metal Storage Container. Air tight container to store silica
gel.

[[Page 487]]

2.2.8 Graduated Cylinder. Glass, 250-ml with 2-ml graduation.
2.2.9 Glass Sample Storage Container. Amber glass bottle for sample
glassware washes, 500- or 1000-ml, with leak free Teflon-lined caps.
2.3 Analysis.
2.3.1 Sample Container. 125- and 250-ml flint glass bottles with
Teflon-lined caps.
2.3.2 Test Tube. Glass.
2.3.3 Soxhlet Extraction Apparatus. Capable of holding 43 x 123 mm
extraction thimbles.
2.3.4 Extraction Thimble. Glass, precleaned cellulosic, or glass
fiber.
2.3.5 Pasteur Pipettes. For preparing liquid chromatographic
columns.
2.3.6 Reacti-vials. Amber glass, 2-ml, silanized prior to use.
2.3.7 Rotary Evaporator. Buchi/Brinkman RF-121 or equivalent.
2.3.8 Nitrogen Evaporative Concentrator. N-Evap Analytical
Evaporator Model III or equivalent.
2.3.9 Separatory Funnels. Glass, 2-liter.
2.3.10 Gas Chromatograph. Consisting of the following components:
2.3.10.1 Oven. Capable of maintaining the separation column at the
proper operating temperature deg.C and performing
programmed increases in temperature at rates of at least 40 deg.C/min.
2.3.10.2 Temperature Gauge. To monitor column oven, detector, and
exhaust temperatures 1 deg.C.
2.3.10.3 Flow System. Gas metering system to measure sample, fuel,
combustion gas, and carrier gas flows.
2.3.10.4 Capillary Columns. A fused silica column, 60 x 0.25 mm
inside diameter (ID), coated with DB-5 and a fused silica column, 30 m
x 0.25 mm ID coated with DB-225. Other column systems may be used
provided that the user is able to demonstrate using calibration and
performance checks that the column system is able to meet the
specifications of section 6.1.2.2.
2.3.11 Mass Spectrometer. Capable of routine operation at a
resolution of 1:10000 with a stability of 5 ppm.
2.3.12 Data System. Compatible with the mass spectrometer and
capable of monitoring at least five groups of 25 ions.
2.3.13 Analytical Balance. To measure within 0.1 mg.

3. Reagents

3.1 Sampling.
3.1.1 Filters. Glass fiber filters, without organic binder,
exhibiting at least 99.95 percent efficiency (<0.05 percent penetration)
on 0.3-micron dioctyl phthalate smoke particles. The filter efficiency
test shall be conducted in accordance with ASTM Standard Method D 2986-
71 (Reapproved 1978) (incorporated by reference--see Sec. 60.17).
3.1.1.1 Precleaning. All filters shall be cleaned before their
initial use. Place a glass extraction thimble and 1 g of silica gel and
a plug of glass wool into a Soxhlet apparatus, charge the apparatus with
toluene, and reflux for a minimum of 3 hours. Remove the toluene and
discard it, but retain the silica gel. Place no more than 50 filters in
the thimble onto the silica gel bed and top with the cleaned glass wool.
Charge the Soxhlet with toluene and reflux for 16 hours. After
extraction, allow the Soxhlet to cool, remove the filters, and dry them
under a clean N2 stream. Store the filters in a glass petri
dish sealed with Teflon tape.
3.1.2 Adsorbent Resin. Amberlite XAD-2 resin. Thoroughly cleaned
before initial use.
3.1.2.1 Cleaning Procedure. This procedure may be carried out in a
giant Soxhlet extractor. An all-glass filter thimble containing an
extra-course frit is used for extraction of XAD-2. The frit is recessed
10-15 mm above a crenelated ring at the bottom of the thimble to
facilitate drainage. The resin must be carefully retained in the
extractor cup with a glass wool plug and a stainless steel ring because
it floats on methylene chloride. This process involves sequential
extraction in the following order.

------------------------------------------------------------------------
Solvent Procedure
------------------------------------------------------------------------
Water..................................... Initial rinse: Place resin
in a beaker, rinse once
with water, and discard.
Fill with water a second
time, let stand overnight,
and discard.
Water..................................... Extract with water for 8
hours.
Methanol.................................. Extract for 22 hours.
Methylene Chloride........................ Extract for 22 hours.
Toluene................................... Extract for 22 hours.
------------------------------------------------------------------------

3.1.2.2 Drying.
3.1.2.2.1 Drying Column. Pyrex pipe, 10.2 cm ID by 0.6 m long, with
suitable retainers.
3.1.2.2.2 Procedure. The adsorbent must be dried with clean inert
gas. Liquid nitrogen from a standard commercial liquid nitrogen cylinder
has proven to be a reliable source of large volumes of gas free from
organic contaminants. Connect the liquid nitrogen cylinder to the column
by a length of cleaned copper tubing, 0.95 cm ID, coiled to pass through
a heat source. A convenient heat source is a water-bath heated from a
steam line. The final nitrogen temperature should only be warm to the
touch and not over 40 deg.C. Continue flowing nitrogen through the
adsorbent until all the residual solvent is removed. The flow rate
should be sufficient to gently agitate the particles but not so
excessive as the cause the particles to fracture.
3.1.2.3 Quality Control Check. The adsorbent must be checked for
residual toluene.
3.1.2.3.1 Extraction. Weigh 1.0 g sample of dried resin into a
small vial, add 3 ml of toluene, cap the vial, and shake it well.

[[Page 488]]

3.1.2.3.2 Analysis. Inject a 2 l sample of the extract
into a gas chromatograph operated under the following conditions:

Column: 6 ft x \1/8\ in stainless steel containing 10 percent OV-
101 on 100/120 Supelcoport.
Carrier Gas: Helium at a rate of 30 ml/min.
Detector: Flame ionization detector operated at a sensitivity of 4
x 10-¹¹ A/mV.
Injection Port Temperature: 250 deg.C.
Detector Temperature: 305 deg.C.
Oven Temperature: 30 deg.C for 4 min; programmed to rise at 40
deg.C/min until it reaches 250 deg.C; return to 30 deg.C after 17
minutes.
Compare the results of the analysis to the results from the
reference solution. Prepare the reference solution by injection 2.5
l of methylene chloride into 100 ml of toluene. This
corresponds to 100 g of methylene chloride per g of adsorbent.
The maximum acceptable concentration is 1000 g/g of adsorbent.
If the adsorbent exceeds this level, drying must be continued until the
excess methylene chloride is removed.
3.1.2.4 Storage. The adsorbent must be used within 4 weeks of
cleaning. After cleaning, it may be stored in a wide mouth amber glass
container with a Teflon-lined cap or placed in one of the glass
adsorbent modules tightly sealed with glass stoppers. If precleaned
adsorbent is purchased in sealed containers, it must be used within 4
weeks after the seal is broken.
3.1.3 Glass Wool. Cleaned by sequential immersion in three aliquots
of methylene chloride, dried in a 110 deg.C oven, and stored in a
methylene chloride-washed glass jar with a Teflon-lined screw cap.
3.1.4 Water. Deionized distilled and stored in a methylene
chloride-rinsed glass container with a Teflon-lined screw cap.
3.1.5 Silica Gel. Indicating type, 6 to 16 mesh. If previously
used, dry at 175 deg.C (350 deg.F) for two hours. New silica gel may
be used as received. Alternately other types of desiccants (equivalent
or better) may be used, subject to the approval of the Administrator.
3.1.6 Chromic Acid Cleaning Solution. Dissolve 20 g of sodium
dichromate in 15 ml of water, and then carefully add 400 ml of
concentrated sulfuric acid.
3.2 Sample Recovery.
3.2.2 Acetone. Pesticide quality.
3.2.2 Methylene Chloride. Pesticide qualtity.
3.2.3 Toluene. Pesticide quality.
3.3 Analysis.
3.3.1 Potassium Hydroxide. ACS grade, 2-percent (weight/volume) in
water.
3.3.2 Sodium Sulfate. Granulated, reagent grade. Purify prior to
use by rinsing with methylene chloride and oven drying. Store the
cleaned material in a glass container with a Teflon-lined screw cap.
3.3.3 Sulfuric Acid. Reagent grade.
3.3.4 Sodium Hydroxide. 1.0 N. Weigh 40 g of sodium hydroxide into
a 1-liter volumetric flask. Dilute to 1 liter with water.
3.3.5 Hexane. Pesticide grade.
3.3.6 Methylene Chloride. Pesticide grade.
3.3.7 Benzene. Pesticide Grade.
3.3.8 Ethyl Acetate.
3.3.9 Methanol. Pesticide Grade.
3.3.10 Toluene. Pesticide Grade.
3.3.11 Nonane. Pesticide Grade.
3.3.12 Cyclohexane. Pesticide Grade.
3.3.13 Basic Alumina. Activity grade 1, 100-200 mesh. Prior to use,
activate the alumina by heating for 16 hours at 130 deg.C before use.
Store in a desiccator. Pre-activated alumina may be purchased from a
supplier and may be used as received.
3.3.14 Silica Gel. Bio-Sil A, 100-200 mesh. Prior to use, activate
the silica gel by heating for at least 30 minutes at 180 deg.C. After
cooling, rinse the silica gel sequentially with methanol and methylene
chloride. Heat the rinsed silica gel at 50 deg.C for 10 minutes, then
increase the temperature gradually to 180 deg.C over 25 minutes and
maintain it at this temperature for 90 minutes. Cool at room temperature
and store in a glass container with a Teflon-lined screw cap.
3.3.15 Silica Gel Impregnated with Sulfuric Acid. Combine 100 g of
silica gel with 44 g of concentrated sulfuric acid in a screw capped
glass bottle and agitate thoroughly. Disperse the solids with a stirring
rod until a uniform mixture is obtained. Store the mixture in a glass
container with a Teflon-lined screw cap.
3.3.16 Silica Gel Impregnated with Sodium Hydroxide. Combine 39 g
of 1 N sodium hydroxide with 100 g of silica gel in a screw capped glass
bottle and agitate thoroughly. Disperse solids with a stirring rod until
a uniform mixture is obtained. Store the mixture in glass container with
a Teflon-lined screw cap.
3.3.17 Carbon/Celite. Combine 10.7 g of AX-21 carbon with 124 g of
Celite 545 in a 250-ml glass bottle with a Teflon-lined screw cap.
Agitate the mixture thoroughly until a uniform mixture is obtained.
Store in the glass container.
3.3.18 Nitrogen. Ultra high purity.
3.3.19 Hydrogen. Ultra high purity.
3.3.20 Internal Standard Solution. Prepare a stock standard
solution containing the isotopically labelled PCDD's and PCDF's at the
concentrations shown in Table 1 under the heading ``Internal Standards''
in 10 ml of nonane.
3.3.21 Surrogate Standard Solution. Prepare a stock standard
solution containing the isotopically labelled PCDD's and PCDF's at the
concentrations shown in Table 1 under the heading ``Surrogate
Standards'' in 10 ml of nonane.
3.3.22 Recovery Standard Solution. Prepare a stock standard
solution containing the isotopically labelled PCDD's and PCDF's

[[Page 489]]

at the concentrations shown in Table 1 under the heading ``Recovery
Standards'' in 10 ml of nonane.

4. Procedure

4.1 Sampling. The complexity of this method is such that, in order
to obtain reliable results, testers should be trained and experienced
with the test procedures.
4.1.1 Pretest Preparation.
4.1.1.1 Cleaning Glassware. All glass components of the train
upstream of and including the adsorbent module, shall be cleaned as
described in section 3A of the ``Manual of Analytical Methods for the
Analysis of Pesticides in Human and Environmental Samples.'' Special
care shall be devoted to the removal of residual silicone grease
sealants on ground glass connections of used glassware. Any residue
shall be removed by soaking the glassware for several hours in a chromic
acid cleaning solution prior to cleaning as described above.
4.1.1.2 Adsorbent Trap. The traps must be loaded in a clean area to
avoid contamination. They may not be loaded in the field. Fill a trap
with 20 to 40 g of XAD-2. Follow the XAD-2 with glass wool and tightly
cap both ends of the trap. Add 100 l of the surrogate standard
solution (section 3.3.21) to each trap.
4.1.1.3 Sample Train. It is suggested that all components be
maintained according to the procedure described in APTD-0576.
4.1.1.4 Silica Gel. Weigh several 200 to 300 g portions of silica
gel in an air tight container to the nearest 0.5 g. Record the total
weight of the silica gel plus container, on each container. As an
alternative, the silica gel may be weighed directly in its impinger or
sampling holder just prior to sampling.
4.1.1.5 Filter. Check each filter against light for irregularities
and flaws or pinhole leaks. Pack the filters flat in a clean glass
container.
4.1.2 Preliminary Determinations. Same as section 4.1.2 of Method
5.
4.1.3 Preparation of Collection Train.
4.1.3.1 During preparation and assembly of the sampling train, keep
all train openings where contamination can enter, sealed until just
prior to assembly or until sampling is about to begin.
Note: Do not use sealant grease in assembling the train.
4.1.3.2 Place approximately 100 ml of water in the second and third
impingers, leave the first and fourth impingers empty, and transfer
approximately 200 to 300 g of preweighed silica gel from its container
to the fifth impinger.
4.1.3.3 Place the silica gel container in a clean place for later
use in the sample recovery. Alternatively, the weight of the silica gel
plus impinger may be determined to the nearest 0.5 g and recorded.
4.1.3.4 Assemble the train as shown in Figure 23-1.
4.1.3.5 Turn on the adsorbent module and condenser coil
recirculating pump and begin monitoring the adsorbent module gas entry
temperature. Ensure proper sorbent temperature gas entry temperature
before proceeding and before sampling is initiated. It is extremely
important that the XAD-2 adsorbent resin temperature never exceed 50
deg.C because thermal decomposition will occur. During testing, the XAD-
2 temperature must not exceed 20 deg.C for efficient capture of the
PCDD's and PCDF's.
4.1.4 Leak-Check Procedure. Same as Method 5, section 4.1.4.
4.1.5 Sample Train Operation. Same as Method 5, section 4.1.5.
4.2 Sample Recovery. Proper cleanup procedure begins as soon as the
probe is removed from the stack at the end of the sampling period. Seal
the nozzle end of the sampling probe with Teflon tape or aluminum foil.
When the probe can be safely handled, wipe off all external
particulate matter near the tip of the probe. Remove the probe from the
train and close off both ends with aluminum foil. Seal off the inlet to
the train with Teflon tape, a ground glass cap, or aluminum foil.
Transfer the probe and impinger assembly to the cleanup area. This
area shall be clean and enclosed so that the chances of losing or
contaminating the sample are minimized. Smoking, which could contaminate
the sample, shall not be allowed in the cleanup area.
Inspect the train prior to and during disassembly and note any
abnormal conditions, e.g., broken filters, colored impinger liquid, etc.
Treat the samples as follows:
4.2.1 Container No. 1. Either seal the filter holder or carefully
remove the filter from the filter holder and place it in its identified
container. Use a pair of cleaned tweezers to handle the filter. If it is
necessary to fold the filter, do so such that the particulate cake is
inside the fold. Carefully transfer to the container any particulate
matter and filter fibers which adhere to the filter holder gasket, by
using a dry inert bristle brush and a sharp-edged blade. Seal the
container.
4.2.2 Adsorbent Module. Remove the module from the train, tightly
cap both ends, label it, cover with aluminum foil, and store it on ice
for transport to the laboratory.
4.2.3 Container No. 2. Quantitatively recover material deposited in
the nozzle, probe transfer lines, the front half of the filter holder,
and the cyclone, if used, first, by brushing while rinsing three times
each with acetone and then, by rinsing the probe three times with
methylene chloride. Collect all the rinses in Container No. 2.

[[Page 490]]

Rinse the back half of the filter holder three times with acetone.
Rinse the connecting line between the filter and the condenser three
times with acetone. Soak the connecting line with three separate
portions of methylene chloride for 5 minutes each. If using a separate
condenser and adsorbent trap, rinse the condenser in the same manner as
the connecting line. Collect all the rinses in Container No. 2 and mark
the level of the liquid on the container.
4.2.4 Container No. 3. Repeat the methylene chloride-rinsing
described in Section 4.2.3 using toluene as the rinse solvent. Collect
the rinses in Container No. 3 and mark the level of the liquid on the
container.
4.2.5 Impinger Water. Measure the liquid in the first three
impingers to within 1 ml by using a graduated cylinder or by
weighing it to within 0.5 g by using a balance. Record the
volume or weight of liquid present. This information is required to
calculate the moisture content of the effluent gas.
Discard the liquid after measuring and recording the volume or
weight.
4.2.7 Silica Gel. Note the color of the indicating silica gel to
determine if it has been completely spent and make a mention of its
condition. Transfer the silica gel from the fifth impinger to its
original container and seal.

5. Analysis

All glassware shall be cleaned as described in section 3A of the
``Manual of Analytical Methods for the Analysis of Pesticides in Human
and Environmental Samples.'' All samples must be extracted within 30
days of collection and analyzed within 45 days of extraction.
5.1 Sample Extraction.
5.1.1 Extraction System. Place an extraction thimble (section
2.3.4), 1 g of silica gel, and a plug of glass wool into the Soxhlet
apparatus, charge the apparatus with toluene, and reflux for a minimum
of 3 hours. Remove the toluene and discard it, but retain the silica
gel. Remove the extraction thimble from the extraction system and place
it in a glass beaker to catch the solvent rinses.
5.1.2 Container No. 1 (Filter). Transfer the contents directly to
the glass thimble of the extraction system and extract them
simultaneously with the XAD-2 resin.
5.1.3 Adsorbent Cartridge. Suspend the adsorbent module directly
over the extraction thimble in the beaker (See section 5.1.1). The glass
frit of the module should be in the up position. Using a Teflon squeeze
bottle containing toluene, flush the XAD-2 into the thimble onto the bed
of cleaned silica gel. Thoroughly rinse the glass module catching the
rinsings in the beaker containing the thimble. If the resin is wet,
effective extraction can be accomplished by loosely packing the resin in
the thimble. Add the XAD-2 glass wool plug into the thimble.
5.1.4 Container No. 2 (Acetone and Methylene Chloride). Concentrate
the sample to a volume of about 1-5 ml using the rotary evaporator
apparatus, at a temperature of less than 37 deg.C. Rinse the sample
container three times with small portions of methylene chloride and add
these to the concentrated solution and concentrate further to near
dryness. This residue contains particulate matter removed in the rinse
of the train probe and nozzle. Add the concentrate to the filter and the
XAD-2 resin in the Soxhlet apparatus described in section 5.1.1.
5.1.5 Extraction. Add 100 l of the internal standard
solution (Section 3.3.20) to the extraction thimble containing the
contents of the adsorbent cartridge, the contents of Container No. 1,
and the concentrate from section 5.1.4. Cover the contents of the
extraction thimble with the cleaned glass wool plug to prevent the XAD-2
resin from floating into the solvent reservoir of the extractor. Place
the thimble in the extractor, and add the toluene contained in the
beaker to the solvent reservoir. Pour additional toluene to fill the
reservoir approximately 2/3 full. Add Teflon boiling chips and assemble
the apparatus. Adjust the heat source to cause the extractor to cycle
three times per hour. Extract the sample for 16 hours. After extraction,
allow the Soxhlet to cool. Transfer the toluene extract and three 10-ml
rinses to the rotary evaporator. Concentrate the extract to
approximately 10 ml. At this point the analyst may choose to split the
sample in half. If so, split the sample, store one half for future use,
and analyze the other according to the procedures in sections 5.2 and
5.3. In either case, use a nitrogen evaporative concentrator to reduce
the volume of the sample being analyzed to near dryness. Dissolve the
residue in 5 ml of hexane.
5.1.6 Container No. 3 (Toluene Rinse). Add 100 l of the
Internal Standard solution (section 3.3.2) to the contents of the
container. Concentrate the sample to a volume of about 1-5 ml using the
rotary evaporator apparatus at a temperature of less than 37 deg.C.
Rinse the sample container apparatus at a temperature of less than 37
deg.C. Rinse the sample container three times with small portions of
toluene and add these to the concentrated solution and concentrate
further to near dryness. Analyze the extract separately according to the
procedures in sections 5.2 and 5.3, but concentrate the solution in a
rotary evaporator apparatus rather than a nitrogen evaporative
concentrator.
5.2 Sample Cleanup and Fractionation.
5.2.1 Silica Gel Column. Pack one end of a glass column, 20 mm x
230 mm, with glass wool. Add in sequence, 1 g silica gel, 2 g of sodium
hydroxide impregnated silica gel, 1 g silica gel, 4 g of acid-modified
silica gel, and 1 g of silica gel. Wash the column with 30 ml

[[Page 491]]

of hexane and discard it. Add the sample extract, dissolved in 5 ml of
hexane to the column with two additional 5-ml rinses. Elute the column
with an additional 90 ml of hexane and retain the entire eluate.
Concentrate this solution to a volume of about 1 ml using the nitrogen
evaporative concentrator (section 2.3.7).
5.2.2 Basic Alumina Column. Shorten a 25-ml disposable Pasteur
pipette to about 16 ml. Pack the lower section with glass wool and 12 g
of basic alumina. Transfer the concentrated extract from the silica gel
column to the top of the basic alumina column and elute the column
sequentially with 120 ml of 0.5 percent methylene chloride in hexane
followed by 120 ml of 35 percent methylene chloride in hexane. Discard
the first 120 ml of eluate. Collect the second 120 ml of eluate and
concentrate it to about 0.5 ml using the nitrogen evaporative
concentrator.
5.2.3 AX-21 Carbon/Celite 545 Column. Remove the botton 0.5 in.
from the tip of a 9-ml disposable Pasteur pipette. Insert a glass fiber
filter disk in the top of the pipette 2.5 cm from the constriction. Add
sufficient carbon/celite mixture to form a 2 cm column. Top with a glass
wool plug. In some cases AX-21 carbon fines may wash through the glass
wool plug and enter the sample. This may be prevented by adding a celite
plug to the exit end of the column. Rinse the column in sequence with 2
ml of 50 percent benzene in ethyl acetate, 1 ml of 50 percent methylene
chloride in cyclohexane, and 2 ml of hexane. Discard these rinses.
Transfer the concentrate in 1 ml of hexane from the basic alumina column
to the carbon/celite column along with 1 ml of hexane rinse. Elute the
column sequentially with 2 ml of 50 percent methylene chloride in hexane
and 2 ml of 50 percent benzene in ethyl acetate and discard these
eluates. Invert the column and elute in the reverse direction with 13 ml
of toluene. Collect this eluate. Concentrate the eluate in a rotary
evaporator at 50 deg.C to about 1 ml. Transfer the concentrate to a
Reacti-vial using a toluene rinse and concentrate to a volume of 200
l using a stream of N2. Store extracts at room
temperature, shielded from light, until the analysis is performed.
5.3 Analysis. Analyze the sample with a gas chromatograph coupled
to a mass spectrometer (GC/MS) using the instrumental parameters in
sections 5.3.1 and 5.3.2. Immediately prior to analysis, add a 20
l aliquot of the Recovery Standard solution from Table 1 to
each sample. A 2 l aliquot of the extract is injected into the
GC. Sample extracts are first analyzed using the DB-5 capillary column
to determine the concentration of each isomer of PCDD's and PCDF's
(tetra-through octa-). If tetra-chlorinated dibenzofurans are detected
in this analysis, then analyze another aliquot of the sample in a
separate run, using the DB-225 column to measure the 2,3,7,8 tetra-
chloro dibenzofuran isomer. Other column systems may be used, provided
that the user is able to demonstrate using calibration and performance
checks that the column system is able to meet the specifications of
section 6.1.2.2.
5.3.1 Gas Chromatograph Operating Conditions.
5.3.1.1 Injector. Configured for capillary column, splitless, 250
deg.C.
5.3.1.2 Carrier Gas. Helium, 1-2 ml/min.
5.3.1.3 Oven. Initially at 150 deg.C. Raise by at least 40 deg.C/
min to 190 deg.C and then at 3 deg.C/min up to 300 deg.C.
5.3.2 High Resolution Mass Spectrometer.
5.3.2.1 Resolution. 10000 m/e.
5.3.2.2 Ionization Mode. Electron impact.
5.3.2.3 Source Temperature 250 deg.C.
5.3.2.4 Monitoring Mode. Selected ion monitoring. A list of the
various ions to be monitored is summarized in Table 3.
5.3.2.5 Identification Criteria. The following identification
criteria shall be used for the characterization of polychlorinated
dibenzodioxins and dibenzofurans.
1. The integrated ion-abundance ratio (M/M+2 or M+2/M+4) shall be
within 15 percent of the theoretical value. The acceptable ion-abundance
ratio ranges for the identification of chlorine-containing compounds are
given in Table 4.
2. The retention time for the analytes must be within 3 seconds of
the corresponding \1\\3\ C-labeled internal standard, surrogate or
alternate standard.
3. The monitored ions, shown in Table 3 for a given analyte, shall
reach their maximum within 2 seconds of each other.
4. The identification of specific isomers that do not have
corresponding \1\\3\ C-labeled standards is done by comparison of the
relative retention time (RRT) of the analyte to the nearest internal
standard retention time with reference (i.e., within 0.005 RRT units) to
the comparable RRT's found in the continuing calibration.
5. The signal to noise ratio for all monitored ions must be greater
than 2.5.
6. The confirmation of 2, 3, 7, 8-TCDD and 2, 3, 7, 8-TCDF shall
satisfy all of the above identification criteria.
7. For the identification of PCDF's, no signal may be found in the
corresponding PCDPE channels.
5.3.2.6 Quantification. The peak areas for the two ions monitored
for each analyte are summed to yield the total response for each
analyte. Each internal standard is used to quantify the indigenous
PCDD's or PCDF's in its homologous series. For example, the \1\\3\ C
12-2,3,7,8-tetra chlorinated dibenzodioxin is used to
calculate the concentrations of all other tetra chlorinated isomers.
Recoveries of the tetra- and penta- internal standards are calculated
using the \1\\3\ C 12-1,2,3,4-TCDD. Recoveries of the hexa-
through octa- internal standards are calculated using \1\\3\ C
12-

[[Page 492]]

1,2,3,7,8,9-HxCDD. Recoveries of the surrogate standards are calculated
using the corresponding homolog from the internal standard.

6. Calibration

Same as Method 5 with the following additions.
6.1 GC/MS System.
6.1.1 Initial Calibration. Calibrate the GC/MS system using the set
of five standards shown in Table 2. The relative standard deviation for
the mean response factor from each of the unlabeled analytes (Table 2)
and of the internal, surrogate, and alternate standards shall be less
than or equal to the values in Table 5. The signal to noise ratio for
the GC signal present in every selected ion current profile shall be
greater than or equal to 2.5. The ion abundance ratios shall be within
the control limits in Table 4.
6.1.2 Daily Performance Check.
6.1.2.1 Calibration Check. Inject on l of solution Number
3 from Table 2. Calculate the relative response factor (RRF) for each
compound and compare each RRF to the corresponding mean RRF obtained
during the initial calibration. The analyzer performance is acceptable
if the measured RRF's for the labeled and unlabeled compounds for the
daily run are within the limits of the mean values shown in Table 5. In
addition, the ion-abundance ratios shall be within the allowable control
limits shown in Table 4.
6.1.2.2 Column Separation Check. Inject a solution of a mixture of
PCDD's and PCDF's that documents resolution between 2,3,7,8-TCDD and
other TCDD isomers. Resolution is defined as a valley between peaks that
is less than 25 percent of the lower of the two peaks. Identify and
record the retention time windows for each homologous series.
Perform a similar resolution check on the confirmation column to
document the resolution between 2,3,7,8 TCDF and other TCDF isomers.
6.2 Lock Channels. Set mass spectrometer lock channels as specified
in Table 3. Monitor the quality control check channels specified in
Table 3 to verify instrument stability during the analysis.

7. Quality Control

7.1 Sampling Train Collection Efficiency Check. Add 100 l
of the surrogate standards in Table 1 to the absorbent cartridge of each
train before collecting the field samples.
7.2 Internal Standard Percent Recoveries. A group of nine carbon
labeled PCDD's and PCDF's representing, the tetra-through
octachlorinated homologues, is added to every sample prior to
extraction. The role of the internal standards is to quantify the native
PCDD's and PCDF's present in the sample as well as to determine the
overall method efficiency. Recoveries of the internal standards must be
between 40 to 130 percent for the tetra-through hexachlorinated
compounds while the range is 25 to 130 percent for the higher hepta- and
octachlorinated homologues.
7.3 Surrogate Recoveries. The five surrogate compounds in Table 2
are added to the resin in the adsorbent sampling cartridge before the
sample is collected. The surrogate recoveries are measured relative to
the internal standards and are a measure of collection efficiency. They
are not used to measure native PCDD's and PCDF's. All recoveries shall
be between 70 and 130 percent. Poor recoveries for all the surrogates
may be an indication of breakthrough in the sampling train. If the
recovery of all standards is below 70 percent, the sampling runs must be
repeated. As an alternative, the sampling runs do not have to be
repeated if the final results are divided by the fraction of surrogate
recovery. Poor recoveries of isolated surrogate compounds should not be
grounds for rejecting an entire set of the samples.
7.4 Toluene QA Rinse. Report the results of the toluene QA rinse
separately from the total sample catch. Do not add it to the total
sample.

8. Quality Assurance

8.1 Applicability. When the method is used to analyze samples to
demonstrate compliance with a source emission regulation, an audit
sample must be analyzed, subject to availability.
8.2 Audit Procedure. Analyze an audit sample with each set of
compliance samples. The audit sample contains tetra through octa isomers
of PCDD and PCDF. Concurrently, analyze the audit sample and a set of
compliance samples in the same manner to evaluate the technique of the
analyst and the standards preparation. The same analyst, analytical
reagents, and analytical system shall be used both for the compliance
samples and the EPA audit sample.
8.3 Audit Sample Availability. Audit samples will be supplied only
to enforcement agencies for compliance tests. The availability of audit
samples may be obtained by writing: Source Test Audit Coordinator (MD-
77B), Quality Assurance Division, Atmospheric Research and Exposure
Assessment Laboratory, U.S. Environmental Protection Agency, Research
Triangle Park, NC 27711, or by calling the Source Test Audit Coordinator
(STAC) at (919) 541-7834. The request for the audit sample must be made
at least 30 days prior to the scheduled compliance sample analysis.
8.4 Audit Results. Calculate the audit sample concentration
according to the calculation procedure described in the audit
instructions included with the audit sample. Fill in the audit sample
concentration and the analyst's name on the audit response form included
with the audit instructions.

[[Page 493]]

Send one copy to the EPA Regional Office or the appropriate enforcement
agency and a second copy to the STAC. The EPA Regional office or the
appropriate enforcement agency will report the results of the audit to
the laboratory being audited. Include this response with the results of
the compliance samples in relevant reports to the EPA Regional Office or
the appropriate enforcement agency.

9. Calculations

Same as Method 5, section 6 with the following additions.
9.1 Nomenclature.

Aai=Integrated ion current of the noise at the retention
time of the analyte.
A*ci=Integrated ion current of the two ions
characteristic of the internal standard i in the calibration standard.
Acij=Integrated ion current of the two ions
characteristic of compound i in the jth calibration standard.
A*cij=Integrated ion current of the two ions
characteristic of the internal standard i in the jth calibration
standard.
Acsi=Integrated ion current of the two ions
characteristic of surrogate compound i in the calibration standard.
Ai=Integrated ion current of the two ions characteristic
of compound i in the sample.
A*i=Integrated ion current of the two ions characteristic
of internal standard i in the sample.
Ars=Integrated ion current of the two ions characteristic
of the recovery standard.
Asi=Integrated ion current of the two ions characteristic
of surrogate compound i in the sample.
Ci=Concentration of PCDD or PCDF i in the sample, pg/M
\3\.
CT=Total concentration of PCDD's or PCDF's in the sample,
pg/M \3\.
mci=Mass of compound i in the calibration standard
injected into the analyzer, pg.
mrs=Mass of recovery standard in the calibration standard
injected into the analyzer, pg.
msi=Mass of surrogate compound in the calibration
standard, pg.
RRFi=Relative response factor.
RRFrs=Recovery standard response factor.
RRFs=Surrogate compound response factor.
9.2 Average Relative Response Factor.

[GRAPHIC] [TIFF OMITTED] TC16NO91.219

9.3 Concentration of the PCDD's and PCDF's.
[GRAPHIC] [TIFF OMITTED] TC16NO91.220

9.4 Recovery Standard Response Factor.
[GRAPHIC] [TIFF OMITTED] TC16NO91.221

9.5 Recovery of Internal Standards (R*).
[GRAPHIC] [TIFF OMITTED] TC16NO91.222

9.6 Surrogate Compound Response Factor.
[GRAPHIC] [TIFF OMITTED] TC16NO91.223

9.7 Recovery of Surrogate Compounds (Rs).
[GRAPHIC] [TIFF OMITTED] TC16NO91.224

9.8 Minimum Detectable Limit (MDL).
[GRAPHIC] [TIFF OMITTED] TC16NO91.225

9.9 Total Concentration of PCDD's and PCDF's in the Sample.
[GRAPHIC] [TIFF OMITTED] TC16NO91.226

Any PCDD's or PCDF's that are reported as nondetected (below the
MDL) shall be counted as zero for the purpose of calculating the total
concentration of PCDD's and PCDF's in the sample.

10. Bibliography

1. American Society of Mechanical Engineers. Sampling for the
Determination of Chlorinated Organic Compounds in Stack Emissions.
Prepared for U.S. Department of Energy and U.S. Environmental Protection
Agency. Washington DC. December 1984. 25 p.
2. American Society of Mechanical Engineers. Analytical Procedures
to Assay Stack Effluent Samples and Residual Combustion Products for
Polychlorinated Dibenzo-p-Dioxins (PCDD) and Polychlorinated
Dibenzofurans (PCDF). Prepared for the U.S. Department of Energy and
U.S. Environmental Protection Agency. Washington, DC. December 1984. 23
p.
3. Thompson, J. R. (ed.). Analysis of Pesticide Residues in Human
and Environmental Samples. U.S. Environmental Protection Agency.
Research Triangle Park, NC. 1974.

[[Page 494]]

4. Triangle Laboratories. Case Study: Analysis of Samples for the
Presence of Tetra Through Octachloro-p-Dibenzodioxins and Dibenzofurans.
Research Triangle Park, NC. 1988. 26 p.
5. U.S. Environmental Protection Agency. Method 8290--The Analysis
of Polychlorinated Dibenzo-p-dioxin and Polychlorinated Dibenzofurans by
High-Resolution Gas Chromotography/High-Resolution Mass Spectrometry.
In: Test Methods for Evaluating Solid Waste. Washington, DC. SW-846.

Table 1--Composition of the Sample Fortification and Recovery Standards
Solutions
------------------------------------------------------------------------
Concentration
Analyte (pg/l)
------------------------------------------------------------------------
Internal Standards:
¹³ C12-2,3,7,8-TCDD.................................... 100
¹³ C12-1,2,3,7,8-PeCDD................................. 100
¹³ C12-1,2,3,6,7,8-HxCDD............................... 100
¹³ C12-1,2,3,4,6,7,8-HpCDD............................. 100
¹³ C12-OCDD............................................ 100
¹³ C12-2,3,7,8-TCDF.................................... 100
¹³ C12-1,2,3,7,8-PeCDF................................. 100
¹³ C12-1,2,3,6,7,8-HxCDF............................... 100
¹³ C12-1,2,3,4,6,7,8-HpCDF............................. 100
Surrogate Standards:
³⁷ Cl4-2,3,7,8-TCDD.................................... 100
¹³ C12-1,2,3,4,7,8-HxCDD............................... 100
¹³ C12-2,3,4,7,8-PeCDF................................. 100
¹³ C12-1,2,3,4,7,8-HxCDF............................... 100
¹³ C12-1,2,3,4,7,8,9-HpCDF............................. 100
Recovery Standards:
¹³ C12-1,2,3,4-TCDD.................................... 500
¹³ C12-1,2,3,7,8,9-HxCDD............................... 500
------------------------------------------------------------------------

Table 2--Composition of the Initial Calibration Solutions
------------------------------------------------------------------------
Concentrations (pg/L)
----------------------------------
Compound Solution No.
----------------------------------
1 2 3 4 5
------------------------------------------------------------------------
Alternate Standard:
¹³ C12-1,2,3,7,8,9-HxCDF........... 2.5 5 25 250 500
Recovery Standards:
¹³ C12-1,2,3,4-TCDD................ 100 100 100 100 100
¹³ C12-1,2,3,7,8,9-HxCDD........... 100 100 100 100 100
------------------------------------------------------------------------

Table 3--Elemental Compositions and Exact Masses of the Ions Monitored by High Resolution Mass Spectrometry for
PCDD's and PCDF's
----------------------------------------------------------------------------------------------------------------
Descriptor
No. Accurate mass Ion type Elemental composition Analyte
----------------------------------------------------------------------------------------------------------------
2 292.9825 LOCK C7F11 PFK
303.9016 M C12H435Cl4O TCDF
305.8987 M+2 C12H435Cl³⁷O TCDF
315.9419 M ¹³C12H435Cl4O TCDF (S)
317.9389 M+2 ¹³C12H435Cl337ClO TCDF (S)
319.8965 M C12H435ClO2 TCDD
321.8936 M+2 C12H435Cl337ClO2 TCDD
327.8847 M C12H437Cl4O2 TCDD (S)
330.9792 QC C7F13 PFK
331.9368 M ¹³C12H435Cl4O2 TCDD (S)
333.9339 M+2 ¹³C12H435Cl³⁷ClO2 TCDD (S)
339.8597 M+2 C12H335Cl437ClO PECDF
341.8567 M+4 C12H335Cl337Cl2O PeCDF
351.9000 M+2 ¹³C12H335Cl437ClO PeCDF (S)
353.8970 M+4 ¹³C12H335Cl³⁵³⁷Cl2O PeCDF (S)
355.8546 M+2 C12H335Cl337ClO2 PeCDD
357.8516 M+4 C12H335Cl337Cl2O2 PeCDD
367.8949 M+2 ¹³C12H335Cl437ClO2 PeCDD (S)
369.8919 M+4 ¹³C12H335Cl337 Cl2O2 PeCDD (S)
375.8364 M+2 C12H435Cl537ClO HxCDPE
409.7974 M+2 C12H335Cl637ClO HpCPDE
3 373.8208 M+2 C12H235Cl537ClO HxCDF
375.8178 M+4 C12H235Cl437Cl2O HxCDF
383.8639 M ¹³C12H235Cl6O HxCDF (S)
385.8610 M+2 ¹³C12H235Cl537ClO HxCDF (S)
389.8157 M+2 C12H235Cl537ClO2 HxCDD
391.8127 M+4 C12H235Cl437Cl2O2 HxCDD
392.9760 LOCK C9F15 PFK
401.8559 M+2 ¹³C12H235Cl537ClO2 HxCDD (S)
403.8529 M+4 ¹³C12H235Cl437Cl2O HxCDD (S)
445.7555 M+4 C12H235Cl637Cl2O OCDPE
430.9729 QC C9F17 PFK
4 407.7818 M+2 C12H³⁵Cl637ClO HpCDF
409.7789 M+4 C12H³⁵Cl537Cl2O HpCDF

[[Page 495]]

417.8253 M ¹³C12H³⁵Cl7O HpCDF (S)
419.8220 M+2 ¹³C12H³⁵Cl637ClO HpCDF (S)
423.7766 M+2 C12H³⁵Cl637ClO2 HpCDD
425.7737 M+4 C12H³⁵Cl537Cl2O2 HpCDD
435.8169 M+2 ¹³C12H³⁵Cl637ClO2 HpCDD (S)
437.8140 M+4 ¹³C12H³⁵Cl537Cl2O2 HpCDD (S)
479.7165 M+4 C12H³⁵Cl737Cl2O NCPDE
430.9729 LOCK C9F17 PFK
441.7428 M+2 C1235Cl737ClO OCDF
443.7399 M+4 C1235Cl637Cl2O OCDF
457.7377 M+2 C1235Cl737ClO2 OCDD
459.7348 M+4 C1235Cl637Cl2O2 OCDD
469.7779 M+2 ¹³C1235Cl737ClO2 OCDD (S)
471.7750 M+4 ¹³C1235Cl637Cl2O2 OCDD (S)
513.6775 M+4 C1235Cl837Cl2O2 DCDPE
442.9728 QC C10F17 PFK
----------------------------------------------------------------------------------------------------------------
(a) The following nuclidic masses were used:
H = 1.007825
C = 12.000000
¹³C = 13.003355
F = 18.9984
O = 15.994915
³⁵Cl = 34.968853
³⁷Cl = 36.965903
S = Labeled Standard
QC = Ion selected for monitoring instrument stability during the GC/MS analysis.

Table 4--Acceptable Ranges for Ion-Abundance Ratios of PCDD's and PCDF's
------------------------------------------------------------------------
No. of Control limits
chlorine Ion type Theoretical -----------------
atoms ratio Lower Upper
------------------------------------------------------------------------
4 M/M+2 0.77 0.65 0.89
5 M+2/M+4 1.55 1.32 1.78
6 M+2/M+4 1.24 1.05 1.43
6 ^a M/M+2 0.51 0.43 0.59
7 ^b M/M+2 0.44 0.37 0.51
7 M+2/M+4 1.04 0.88 1.20
8 M+2/M+4 0.89 0.76 1.02
------------------------------------------------------------------------
^a Used only for \13\C-HxCDF.
^b Used only for \13\C-HpCDF.

Table 5--Minimum Requirements for Initial and Daily Calibration Response
Factors
------------------------------------------------------------------------
Relative response factors
-------------------------------
Compound Initial Daily
calibration calibration %
RSD difference
------------------------------------------------------------------------
Unlabeled
Analytes:
2,3,7,8-TCDD.......................... 25 25
2,3,7,8-TCDF.......................... 25 25
1,2,3,7,8-PeCDD....................... 25 25
1,2,3,7,8-PeCDF....................... 25 25
2,3,4,7,8-PeCDF....................... 25 25
1,2,4,5,7,8-HxCDD..................... 25 25
1,2,3,6,7,8-HxCDD..................... 25 25
1,2,3,7,8,9-HxCDD..................... 25 25
1,2,3,4,7,8-HxCDF..................... 25 25
1,2,3,6,7,8-HxCDF..................... 25 25
1,2,3,7,8,9-HxCDF..................... 25 25
2,3,4,6,7,8-HxCDF..................... 25 25
1,2,3,4,6,7,8-HpCDD................... 25 25
1,2,3,4,6,7,8-HpCDF................... 25 25
OCDD.................................. 25 25
OCDF.................................. 30 30
Internal
Standards:
\13\C12-2,3,7,8-TCDD.................. 25 25
\13\C12-1,2,3,7,8-PeCDD............... 30 30
\13\C12-1,2,3,6,7,8-HxCDD............. 25 25
\13\C12-1,2,3,4,6,7,8-HpCDD........... 30 30
\13\C12-OCDD.......................... 30 30
\13\C12-2,3,7,8-TCDF.................. 30 30
\13\C12-1,2,3,7,8-PeCDF............... 30 30
\13\C12-1,2,3,6,7,8-HxCDF............. 30 30
\13\C12-1,2,3,4,6,7,8-HpCDF........... 30 30
Surrogate
Standards:
\37\Cl4-2,3,7,8-TCDD.................. 25 25
\13\C12-2,3,4,7,8-PeCDF............... 25 25
\13\C12-1,2,3,4,7,8-HxCDD............. 25 25
\13\C12-1,2,3,4,7,8-HxCDF............. 25 25
\13\C12-1,2,3,4,7,8,9-HpCDF........... 25 25
Alternate
Standard:
\13\C12-1,2,3,7,8,9-HxCDF............. 25 25
------------------------------------------------------------------------

[[Page 496]]

Method 24--Determination of Volatile Matter Content, Water Content,
Density, Volume Solids, and Weight Solids of Surface Coatings

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile organic compounds Water.......... No CAS Number assigned 7732-
18-5
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of volatile matter content, water content, density, volume solids, and
weight solids of paint, varnish, lacquer, or other related surface
coatings.
1.3 Precision and Bias. Intra-and inter-laboratory analytical
precision statements are presented in Section 13.1. No bias has been
identified.

2.0 Summary of Method

2.1 Standard methods are used to determine the volatile matter
content, water content, density, volume solids, and weight solids of
paint, varnish, lacquer, or other related surface coatings.

3.0 Definitions

3.1 Waterborne coating means any coating which contains more than 5
percent water by weight in its volatile fraction.
3.2 Multicomponent coatings are coatings that are packaged in two
or more parts, which are combined before application. Upon combination a
coreactant from one part of the coating chemically reacts, at ambient
conditions, with a coreactant from another part of the coating.
3.3 Ultraviolet (UV) radiation-cured coatings are coatings which
contain unreacted monomers that are polymerized by exposure to
ultraviolet light.

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

The equipment and supplies specified in the ASTM methods listed in
Sections 6.1 through 6.6 (incorporated by reference--see Sec. 60.17 for
acceptable versions of the methods) are required:
6.1 ASTM D 1475-60, 80, or 90, Standard Test Method for Density of
Paint, Varnish, Lacquer, and Related Products.
6.2 ASTM D 2369-81, 87, 90, 92, 93, or 95, Standard Test Method for
Volatile Content of Coatings.
6.3 ASTM D 3792-79 or 91, Standard Test Method for Water Content of
Water Reducible Paints by Direct Injection into a Gas Chromatograph.
6.4 ASTM D 4017-81, 90, or 96a, Standard Test Method for Water in
Paints and Paint Materials by the Karl Fischer Titration Method.
6.5 ASTM 4457-85 91, Standard Test Method for Determination of
Dichloromethane and 1,1,1-Trichloroethane in Paints and Coatings by
Direct Injection into a Gas Chromatograph.
6.6 ASTM D 5403-93, Standard Test Methods for Volatile Content of
Radiation Curable Materials.

7.0 Reagents and Standards

7.1 The reagents and standards specified in the ASTM methods listed
in Sections 6.1 through 6.6 are required.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Follow the sample collection, preservation, storage, and
transport procedures described in Reference 1 of Section 16.0.

9.0 Quality Control

9.1 Reproducibility
Note: Not applicable to UV radiation-cured coatings). The variety of
coatings that may be subject to analysis makes it necessary to verify
the ability of the analyst and the analytical procedures to obtain
reproducible results for the coatings tested. Verification is
accomplished by running duplicate analyses on each sample tested
(Sections 11.2 through 11.4) and comparing the results with the intra-
laboratory precision statements (Section 13.1) for each parameter.

9.2 Confidence Limits for Waterborne Coatings. Because of the
inherent increased imprecision in the determination of the VOC content
of waterborne coatings as the weight percent of water increases,
measured parameters for waterborne coatings are replaced with
appropriate confidence limits (Section 12.6). These confidence limits
are based on measured parameters and inter-laboratory precision
statements.

[[Page 497]]

10.0 Calibration and Standardization

10.1 Perform the calibration and standardization procedures
specified in the ASTM methods listed in Sections 6.1 through 6.6.

11.0 Analytical Procedure

Additional guidance can be found in Reference 2 of Section 16.0.
11.1 Non Thin-film Ultraviolet Radiation-cured (UV radiation-cured)
Coatings.
11.1.1 Volatile Content. Use the procedure in ASTM D 5403 to
determine the volatile matter content of the coating except the curing
test described in NOTE 2 of ASTM D 5403 is required.
11.1.2 Water Content. To determine water content, follow Section
11.3.2.
11.1.3 Coating Density. To determine coating density, follow
Section 11.3.3.
11.1.4 Solids Content. To determine solids content, follow Section
11.3.4.
11.1.5 To determine if a coating or ink can be classified as a
thin-film UV cured coating or ink, use the equation in Section 12.2. If
C is less than 0.2 g and A is greater than or equal to 225 cm\2\ (35
in\2\) then the coating or ink is considered a thin-film UV radiation-
cured coating and ASTM D 5403 is not applicable.
Note: As noted in Section 1.4 of ASTM D 5403, this method may not be
applicable to radiation curable materials wherein the volatile material
is water.
11.2 Multi-component Coatings.
11.2.1 Sample Preparation.
11.2.1.1 Prepare about 100 ml of sample by mixing the components in
a storage container, such as a glass jar with a screw top or a metal can
with a cap. The storage container should be just large enough to hold
the mixture. Combine the components (by weight or volume) in the ratio
recommended by the manufacturer. Tightly close the container between
additions and during mixing to prevent loss of volatile materials.
However, most manufacturers mixing instructions are by volume. Because
of possible error caused by expansion of the liquid when measuring the
volume, it is recommended that the components be combined by weight.
When weight is used to combine the components and the manufacturer's
recommended ratio is by volume, the density must be determined by
Section 11.3.3.
11.2.1.2 Immediately after mixing, take aliquots from this 100 ml
sample for determination of the total volatile content, water content,
and density.
11.2.2 Volatile Content. To determine total volatile content, use
the apparatus and reagents described in ASTM D2369 Sections 3 and 4
(incorporated by reference--see Sec. 60.17 for the approved versions of
the standard), respectively, and use the following procedures:
11.2.2.1 Weigh and record the weight of an aluminum foil weighing
dish. Add 3 1 ml of suitable solvent as specified in ASTM
D2369 to the weighing dish. Using a syringe as specified in ASTM D2369,
weigh to 1 mg, by difference, a sample of coating into the weighing
dish. For coatings believed to have a volatile content less than 40
weight percent, a suitable size is 0.3 + 0.10 g, but for coatings
believed to have a volatile content greater than 40 weight percent, a
suitable size is 0.5 0.1 g.
Note: If the volatile content determined pursuant to Section 12.4 is
not in the range corresponding to the sample size chosen repeat the test
with the appropriate sample size. Add the specimen dropwise, shaking
(swirling) the dish to disperse the specimen completely in the solvent.
If the material forms a lump that cannot be dispersed, discard the
specimen and prepare a new one. Similarly, prepare a duplicate. The
sample shall stand for a minimum of 1 hour, but no more than 24 hours
prior to being oven cured at 110 5 deg.C (230
9 deg.F) for 1 hour.
11.2.2.2 Heat the aluminum foil dishes containing the dispersed
specimens in the forced draft oven for 60 min at 110 5
deg.C (230 9 deg.F). Caution--provide adequate
ventilation, consistent with accepted laboratory practice, to prevent
solvent vapors from accumulating to a dangerous level.
11.2.2.3 Remove the dishes from the oven, place immediately in a
desiccator, cool to ambient temperature, and weigh to within 1 mg.
11.2.2.4 Run analyses in pairs (duplicate sets) for each coating
mixture until the criterion in Section 11.4 is met. Calculate
WV following Equation 24-2 and record the arithmetic average.
11.2.3 Water Content. To determine water content, follow Section
11.3.2.
11.2.4 Coating Density. To determine coating density, follow
Section 11.3.3.
11.2.5 Solids Content. To determine solids content, follow Section
11.3.4.
11.2.6 Exempt Solvent Content. To determine the exempt solvent
content, follow Section 11.3.5.
Note: For all other coatings (i.e., water-or solvent-borne coatings)
not covered by multicomponent or UV radiation-cured coatings, analyze as
shown below:
11.3 Water-or Solvent-borne coatings.
11.3.1 Volatile Content. Use the procedure in ASTM D 2369 to
determine the volatile matter content (may include water) of the
coating.
11.3.1.1 Record the following information:

W1 = weight of dish and sample before heating, g
W2 = weight of dish and sample after heating, g
W3 = sample weight, g.

[[Page 498]]

11.3.1.2 Calculate the weight fraction of the volatile matter
(Wv) for each analysis as shown in Section 12.3.
11.3.1.3 Run duplicate analyses until the difference between the
two values in a set is less than or equal to the intra-laboratory
precision statement in Section 13.1.
11.3.1.4 Record the arithmetic average (Wv).
11.3.2 Water Content. For waterborne coatings only, determine the
weight fraction of water (Ww) using either ASTM D 3792 or
ASTM D 4017.
11.3.2.1 Run duplicate analyses until the difference between the
two values in a set is less than or equal to the intra-laboratory
precision statement in Section 13.1.
11.3.2.2 Record the arithmetic average (ww).
11.3.3 Coating Density. Determine the density (Dc, kg/l) of the
surface coating using the procedure in ASTM D 1475.
11.3.3.1 Run duplicate analyses until each value in a set deviates
from the mean of the set by no more than the intra-laboratory precision
statement in Section 13.1.
11.3.3.2 Record the arithmetic average (Dc).
11.3.4 Solids Content. Determine the volume fraction
(Vs) solids of the coating by calculation using the
manufacturer's formulation.
11.3.5 Exempt Solvent Content. Determine the weight fraction of
exempt solvents (WE) by using ASTM Method D4457. Run a
duplicate set of determinations and record the arithmetic average
(WE).
11.4 Sample Analysis Criteria. For Wv and Ww,
run duplicate analyses until the difference between the two values in a
set is less than or equal to the intra-laboratory precision statement
for that parameter. For Dc, run duplicate analyses until each
value in a set deviates from the mean of the set by no more than the
intra-laboratory precision statement. If, after several attempts, it is
concluded that the ASTM procedures cannot be used for the specific
coating with the established intra-laboratory precision (excluding UV
radiation-cured coatings), the U.S. Environmental Protection Agency
(EPA) will assume responsibility for providing the necessary procedures
for revising the method or precision statements upon written request to:
Director, Emissions, Monitoring, and Analysis Division, MD-14, Office of
Air Quality Planning and Standards, U.S. Environmental Protection
Agency, Research Triangle Park, NC 27711.

12.0 Calculations and Data Analysis

12.1 Nomenclature.

A = Area of substrate, cm², (in²).
C = Amount of coating or ink added to the substrate, g.
Dc = Density of coating or ink, g/cm\3\ (g/in\3\).
F = Manufacturer's recommended film thickness, cm (in).
Wo = Weight fraction of nonaqueous volatile matter, g/g.
Ws = Weight fraction of solids, g/g.
Wv = Weight fraction of the volatile matter, g/g.
Ww = Weight fraction of the water, g/g.
12.2 To determine if a coating or ink can be classified as a thin-
film UV cured coating or ink, use the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.356

12.3 Calculate Wv for each analysis as shown below:
[GRAPHIC] [TIFF OMITTED] TR17OC00.357

12.4 Nonaqueous Volatile Matter.
12.4.1 Solvent-borne Coatings.
[GRAPHIC] [TIFF OMITTED] TR17OC00.358

12.4.2 Waterborne Coatings.
[GRAPHIC] [TIFF OMITTED] TR17OC00.359

12.4.3 Coatings Containing Exempt Solvents.
[GRAPHIC] [TIFF OMITTED] TR17OC00.360

12.5 Weight Fraction Solids.
[GRAPHIC] [TIFF OMITTED] TR17OC00.361

12.6 Confidence Limit Calculations for Waterborne Coatings. To
calculate the lower confidence limit, subtract the appropriate inter-
laboratory precision value from the measured mean value for that
parameter. To calculate the upper confidence limit, add the appropriate
inter-laboratory precision value to the measured mean value for that
parameter. For Wv and Dc, use the lower confidence
limits; for Ww, use the upper confidence limit. Because
Ws is calculated, there is no adjustment for this parameter.

13.0 Method Performance

13.1 Analytical Precision Statements. The intra-and inter-
laboratory precision statements are given in Table 24-1 in Section 17.0.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as specified in Section 6.0, with the addition of the
following:
1. Standard Procedure for Collection of Coating and Ink Samples for
Analysis by Reference Methods 24 and 24A. EPA-340/1-91-010. U.S.
Environmental Protection Agency, Stationary Source Compliance Division,
Washington, D.C. September 1991.

[[Page 499]]

2. Standard Operating Procedure for Analysis of Coating and Ink
Samples by Reference Methods 24 and 24A.
EPA-340/1-91-011. U.S. Environmental Protection Agency, Stationary
Source Compliance Division, Washington, D.C. September 1991.
3. Handbook of Hazardous Materials: Fire, Safety, Health. Alliance
of American Insurers. Schaumberg, IL. 1983.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 24-1.--Analytical Precision Statements
----------------------------------------------------------------------------------------------------------------
Intra-laboratory Inter-laboratory
----------------------------------------------------------------------------------------------------------------
Volatile matter content, Wv............ 0.015 Wv.............. 0.047 W8v
Water content, Ww...................... 0.029 W8w............. 0.075 Ww
Density, Dc............................ 0.001 kg/l............ 0.002 kg/l
----------------------------------------------------------------------------------------------------------------

Method 24A--Determination of Volatile Matter Content and Density of
Publication Rotogravure Inks and Related Publication Rotogravure
Coatings

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Volatile organic compounds (VOC).......... No CAS number assigned.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of the VOC content and density of solvent-borne (solvent-reducible)
publication rotogravure inks and related publication rotogravure
coatings.

2.0 Summary of Method

2.1 Separate procedures are used to determine the VOC weight
fraction and density of the ink or related coating and the density of
the solvent in the ink or related coating. The VOC weight fraction is
determined by measuring the weight loss of a known sample quantity which
has been heated for a specified length of time at a specified
temperature. The density of both the ink or related coating and solvent
are measured by a standard procedure. From this information, the VOC
volume fraction is calculated.

3.0 Definitions [Reserved]

4.0 Interferences [Reserved]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method does not purport to address
all of the safety problems associated with its use. It is the
responsibility of the user of this test method to establish appropriate
safety and health practices and to determine the applicability of
regulatory limitations prior to performing this test method.
5.2 Hazardous Components. Some of the compounds that may be
contained in the inks or related coatings analyzed by this method may be
irritating or corrosive to tissues or may be toxic. Nearly all are fire
hazards. Appropriate precautions can be found in reference documents,
such as Reference 6 of Section 16.0.

6.0 Equipment and Supplies

The following equipment and supplies are required for sample
analysis:
6.1 Weighing Dishes. Aluminum foil, 58 mm (2.3 in.) in diameter by
18 mm (0.7 in.) high, with a flat bottom. There must be at least three
weighing dishes per sample.
6.2 Disposable Syringe. 5 ml.
6.3 Analytical Balance. To measure to within 0.1 mg.
6.4 Oven. Vacuum oven capable of maintaining a temperature of 120
2 deg.C (248 4 deg.F) and an absolute
pressure of 510 51 mm Hg (20 2 in. Hg) for 4
hours. Alternatively, a forced draft oven capable of maintaining a
temperature of 120 2 deg.C (248 4 deg.F) for
24 hours.
6.5 The equipment and supplies specified in ASTM D 1475-60, 80, or
90 (incorporated by reference--see Sec. 60.17).

7.0 Reagents and Standards

7.1 The reagents and standards specified in ASTM D 1475-60, 80, or
90 are required.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Follow the sample collection, preservation, storage, and
transport procedures described in Reference 4 of Section 16.0.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Additional guidance can be found in Reference 5 of Section 16.0.
11.1 VOC Weight Fraction. Shake or mix the ink or related coating
sample thoroughly to assure that all the solids are completely
suspended. Label and weigh to the nearest 0.1 mg a weighing dish and
record this weight

[[Page 500]]

(Mx1). Using a 5 ml syringe, without a needle, extract an
aliquot from the ink or related coating sample. Weigh the syringe and
aliquot to the nearest 0.1 mg and record this weight (Mcy1).
Transfer 1 to 3 g of the aliquot to the tared weighing dish. Reweigh the
syringe and remaining aliquot to the nearest 0.1 mg and record this
weight (Mcy2). Heat the weighing dish with the transferred
aliquot in a vacuum oven at an absolute pressure of 510 51
mm Hg (20 2 in. Hg) and a temperature of 120 2
deg.C (248 4 deg.F) for 4 hours. Alternatively, heat the
weighing dish with the transferred aliquot in a forced draft oven at a
temperature of 120 2 deg.C for 24 hours. After the
weighing dish has cooled, reweigh it to the nearest 0.1 mg and record
the weight (Mx2). Repeat this procedure two times for each
ink or related coating sample, for a total of three samples.
11.2 Ink or Related Coating Density. Determine the density of the
ink or related coating (Dc) according to the procedure
outlined in ASTM D 1475. Make a total of three determinations for each
ink or related coating sample. Report the ink or related coating density
as the arithmetic average (Dc) of the three determinations.
11.3 Solvent Density. Determine the density of the solvent
(Do) according to the procedure outlined in ASTM D 1475. Make
a total of three determinations for each ink or related coating sample.
Report the solvent density as the arithmetic average (Do) of
the three determinations.

12.0 Calculations and Data Analysis

12.1 VOC Weight Fraction. For each determination, calculate the
volatile organic content weight fraction (Wo) using the
following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.362

Wo) of the three determinations.12.2 VOC Volume Fraction.
Calculate the volume fraction volatile organic content (Vo)
using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.363

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Standard Test Method for Density of Paint, Varnish, Lacquer, and
Related Products. ASTM Designation D 1475.
2. Teleconversation. Wright, Chuck, Inmont Corporation with Reich, R.,
A., Radian Corporation. September 25, 1979, Gravure Ink Analysis.
3. Teleconversation. Oppenheimer, Robert, Gravure Research Institute
with Burt, Rick, Radian Corporation, November 5, 1979, Gravure Ink
Analysis.
4. Standard Procedure for Collection of Coating and Ink Samples for
Analysis by Reference Methods 24 and 24A. EPA-340/1-91-010. U.S.
Environmental Protection Agency, Stationary Source Compliance Division,
Washington, D.C. September 1991.
5. Standard Operating Procedure for Analysis of Coating and Ink Samples
by Reference Methods 24 and 24A. EPA-340/1-91-011. U.S. Environmental
Protection Agency, Stationary Source Compliance Division, Washington,
D.C. September 1991.
6. Handbook of Hazardous Materials: Fire, Safety, Health. Alliance of
American Insurers. Schaumberg, IL. 1983.

[[Page 501]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Method 25--Determination of Total Gaseous Nonmethane Organic Emissions
as Carbon

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total gaseous nonmethane organic N/A Dependent upon
compounds (TGNMO). analytical
equipment.
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This method is applicable for the determination of volatile
organic compounds (VOC) (measured as total gaseous nonmethane organics
(TGNMO) and reported as carbon) in stationary source emissions. This
method is not applicable for the determination of organic particulate
matter.
1.2.2 This method is not the only method that applies to the
measurement of VOC. Costs, logistics, and other practicalities of source
testing may make other test methods more desirable for measuring VOC
contents of certain effluent streams. Proper judgment is required in
determining the most applicable VOC test method. For example, depending
upon the molecular composition of the organics in the effluent stream, a
totally automated semicontinuous nonmethane organics (NMO) analyzer
interfaced directly to the source may yield accurate results. This
approach has the advantage of providing emission data semicontinuously
over an extended time period.
1.2.3 Direct measurement of an effluent with a flame ionization
detector (FID) analyzer may be appropriate with prior characterization
of the gas stream and knowledge that the detector responds predictably
to the organic compounds in the stream. If present, methane
(CH4) will, of course, also be measured. The FID can be used
under any of the following limited conditions: (1) Where only one
compound is known to exist; (2) when the organic compounds consist of
only hydrogen and carbon; (3) where the relative percentages of the
compounds are known or can be determined, and the FID responses to the
compounds are known; (4) where a consistent mixture of the compounds
exists before and after emission control and only the relative
concentrations are to be assessed; or (5) where the FID can be
calibrated against mass standards of the compounds emitted (solvent
emissions, for example).
1.2.4 Another example of the use of a direct FID is as a screening
method. If there is enough information available to provide a rough
estimate of the analyzer accuracy, the FID analyzer can be used to
determine the VOC content of an uncharacterized gas stream. With a
sufficient buffer to account for possible inaccuracies, the direct FID
can be a useful tool to obtain the desired results without costly exact
determination.
1.2.5 In situations where a qualitative/quantitative analysis of an
effluent stream is desired or required, a gas chromatographic FID system
may apply. However, for sources emitting numerous organics, the time and
expense of this approach will be formidable.

2.0 Summary of Method

2.1 An emission sample is withdrawn from the stack at a constant
rate through a heated filter and a chilled condensate trap by means of
an evacuated sample tank. After sampling is completed, the TGNMO are
determined by independently analyzing the condensate trap and sample
tank fractions and combining the analytical results. The organic content
of the condensate trap fraction is determined by oxidizing the NMO to
carbon dioxide (CO2) and quantitatively collecting in the
effluent in an evacuated vessel; then a portion of the CO2 is
reduced to CH4 and measured by an FID. The organic content of
the sample tank fraction is measured by injecting a portion of the
sample into a gas chromatographic column to separate the NMO from carbon
monoxide (CO), CO2, and CH4; the NMO are oxidized
to CO2, reduced to CH4, and measured by an FID. In
this manner, the variable response of the FID associated with different
types of organics is eliminated.

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Carbon Dioxide and Water Vapor. When carbon dioxide
(CO2) and water vapor are present together in the stack, they
can produce a positive bias in the sample. The magnitude of the bias
depends on the concentrations of CO2 and water vapor. As a
guideline, multiply the CO2 concentration, expressed as
volume percent, times the water vapor concentration. If this product
does not exceed 100, the bias can be considered insignificant. For
example, the bias is not significant for a source having 10 percent
CO2 and 10 percent water vapor, but it might be significant
for a source having 10 percent CO2 and 20 percent water
vapor.

[[Page 502]]

4.2. Particulate Matter. Collection of organic particulate matter
in the condensate trap would produce a positive bias. A filter is
included in the sampling equipment to minimize this bias.

5.0 Safety

6.0 Equipment and Supplies

6.1 Sample Collection. The sampling system consists of a heated
probe, heated filter, condensate trap, flow control system, and sample
tank (see Figure 25-1). The TGNMO sampling equipment can be constructed
from commercially available components and components fabricated in a
machine shop. The following equipment is required:
6.1.1 Heated Probe. 6.4-mm (\1/4\-in.) OD stainless steel tubing
with a heating system capable of maintaining a gas temperature at the
exit end of at least 129 deg.C (265 deg.F). The probe shall be
equipped with a temperature sensor at the exit end to monitor the gas
temperature. A suitable probe is shown in Figure 25-1. The nozzle is an
elbow fitting attached to the front end of the probe while the
temperature sensor is inserted in the side arm of a tee fitting attached
to the rear of the probe. The probe is wrapped with a suitable length of
high temperature heating tape, and then covered with two layers of glass
cloth insulation and one layer of aluminum foil or an equivalent
wrapping.
Note: If it is not possible to use a heating system for safety
reasons, an unheated system with an in-stack filter is a suitable
alternative.

6.1.2 Filter Holder. 25-mm (\15/16\-in.) ID Gelman filter holder
with 303 stainless steel body and 316 stainless steel support screen
with the Viton O-ring replaced by a Teflon O-ring.
6.1.3 Filter Heating System.
6.1.3.1 A metal box consisting of an inner and an outer shell
separated by insulating material with a heating element in the inner
shell capable of maintaining a gas temperature at the filter of 121
3 deg.C (250 5 deg.F). The heating box shall
include temperature sensors to monitor the gas temperature immediately
upstream and immediately downstream of the filter.
6.1.3.2 A suitable heating box is shown in Figure 25-2. The outer
shell is a metal box that measures 102 mm x 280 mm x 292 mm (4 in. x 11
in. x 11\1/2\ in.), while the inner shell is a metal box measuring 76 mm
x 229 mm x 241 mm (3 in. x 9 in. x 9\1/2\ in.). The inner box is
supported by 13-mm (\1/2\-in.) phenolic rods. The void space between the
boxes is filled with ceramic fiber insulation which is sealed in place
by means of a silicon rubber bead around the upper sides of the box. A
removable lid made in a similar manner, with a 25-mm (1-in.) gap between
the parts is used to cover the heating chamber. The inner box is heated
with a 250-watt cartridge heater, shielded by a stainless steel shroud.
The heater is regulated by a thermostatic temperature controller which
is set to maintain a gas temperature of 121 deg.C (250 deg.F) as
measured by the temperature sensor upstream of the filter.
Note: If it is not possible to use a heating system for safety
reasons, an unheated system with an in-stack filter is a suitable
alternative.
6.1.4 Condensate Trap. 9.5-mm (\3/8\-in.) OD 316 stainless steel
tubing bent into a U-shape. Exact dimensions are shown in Figure 25-3.
The tubing shall be packed with coarse quartz wool, to a density of
approximately 0.11 g/cm\3\ before bending. While the condensate trap is
packed with dry ice in the Dewar, an ice bridge may form between the
arms of the condensate trap making it difficult to remove the condensate
trap. This problem can be prevented by attaching a steel plate between
the arms of the condensate trap in the same plane as the arms to
completely fill the intervening space.
6.1.5 Valve. Stainless steel control valve for starting and
stopping sample flow.
6.1.6 Metering Valve. Stainless steel valve for regulating the
sample flow rate through the sample train.
6.1.7 Rate Meter. Rotameter, or equivalent, capable of measuring
sample flow in the range of 60 to 100 cm\3\/min (0.13 to 0.21 ft\3\/hr).
6.1.8 Sample Tank. Stainless steel or aluminum tank with a minimum
volume of 4 liters (0.14 ft\3\).
Note: Sample volumes greater than 4 liters may be required for
sources with low organic concentrations.
6.1.9 Mercury Manometer. U-tube manometer or absolute pressure
gauge capable of measuring pressure to within 1 mm Hg in the range of 0
to 900 mm.
6.1.10 Vacuum Pump. Capable of evacuating to an absolute pressure
of 10 mm Hg.
6.2 Condensate Recovery. The system for the recovery of the
organics captured in the condensate trap consists of a heat source, an
oxidation catalyst, a nondispersive infrared (NDIR) analyzer, and an
intermediate collection vessel (ICV). Figure 25-4 is a schematic of a
typical system. The system shall be capable of proper oxidation and
recovery, as specified in Section 10.1.1. The following major components
are required:

[[Page 503]]

6.2.1 Heat Source. Sufficient to heat the condensate trap
(including probe) to a temperature of 200 deg.C (390 deg.F). A system
using both a heat gun and an electric tube furnace is recommended.
6.2.2 Heat Tape. Sufficient to heat the connecting tubing between
the water trap and the oxidation catalyst to 100 deg.C (212 deg.F).
6.2.3 Oxidation Catalyst. A suitable length of 9.5 mm (\3/8\-in.)
OD Inconel 600 tubing packed with 15 cm (6 in.) of 3.2 mm (\3/8\-in.)
diameter 19 percent chromia on alumina pellets. The catalyst material is
packed in the center of the catalyst tube with quartz wool packed on
either end to hold it in place.
6.2.4 Water Trap. Leak-proof, capable of removing moisture from the
gas stream.
6.2.5 Syringe Port. A 6.4-mm (\1/4\-in.) OD stainless steel tee
fitting with a rubber septum placed in the side arm.
6.2.6 NDIR Detector. Capable of indicating CO2
concentration in the range of zero to 5 percent, to monitor the progress
of combustion of the organic compounds from the condensate trap.
6.2.7 Flow-Control Valve. Stainless steel, to maintain the trap
conditioning system near atmospheric pressure.
6.2.8 Intermediate Collection Vessel. Stainless steel or aluminum,
equipped with a female quick connect. Tanks with nominal volumes of at
least 6 liters (0.2 ft\3\) are recommended.
6.2.9 Mercury Manometer. Same as described in Section 6.1.9.
6.2.10 Syringe. 10-ml gas-tight glass syringe equipped with an
appropriate needle.
6.2.11 Syringes. 10-l and 50-l liquid injection
syringes.
6.2.12 Liquid Sample Injection Unit. 316 Stainless steel U-tube
fitted with an injection septum (see Figure 25-7).
6.3 Analysis.
6.3.1 NMO Analyzer. The NMO analyzer is a gas chromatograph (GC)
with backflush capability for NMO analysis and is equipped with an
oxidation catalyst, reduction catalyst, and FID. Figures 25-5 and 25-6
are schematics of a typical NMO analyzer. This semicontinuous GC/FID
analyzer shall be capable of: (1) Separating CO, CO2, and
CH4 from NMO, (2) reducing the CO2 to
CH4 and quantifying as CH4, and (3) oxidizing the
NMO to CO2, reducing the CO2 to CH4 and
quantifying as CH4, according to Section 10.1.2. The analyzer
consists of the following major components:
6.3.1.1 Oxidation Catalyst. A suitable length of 9.5-mm (\3/8\-in.)
OD Inconel 600 tubing packed with 5.1 cm (2 in.) of 19 percent chromia
on 3.2-mm (\1/8\-in.) alumina pellets. The catalyst material is packed
in the center of the tube supported on either side by quartz wool. The
catalyst tube must be mounted vertically in a 650 deg.C (1200 deg.F)
furnace. Longer catalysts mounted horizontally may be used, provided
they can meet the specifications of Section 10.1.2.1.
6.3.1.2 Reduction Catalyst. A 7.6-cm (3-in.) length of 6.4-mm (\1/
4\-in.) OD Inconel tubing fully packed with 100-mesh pure nickel powder.
The catalyst tube must be mounted vertically in a 400 deg.C (750
deg.F) furnace.
6.3.1.3 Separation Column(s). A 30-cm (1-ft) length of 3.2-mm (\1/
8\-in.) OD stainless steel tubing packed with 60/80 mesh Unibeads 1S
followed by a 61-cm (2-ft) length of 3.2-mm (\1/8\-in.) OD stainless
steel tubing packed with 60/80 mesh Carbosieve G. The Carbosieve and
Unibeads columns must be baked separately at 200 deg.C (390 deg.F)
with carrier gas flowing through them for 24 hours before initial use.
6.3.1.4 Sample Injection System. A single 10-port GC sample
injection valve or a group of valves with sufficient ports fitted with a
sample loop properly sized to interface with the NMO analyzer (1-cc loop
recommended).
6.3.1.5 FID. An FID meeting the following specifications is
required:
6.3.1.5.1 Linearity. A linear response (5 percent) over
the operating range as demonstrated by the procedures established in
Section 10.1.2.3.
6.3.1.5.2 Range. A full scale range of 10 to 50,000 ppm
CH4. Signal attenuators shall be available to produce a
minimum signal response of 10 percent of full scale.
6.3.1.6 Data Recording System. Analog strip chart recorder or
digital integration system compatible with the FID for permanently
recording the analytical results.
6.3.2 Barometer. Mercury, aneroid, or other barometer capable of
measuring atmospheric pressure to within 1 mm Hg.
6.3.3 Temperature Sensor. Capable of measuring the laboratory
temperature within 1 deg.C (2 deg.F).
6.3.4 Vacuum Pump. Capable of evacuating to an absolute pressure of
10 mm Hg.

7.0 Reagents and Standards

7.1 Sample Collection. The following reagents are required for
sample collection:
7.1.1 Dry Ice. Solid CO2, crushed.
7.1.2 Coarse Quartz Wool. 8 to 15 um.
7.1.3 Filters. Glass fiber filters, without organic binder.
7.2 NMO Analysis. The following gases are required for NMO
analysis:
7.2.1 Carrier Gases. Helium (He) and oxygen (O2)
containing less than 1 ppm CO2 and less than 0.1 ppm
hydrocarbon.
7.2.2 Fuel Gas. Hydrogen (H2), at least 99.999 percent
pure.
7.2.3 Combustion Gas. Either air (less than 0.1 ppm total
hydrocarbon content) or O2 (purity 99.99 percent or greater),
as required by the detector.
7.3 Condensate Analysis. The following are required for condensate
analysis:
7.3.1 Gases. Containing less than 1 ppm carbon.
7.3.1.1 Air.

[[Page 504]]

7.3.1.2 Oxygen.
7.3.2 Liquids. To conform to the specifications established by the
Committee on Analytical Reagents of the American Chemical Society.
7.3.2.1 Hexane.
7.3.2.2 Decane.
7.4 Calibration. For all calibration gases, the manufacturer must
recommend a maximum shelf life for each cylinder (i.e., the length of
time the gas concentration is not expected to change more than
5 percent from its certified value). The date of gas
cylinder preparation, certified organic concentration, and recommended
maximum shelf life must be affixed to each cylinder before shipment from
the gas manufacturer to the buyer. The following calibration gases are
required:
7.4.1 Oxidation Catalyst Efficiency Check Calibration Gas. Gas
mixture standard with nominal concentration of 1 percent methane in air.
7.4.2 FID Linearity and NMO Calibration Gases. Three gas mixture
standards with nominal propane concentrations of 20 ppm, 200 ppm, and
3000 ppm, in air.
7.4.3 CO2 Calibration Gases. Three gas mixture standards
with nominal CO2 concentrations of 50 ppm, 500 ppm, and 1
percent, in air.

Note: Total NMO less than 1 ppm required for 1 percent mixture.

7.4.4 NMO Analyzer System Check Calibration Gases. Four calibration
gases are needed as follows:
7.4.4.1 Propane Mixture. Gas mixture standard containing (nominal)
50 ppm CO, 50 ppm CH4, 1 percent CO2, and 20 ppm
C3H8, prepared in air.
7.4.4.2 Hexane. Gas mixture standard containing (nominal) 50 ppm
hexane in air.
7.4.4.3 Toluene. Gas mixture standard containing (nominal) 20 ppm
toluene in air.
7.4.4.4 Methanol. Gas mixture standard containing (nominal) 100 ppm
methanol in air.
7.5 Quality Assurance Audit Samples.
7.5.1 It is recommended, but not required, that a performance audit
sample be analyzed in conjunction with the field samples. The audit
sample should be in a suitable sample matrix at a concentration similar
to the actual field samples.
7.5.2 When making compliance determinations, and upon availability,
audit samples may be obtained from the appropriate EPA Regional Office
or from the responsible enforcement authority and analyzed in
conjunction with the field samples.

Note: The responsible enforcement authority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Sampling Equipment Preparation.
8.1.1 Condensate Trap Cleaning. Before its initial use and after
each use, a condensate trap should be thoroughly cleaned and checked to
ensure that it is not contaminated. Both cleaning and checking can be
accomplished by installing the trap in the condensate recovery system
and treating it as if it were a sample. The trap should be heated as
described in Section 11.1.3. A trap may be considered clean when the
CO2 concentration in its effluent gas drops below 10 ppm.
This check is optional for traps that most recently have been used to
collect samples which were then recovered according to the procedure in
Section 11.1.3.
8.1.2 Sample Tank Evacuation and Leak-Check. Evacuate the sample
tank to 10 mm Hg absolute pressure or less. Then close the sample tank
valve, and allow the tank to sit for 60 minutes. The tank is acceptable
if a change in tank vacuum of less than 1 mm Hg is noted. The evacuation
and leak-check may be conducted either in the laboratory or the field.
8.1.3 Sampling Train Assembly. Just before assembly, measure the
tank vacuum using a mercury manometer. Record this vacuum, the ambient
temperature, and the barometric pressure at this time. Close the sample
tank valve and assemble the sampling system as shown in Figure 25-1.
Immerse the condensate trap body in dry ice at least 30 minutes before
commencing sampling to improve collection efficiency. The point where
the inlet tube joins the trap body should be 2.5 to 5 cm (1 to 2 in.)
above the top of the dry ice.
8.1.4 Pretest Leak-Check. A pretest leak-check is required.
Calculate or measure the approximate volume of the sampling train from
the probe tip to the sample tank valve. After assembling the sampling
train, plug the probe tip, and make certain that the sample tank valve
is closed. Turn on the vacuum pump, and evacuate the sampling system
from the probe tip to the sample tank valve to an absolute pressure of
10 mm Hg or less. Close the purge valve, turn off the pump, wait a
minimum period of 10 minutes, and recheck the indicated vacuum.
Calculate the maximum allowable pressure change based on a leak rate of
1 percent of the sampling rate using Equation 25-1, Section 12.2. If the
measured pressure change exceeds the allowable, correct the problem and
repeat the leak-check before beginning sampling.
8.2 Sample Collection.
8.2.1 Unplug the probe tip, and place the probe into the stack such
that the probe is perpendicular to the duct or stack axis; locate the
probe tip at a single preselected point of average velocity facing away
from the direction of gas flow. For stacks having

[[Page 505]]

a negative static pressure, seal the sample port sufficiently to prevent
air in-leakage around the probe. Set the probe temperature controller to
129 deg.C (265 deg.F) and the filter temperature controller to 121
deg.C (250 deg.F). Allow the probe and filter to heat for about 30
minutes before purging the sample train.
8.2.2 Close the sample valve, open the purge valve, and start the
vacuum pump. Set the flow rate between 60 and 100 cm³/min
(0.13 and 0.21 ft³/hr), and purge the train with stack gas
for at least 10 minutes.
8.2.3 When the temperatures at the exit ends of the probe and
filter are within the corresponding specified ranges, check the dry ice
level around the condensate trap, and add dry ice if necessary. Record
the clock time. To begin sampling, close the purge valve and stop the
pump. Open the sample valve and the sample tank valve. Using the flow
control valve, set the flow through the sample train to the proper rate.
Adjust the flow rate as necessary to maintain a constant rate
(10 percent) throughout the duration of the sampling period.
Record the sample tank vacuum and flowmeter setting at 5-minute
intervals. (See Figure 25-8.) Select a total sample time greater than or
equal to the minimum sampling time specified in the applicable subpart
of the regulations; end the sampling when this time period is reached or
when a constant flow rate can no longer be maintained because of reduced
sample tank vacuum.

Note: If sampling had to be stopped before obtaining the minimum
sampling time (specified in the applicable subpart) because a constant
flow rate could not be maintained, proceed as follows: After closing the
sample tank valve, remove the used sample tank from the sampling train
(without disconnecting other portions of the sampling train). Take
another evacuated and leak-checked sample tank, measure and record the
tank vacuum, and attach the new tank to the sampling train. After the
new tank is attached to the sample train, proceed with the sampling
until the required minimum sampling time has been exceeded.

8.3 Sample Recovery. After sampling is completed, close the flow
control valve, and record the final tank vacuum; then record the tank
temperature and barometric pressure. Close the sample tank valve, and
disconnect the sample tank from the sample system. Disconnect the
condensate trap at the inlet to the rate meter, and tightly seal both
ends of the condensate trap. Do not include the probe from the stack to
the filter as part of the condensate sample.
8.4 Sample Storage and Transport. Keep the trap packed in dry ice
until the samples are returned to the laboratory for analysis. Ensure
that run numbers are identified on the condensate trap and the sample
tank(s).

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.1.1........................ Initial Ensure acceptable
performance condensate recovery
check of efficiency.
condensate
recovery
apparatus.
10.1.2, 10.2.................. NMO analyzer Ensure precision of
initial and analytical results.
daily
performance
checks.
11.3.......................... Audit Sample Evaluate analytical
Analyses. technique and
instrument
calibration.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.

10.1 Initial Performance Checks.
10.1.1 Condensate Recovery Apparatus. Perform these tests before
the system is first placed in operation, after any shutdown of 6 months
or more, and after any major modification of the system, or at the
frequency recommended by the manufacturer.
10.1.1.1 Carrier Gas and Auxiliary O2 Blank Check.
Analyze each new tank of carrier gas or auxiliary O2 with the
NMO analyzer to check for contamination. Treat the gas cylinders as
noncondensible gas samples, and analyze according to the procedure in
Section 11.2.3. Add together any measured CH4, CO,
CO2, or NMO. The total concentration must be less than 5 ppm.
10.1.1.2 Oxidation Catalyst Efficiency Check.
10.1.1.2.1 With a clean condensate trap installed in the recovery
system or a \1/8\" stainless steel connector tube, replace the carrier
gas cylinder with the high level methane standard gas cylinder (Section
7.4.1). Set the four-port valve to the recovery position, and attach an
ICV to the recovery system. With the sample recovery valve in vent
position and the flow-control and ICV valves fully open, evacuate the
manometer or gauge, the connecting tubing, and the ICV to 10 mm Hg
absolute pressure. Close the flow-control and vacuum pump valves.
10.1.1.2.2 After the NDIR response has stabilized, switch the
sample recovery valve from vent to collect. When the manometer or
pressure gauge begins to register a slight positive pressure, open the
flow-control valve. Keep the flow adjusted such that the pressure in the
system is maintained within 10 percent of atmospheric pressure. Continue
collecting the sample in a normal manner

[[Page 506]]

until the ICV is filled to a nominal gauge pressure of 300 mm Hg. Close
the ICV valve, and remove the ICV from the system. Place the sample
recovery valve in the vent position, and return the recovery system to
its normal carrier gas and normal operating conditions. Analyze the ICV
for CO2 using the NMO analyzer; the catalyst efficiency is
acceptable if the CO2 concentration is within 2 percent of
the methane standard concentration.
10.1.1.3 System Performance Check. Construct a liquid sample
injection unit similar in design to the unit shown in Figure 25-7.
Insert this unit into the condensate recovery and conditioning system in
place of a condensate trap, and set the carrier gas and auxiliary
O2 flow rates to normal operating levels. Attach an evacuated
ICV to the system, and switch from system vent to collect. With the
carrier gas routed through the injection unit and the oxidation
catalyst, inject a liquid sample (see Sections 10.1.1.3.1 to 10.1.1.3.4)
into the injection port. Operate the trap recovery system as described
in Section 11.1.3. Measure the final ICV pressure, and then analyze the
vessel to determine the CO2 concentration. For each
injection, calculate the percent recovery according to Section 12.7.
Calculate the relative standard deviation for each set of triplicate
injections according to Section 12.8. The performance test is acceptable
if the average percent recovery is 100 5 percent and the
relative standard deviation is less than 2 percent for each set of
triplicate injections.
10.1.1.3.1 50 l hexane.
10.1.1.3.2 10 l hexane.
10.1.1.3.3 50 l decane.
10.1.1.3.4 10 l decane.
10.1.2 NMO Analyzer. Perform these tests before the system is first
placed in operation, after any shutdown longer than 6 months, and after
any major modification of the system.
10.1.2.1 Oxidation Catalyst Efficiency Check. Turn off or bypass
the NMO analyzer reduction catalyst. Make triplicate injections of the
high level methane standard (Section 7.4.1). The oxidation catalyst
operation is acceptable if the FID response is less than 1 percent of
the injected methane concentration.
10.1.2.2 Reduction Catalyst Efficiency Check. With the oxidation
catalyst unheated or bypassed and the heated reduction catalyst
bypassed, make triplicate injections of the high level methane standard
(Section 7.4.1). Repeat this procedure with both catalysts operative.
The reduction catalyst operation is acceptable if the responses under
both conditions agree within 5 percent of their average.
10.1.2.3 NMO Analyzer Linearity Check Calibration. While operating
both the oxidation and reduction catalysts, conduct a linearity check of
the analyzer using the propane standards specified in Section 7.4.2.
Make triplicate injections of each calibration gas. For each gas (i.e.,
each set of triplicate injections), calculate the average response
factor (area/ppm C) for each gas, as well as and the relative standard
deviation (according to Section 12.8). Then calculate the overall mean
of the response factor values. The instrument linearity is acceptable if
the average response factor of each calibration gas is within 2.5
percent of the overall mean value and if the relative standard deviation
gas is less than 2 percent of the overall mean value. Record the overall
mean of the propane response factor values as the NMO calibration
response factor (RFNMO). Repeat the linearity check using the
CO2 standards specified in Section 7.4.3. Make triplicate
injections of each gas, and then calculate the average response factor
(area/ppm C) for each gas, as well as the overall mean of the response
factor values. Record the overall mean of the response factor values as
the CO2 calibration response factor (RFCO2). The
RFCO2 must be within 10 percent of the RFNMO.
10.1.2.4 System Performance Check. Check the column separation and
overall performance of the analyzer by making triplicate injections of
the calibration gases listed in Section 7.4.4. The analyzer performance
is acceptable if the measured NMO value for each gas (average of
triplicate injections) is within 5 percent of the expected value.
10.2 NMO Analyzer Daily Calibration. The following calibration
procedures shall be performed before and immediately after the analysis
of each set of samples, or on a daily basis, whichever is more
stringent:
10.2.1 CO2 Response Factor. Inject triplicate samples of
the high level CO2 calibration gas (Section 7.4.3), and
calculate the average response factor. The system operation is adequate
if the calculated response factor is within 5 percent of the
RFCO2 calculated during the initial performance test (Section
10.1.2.3). Use the daily response factor (DRFCO2) for
analyzer calibration and the calculation of measured CO2
concentrations in the ICV samples.
10.2.2 NMO Response Factors. Inject triplicate samples of the mixed
propane calibration cylinder gas (Section 7.4.4.1), and calculate the
average NMO response factor. The system operation is adequate if the
calculated response factor is within 10 percent of the RFNMO
calculated during the initial performance test (Section 10.1.2.4). Use
the daily response factor (DRFNMO) for analyzer calibration
and calculation of NMO concentrations in the sample tanks.
10.3 Sample Tank and ICV Volume. The volume of the gas sampling
tanks used must be determined. Determine the tank and ICV volumes by
weighing them empty and then filled with deionized distilled water;
weigh to

[[Page 507]]

the nearest 5 g, and record the results. Alternatively, measure the
volume of water used to fill them to the nearest 5 ml.

11.0 Analytical Procedure

11.1 Condensate Recovery. See Figure 25-9. Set the carrier gas flow
rate, and heat the catalyst to its operating temperature to condition
the apparatus.
11.1.1 Daily Performance Checks. Each day before analyzing any
samples, perform the following tests:
11.1.1.1 Leak-Check. With the carrier gas inlets and the sample
recovery valve closed, install a clean condensate trap in the system,
and evacuate the system to 10 mm Hg absolute pressure or less. Monitor
the system pressure for 10 minutes. The system is acceptable if the
pressure change is less than 2 mm Hg.
11.1.1.2 System Background Test. Adjust the carrier gas and
auxiliary oxygen flow rate to their normal values of 100 cc/min and 150
cc/min, respectively, with the sample recovery valve in vent position.
Using a 10-ml syringe, withdraw a sample from the system effluent
through the syringe port. Inject this sample into the NMO analyzer, and
measure the CO2 content. The system background is acceptable
if the CO2 concentration is less than 10 ppm.
11.1.1.3 Oxidation Catalyst Efficiency Check. Conduct a catalyst
efficiency test as specified in Section 10.1.1.2. If the criterion of
this test cannot be met, make the necessary repairs to the system before
proceeding.
11.1.2 Condensate Trap CO2 Purge and Sample Tank
Pressurization.
11.1.2.1 After sampling is completed, the condensate trap will
contain condensed water and organics and a small volume of sampled gas.
This gas from the stack may contain a significant amount of
CO2 which must be removed from the condensate trap before the
sample is recovered. This is accomplished by purging the condensate trap
with zero air and collecting the purged gas in the original sample tank.
11.1.2.2 Begin with the sample tank and condensate trap from the
test run to be analyzed. Set the four-port valve of the condensate
recovery system in the CO2 purge position as shown in Figure
25-9. With the sample tank valve closed, attach the sample tank to the
sample recovery system. With the sample recovery valve in the vent
position and the flow control valve fully open, evacuate the manometer
or pressure gauge to the vacuum of the sample tank. Next, close the
vacuum pump valve, open the sample tank valve, and record the tank
pressure.
11.1.2.3 Attach the dry ice-cooled condensate trap to the recovery
system, and initiate the purge by switching the sample recovery valve
from vent to collect position. Adjust the flow control valve to maintain
atmospheric pressure in the recovery system. Continue the purge until
the CO2 concentration of the trap effluent is less than 5
ppm. CO2 concentration in the trap effluent should be
measured by extracting syringe samples from the recovery system and
analyzing the samples with the NMO analyzer. This procedure should be
used only after the NDIR response has reached a minimum level. Using a
10-ml syringe, extract a sample from the syringe port prior to the NDIR,
and inject this sample into the NMO analyzer.
11.1.2.4 After the completion of the CO2 purge, use the
carrier gas bypass valve to pressurize the sample tank to approximately
1,060 mm Hg absolute pressure with zero air.
11.1.3 Recovery of the Condensate Trap Sample (See Figure 25-10).
11.1.3.1 Attach the ICV to the sample recovery system. With the
sample recovery valve in a closed position, between vent and collect,
and the flow control and ICV valves fully open, evacuate the manometer
or gauge, the connecting tubing, and the ICV to 10 mm Hg absolute
pressure. Close the flow-control and vacuum pump valves.
11.1.3.2 Begin auxiliary oxygen flow to the oxidation catalyst at a
rate of 150 cc/min, then switch the four-way valve to the trap recovery
position and the sample recovery valve to collect position. The system
should now be set up to operate as indicated in Figure 25-10. After the
manometer or pressure gauge begins to register a slight positive
pressure, open the flow control valve. Adjust the flow-control valve to
maintain atmospheric pressure in the system within 10 percent.
11.1.3.3 Remove the condensate trap from the dry ice, and allow it
to warm to ambient temperature while monitoring the NDIR response. If,
after 5 minutes, the CO2 concentration of the catalyst
effluent is below 10,000 ppm, discontinue the auxiliary oxygen flow to
the oxidation catalyst. Begin heating the trap by placing it in a
furnace preheated to 200 deg.C (390 deg.F). Once heating has begun,
carefully monitor the NDIR response to ensure that the catalyst effluent
concentration does not exceed 50,000 ppm. Whenever the CO2
concentration exceeds 50,000 ppm, supply auxiliary oxygen to the
catalyst at the rate of 150 cc/min. Begin heating the tubing that
connected the heated sample box to the condensate trap only after the
CO2 concentration falls below 10,000 ppm. This tubing may be
heated in the same oven as the condensate trap or with an auxiliary heat
source such as a heat gun. Heating temperature must not exceed 200
deg.C (390 deg.F). If a heat gun is used, heat the tubing slowly along
its entire length from the upstream end to the downstream end, and
repeat the pattern for a total of three times. Continue the recovery
until the CO2 concentration drops to less

[[Page 508]]

than 10 ppm as determined by syringe injection as described under the
condensate trap CO2 purge procedure (Section 11.1.2).
11.1.3.4 After the sample recovery is completed, use the carrier
gas bypass valve to pressurize the ICV to approximately 1060 mm Hg
absolute pressure with zero air.
11.2 Analysis. Once the initial performance test of the NMO
analyzer has been successfully completed (see Section 10.1.2) and the
daily CO2 and NMO response factors have been determined (see
Section 10.2), proceed with sample analysis as follows:
11.2.1 Operating Conditions. The carrier gas flow rate is 29.5 cc/
min He and 2.2 cc/min O2. The column oven is heated to 85
deg.C (185 deg.F). The order of elution for the sample from the column
is CO, CH4, CO2, and NMO.
11.2.2 Analysis of Recovered Condensate Sample. Purge the sample
loop with sample, and then inject the sample. Under the specified
operating conditions, the CO2 in the sample will elute in
approximately 100 seconds. As soon as the detector response returns to
baseline following the CO2 peak, switch the carrier gas flow
to backflush, and raise the column oven temperature to 195 deg.C (380
deg.F) as rapidly as possible. A rate of 30 deg.C/min (90 deg.F) has
been shown to be adequate. Record the value obtained for the condensible
organic material (Ccm) measured as CO2 and any
measured NMO. Return the column oven temperature to 85 deg.C (185
deg.F) in preparation for the next analysis. Analyze each sample in
triplicate, and report the average Ccm.
11.2.3 Analysis of Sample Tank. Perform the analysis as described
in Section 11.2.2, but record only the value measured for NMO
(Ctm).
11.3 Audit Sample Analysis.
11.3.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, an audit sample, if
available, must be analyzed.
11.3.2 Concurrently analyze the audit sample and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.3.3 The same analyst, analytical reagents, and analytical system
must be used for the compliance samples and the audit sample. If this
condition is met, duplicate auditing of subsequent compliance analyses
for the same enforcement agency within a 30-day period is waived. An
audit sample set may not be used to validate different sets of
compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both enforcement
agencies.
11.4 Audit Sample Results.
11.4.1 Calculate the audit sample concentrations and submit results
using the instructions provided with the audit samples.
11.4.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.4.3 The concentrations of the audit samples obtained by the
analyst must agree within 20 percent of the actual concentration. If the
20-percent specification is not met, reanalyze the compliance and audit
samples, and include initial and reanalysis values in the test report.
11.4.4 Failure to meet the 20-percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to determine
the compliance or noncompliance status of the affected facility.

12.0 Data Analysis and Calculations

Carry out the calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figures after final
calculations. All equations are written using absolute pressure;
absolute pressures are determined by adding the measured barometric
pressure to the measured gauge or manometer pressure.
12.1 Nomenclature.

C = TGNMO concentration of the effluent, ppm C equivalent.
Cc = Calculated condensible organic (condensate trap)
concentration of the effluent, ppm C equivalent.
Ccm = Measured concentration (NMO analyzer) for the
condensate trap ICV, ppm CO2.
Ct = Calculated noncondensible organic concentration (sample
tank) of the effluent, ppm C equivalent.
Ctm = Measured concentration (NMO analyzer) for the sample
tank, ppm NMO.
F = Sampling flow rate, cc/min.
L = Volume of liquid injected, l.
M = Molecular weight of the liquid injected, g/g-mole.
Mc = TGNMO mass concentration of the effluent, mg C/dsm\3\.
N = Carbon number of the liquid compound injected (N = 12 for decane, N
= 6 for hexane).
n = Number of data points.
Pf = Final pressure of the intermediate collection vessel, mm
Hg absolute.
Pb = Barometric pressure, cm Hg.
Pti = Gas sample tank pressure before sampling, mm Hg
absolute.

[[Page 509]]

Pt = Gas sample tank pressure after sampling, but before
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm
Hg absolute.
q = Total number of analyzer injections of intermediate collection
vessel during analysis (where k = injection number, 1 * * *
q).
r = Total number of analyzer injections of sample tank during analysis
(where j = injection number, 1 * * * r).
r = Density of liquid injected, g/cc.
Tf = Final temperature of intermediate collection vessel,
deg.K.
Tti = Sample tank temperature before sampling, deg.K.
Tt = Sample tank temperature at completion of sampling,
deg.K.
Ttf = Sample tank temperature after pressurizing, deg.K.
V = Sample tank volume, m\3\.
Vt = Sample train volume, cc.
Vv = Intermediate collection vessel volume, m\3\.
Vs = Gas volume sampled, dsm\3\.
xi = Individual measurements.
x= Mean value.
P = Allowable pressure change, cm Hg.
= Leak-check period, min.

12.2 Allowable Pressure Change. For the pretest leak-check,
calculate the allowable pressure change using Equation 25-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.364

12.3 Sample Volume. For each test run, calculate the gas volume
sampled using Equation 25-2:
[GRAPHIC] [TIFF OMITTED] TR17OC00.365

12.4 Noncondensible Organics. For each sample tank, determine the
concentration of nonmethane organics (ppm C) using Equation 25-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.366

12.5 Condensible Organics. For each condensate trap determine the
concentration of organics (ppm C) using Equation 25-4:
[GRAPHIC] [TIFF OMITTED] TR17OC00.367

12.6 TGNMO Mass Concentration. Determine the TGNMO mass concentration
as carbon for each test run, using Equation 25-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.368

12.7 Percent Recovery. Calculate the percent recovery for the liquid
injections to the condensate recovery and conditioning system using
Equation 25-6:
[GRAPHIC] [TIFF OMITTED] TR17OC00.369

where K = 1.604 ( deg.K)(g-mole)(%)/(mm Hg)(ml)(m\3\)(ppm).
12.8 Relative Standard Deviation. Use Equation 25-7 to calculate the
relative standard deviation (RSD) of percent recovery and analyzer
linearity.
[GRAPHIC] [TIFF OMITTED] TR17OC00.370

[[Page 510]]

13.0 Method Performance

13.1 Range. The minimum detectable limit of the method has been
determined to be 50 parts per million by volume (ppm). No upper limit
has been established.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Salo, A.E., S. Witz, and R.D. MacPhee. Determination of Solvent Vapor
Concentrations by Total Combustion Analysis: A Comparison of Infrared
with Flame Ionization Detectors. Paper No. 75-33.2. (Presented at the
68th Annual Meeting of the Air Pollution Control Association. Boston,
MA. June 15-20, 1975.) 14 p.
2. Salo, A.E., W.L. Oaks, and R.D. MacPhee. Measuring the Organic Carbon
Content of Source Emissions for Air Pollution Control. Paper No. 74-190.
(Presented at the 67th Annual Meeting of the Air Pollution Control
Association. Denver, CO. June 9-13, 1974.) 25 p.

[[Page 511]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
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[[Page 520]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.380

Method 25A--Determination of Total Gaseous Organic Concentration Using a
Flame Ionization Analyzer

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total Organic Compounds........ N/A 2% of span.
------------------------------------------------------------------------

[[Page 521]]

1.2 Applicability. This method is applicable for the determination
of total gaseous organic concentration of vapors consisting primarily of
alkanes, alkenes, and/or arenes (aromatic hydrocarbons). The
concentration is expressed in terms of propane (or other appropriate
organic calibration gas) or in terms of carbon.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from the source through a heated
sample line and glass fiber filter to a flame ionization analyzer (FIA).
Results are reported as volume concentration equivalents of the
calibration gas or as carbon equivalents.

3.0 Definitions

3.1 Calibration drift means the difference in the measurement
system response to a mid-level calibration gas before and after a stated
period of operation during which no unscheduled maintenance, repair, or
adjustment took place.
3.2 Calibration error means the difference between the gas
concentration indicated by the measurement system and the know
concentration of the calibration gas.
3.3 Calibration gas means a known concentration of a gas in an
appropriate diluent gas.
3.4 Measurement system means the total equipment required for the
determination of the gas concentration. The system consists of the
following major subsystems:
3.4.1 Sample interface means that portion of a system used for one
or more of the following: sample acquisition, sample transportation,
sample conditioning, or protection of the analyzer(s) from the effects
of the stack effluent.
3.4.2 Organic analyzer means that portion of the measurement system
that senses the gas to be measured and generates an output proportional
to its concentration.
3.5 Response time means the time interval from a step change in
pollutant concentration at the inlet to the emission measurement system
to the time at which 95 percent of the corresponding final value is
reached as displayed on the recorder.
3.6 Span Value means the upper limit of a gas concentration
measurement range that is specified for affected source categories in
the applicable part of the regulations. The span value is established in
the applicable regulation and is usually 1.5 to 2.5 times the applicable
emission limit. If no span value is provided, use a span value
equivalent to 1.5 to 2.5 times the expected concentration. For
convenience, the span value should correspond to 100 percent of the
recorder scale.
3.7 Zero drift means the difference in the measurement system
response to a zero level calibration gas before or after a stated period
of operation during which no unscheduled maintenance, repair, or
adjustment took place.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Measurement System. Any measurement system for total organic
concentration that meets the specifications of this method. A schematic
of an acceptable measurement system is shown in Figure 25A-1. All
sampling components leading to the analyzer shall be heated
110 deg.C (220 deg.F) throughout the sampling period, unless safety
reasons are cited (Section 5.2) The essential components of the
measurement system are described below:
6.1.1 Organic Concentration Analyzer. A flame ionization analyzer
(FIA) capable of meeting or exceeding the specifications of this method.
The flame ionization detector block shall be heated >120 deg.C (250
deg.F).
6.1.2 Sample Probe. Stainless steel, or equivalent, three-hole rake
type. Sample holes shall be 4 mm (0.16-in.) in diameter or smaller and
located at 16.7, 50, and 83.3 percent of the equivalent stack diameter.
Alternatively, a single opening probe may be used so that a gas sample
is collected from the centrally located 10 percent area of the stack
cross-section.
6.1.3 Heated Sample Line. Stainless steel or Teflon'' tubing to
transport the sample gas to the analyzer. The sample line should be
heated (110 deg.C) to prevent any condensation.
6.1.4 Calibration Valve Assembly. A three-way valve assembly to
direct the zero and calibration gases to the analyzers is recommended.
Other methods, such as quick-connect lines, to route calibration gas to
the analyzers are applicable.
6.1.5 Particulate Filter. An in-stack or an out-of-stack glass
fiber filter is recommended if exhaust gas particulate loading

[[Page 522]]

is significant. An out-of-stack filter should be heated to prevent any
condensation.
6.1.6 Recorder. A strip-chart recorder, analog computer, or digital
recorder for recording measurement data. The minimum data recording
requirement is one measurement value per minute.

7.0 Reagents and Standards

7.1 Calibration Gases. The calibration gases for the gas analyzer
shall be propane in air or propane in nitrogen. Alternatively, organic
compounds other than propane can be used; the appropriate corrections
for response factor must be made. Calibration gases shall be prepared in
accordance with the procedure listed in Citation 2 of Section 16.
Additionally, the manufacturer of the cylinder should provide a
recommended shelf life for each calibration gas cylinder over which the
concentration does not change more than 2 percent from the
certified value. For calibration gas values not generally available
(i.e., organics between 1 and 10 percent by volume), alternative methods
for preparing calibration gas mixtures, such as dilution systems (Test
Method 205, 40 CFR Part 51, Appendix M), may be used with prior approval
of the Administrator.
7.1.1 Fuel. A 40 percent H2/60 percent N2 gas
mixture is recommended to avoid an oxygen synergism effect that
reportedly occurs when oxygen concentration varies significantly from a
mean value.
7.1.2 Zero Gas. High purity air with less than 0.1 part per million
by volume (ppmv) of organic material (propane or carbon equivalent) or
less than 0.1 percent of the span value, whichever is greater.
7.1.3 Low-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 25 to 35 percent of the applicable span
value.
7.1.4 Mid-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 45 to 55 percent of the applicable span
value.
7.1.5 High-level Calibration Gas. An organic calibration gas with a
concentration equivalent to 80 to 90 percent of the applicable span
value.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Selection of Sampling Site. The location of the sampling site
is generally specified by the applicable regulation or purpose of the
test (i.e., exhaust stack, inlet line, etc.). The sample port shall be
located to meet the testing requirements of Method 1.
8.2 Location of Sample Probe. Install the sample probe so that the
probe is centrally located in the stack, pipe, or duct and is sealed
tightly at the stack port connection.
8.3 Measurement System Preparation. Prior to the emission test,
assemble the measurement system by following the manufacturer's written
instructions for preparing sample interface and the organic analyzer.
Make the system operable (Section 10.1).
8.4 Calibration Error Test. Immediately prior to the test series
(within 2 hours of the start of the test), introduce zero gas and high-
level calibration gas at the calibration valve assembly. Adjust the
analyzer output to the appropriate levels, if necessary. Calculate the
predicted response for the low-level and mid-level gases based on a
linear response line between the zero and high-level response. Then
introduce low-level and mid-level calibration gases successively to the
measurement system. Record the analyzer responses for low-level and mid-
level calibration gases and determine the differences between the
measurement system responses and the predicted responses. These
differences must be less than 5 percent of the respective calibration
gas value. If not, the measurement system is not acceptable and must be
replaced or repaired prior to testing. No adjustments to the measurement
system shall be conducted after the calibration and before the drift
check (Section 8.6.2). If adjustments are necessary before the
completion of the test series, perform the drift checks prior to the
required adjustments and repeat the calibration following the
adjustments. If multiple electronic ranges are to be used, each
additional range must be checked with a mid-level calibration gas to
verify the multiplication factor.
8.5 Response Time Test. Introduce zero gas into the measurement
system at the calibration valve assembly. When the system output has
stabilized, switch quickly to the high-level calibration gas. Record the
time from the concentration change to the measurement system response
equivalent to 95 percent of the step change. Repeat the test three times
and average the results.
8.6 Emission Measurement Test Procedure.
8.6.1 Organic Measurement. Begin sampling at the start of the test
period, recording time and any required process information as
appropriate. In particulate, note on the recording chart, periods of
process interruption or cyclic operation.
8.6.2 Drift Determination. Immediately following the completion of
the test period and hourly during the test period, reintroduce the zero
and mid-level calibration gases, one at a time, to the measurement
system at the calibration valve assembly. (Make no adjustments to the
measurement system until both the zero and calibration drift checks are
made.) Record the analyzer response. If the drift values exceed the
specified limits, invalidate the test results preceding the check and
repeat the test following corrections to the measurement system.
Alternatively, recalibrate the test measurement system as in Section 8.4
and

[[Page 523]]

report the results using both sets of calibration data (i.e., data
determined prior to the test period and data determined following the
test period).

Note: Note on the recording chart periods of process interruption or
cyclic operation.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Method section measure Effect
------------------------------------------------------------------------
8.4........................... Zero and Ensures that bias
calibration introduced by drift
drift tests. in the measurement
system output during
the run is no
greater than 3
percent of span.
------------------------------------------------------------------------

10.0 Calibration and Standardization

10.1 FIA equipment can be calibrated for almost any range of total
organic concentrations. For high concentrations of organics (> 1.0
percent by volume as propane), modifications to most commonly available
analyzers are necessary. One accepted method of equipment modification
is to decrease the size of the sample to the analyzer through the use of
a smaller diameter sample capillary. Direct and continuous measurement
of organic concentration is a necessary consideration when determining
any modification design.

11.0 Analytical Procedure

The sample collection and analysis are concurrent for this method
(see Section 8.0).

12.0 Calculations and Data Analysis

12.1 Determine the average organic concentration in terms of ppmv
as propane or other calibration gas. The average shall be determined by
integration of the output recording over the period specified in the
applicable regulation. If results are required in terms of ppmv as
carbon, adjust measured concentrations using Equation 25A-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.381

Where:
Cc = Organic concentration as carbon, ppmv.
Cmeas = Organic concentration as measured, ppmv.
K = Carbon equivalent correction factor.
= 2 for ethane.
= 3 for propane.
= 4 for butane.
= Appropriate response factor for other organic calibration gases.

13.0 Method Performance

13.1 Measurement System Performance Specifications.
13.1.1 Zero Drift. Less than 3 percent of the span
value.
13.1.2 Calibration Drift. Less than 3 percent of span
value.
13.1.3 Calibration Error. Less than 5 percent of the
calibration gas value.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Measurement of Volatile Organic Compounds--Guideline Series. U.S.
Environmental Protection Agency. Research Triangle Park, NC. Publication
No. EPA-450/2-78-041. June 1978. p. 46-54.
2. EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards. U.S. Environmental Protection Agency, Quality
Assurance and Technical Support Division. Research Triangle Park, N.C.
September 1993.
3. Gasoline Vapor Emission Laboratory Evaluation--Part 2. U.S.
Environmental Protection Agency, Office of Air Quality Planning and
Standards. Research Triangle Park, NC. EMB Report No. 75-GAS-6. August
1975.

[[Page 524]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.382

Method 25B--Determination of Total Gaseous Organic Concentration Using a
Nondispersive Infrared Analyzer

[[Page 525]]

edge of at least the following additional test methods: Method 1, Method
6C, and Method 25A.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No. Sensitivity
------------------------------------------------------------------------
Total Organic Compounds........... N/A 2% of span.
------------------------------------------------------------------------

1.2 Applicability. This method is applicable for the determination
of total gaseous organic concentration of vapors consisting primarily of
alkanes. Other organic materials may be measured using the general
procedure in this method, the appropriate calibration gas, and an
analyzer set to the appropriate absorption band.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

A gas sample is extracted from the source through a heated sample
line, if necessary, and glass fiber filter to a nondispersive infrared
analyzer (NDIR). Results are reported as volume concentration
equivalents of the calibration gas or as carbon equivalents.

3.0 Definitions

Same as Method 25A, Section 3.0.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Method 25A, Section 6.0, with the exception of the
following:
6.1 Organic Concentration Analyzer. A nondispersive infrared
analyzer designed to measure alkane organics and capable of meeting or
exceeding the specifications in this method.

7.0 Reagents and Standards

Same as Method 25A, Section 7.1. No fuel gas is required for an
NDIR.

8.0 Sample Collection, Preservation, Storage, and Transport

Same as Method 25A, Section 8.0.

9.0 Quality Control

Same as Method 25A, Section 9.0.

10.0 Calibration and Standardization

Same as Method 25A, Section 10.0.

11.0 Analytical Procedure

The sample collection and analysis are concurrent for this method
(see Section 8.0).

12.0 Calculations and Data Analysis

Same as Method 25A, Section 12.0.

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as Method 25A, Section 16.0.

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 25C--Determination of Nonmethane Organic Compounds (NMOC) in
Landfill Gases

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Nonmethane organic compounds (NMOC)....... No CAS number assigned.
------------------------------------------------------------------------

[[Page 526]]

1.2 Applicability. This method is applicable to the sampling and
measurement of NMOC as carbon in landfill gases (LFG).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A sample probe that has been perforated at one end is driven or
augured to a depth of 0.9 m (3 ft) below the bottom of the landfill
cover. A sample of the landfill gas is extracted with an evacuated
cylinder. The NMOC content of the gas is determined by injecting a
portion of the gas into a gas chromatographic column to separate the
NMOC from carbon monoxide (CO), carbon dioxide (CO2), and
methane (CH4); the NMOC are oxidized to CO2,
reduced to CH4, and measured by a flame ionization detector
(FID). In this manner, the variable response of the FID associated with
different types of organics is eliminated.

3.0 Definitions. [Reserved]

4.0 Interferences. [Reserved]

5.0 Safety

5.1 Since this method is complex, only experienced personnel should
perform this test. LFG contains methane, therefore explosive mixtures
may exist on or near the landfill. It is advisable to take appropriate
safety precautions when testing landfills, such as refraining from
smoking and installing explosion-proof equipment.

6.0 Equipment and Supplies

6.1 Sample Probe. Stainless steel, with the bottom third
perforated. The sample probe must be capped at the bottom and must have
a threaded cap with a sampling attachment at the top. The sample probe
must be long enough to go through and extend no less than 0.9 m (3 ft)
below the landfill cover. If the sample probe is to be driven into the
landfill, the bottom cap should be designed to facilitate driving the
probe into the landfill.
6.2 Sampling Train.
6.2.1 Rotameter with Flow Control Valve. Capable of measuring a
sample flow rate of 100 10 ml/min. The control valve must
be made of stainless steel.
6.2.2 Sampling Valve. Stainless steel.
6.2.3 Pressure Gauge. U-tube mercury manometer, or equivalent,
capable of measuring pressure to within 1 mm Hg (0.5 in H2O)
in the range of 0 to 1,100 mm Hg (0 to 590 in H2O).
6.2.4 Sample Tank. Stainless steel or aluminum cylinder, equipped
with a stainless steel sample tank valve.
6.3 Vacuum Pump. Capable of evacuating to an absolute pressure of
10 mm Hg (5.4 in H2O).
6.4 Purging Pump. Portable, explosion proof, and suitable for
sampling NMOC.
6.5 Pilot Probe Procedure. The following are needed only if the
tester chooses to use the procedure described in Section 8.2.1.
6.5.1 Pilot Probe. Tubing of sufficient strength to withstand being
driven into the landfill by a post driver and an outside diameter of at
least 6 mm (0.25 in.) smaller than the sample probe. The pilot probe
shall be capped on both ends and long enough to go through the landfill
cover and extend no less than 0.9 m (3 ft) into the landfill.
6.5.2 Post Driver and Compressor. Capable of driving the pilot
probe and the sampling probe into the landfill. The Kitty Hawk portable
post driver has been found to be acceptable.
6.6 Auger Procedure. The following are needed only if the tester
chooses to use the procedure described in Section 8.2.2.
6.6.1 Auger. Capable of drilling through the landfill cover and to
a depth of no less than 0.9 m (3 ft) into the landfill.
6.6.2 Pea Gravel.
6.6.3 Bentonite.
6.7 NMOC Analyzer, Barometer, Thermometer, and Syringes. Same as in
Sections 6.3.1, 6.3.2, 6.33, and 6.2.10, respectively, of Method 25.

7.0 Reagents and Standards

7.1 NMOC Analysis. Same as in Method 25, Section 7.2.
7.2 Calibration. Same as in Method 25, Section 7.4, except omit
Section 7.4.3.
7.3 Quality Assurance Audit Samples.
7.3.1 It is recommended, but not required, that a performance audit
sample be analyzed in conjunction with the field samples. The audit
sample should be in a suitable sample matrix at a concentration similar
to the actual field samples.
7.3.2 When making compliance determinations, and upon availability,
audit samples may be obtained from the appropriate EPA Regional Office
or from the responsible enforcement authority and analyzed in
conjunction with the field samples.

Note: The responsible enforcement authority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sample Tank Evacuation and Leak-Check. Conduct the sample tank
evacuation and leak-check either in the laboratory or the field. Connect
the pressure gauge and sampling valve to the sample tank. Evacuate the
sample tank to 10 mm Hg (5.4 in H2O) absolute pressure or
less. Close the sampling

[[Page 527]]

valve, and allow the tank to sit for 30 minutes. The tank is acceptable
if no change more than 2 mm is noted. Include the results
of the leak-check in the test report.
8.2 Sample Probe Installation. The tester may use the procedure in
Section 8.2.1 or 8.2.2.
8.2.1 Pilot Probe Procedure. Use the post driver to drive the pilot
probe at least 0.9 m (3 ft) below the landfill cover. Alternative
procedures to drive the probe into the landfill may be used subject to
the approval of the Administrator's designated representative.
8.2.1.1 Remove the pilot probe and drive the sample probe into the
hole left by the pilot probe. The sample probe shall extend at least 0.9
m (3 ft) below the landfill cover and shall protrude about 0.3 m (1 ft)
above the landfill cover. Seal around the sampling probe with bentonite
and cap the sampling probe with the sampling probe cap.
8.2.2 Auger Procedure. Use an auger to drill a hole to at least 0.9
m (3 ft) below the landfill cover. Place the sample probe in the hole
and backfill with pea gravel to a level 0.6 m (2 ft) from the surface.
The sample probe shall protrude at least 0.3 m (1 ft) above the landfill
cover. Seal the remaining area around the probe with bentonite. Allow 24
hours for the landfill gases to equilibrate inside the augured probe
before sampling.
8.3 Sample Train Assembly. Just before assembling the sample train,
measure the sample tank vacuum using the pressure gauge. Record the
vacuum, the ambient temperature, and the barometric pressure at this
time. Assemble the sampling probe purging system as shown in Figure 25C-
1.
8.4 Sampling Procedure. Open the sampling valve and use the purge
pump and the flow control valve to evacuate at least two sample probe
volumes from the system at a flow rate of 500 ml/min or less. Close the
sampling valve and replace the purge pump with the sample tank apparatus
as shown in Figure 25C-2. Open the sampling valve and the sample tank
valve and, using the flow control valve, sample at a flow rate of 500
ml/min or less until either a constant flow rate can no longer be
maintained because of reduced sample tank vacuum or the appropriate
composite volume is attained. Disconnect the sampling tank apparatus and
pressurize the sample cylinder to approximately 1,060 mm Hg (567 in.
H2O) absolute pressure with helium, and record the final
pressure. Alternatively, the sample tank may be pressurized in the lab.
8.4.1 The following restrictions apply to compositing samples from
different probe sites into a single cylinder: (1) Individual composite
samples per cylinder must be of equal volume; this must be verified by
recording the flow rate, sampling time, vacuum readings, or other
appropriate volume measuring data, (2) individual composite samples must
have a minimum volume of 1 liter unless data is provided showing smaller
volumes can be accurately measured, and (3) composite samples must not
be collected using the final cylinder vacuum as it diminishes to ambient
pressure.
8.4.2 Use Method 3C to determine the percent N2 in each
cylinder. The presence of N2 indicates either infiltration of
ambient air into the landfill gas sample or an inappropriate testing
site has been chosen where anaerobic decomposition has not begun. The
landfill gas sample is acceptable if the concentration of N2
is less than 20 percent. Alternatively, Method 3C may be used to
determine the oxygen content of each cylinder as an air infiltration
test. With this option, the oxygen content of each cylinder must be less
than 5 percent.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.

10.1 Initial NMOC Analyzer Performance Test. Same as in Method 25,
Section 10.1, except omit the linearity checks for CO2
standards.
10.2 NMOC Analyzer Daily Calibration.
10.2.1 NMOC Response Factors. Same as in Method 25, Section 10.2.2.
10.3 Sample Tank Volume. The volume of the gas sampling tanks must
be determined. Determine the tank volumes by weighing them empty and
then filled with deionized water; weigh to the nearest 5 g, and record

[[Page 528]]

the results. Alternatively, measure the volume of water used to fill
them to the nearest 5 ml.

11.0 Analytical Procedures

11.1 The oxidation, reduction, and measurement of NMOC's is similar
to Method 25. Before putting the NMOC analyzer into routine operation,
conduct an initial performance test. Start the analyzer, and perform all
the necessary functions in order to put the analyzer into proper working
order. Conduct the performance test according to the procedures
established in Section 10.1. Once the performance test has been
successfully completed and the NMOC calibration response factor has been
determined, proceed with sample analysis as follows:
11.1.1 Daily Operations and Calibration Checks. Before and
immediately after the analysis of each set of samples or on a daily
basis (whichever occurs first), conduct a calibration test according to
the procedures established in Section 10.2. If the criteria of the daily
calibration test cannot be met, repeat the NMOC analyzer performance
test (Section 10.1) before proceeding.
11.1.2 Operating Conditions. Same as in Method 25, Section 11.2.1.
11.1.3 Analysis of Sample Tank. Purge the sample loop with sample,
and then inject the sample. Under the specified operating conditions,
the CO2 in the sample will elute in approximately 100
seconds. As soon as the detector response returns to baseline following
the CO2 peak, switch the carrier gas flow to backflush, and
raise the column oven temperature to 195 deg.C (383 deg.F) as rapidly
as possible. A rate of 30 deg.C/min (54 deg.F/min) has been shown to
be adequate. Record the value obtained for any measured NMOC. Return the
column oven temperature to 85 deg.C (185 deg.F) in preparation for the
next analysis. Analyze each sample in triplicate, and report the average
as Ctm.
11.2 Audit Sample Analysis. When the method is used to analyze
samples to demonstrate compliance with a source emission regulation, an
audit sample, if available, must be analyzed.
11.2.1 Concurrently analyze the audit sample and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.2.2 The same analyst, analytical reagents, and analytical system
must be used for the compliance samples and the audit sample. If this
condition is met, duplicate auditing of subsequent compliance analyses
for the same enforcement agency within a 30-day period is waived. An
audit sample set may not be used to validate different sets of
compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both enforcement
agencies.
11.3 Audit Sample Results.
11.3.1 Calculate the audit sample concentrations and submit results
using the instructions provided with the audit samples.
11.3.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.3.3 The concentrations of the audit samples obtained by the
analyst must agree within 20 percent of the actual concentration. If the
20-percent specification is not met, reanalyze the compliance and audit
samples, and include initial and reanalysis values in the test report.
11.3.4 Failure to meet the 20-percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to determine
the compliance or noncompliance status of the affected facility.

12.0 Data Analysis and Calculations

Note: All equations are written using absolute pressure; absolute
pressures are determined by adding the measured barometric pressure to
the measured gauge or manometer pressure.

12.1 Nomenclature.

Bw = Moisture content in the sample, fraction.
CN2 = Measured N2 concentration, fraction.
Ct = Calculated NMOC concentration, ppmv C equivalent.
Ctm = Measured NMOC concentration, ppmv C equivalent.
Pb = Barometric pressure, mm Hg.
Pt = Gas sample tank pressure after sampling, but before
pressurizing, mm Hg absolute.
Ptf = Final gas sample tank pressure after pressurizing, mm
Hg absolute.
Pti = Gas sample tank pressure after evacuation, mm Hg
absolute.
Pw = Vapor pressure of H2O (from Table 25C-1), mm
Hg.
r = Total number of analyzer injections of sample tank during analysis
(where j = injection number, 1 * * * r).
Tt = Sample tank temperature at completion of sampling,
deg.K.
Tti = Sample tank temperature before sampling, deg.K.
Ttf = Sample tank temperature after pressurizing, deg.K.

[[Page 529]]

12.2 Water Correction. Use Table 25C-1 (Section 17.0), the LFG
temperature, and barometric pressure at the sampling site to calculate
Bw.
[GRAPHIC] [TIFF OMITTED] TR17OC00.383

12.3 NMOC Concentration. Use the following equation to calculate
the concentration of NMOC for each sample tank.
[GRAPHIC] [TIFF OMITTED] TR17OC00.384

13.0 Method Performance [Reserved]

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Salo, Albert E., Samuel Witz, and Robert D. MacPhee.
Determination of Solvent Vapor Concentrations by Total Combustion
Analysis: A Comparison of Infrared with Flame Ionization Detectors.
Paper No. 75-33.2. (Presented at the 68th Annual Meeting of the Air
Pollution Control Association. Boston, Massachusetts. June 15-20, 1975.)
14 p.
2. Salo, Albert E., William L. Oaks, and Robert D. MacPhee.
Measuring the Organic Carbon Content of Source Emissions for Air
Pollution Control. Paper No. 74-190. (Presented at the 67th Annual
Meeting of the Air Pollution Control Association. Denver, Colorado. June
9-13, 1974.) 25 p.

[[Page 530]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.385

Table 25C-1.--Moisture Correction
------------------------------------------------------------------------
Vapor Vapor
Pressure Temperature, Pressure
Temperature, deg.C of H2O, deg.C of H2O,
mm Hg mm Hg
------------------------------------------------------------------------
4................................... 6.1 18 15.5
6................................... 7.0 20 17.5
8................................... 8.0 22 19.8
10.................................. 9.2 24 22.4
12.................................. 10.5 26 25.2
14.................................. 12.0 28 28.3

[[Page 531]]

16.................................. 13.6 30 31.8
------------------------------------------------------------------------

Method 25D--Determination of the Volatile Organic Concentration of Waste
Samples

Note: Performance of this method should not be attempted by persons
unfamiliar with the operation of a flame ionization detector (FID) or an
electrolytic conductivity detector (ELCD) because knowledge beyond the
scope of this presentation is required.

1.0 Scope and Application

1.1 Analyte. Volatile Organic Compounds. No CAS No. assigned.
1.2 Applicability. This method is applicable for determining the
volatile organic (VO) concentration of a waste sample.

2.0 Summary of Method

2.1 Principle. A sample of waste is obtained at a point which is
most representative of the unexposed waste (where the waste has had
minimum opportunity to volatilize to the atmosphere). The sample is
suspended in an organic/aqueous matrix, then heated and purged with
nitrogen for 30 min. in order to separate certain organic compounds.
Part of the sample is analyzed for carbon concentration, as methane,
with an FID, and part of the sample is analyzed for chlorine
concentration, as chloride, with an ELCD. The VO concentration is the
sum of the carbon and chlorine content of the sample.

3.0 Definitions

3.1 Well-mixed in the context of this method refers to turbulent
flow which results in multiple-phase waste in effect behaving as single-
phase waste due to good mixing.

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The following equipment is required:
6.1.1 Sampling Tube. Flexible Teflon, 0.25 in. ID (6.35 mm).
6.1.2 Sample Container. Borosilicate glass, 40-mL, and a Teflon-
lined screw cap capable of forming an air tight seal.
6.1.3 Cooling Coil. Fabricated from 0.25 in (6.35 mm). ID 304
stainless steel tubing with a thermocouple at the coil outlet.
6.2 Analysis. The following equipment is required.
6.2.1 Purging Apparatus. For separating the VO from the waste
sample. A schematic of the system is shown in Figure 25D-1. The purging
apparatus consists of the following major components.
6.2.1.1 Purging Flask. A glass container to hold the sample while
it is heated and purged with dry nitrogen. The cap of the purging flask
is equipped with three fittings: one for a purging lance (fitting with
the 7 Ace-thread), one for the Teflon exit tubing (side fitting, also a
7 Ace-thread), and a third (a 50-mm Ace-thread) to attach the base of
the purging flask as shown in Figure 25D-2. The base of the purging
flask is a 50-mm ID (2 in) cylindrical glass tube. One end of the tube
is open while the other end is sealed. Exact dimensions are shown in
Figure 25D-2.
6.2.1.2 Purging Lance. Glass tube, 6-mm OD (0.2 in) by 30 cm (12
in) long. The purging end of the tube is fitted with a four-arm bubbler
with each tip drawn to an opening 1 mm (0.04 in) in diameter. Details
and exact dimensions are shown in Figure 25D-2.
6.2.1.3 Coalescing Filter. Porous fritted disc incorporated into a
container with the same dimensions as the purging flask. The details of
the design are shown in Figure 25D-3.
6.2.1.4 Constant Temperature Chamber. A forced draft oven capable
of maintaining a uniform temperature around the purging flask and
coalescing filter of 75 2 deg.C (167 3.6
deg.F).
6.2.1.5 Three-way Valve. Manually operated, stainless steel. To
introduce calibration gas into system.
6.2.1.6 Flow Controllers. Two, adjustable. One capable of
maintaining a purge gas flow rate of 6 0.06 L/min (0.2
0.002 ft³/min) The other capable of maintaining
a calibration gas flow rate of 1-100 mL/min (0.00004-0.004
ft³/min).
6.2.1.7 Rotameter. For monitoring the air flow through the purging
system (0-10 L/min)(0-0.4 ft³/min).
6.2.1.8 Sample Splitters. Two heated flow restrictors (placed
inside oven or heated to 120 10 deg.C (248 18
deg.F) ). At a purge rate of 6 L/min (0.2 ft³/min), one will
supply a constant flow to the first detector (the rest of the flow will
be directed to the second sample splitter). The second splitter will
split

[[Page 532]]

the analytical flow between the second detector and the flow restrictor.
The approximate flow to the FID will be 40 mL/min (0.0014
ft³/min) and to the ELCD will be 15 mL/min (0.0005
ft³/min), but the exact flow must be adjusted to be
compatible with the individual detector and to meet its linearity
requirement. The two sample splitters will be connected to each other by
1/8' OD (3.175 mm) stainless steel tubing.
6.2.1.9 Flow Restrictor. Stainless steel tubing, 1/8' OD (3.175
mm), connecting the second sample splitter to the ice bath. Length is
determined by the resulting pressure in the purging flask (as measured
by the pressure gauge). The resulting pressure from the use of the flow
restrictor shall be 6-7 psig.
6.2.1.10 Filter Flask. With one-hole stopper. Used to hold ice
bath. Excess purge gas is vented through the flask to prevent
condensation in the flowmeter and to trap volatile organic compounds.
6.2.1.11 Four-way Valve. Manually operated, stainless steel. Placed
inside oven, used to bypass purging flask.
6.2.1.12 On/Off Valves. Two, stainless steel. One heat resistant up
to 130 deg.C (266 deg.F) and placed between oven and ELCD. The other a
toggle valve used to control purge gas flow.
6.2.1.13 Pressure Gauge. Range 0-40 psi. To monitor pressure in
purging flask and coalescing filter.
6.2.1.14 Sample Lines. Teflon, 1/4' OD (6.35 mm), used inside the
oven to carry purge gas to and from purging chamber and to and from
coalescing filter to four-way valve. Also used to carry sample from
four-way valve to first sample splitter.
6.2.1.15 Detector Tubing. Stainless steel, 1/8' OD (3.175 mm),
heated to 120 10 deg.C (248 18 deg.F) . Used
to carry sample gas from each sample splitter to a detector. Each piece
of tubing must be wrapped with heat tape and insulating tape in order to
insure that no cold spots exist. The tubing leading to the ELCD will
also contain a heat-resistant on-off valve (Section 6.2.1.12) which
shall also be wrapped with heat-tape and insulation.
6.2.2 Volatile Organic Measurement System. Consisting of an FID to
measure the carbon concentration of the sample and an ELCD to measure
the chlorine concentration.
6.2.2.1 FID. A heated FID meeting the following specifications is
required.
6.2.2.1.1 Linearity. A linear response ( 5 percent)
over the operating range as demonstrated by the procedures established
in Section 10.1.1.
6.2.2.1.2 Range. A full scale range of 50 pg carbon/sec to 50
g carbon/sec. Signal attenuators shall be available to produce
a minimum signal response of 10 percent of full scale.
6.2.2.1.3 Data Recording System. A digital integration system
compatible with the FID for permanently recording the output of the
detector. The recorder shall have the capability to start and stop
integration at points selected by the operator or it shall be capable of
the ``integration by slices'' technique (this technique involves
breaking down the chromatogram into smaller increments, integrating the
area under the curve for each portion, subtracting the background for
each portion, and then adding all of the areas together for the final
area count).
6.2.2.2 ELCD. An ELCD meeting the following specifications is
required. 1-propanol must be used as the electrolyte. The electrolyte
flow through the conductivity cell shall be 1 to 2 mL/min (0.00004 to
0.00007 ft\3\/min).
Note: A \1/4\-in. ID (6.35 mm) quartz reactor tube is strongly
recommended to reduce carbon buildup and the resulting detector
maintenance.
6.2.2.2.1 Linearity. A linear response ( 10 percent)
over the response range as demonstrated by the procedures in Section
10.1.2.
6.2.2.2.2 Range. A full scale range of 5.0 pg/sec to 500 ng/sec
chloride. Signal attenuators shall be available to produce a minimum
signal response of 10 percent of full scale.
6.2.2.2.3 Data Recording System. A digital integration system
compatible with the output voltage range of the ELCD. The recorder must
have the capability to start and stop integration at points selected by
the operator or it shall be capable of performing the ``integration by
slices'' technique.

7.0 Reagents and Standards

7.1 Sampling.
7.1.1 Polyethylene Glycol (PEG). Ninety-eight percent pure with an
average molecular weight of 400. Before using the PEG, remove any
organic compounds that might be detected as volatile organics by heating
it to 120 deg.C (248 deg.F) and purging it with nitrogen at a flow
rate of 1 to 2 L/min (0.04 to 0.07 ft\3\/min) for 2 hours. The cleaned
PEG must be stored under a 1 to 2 L/min (0.04 to 0.07 ft\3\/min)
nitrogen purge until use. The purge apparatus is shown in Figure 25D-4.
7.2 Analysis.
7.2.1 Sample Separation. The following are required for the sample
purging step.
7.2.1.1 PEG. Same as Section 7.1.1.
7.2.1.2 Purge Gas. Zero grade nitrogen (N2), containing
less than 1 ppm carbon.
7.2.2 Volatile Organics Measurement. The following are required for
measuring the VO concentration.
7.2.2.1 Hydrogen (H2). Zero grade H2, 99.999
percent pure.
7.2.2.2 Combustion Gas. Zero grade air or oxygen as required by the
FID.
7.2.2.3 Calibration Gas. Pressurized gas cylinder containing 10
percent propane and 1 percent 1,1-dichloroethylene by volume in
nitrogen.

[[Page 533]]

7.2.2.4 Water. Deionized distilled water that conforms to American
Society for Testing and Materials Specification D 1193-74, Type 3, is
required for analysis. At the option of the analyst, the
KMnO4 test for oxidizable organic matter may be omitted when
high concentrations are not expected to be present.
7.2.2.5 1-Propanol. ACS grade or better. Electrolyte Solution. For
use in the ELCD.
7.3 Quality Assurance Audit Samples.
7.3.1 It is recommended, but not required, that a performance audit
sample be analyzed in conjunction with the field samples. The audit
sample should be in a suitable sample matrix at a concentration similar
to the actual field samples.
7.3.2 When making compliance determinations, and upon availability,
audit samples may be obtained from the appropriate EPA regional Office
or from the responsible enforcement authority and analyzed in
conjunction with the field samples.

Note: The responsible enforcement authority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Sampling.
8.1.1 Sampling Plan Design and Development. Use the procedures in
chapter nine of Reference 1 in Section 16 as guidance in developing a
sampling plan.
8.1.2 Single Phase or Well-mixed Waste.
8.1.2.1 Install a sampling tap to obtain the sample at a point
which is most representative of the unexposed waste (where the waste has
had minimum opportunity to volatilize to the atmosphere). Assemble the
sampling apparatus as shown in Figure 25D-5.
8.1.2.2 Prepare the sampling containers as follows: Pour 30 mL of
clean PEG into the container. PEG will reduce but not eliminate the loss
of organics during sample collection. Weigh the sample container with
the screw cap, the PEG, and any labels to the nearest 0.01 g and record
the weight (mst). Store the containers in an ice bath until 1
hour before sampling (PEG will solidify at ice bath temperatures; allow
the containers to reach room temperature before sampling).
8.1.2.3 Begin sampling by purging the sample lines and cooling coil
with at least four volumes of waste. Collect the purged material in a
separate container and dispose of it properly.
8.1.2.4 After purging, stop the sample flow and direct the sampling
tube to a preweighed sample container, prepared as described in Section
8.1.2.2. Keep the tip of the tube below the surface of the PEG during
sampling to minimize contact with the atmosphere. Sample at a flow rate
such that the temperature of the waste is less than 10 deg.C (50
deg.F). Fill the sample container and immediately cap it (within 5
seconds) so that a minimum headspace exists in the container. Store
immediately in a cooler and cover with ice.
8.1.3 Multiple-phase Waste. Collect a 10 g sample of each phase of
waste generated using the procedures described in Section 8.1.2 or
8.1.5. Each phase of the waste shall be analyzed as a separate sample.
Calculate the weighted average VO concentration of the waste using
Equation 25D-13 (Section 12.14).
8.1.4 Solid waste. Add approximately 10 g of the solid waste to a
container prepared in the manner described in Section 8.1.2.2,
minimizing headspace. Cap and chill immediately.
8.1.5 Alternative to Tap Installation. If tap installation is
impractical or impossible, fill a large, clean, empty container by
submerging the container into the waste below the surface of the waste.
Immediately fill a container prepared in the manner described in Section
8.1.2.2 with approximately 10 g of the waste collected in the large
container. Minimize headspace, cap and chill immediately.
8.1.6 Alternative sampling techniques may be used upon the approval
of the Administrator.
8.2 Sample Recovery.
8.2.1 Assemble the purging apparatus as shown in Figures 25D-1 and
25D-2. The oven shall be heated to 75 2 deg.C (167
3.6 deg.F). The sampling lines leading from the oven to
the detectors shall be heated to 120 10 deg.C (248
18 deg.F) with no cold spots. The flame ionization
detector shall be operated with a heated block. Adjust the purging lance
so that it reaches the bottom of the chamber.
8.2.2 Remove the sample container from the cooler, and wipe the
exterior of the container to remove any extraneous ice, water, or other
debris. Reweigh the sample container to the nearest 0.01 g, and record
the weight (msf). Pour the contents of the sample container
into the purging flask, rinse the sample container three times with a
total of 20 mL of PEG (since the sample container originally held 30 mL
of PEG, the total volume of PEG added to the purging flask will be 50
mL), transferring the rinsings to the purging flask after each rinse.
Cap purging flask between rinses. The total volume of PEG in the purging
flask shall be 50 mL. Add 50 mL of water to the purging flask.

9.0 Quality Control

9.1 Quality Control Samples. If audit samples are not available,
prepare and analyze the two types of quality control samples (QCS)
listed in Sections 9.4.1 and 9.4.2. Before placing the system in
operation, after a shutdown of greater than six months, and after any
major modifications, analyze each QCS in triplicate. For each detector,
calculate the percent recovery by dividing

[[Page 534]]

measured concentration by theoretical concentration and multiplying by
100. Determine the mean percent recovery for each detector for each QCS
triplicate analysis. The RSD for any triplicate analysis shall be
10 percent. For QCS 1 (methylene chloride), the percent
recovery shall be 90 percent for carbon as methane, and
55 percent for chlorine as chloride. For QCS 2 (1,3-dichloro-
2-propanol), the percent recovery shall be 15 percent for
carbon as methane, and 6 percent for chlorine as chloride. If
the analytical system does not meet the above-mentioned criteria for
both detectors, check the system parameters (temperature, system
pressure, purge rate, etc.), correct the problem, and repeat the
triplicate analysis of each QCS.
9.1.1 QCS 1, Methylene Chloride. Prepare a stock solution by
weighing, to the nearest 0.1 mg, 55 L of HPLC grade methylene
chloride in a tared 5 mL volumetric flask. Record the weight in
milligrams, dilute to 5 mL with cleaned PEG, and inject 100 L
of the stock solution into a sample prepared as a water blank (50 mL of
cleaned PEG and 60 mL of water in the purging flask). Analyze the QCS
according to the procedures described in Sections 10.2 and 10.3,
excluding Section 10.2.2. To calculate the theoretical carbon
concentration (in mg) in QCS 1, multiply mg of methylene chloride in the
stock solution by 3.777 x 10^-3. To calculate the
theoretical chlorine concentration (in mg) in QCS 1, multiply mg of
methylene chloride in the stock solution by 1.670 x 10^-2.
9.1.2 QCS 2, 1,3-dichloro-2-propanol. Prepare a stock solution by
weighing, to the nearest 0.1 mg, 60 L of high purity grade 1,3-
dichloro-2-propanol in a tared 5 mL volumetric flask. Record the weight
in milligrams, dilute to 5 mL with cleaned PEG, and inject 100
L of the stock solution into a sample prepared as a water blank
(50 mL of cleaned PEG and 60 mL of water in the purging flask). Analyze
the QCS according to the procedures described in Sections 10.2 and 10.3,
excluding Section 10.2.2. To calculate the theoretical carbon
concentration (in mg) in QCS 2, multiply mg of 1,3-dichloro-2-propanol
in the stock solution by 7.461 x 10^-3. To calculate the
theoretical chlorine concentration (in mg) in QCS 2, multiply mg of 1,3-
dichloro-2-propanol in the stock solution by 1.099 x 10^-2.
9.1.3 Routine QCS Analysis. For each set of compliance samples (in
this context, set is per facility, per compliance test), analyze one QCS
1 and one QCS 2 sample. The percent recovery for each sample for each
detector shall be 13 percent of the mean recovery
established for the most recent set of QCS triplicate analysis (Section
9.4). If the sample does not meet this criteria, check the system
components and analyze another QCS 1 and 2 until a single set of QCS
meet the 13 percent criteria.

10.0 Calibration and Standardization

10.1 Initial Performance Check of Purging System. Before placing
the system in operation, after a shutdown of greater than six months,
after any major modifications, and at least once per month during
continuous operation, conduct the linearity checks described in Sections
10.1.1 and 10.1.2. Install calibration gas at the three-way calibration
gas valve. See Figure 25D-1.
10.1.1 Linearity Check Procedure. Using the calibration standard
described in Section 7.2.2.3 and by varying the injection time, it is
possible to calibrate at multiple concentration levels. Use Equation
25D-3 to calculate three sets of calibration gas flow rates and run
times needed to introduce a total mass of carbon, as methane,
(mc) of 1, 5, and 10 mg into the system (low, medium and high
FID calibration, respectively). Use Equation 25D-4 to calculate three
sets of calibration gas flow rates and run times needed to introduce a
total chloride mass (mch) of 1, 5, and 10 mg into the system
(low, medium and high ELCD calibration, respectively). With the system
operating in standby mode, allow the FID and the ELCD to establish a
stable baseline. Set the secondary pressure regulator of the calibration
gas cylinder to the same pressure as the purge gas cylinder and set the
proper flow rate with the calibration flow controller (see Figure 25D-
1). The calibration gas flow rate can be measured with a flowmeter
attached to the vent position of the calibration gas valve. Set the
four-way bypass valve to standby position so that the calibration gas
flows through the coalescing filter only. Inject the calibration gas by
turning the calibration gas valve from vent position to inject position.
Continue the calibration gas flow for the appropriate period of time
before switching the calibration valve to vent position. Continue
recording the response of the FID and the ELCD for 5 min after switching
off calibration gas flow. Make triplicate injections of all six levels
of calibration.
10.1.2 Linearity Criteria. Calculate the average response factor
(Equations 25D-5 and 25D-6) and the relative standard deviation (RSD)
(Equation 25D-10) at each level of the calibration curve for both
detectors. Calculate the overall mean of the three response factor
averages for each detector. The FID linearity is acceptable if each
response factor is within 5 percent of the overall mean and if the RSD
for each set of triplicate injections is less than 5 percent. The ELCD
linearity is acceptable if each response factor is within 10 percent of
the overall mean and if the RSD for each set of triplicate injections is
less than 10 percent. Record the overall mean value of the response
factors for the FID and the ELCD. If the calibration for either the FID
or the ELCD does not meet the

[[Page 535]]

criteria, correct the detector/system problem and repeat Sections 10.1.1
and 10.1.2.
10.2 Daily Calibrations.
10.2.1 Daily Linearity Check. Follow the procedures outlined in
Section 10.1.1 to analyze the medium level calibration for both the FID
and the ELCD in duplicate at the start of the day. Calculate the
response factors and the RSDs for each detector. For the FID, the
calibration is acceptable if the average response factor is within 5
percent of the overall mean response factor (Section 10.1.2) and if the
RSD for the duplicate injection is less than 5 percent. For the ELCD,
the calibration is acceptable if the average response factor is within
10 percent of the overall mean response factor (Section 10.1.2) and if
the RSD for the duplicate injection is less than 10 percent. If the
calibration for either the FID or the ELCD does not meet the criteria,
correct the detector/system problem and repeat Sections 10.1.1 and
10.1.2.
10.2.2 Calibration Range Check.
10.2.2.1 If the waste concentration for either detector falls below
the range of calibration for that detector, use the procedure outlined
in Section 10.1.1 to choose two calibration points that bracket the new
target concentration. Analyze each of these points in triplicate (as
outlined in Section 10.1.1) and use the criteria in Section 10.1.2 to
determine the linearity of the detector in this ``mini-calibration''
range.
10.2.2.2 After the initial linearity check of the mini-calibration
curve, it is only necessary to test one of the points in duplicate for
the daily calibration check (in addition to the points specified in
Section 10.2.1). The average daily mini-calibration point should fit the
linearity criteria specified in Section 10.2.1. If the calibration for
either the FID or the ELCD does not meet the criteria, correct the
detector/system problem and repeat the calibration procedure mentioned
in the first paragraph of Section 10.2.2. A mini-calibration curve for
waste concentrations above the calibration curve for either detector is
optional.
10.3 Analytical Balance. Calibrate against standard weights.

11.0 Analysis

11.1 Sample Analysis.
11.1.1 Turn on the constant temperature chamber and allow the
temperature to equilibrate at 75 2 deg.C (167
3.6 deg.F). Turn the four-way valve so that the purge gas bypasses the
purging flask, the purge gas flowing through the coalescing filter and
to the detectors (standby mode). Turn on the purge gas. Allow both the
FID and the ELCD to warm up until a stable baseline is achieved on each
detector. Pack the filter flask with ice. Replace ice after each run and
dispose of the waste water properly. When the temperature of the oven
reaches 75 2 deg.C (167 3.6 deg.F), start
both integrators and record baseline. After 1 min, turn the four-way
valve so that the purge gas flows through the purging flask, to the
coalescing filter and to the sample splitters (purge mode). Continue
recording the response of the FID and the ELCD. Monitor the readings of
the pressure gauge and the rotameter. If the readings fall below
established setpoints, stop the purging, determine the source of the
leak, and resolve the problem before resuming. Leaks detected during a
sampling period invalidate that sample.
11.1.2 As the purging continues, monitor the output of the
detectors to make certain that the analysis is proceeding correctly and
that the results are being properly recorded. Every 10 minutes read and
record the purge flow rate, the pressure and the chamber temperature.
Continue the purging for 30 minutes.
11.1.3 For each detector output, integrate over the entire area of
the peak starting at 1 minute and continuing until the end of the run.
Subtract the established baseline area from the peak area. Record the
corrected area of the peak. See Figure 25D-6 for an example integration.
11.2 Water Blank. A water blank shall be analyzed for each batch of
cleaned PEG prepared. Transfer about 60 mL of water into the purging
flask. Add 50 mL of the cleaned PEG to the purging flask. Treat the
blank as described in Sections 8.2 and 8.3, excluding Section 8.2.2.
Calculate the concentration of carbon and chlorine in the blank sample
(assume 10 g of waste as the mass). A VO concentration equivalent to
10 percent of the applicable standard may be subtracted from
the measured VO concentration of the waste samples. Include all blank
results and documentation in the test report.
11.3 Audit Sample Analysis.
11.3.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, an audit sample, if
available, must be analyzed.
11.3.2 Concurrently analyze the audit sample and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.3.3 The same analyst, analytical reagents, and analytical system
must be used for the compliance samples and the audit sample. If this
condition is met, duplicate auditing of subsequent compliance analyses
for the same enforcement agency within a 30-day period is waived. An
audit sample may not be used to validate different sets of compliance
samples under the jurisdiction of separate enforcement agencies, unless
prior arrangements have been made with both enforcement agencies.
11.4 Audit Sample Results.
11.4.1 Calculate the audit sample concentrations and submit results
using the instructions provided with the audit samples.

[[Page 536]]

11.4.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

Ab = Area under the water blank response curve, counts.
Ac = Area under the calibration response curve, counts.
As = Area under the sample response curve, counts.
C = Concentration of volatile organics in the sample, ppmw.
Cc = Concentration of carbon, as methane, in the calibration
gas, mg/L.
Cch = Concentration of chloride in the calibration gas, mg/L.
Cj = VO concentration of phase j, ppmw.
DRt = Average daily response factor of the FID, mg
CH4/counts.
Drth = Average daily response factor of the ELCD, mg
Cl^-/counts.
Fj = Weight fraction of phase j present in the waste.
mc = Mass of carbon, as methane, in a calibration run, mg.
mch = Mass of chloride in a calibration run, mg.
ms = Mass of the waste sample, g.
msc = Mass of carbon, as methane, in the sample, mg.
msf = Mass of sample container and waste sample, g.
msh = Mass of chloride in the sample, mg.
mst = Mass of sample container prior to sampling, g.
mVO = Mass of volatile organics in the sample, mg.
n = Total number of phases present in the waste.
Pp = Percent propane in calibration gas (L/L).
Pvc = Percent 1,1-dichloroethylene in calibration gas (L/L).
Qc = Flow rate of calibration gas, L/min.
tc = Length of time standard gas is delivered to the
analyzer, min.
W = Weighted average VO concentration, ppmw.

12.2 Concentration of Carbon, as Methane, in the Calibration Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.386

12.3 Concentration of Chloride in the Calibration Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.387

12.4 Mass of Carbon, as Methane, in a Calibration Run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.388

12.5 Mass of Chloride in a Calibration Run.
[GRAPHIC] [TIFF OMITTED] TR17OC00.389

12.6 FID Response Factor, mg/counts.
[GRAPHIC] [TIFF OMITTED] TR17OC00.390

12.7 ELCD Response Factor, mg/counts.
[GRAPHIC] [TIFF OMITTED] TR17OC00.391

12.8 Mass of Carbon in the Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.392

12.9 Mass of Chloride in the Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.393

12.10 Mass of Volatile Organics in the Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.394

12.11 Relative Standard Deviation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.395

[[Page 537]]

12.12 Mass of Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.396

12.13 Concentration of Volatile Organics in Waste.
[GRAPHIC] [TIFF OMITTED] TR17OC00.397

12.14 Weighted Average VO Concentration of Multi-phase Waste.
[GRAPHIC] [TIFF OMITTED] TR17OC00.398

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. ``Test Methods for Evaluating Solid Waste, Physical/Chemistry
Methods'', U.S. Environmental Protection Agency. Publication SW-846, 3rd
Edition, November 1986 as amended by Update I, November 1990.

[[Page 538]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.399

[[Page 539]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.400

[[Page 540]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.401

[[Page 541]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.402

[[Page 542]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.403

[[Page 543]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.404

Method 25E--Determination of Vapor Phase Organic Concentration in Waste
Samples

Note: Performance of this method should not be attempted by persons
unfamiliar with the operation of a flame ionization detector (FID) nor
by those who are unfamiliar with source sampling because knowledge
beyond the scope of this presentation is required. This method is not
inclusive with respect to specifications (e.g., reagents and standards)
and calibration procedures. Some material is incorporated by reference
from other methods. Therefore, to obtain reliable results, persons using
this method should have a thorough knowledge of at least the following
additional test methods: Method 106, part 61, Appendix B, and Method 18,
part 60, Appendix A.

[[Page 544]]

1.0 Scope and Application

1.1 Applicability. This method is applicable for determining the
vapor pressure of waste cited by an applicable regulation.
1.2 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 The headspace vapor of the sample is analyzed for carbon
content by a headspace analyzer, which uses an FID.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 The analyst shall select the operating parameters best suited
to the requirements for a particular analysis. The analyst shall produce
confirming data through an adequate supplemental analytical technique
and have the data available for review by the Administrator.

5.0 Safety. [Reserved]

6.0 Equipment and Supplies

6.1 Sampling. The following equipment is required:
6.1.1 Sample Containers. Vials, glass, with butyl rubber septa,
Perkin-Elmer Corporation Numbers 0105-0129 (glass vials), B001-0728
(gray butyl rubber septum, plug style), 0105-0131 (butyl rubber septa),
or equivalent. The seal must be made from butyl rubber. Silicone rubber
seals are not acceptable.
6.1.2 Vial Sealer. Perkin-Elmer Number 105-0106, or equivalent.
6.1.3 Gas-Tight Syringe. Perkin-Elmer Number 00230117, or
equivalent.
6.1.4 The following equipment is required for sampling.
6.1.4.1 Tap.
6.1.4.2 Tubing. Teflon, 0.25-in. ID.

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1.4.3 Cooling Coil. Stainless steel (304), 0.25 in.-ID, equipped
with a thermocouple at the coil outlet.
6.2 Analysis. The following equipment is required.
6.2.1 Balanced Pressure Headspace Sampler. Perkin-Elmer HS-6, HS-
100, or equivalent, equipped with a glass bead column instead of a
chromatographic column.
6.2.2 FID. An FID meeting the following specifications is required.
6.2.2.1 Linearity. A linear response (5 percent) over
the operating range as demonstrated by the procedures established in
Section 10.2.
6.2.2.2 Range. A full scale range of 1 to 10,000 parts per million
(ppm) propane (C3H8). Signal attenuators shall be
available to produce a minimum signal response of 10 percent of full
scale.
6.2.3 Data Recording System. Analog strip chart recorder or digital
integration system compatible with the FID for permanently recording the
output of the detector.
6.2.4 Temperature Sensor. Capable of reading temperatures in the
range of 30 to 60 deg.C (86 to 140 deg.F) with an accuracy of
0.1 deg.C (0.2 deg.F).

7.0 Reagents and Standards

7.1 Analysis. The following items are required for analysis.
7.1.1 Hydrogen (H2). Zero grade hydrogen, as required by
the FID.
7.1.2 Carrier Gas. Zero grade nitrogen, containing less than 1 ppm
carbon (C) and less than 1 ppm carbon dioxide.
7.1.3 Combustion Gas. Zero grade air or oxygen as required by the
FID.
7.2 Calibration and Linearity Check.
7.2.1 Stock Cylinder Gas Standard. 100 percent propane. The
manufacturer shall: (a) Certify the gas composition to be accurate to
3 percent or better (see Section 7.2.1.1); (b) recommend a
maximum shelf life over which the gas concentration does not change by
greater than 5 percent from the certified value; and (c)
affix the date of gas cylinder preparation, certified propane
concentration, and recommended maximum shelf life to the cylinder before
shipment to the buyer.
7.2.1.1 Cylinder Standards Certification. The manufacturer shall
certify the concentration of the calibration gas in the cylinder by (a)
directly analyzing the cylinder and (b) calibrating his analytical
procedure on the day of cylinder analysis. To calibrate his analytical
procedure, the manufacturer shall use, as a minimum, a three-point
calibration curve.
7.2.1.2 Verification of Manufacturer's Calibration Standards.
Before using, the manufacturer shall verify each calibration standard by
(a) comparing it to gas mixtures prepared in accordance with the
procedure described in Section 7.1 of Method 106 of Part 61, Appendix B,
or by (b) calibrating it against Standard Reference Materials (SRM's)
prepared by the National Bureau of Standards, if such SRM's are
available. The agreement between the initially determined concentration
value and the verification concentration value must be within
5 percent. The manufacturer must reverify all calibration
standards on a time interval consistent with the shelf life of the
cylinder standards sold.

8.0 Sampling Collection, Preservation, Storage, and Transport

8.1 Install a sampling tap to obtain a sample at a point which is
most representative of the unexposed waste (where the waste has had
minimum opportunity to volatilize to

[[Page 545]]

the atmosphere). Assemble the sampling apparatus as shown in Figure 25E-
1.
8.2 Begin sampling by purging the sample lines and cooling coil
with at least four volumes of waste. Collect the purged material in a
separate container and dispose of it properly.
8.3 After purging, stop the sample flow and transfer the Teflon
sampling tube to a sample container. Sample at a flow rate such that the
temperature of the waste is 10 deg.C (50 deg.F). Fill the sample
container halfway (5 percent) and cap it within 5 seconds.
Store immediately in a cooler and cover with ice.
8.4 Alternative sampling techniques may be used upon the approval
of the Administrator.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
10.2, 10.3.................... FID calibration Ensure precision of
and response analytical results.
check.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a record of performance of each item.
10.1 Use the procedures in Sections 10.2 to calibrate the headspace
analyzer and FID and check for linearity before the system is first
placed in operation, after any shutdown longer than 6 months, and after
any modification of the system.
10.2 Calibration and Linearity. Use the procedures in Section 10 of
Method 18 of Part 60, Appendix A, to prepare the standards and calibrate
the flowmeters, using propane as the standard gas. Fill the calibration
standard vials halfway (5 percent) with deionized water.
Purge and fill the airspace with calibration standard. Prepare a minimum
of three concentrations of calibration standards in triplicate at
concentrations that will bracket the applicable cutoff. For a cutoff of
5.2 kPa (0.75 psi), prepare nominal concentrations of 30,000, 50,000,
and 70,000 ppm as propane. For a cutoff of 27.6 kPa (4.0 psi), prepare
nominal concentrations of 200,000, 300,000, and 400,000 ppm as propane.
10.2.1 Use the procedures in Section 11.3 to measure the FID
response of each standard. Use a linear regression analysis to calculate
the values for the slope (k) and the y-intercept (b). Use the procedures
in Sections 12.3 and 12.2 to test the calibration and the linearity.
10.3 Daily FID Calibration Check. Check the calibration at the
beginning and at the end of the daily runs by using the following
procedures. Prepare 2 calibration standards at the nominal cutoff
concentration using the procedures in Section 10.2. Place one at the
beginning and one at the end of the daily run. Measure the FID response
of the daily calibration standard and use the values for k and b from
the most recent calibration to calculate the concentration of the daily
standard. Use an equation similar to 25E-2 to calculate the percent
difference between the daily standard and Cs. If the
difference is within 5 percent, then the previous values for k and b can
be used. Otherwise, use the procedures in Section 10.2 to recalibrate
the FID.

11.0 Analytical Procedures

11.1 Allow one hour for the headspace vials to equilibrate at the
temperature specified in the regulation. Allow the FID to warm up until
a stable baseline is achieved on the detector.
11.2 Check the calibration of the FID daily using the procedures in
Section 10.3.
11.3 Follow the manufacturer's recommended procedures for the
normal operation of the headspace sampler and FID.
11.4 Use the procedures in Sections 12.4 and 12.5 to calculate the
vapor phase organic vapor pressure in the samples.
11.5 Monitor the output of the detector to make certain that the
results are being properly recorded.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

A = Measurement of the area under the response curve, counts.
b = y-intercept of the linear regression line.
Ca = Measured vapor phase organic concentration of sample,
ppm as propane.
Cma = Average measured vapor phase organic concentration of
standard, ppm as propane.
Cm = Measured vapor phase organic concentration of standard,
ppm as propane.
Cs = Calculated standard concentration, ppm as propane.
k = Slope of the linear regression line.
Pbar = Atmospheric pressure at analysis conditions, mm Hg
(in. Hg).
P* = Organic vapor pressure in the sample, kPa (psi).
PD = Percent difference between the average measured vapor phase organic
concentration (Cm) and the calculated standard
concentration (Cs).
RSD = Relative standard deviation.
=1.333 x 10^-\7\ kPa/[(mm Hg)(ppm)], (4.91 x
10^-\7\ psi/[(in. Hg)(ppm)])

[[Page 546]]

12.2 Linearity. Use the following equation to calculate the
measured standard concentration for each standard vial.
[GRAPHIC] [TIFF OMITTED] TR17OC00.405

12.2.1 Calculate the average measured standard concentration
(Cma) for each set of triplicate standards and use the
following equation to calculate PD between Cma and
Cs. The instrument linearity is acceptable if the PD is
within five for each standard.
[GRAPHIC] [TIFF OMITTED] TR17OC00.406

12.3. Relative Standard Deviation (RSD). Use the following equation
to calculate the RSD for each triplicate set of standards.
[GRAPHIC] [TIFF OMITTED] TR17OC00.407

The calibration is acceptable if the RSD is within five for each
standard concentration.
12.4 Concentration of organics in the headspace. Use the following
equation to calculate the concentration of vapor phase organics in each
sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.408

12.5 Vapor Pressure of Organics in the Headspace Sample. Use the
following equation to calculate the vapor pressure of organics in the
sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.409

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. Salo, Albert E., Samuel Witz, and Robert D. MacPhee.
``Determination of Solvent Vapor Concentrations by Total Combustion
Analysis: a Comparison of Infared with Flame Ionization Detectors. Paper
No. 75-33.2. (Presented at the 68th Annual Meeting of the Air Pollution
Control Association. Boston, Massachusetts.
2. Salo, Albert E., William L. Oaks, and Robert D. MacPhee.
``Measuring the Organic Carbon Content of Source Emissions for Air
Pollution Control. Paper No. 74-190. (Presented at the 67th Annual
Meeting of the Air Pollution Control Association. Denver, Colorado. June
9-13, 1974.) p. 25.

[[Page 547]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.412

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A see the List of CFR Sections Affected, which appears in the
Finding Aids section of the printed volume and on GPO Access.

[[Page 548]]

Appendix A-8 to Part 60--Test Methods 26 through 29

Method 26--Determination of Hydrogen Chloride Emissions From Stationary
Sources
Method 26A--Determination of hydrogen halide and halogen emissions from
stationary sources--isokinetic method
Method 27--Determination of vapor tightness of gasoline delivery tank
using pressure-vacuum test
Method 28--Certification and auditing of wood heaters
Method 28A--Measurement of air to fuel ratio and minimum achievable burn
rates for wood-fired appliances
Method 29--Determination of metals emissions from stationary sources
The test methods in this appendix are referred to in Sec. 60.8
(Performance Tests) and Sec. 60.11 (Compliance With Standards and
Maintenance Requirements) of 40 CFR part 60, subpart A (General
Provisions). Specific uses of these test methods are described in the
standards of performance contained in the subparts, beginning with
Subpart D.
Within each standard of performance, a section title ``Test Methods
and Procedures'' is provided to: (1) Identify the test methods to be
used as reference methods to the facility subject to the respective
standard and (2) identify any special instructions or conditions to be
followed when applying a method to the respective facility. Such
instructions (for example, establish sampling rates, volumes, or
temperatures) are to be used either in addition to, or as a substitute
for procedures in a test method. Similarly, for sources subject to
emission monitoring requirements, specific instructions pertaining to
any use of a test method as a reference method are provided in the
subpart or in Appendix B.
Inclusion of methods in this appendix is not intended as an
endorsement or denial of their applicability to sources that are not
subject to standards of performance. The methods are potentially
applicable to other sources; however, applicability should be confirmed
by careful and appropriate evaluation of the conditions prevalent at
such sources.
The approach followed in the formulation of the test methods
involves specifications for equipment, procedures, and performance. In
concept, a performance specification approach would be preferable in all
methods because this allows the greatest flexibility to the user. In
practice, however, this approach is impractical in most cases because
performance specifications cannot be established. Most of the methods
described herein, therefore, involve specific equipment specifications
and procedures, and only a few methods in this appendix rely on
performance criteria.
Minor changes in the test methods should not necessarily affect the
validity of the results and it is recognized that alternative and
equivalent methods exist. Section 60.8 provides authority for the
Administrator to specify or approve (1) equivalent methods, (2)
alternative methods, and (3) minor changes in the methodology of the
test methods. It should be clearly understood that unless otherwise
identified all such methods and changes must have prior approval of the
Administrator. An owner employing such methods or deviations from the
test methods without obtaining prior approval does so at the risk of
subsequent disapproval and retesting with approved methods.
Within the test methods, certain specific equipment or procedures
are recognized as being acceptable or potentially acceptable and are
specifically identified in the methods. The items identified as
acceptable options may be used without approval but must be identified
in the test report. The potentially approvable options are cited as
``subject to the approval of the Administrator'' or as ``or
equivalent.'' Such potentially approvable techniques or alternatives may
be used at the discretion of the owner without prior approval. However,
detailed descriptions for applying these potentially approvable
techniques or alternatives are not provided in the test methods. Also,
the potentially approvable options are not necessarily acceptable in all
applications. Therefore, an owner electing to use such potentially
approvable techniques or alternatives is responsible for: (1) assuring
that the techniques or alternatives are in fact applicable and are
properly executed; (2) including a written description of the
alternative method in the test report (the written method must be clear
and must be capable of being performed without additional instruction,
and the the degree of detail should be similar to the detail contained
in the test methods); and (3) providing any rationale or supporting data
necessary to show the validity of the alternative in the particular
application. Failure to meet these requirements can result in the
Administrator's disapproval of the alternative.

Method 26--Determination of Hydrogen Halide and Halogen Emissions From
Stationary Sources Non-Isokinetic Method

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analytes CAS No.
------------------------------------------------------------------------
Hydrogen Chloride (HCl)................................. 7647-01-0
Hydrogen Bromide (HBr).................................. 10035-10-6
Hydrogen Fluoride (HF).................................. 7664-39-3
Chlorine (Cl2).......................................... 7882-50-5
Bromine (Br2)........................................... 7726-95-6
------------------------------------------------------------------------

[[Page 549]]

1.2 Applicability. This method is applicable for determining
emissions of hydrogen halides (HX) (HCl, HBr, and HF) and halogens
(X2) (Cl2 and Br2) from stationary
sources when specified by the applicable subpart. Sources, such as those
controlled by wet scrubbers, that emit acid particulate matter must be
sampled using Method 26A.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 An integrated sample is extracted from the source and passed
through a prepurged heated probe and filter into dilute sulfuric acid
and dilute sodium hydroxide solutions which collect the gaseous hydrogen
halides and halogens, respectively. The filter collects particulate
matter including halide salts but is not routinely recovered and
analyzed. The hydrogen halides are solubilized in the acidic solution
and form chloride (Cl^-), bromide (Br^-), and
fluoride (F^-) ions. The halogens have a very low solubility
in the acidic solution and pass through to the alkaline solution where
they are hydrolyzed to form a proton (H⁺), the halide ion,
and the hypohalous acid (HClO or HBrO). Sodium thiosulfate is added in
excess to the alkaline solution to assure reaction with the hypohalous
acid to form a second halide ion such that 2 halide ions are formed for
each molecule of halogen gas. The halide ions in the separate solutions
are measured by ion chromatography (IC).

3.0 Definitions [Reserved]

4.0 Interferences

4.1 Volatile materials, such as chlorine dioxide (ClO2)
and ammonium chloride (NH4Cl), which produce halide ions upon
dissolution during sampling are potential interferents. Interferents for
the halide measurements are the halogen gases which disproportionate to
a hydrogen halide and a hydrohalous acid upon dissolution in water.
However, the use of acidic rather than neutral or basic solutions for
collection of the hydrogen halides greatly reduces the dissolution of
any halogens passing through this solution.
4.2 The simultaneous presence of HBr and CL2 may cause a
positive bias in the HCL result with a corresponding negative bias in
the Cl2 result as well as affecting the HBr/Br2
split.
4.3 High concentrations of nitrogen oxides (NOX) may
produce sufficient nitrate (NO3^- to interfere with
measurements of very low Br^- levels.
4.4 A glass wool plug should not be used to remove particulate
matter since a negative bias in the data could result.
4.5 There is anecdotal evidence that HF may be outgassed from new
teflon components. If HF is a target analyte, then preconditioning of
new teflon components, by heating should be considered.

5.0 Safety

6.0 Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The sampling train is shown in Figure 26-1, and
component parts are discussed below.
6.1.1 Probe. Borosilicate glass, approximately \3/8\-in. (9-mm)
I.D. with a heating system to prevent moisture condensation. A Teflon-
glass filter in a mat configuration should be installed to remove
particulate matter from the gas stream (see Section 6.1.6).
6.1.2 Three-way Stopcock. A borosilicate-glass three-way stopcock
with a heating system to prevent moisture condensation. The heated
stopcock should connect to the outlet of the heated filter and the inlet
of the first impinger. The heating system should be capable of
preventing condensation up to the inlet of the first impinger. Silicone
grease may be used, if necessary, to prevent leakage.

[[Page 550]]

6.1.3 Impingers. Four 30-ml midget impingers with leak-free glass
connectors. Silicone grease may be used, if necessary, to prevent
leakage. For sampling at high moisture sources or for sampling times
greater than one hour, a midget impinger with a shortened stem (such
that the gas sample does not bubble through the collected condensate)
should be used in front of the first impinger.
6.1.4 Drying Tube or Impinger. Tube or impinger, of Mae West
design, filled with 6- to 16-mesh indicating type silica gel, or
equivalent, to dry the gas sample and to protect the dry gas meter and
pump. If the silica gel has been used previously, dry at 175 deg.C (350
deg.F) for 2 hours. New silica gel may be used as received.
Alternatively, other types of desiccants (equivalent or better) may be
used.
6.1.5 Heating System. Any heating system capable of maintaining a
temperature around the probe and filter holder greater than 120 deg.C
(248 deg.F) during sampling, or such other temperature as specified by
an applicable subpart of the standards or approved by the Administrator
for a particular application.
6.1.6 Filter Holder and Support. The filter holder shall be made of
Teflon or quartz. The filter support shall be made of Teflon. All Teflon
filter holders and supports are available from Savillex Corp., 5325 Hwy
101, Minnetonka, MN 55345.
6.1.7 Sample Line. Leak-free, with compatible fittings to connect
the last impinger to the needle valve.
6.1.8 Rate Meter. Rotameter, or equivalent, capable of measuring
flow rate to within 2 percent of the selected flow rate of 2 liters/min
(0.07 ft³/min).
6.1.9 Purge Pump, Purge Line, Drying Tube, Needle Valve, and Rate
Meter. Pump capable of purging the sampling probe at 2 liters/min, with
drying tube, filled with silica gel or equivalent, to protect pump, and
a rate meter capable of measuring 0 to 5 liters/min (0.2 ft³/
min).
6.1.10 Stopcock Grease, Valve, Pump, Volume Meter, Barometer, and
Vacuum Gauge. Same as in Method 6, Sections 6.1.1.4, 6.1.1.7, 6.1.1.8,
6.1.1.10, 6.1.2, and 6.1.3.
6.1.11 Temperature Measuring Devices. Temperature sensors to
monitor the temperature of the probe and to monitor the temperature of
the sampling system from the outlet of the probe to the inlet of the
first impinger.
6.1.12 Ice Water Bath. To minimize loss of absorbing solution.
6.2 Sample Recovery.
6.2.1 Wash Bottles. Polyethylene or glass, 500-ml or larger, two.
6.2.2 Storage Bottles. 100- or 250-ml, high-density polyethylene
bottles with Teflon screw cap liners to store impinger samples.
6.3 Sample Preparation and Analysis. The materials required for
volumetric dilution and chromatographic analysis of samples are
described below.
6.3.1 Volumetric Flasks. Class A, 100-ml size.
6.3.2 Volumetric Pipets. Class A, assortment. To dilute samples to
the calibration range of the ion chromatograph.
6.3.3 Ion Chromatograph (IC). Suppressed or non-suppressed, with a
conductivity detector and electronic integrator operating in the peak
area mode. Other detectors, strip chart recorders, and peak height
measurements may be used.

7.0 Reagents and Standards

7.1 Sampling.
7.1.1 Filter. A 25-mm (1 in) (or other size) Teflon glass mat,
Pallflex TX40HI75 (Pallflex Inc., 125 Kennedy Drive, Putnam, CT 06260).
This filter is in a mat configuration to prevent fine particulate matter
from entering the sampling train. Its composition is 75% Teflon/25%
borosilicate glass. Other filters may be used, but they must be in a mat
(as opposed to a laminate) configuration and contain at least 75%
Teflon. For practical rather than scientific reasons, when the stack gas
temperature exceeds 210 deg.C (410 deg.F) and the HCl concentration is
greater than 20 ppm, a quartz-fiber filter may be used since Teflon
becomes unstable above this temperature.
7.1.2 Water. Deionized, distilled water that conforms to American
Society of Testing and Materials (ASTM) Specification D 1193-77 or 91,
Type 3 (incorporated by reference--see Sec. 60.17).
7.1.3 Acidic Absorbing Solution, 0.1 N Sulfuric Acid
(H2SO4). To prepare 100 ml of the absorbing
solution for the front impinger pair, slowly add 0.28 ml of concentrated
H2SO4 to about 90 ml of water while stirring, and
adjust the final volume to 100 ml using additional water. Shake well to
mix the solution.
7.1.4 Silica Gel. Indicating type, 6 to 16 mesh. If previously
used, dry at 180 deg.C (350 deg.F) for 2 hours. New silica gel may be
used as received. Alternatively, other types of desiccants may be used,
subject to the approval of the Administrator.
7.1.5 Alkaline Adsorbing Solution, 0.1 N Sodium Hydroxide (NaOH).
To prepare 100 ml of the scrubber solution for the third and fourth
impinger, dissolve 0.40 g of solid NaOH in about 90 ml of water, and
adjust the final

[[Page 551]]

solution volume to 100 ml using additional water. Shake well to mix the
solution.
7.1.6 Sodium Thiosulfate (Na2S2O3
5 H2O)
7.2 Sample Preparation and Analysis.
7.2.1 Water. Same as in Section 7.1.2.
7.2.2 Absorbing Solution Blanks. A separate blank solution of each
absorbing reagent should be prepared for analysis with the field
samples. Dilute 30 ml of each absorbing solution to approximately the
same final volume as the field samples using the blank sample of rinse
water.
7.2.3 Halide Salt Stock Standard Solutions. Prepare concentrated
stock solutions from reagent grade sodium chloride (NaCl), sodium
bromide (NaBr), and sodium fluoride (NaF). Each must be dried at 110
deg.C (230 deg.F) for two or more hours and then cooled to room
temperature in a desiccator immediately before weighing. Accurately
weigh 1.6 to 1.7 g of the dried NaCl to within 0.1 mg, dissolve in
water, and dilute to 1 liter. Calculate the exact Cl^-
concentration using Equation 26-1 in Section 12.2. In a similar manner,
accurately weigh and solubilize 1.2 to 1.3 g of dried NaBr and 2.2 to
2.3 g of NaF to make 1-liter solutions. Use Equations 26-2 and 26-3 in
Section 12.2, to calculate the Br^- and F^-
concentrations. Alternately, solutions containing a nominal certified
concentration of 1000 mg/l NaCl are commercially available as convenient
stock solutions from which standards can be made by appropriate
volumetric dilution. Refrigerate the stock standard solutions and store
no longer than one month.
7.2.4 Chromatographic Eluent. Effective eluents for nonsuppressed
IC using a resin-or silica-based weak ion exchange column are a 4 mM
potassium hydrogen phthalate solution, adjusted to pH 4.0 using a
saturated sodium borate solution, and a 4 mM 4-hydroxy benzoate
solution, adjusted to pH 8.6 using 1 N NaOH. An effective eluent for
suppressed ion chromatography is a solution containing 3 mM sodium
bicarbonate and 2.4 mM sodium carbonate. Other dilute solutions buffered
to a similar pH and containing no interfering ions may be used. When
using suppressed ion chromatography, if the ``water dip'' resulting from
sample injection interferes with the chloride peak, use a 2 mM NaOH/2.4
mM sodium bicarbonate eluent.
7.3 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, audit samples may be obtained
from the appropriate EPA regional Office or from the responsible
enforcement authority.
Note: The responsible enforcement authority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: Because of the complexity of this method, testers and analyst
should be trained and experienced with the procedure to ensure reliable
results.

8.1 Sampling.
8.1.1 Preparation of Collection Train. Prepare the sampling train
as follows: Pour 15 ml of the acidic absorbing solution into each one of
the first pair of impingers, and 15 ml of the alkaline absorbing
solution into each one of the second pair of impingers. Connect the
impingers in series with the knockout impinger first, if used, followed
by the two impingers containing the acidic absorbing solution and the
two impingers containing the alkaline absorbing solution. Place a fresh
charge of silica gel, or equivalent, in the drying tube or impinger at
the end of the impinger train.
8.1.2 Adjust the probe temperature and the temperature of the
filter and the stopcock, i.e., the heated area in Figure 26-1 to a
temperature sufficient to prevent water condensation. This temperature
should be at least 20 deg.C (68 deg.F) above the source temperature,
and greater than 120 deg.C (248 deg.F). The temperature should be
monitored throughout a sampling run to ensure that the desired
temperature is maintained. It is important to maintain a temperature
around the probe and filter of greater than 120 deg.C (248 deg.F)
since it is extremely difficult to purge acid gases off these
components. (These components are not quantitatively recovered and hence
any collection of acid gases on these components would result in
potential undereporting of these emission. The applicable subparts may
specify alternative higher temperatures.)
8.1.3 Leak-Check Procedure.
8.1.3.1 Sampling Train. A leak-check prior to the sampling run is
optional; however, a leak-check after the sampling run is mandatory. The
leak-check procedure is as follows: Temporarily attach a suitable [e.g.,
0-40 cc/min (0-2.4 in\3\/min)] rotameter to the outlet of the dry gas
meter and place a vacuum gauge at or near the probe inlet. Plug the
probe inlet, pull a vacuum of at least 250 mm Hg (10 in. Hg), and note
the flow rate as indicated by the rotameter. A leakage rate not in
excess of 2 percent of the average sampling rate is acceptable.

Note: Carefully release the probe inlet plug before turning off the
pump.

8.1.3.2 Pump. It is suggested (not mandatory) that the pump be
leak-checked separately, either prior to or after the sampling run. If
done prior to the sampling run, the pump leak-check shall precede the
leak-check of the sampling train described immediately above; if done
after the sampling run, the pump leak-check shall follow the train leak-
check. To leak-check the pump, proceed as follows: Disconnect the drying
tube from

[[Page 552]]

the probe-impinger assembly. Place a vacuum gauge at the inlet to either
the drying tube or pump, pull a vacuum of 250 mm (10 in) Hg, plug or
pinch off the outlet of the flow meter, and then turn off the pump. The
vacuum should remain stable for at least 30 sec. Other leak-check
procedures may be used, subject to the approval of the Administrator,
U.S. Environmental Protection Agency.
8.1.4 Purge Procedure. Immediately before sampling, connect the
purge line to the stopcock, and turn the stopcock to permit the purge
pump to purge the probe (see Figure 1A of Figure 26-1). Turn on the
purge pump, and adjust the purge rate to 2 liters/min (0.07 ft\3\/min).
Purge for at least 5 minutes before sampling.
8.1.5 Sample Collection. Turn on the sampling pump, pull a slight
vacuum of approximately 25 mm Hg (1 in Hg) on the impinger train, and
turn the stopcock to permit stack gas to be pulled through the impinger
train (see Figure 1C of Figure 26-1). Adjust the sampling rate to 2
liters/min, as indicated by the rate meter, and maintain this rate to
within 10 percent during the entire sampling run. Take readings of the
dry gas meter volume and temperature, rate meter, and vacuum gauge at
least once every five minutes during the run. A sampling time of one
hour is recommended. Shorter sampling times may introduce a significant
negative bias in the HCl concentration. At the conclusion of the
sampling run, remove the train from the stack, cool, and perform a leak-
check as described in Section 8.1.3.1.
8.2 Sample Recovery.
8.2.1 Disconnect the impingers after sampling. Quantitatively
transfer the contents of the acid impingers and the knockout impinger,
if used, to a leak-free storage bottle. Add the water rinses of each of
these impingers and connecting glassware to the storage bottle.
8.2.2 Repeat this procedure for the alkaline impingers and
connecting glassware using a separate storage bottle. Add 25 mg of
sodium thiosulfate per the product of ppm of halogen anticipated to be
in the stack gas times the volume (dscm) of stack gas sampled (0.7 mg
per ppm-dscf).

Note: This amount of sodium thiosulfate includes a safety factor of
approximately 5 to assure complete reaction with the hypohalous acid to
form a second Cl^- ion in the alkaline solution.

8.2.3 Save portions of the absorbing reagents (0.1 N
H2SO4 and 0.1 N NaOH) equivalent to the amount
used in the sampling train (these are the absorbing solution blanks
described in Section 7.2.2); dilute to the approximate volume of the
corresponding samples using rinse water directly from the wash bottle
being used. Add the same amount of sodium thiosulfate solution to the
0.1 N NaOH absorbing solution blank. Also, save a portion of the rinse
water used to rinse the sampling train. Place each in a separate,
prelabeled storage bottle. The sample storage bottles should be sealed,
shaken to mix, and labeled. Mark the fluid level.
8.3 Sample Preparation for Analysis. Note the liquid levels in the
storage bottles and confirm on the analysis sheet whether or not leakage
occurred during transport. If a noticeable leakage has occurred, either
void the sample or use methods, subject to the approval of the
Administrator, to correct the final results. Quantitatively transfer the
sample solutions to 100-ml volumetric flasks, and dilute to 100 ml with
water.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
11.2.......................... Audit sample Evaluate analytical
analysis. technique,
preparation of
standards.
------------------------------------------------------------------------

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.
10.1 Volume Metering System, Temperature Sensors, Rate Meter, and
Barometer. Same as in Method 6, Sections 10.1, 10.2, 10.3, and 10.4.
10.2 Ion Chromatograph.
10.2.1 To prepare the calibration standards, dilute given amounts
(1.0 ml or greater) of the stock standard solutions to convenient
volumes, using 0.1 N H2SO4 or 0.1 N NaOH, as
appropriate. Prepare at least four calibration standards for each
absorbing reagent containing the appropriate stock solutions such that
they are within the linear range of the field samples.
10.2.2 Using one of the standards in each series, ensure adequate
baseline separation for the peaks of interest.
10.2.3 Inject the appropriate series of calibration standards,
starting with the lowest concentration standard first both before and
after injection of the quality control check sample, reagent blanks, and
field samples. This allows compensation for any instrument drift
occurring during sample analysis. The values from duplicate injections
of these calibration samples should agree within 5 percent of their mean
for the analysis to be valid.

[[Page 553]]

10.2.4 Determine the peak areas, or heights, for the standards and
plot individual values versus halide ion concentrations in g/
ml.
10.2.5 Draw a smooth curve through the points. Use linear
regression to calculate a formula describing the resulting linear curve.

11.0 Analytical Procedures

11.1 Sample Analysis.
11.1.1 The IC conditions will depend upon analytical column type
and whether suppressed or non-suppressed IC is used. An example
chromatogram from a non-suppressed system using a 150-mm Hamilton PRP-
X100 anion column, a 2 ml/min flow rate of a 4 mM 4-hydroxy benzoate
solution adjusted to a pH of 8.6 using 1 N NaOH, a 50 l sample
loop, and a conductivity detector set on 1.0 S full scale is
shown in Figure 26-2.
11.1.2 Before sample analysis, establish a stable baseline. Next,
inject a sample of water, and determine if any Cl^-,
Br^-, or F^- appears in the chromatogram. If any of
these ions are present, repeat the load/injection procedure until they
are no longer present. Analysis of the acid and alkaline absorbing
solution samples requires separate standard calibration curves; prepare
each according to Section 10.2. Ensure adequate baseline separation of
the analyses.
11.1.3 Between injections of the appropriate series of calibration
standards, inject in duplicate the reagent blanks, quality control
sample, and the field samples. Measure the areas or heights of the
Cl^-, Br^-, and F^- peaks. Use the mean
response of the duplicate injections to determine the concentrations of
the field samples and reagent blanks using the linear calibration curve.
The values from duplicate injections should agree within 5 percent of
their mean for the analysis to be valid. If the values of duplicate
injections are not within 5 percent of the mean, the duplicate
injections shall be repeated and all four values used to determine the
average response. Dilute any sample and the blank with equal volumes of
water if the concentration exceeds that of the highest standard.
11.2 Audit Sample Analysis.
11.2.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, a set of two EPA audit
samples must be analyzed, subject to availability.
11.2.2 Concurrently analyze the audit samples and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.2.3 The same analyst, analytical reagents, and analytical system
shall be used for the compliance samples and the EPA audit samples. If
this condition is met, duplicate auditing of subsequent compliance
analyses for the same enforcement agency within a 30-day period is
waived. An audit sample set may not be used to validate different sets
of compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both enforcement
agencies.
11.3 Audit Sample Results.
11.3.1 Calculate the concentrations in mg/L of audit sample and
submit results following the instructions provided with the audit
samples.
11.3.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.3.3 The concentrations of the audit samples obtained by the
analyst shall agree within 10 percent of the actual concentrations. If
the 10 percent specification is not met, reanalyze the compliance and
audit samples, and include initial and reanalysis values in the test
report.
11.3.4 Failure to meet the 10 percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis
requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to determine
the compliance or noncompliance status of the affected facility.

12.0 Data Analysis and Calculations

Note: Retain at least one extra decimal figure beyond those
contained in the available data in intermediate calculations, and round
off only the final answer appropriately.

12.1 Nomenclature.

BX^-=Mass concentration of applicable absorbing
solution blank, g halide ion (Cl^-,
Br^-, F^-) /ml, not to exceed 1
g/ml which is 10 times the published analytical
detection limit of 0.1 g/ml.
C=Concentration of hydrogen halide (HX) or halogen (X2), dry
basis, mg/dscm.
K = 10^-3 mg/g.
KHCl = 1.028 (g HCl/g-mole)/(g
Cl^-/g-mole).
KHBr = 1.013 (g HBr/g-mole)/(g
Br^-/g-mole).
KHF = 1.053 (g HF/g-mole)/(g
F^-/g-mole).
mHX = Mass of HCl, HBr, or HF in sample, g.
mX2 = Mass of Cl2 or Br2 in sample,
g.
SX^- = Analysis of sample, g halide ion
(Cl^-, Br^-, F^-)/ml.

[[Page 554]]

Vm(std)= Dry gas volume measured by the dry gas meter,
corrected to standard conditions, dscm.
Vs = Volume of filtered and diluted sample, ml.

12.2 Calculate the exact Cl^-, Br^-, and
F^- concentration in the halide salt stock standard solutions
using the following equations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.413

12.3 Sample Volume, Dry Basis, Corrected to Standard Conditions.
Calculate the sample volume using Eq. 6-1 of Method 6.
12.4 Total g HCl, HBr, or HF Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.414

12.5 Total g Cl2 or Br2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.415

12.6 Concentration of Hydrogen Halide or Halogen in Flue Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.416

13.0 Method Performance

13.1 Precision and Bias. The within-laboratory relative standard
deviations are 6.2 and 3.2 percent at HCl concentrations of 3.9 and 15.3
ppm, respectively. The method does not exhibit a bias to Cl2
when sampling at concentrations less than 50 ppm.
13.2 Sample Stability. The collected Cl^-samples can be
stored for up to 4 weeks.
13.3 Detection Limit. A typical IC instrumental detection limit for
Cl^- is 0.2 g/ml. Detection limits for the other
analyses should be similar. Assuming 50 ml liquid recovered from both
the acidified impingers, and the basic impingers, and 0.06 dscm of stack
gas sampled, then the analytical detection limit in the stack gas would
be about 0.1 ppm for HCl and Cl2, respectively.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Steinsberger, S. C. and J. H. Margeson, ``Laboratory and Field
Evaluation of a Methodology for Determination of Hydrogen Chloride
Emissions from Municipal and Hazardous Waste Incinerators,'' U.S.
Environmental Protection Agency, Office of Research and Development,
Report No. 600/3-89/064, April 1989. Available from the National
Technical Information Service, Springfield, VA 22161 as PB89220586/AS.
2. State of California, Air Resources Board, Method 421,
``Determination of Hydrochloric Acid Emissions from Stationary
Sources,'' March 18, 1987.
3. Cheney, J.L. and C.R. Fortune. Improvements in the Methodology
for Measuring Hydrochloric Acid in Combustion Source Emissions. J.
Environ. Sci. Health. A19(3): 337-350. 1984.
4. Stern, D. A., B. M. Myatt, J. F. Lachowski, and K. T. McGregor.
Speciation of Halogen and Hydrogen Halide Compounds in Gaseous
Emissions. In: Incineration and Treatment of Hazardous Waste:
Proceedings of the 9th Annual Research Symposium, Cincinnati, Ohio, May
2-4, 1983. Publication No. 600/9-84-015. July 1984. Available from
National Technical Information Service, Springfield, VA 22161 as PB84-
234525.
5. Holm, R. D. and S. A. Barksdale. Analysis of Anions in Combustion
Products. In: Ion Chromatographic Analysis of Environmental Pollutants.
E. Sawicki, J. D. Mulik, and E. Wittgenstein (eds.). Ann Arbor,
Michigan, Ann Arbor Science Publishers. 1978. pp. 99-110.

[[Page 555]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.417

[[Page 556]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.418

Method 26A--Determination of Hydrogen Halide and Halogen Emissions From
Stationary Sources Isokinetic Method

Note: This method does not include all of the specifications (e.g.
equipment and supplies) and procedures (e.g. sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 2, Method 5, and Method
26.

1.0 Scope and Application

1.1 Analytes.

1.2 This method is applicable for determining emissions of hydrogen
halides (HX) [HCl, HBr, and HF] and halogens (X2)
[Cl2 and Br2] from stationary sources when
specified by the applicable subpart. This method collects the emission
sample isokinetically and is therefore particularly suited for sampling
at sources, such as those controlled by wet scrubbers, emitting acid
particulate matter (e.g., hydrogen halides dissolved in water droplets).
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Principle. Gaseous and particulate pollutants are withdrawn
isokinetically from the source and collected in an optional cyclone, on
a filter, and in absorbing solutions. The cyclone collects any liquid
droplets and is not necessary if the source emissions do not contain
them; however, it is preferable to include the cyclone in the sampling
train to protect the filter from any liquid present. The filter collects
particulate matter including halide salts but is not routinely recovered
or analyzed. Acidic and alkaline absorbing solutions collect the gaseous
hydrogen halides and halogens, respectively. Following sampling of
emissions containing liquid droplets, any halides/halogens dissolved in
the liquid in the cyclone and on the filter are vaporized to gas and
collected in the impingers by pulling conditioned ambient air through
the sampling train. The hydrogen halides are solubilized in the acidic
solution and form chloride (Cl^-), bromide (Br^-),

[[Page 557]]

and fluoride (F^-) ions. The halogens have a very low
solubility in the acidic solution and pass through to the alkaline
solution where they are hydrolyzed to form a proton (H⁺), the
halide ion, and the hypohalous acid (HClO or HBrO). Sodium thiosulfate
is added to the alkaline solution to assure reaction with the hypohalous
acid to form a second halide ion such that 2 halide ions are formed for
each molecule of halogen gas. The halide ions in the separate solutions
are measured by ion chromatography (IC). If desired, the particulate
matter recovered from the filter and the probe is analyzed following the
procedures in Method 5.

Note: If the tester intends to use this sampling arrangement to
sample concurrently for particulate matter, the alternative Teflon probe
liner, cyclone, and filter holder should not be used. The Teflon filter
support must be used. The tester must also meet the probe and filter
temperature requirements of both sampling trains.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Volatile materials, such as chlorine dioxide (ClO2)
and ammonium chloride (NH4Cl), which produce halide ions upon
dissolution during sampling are potential interferents. Interferents for
the halide measurements are the halogen gases which disproportionate to
a hydrogen halide and an hypohalous acid upon dissolution in water. The
use of acidic rather than neutral or basic solutions for collection of
the hydrogen halides greatly reduces the dissolution of any halogens
passing through this solution.
4.2 The simultaneous presence of both HBr and Cl2 may
cause a positive bias in the HCl result with a corresponding negative
bias in the Cl2 result as well as affecting the HBr/
Br2 split.
4.3 High concentrations of nitrogen oxides (NOX) may
produce sufficient nitrate (NO3^-) to interfere
with measurements of very low Br^-levels.
4.4 There is anecdotal evidence that HF may be outgassed from new
Teflon components. If HF is a target analyte then preconditioning of new
Teflon components, by heating, should be considered.

5.0 Safety

6.0. Equipment and Supplies

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

6.1 Sampling. The sampling train is shown in Figure 26A-1; the
apparatus is similar to the Method 5 train where noted as follows:
6.1.1 Probe Nozzle. Borosilicate or quartz glass; constructed and
calibrated according to Method 5, Sections 6.1.1.1 and 10.1, and coupled
to the probe liner using a Teflon union; a stainless steel nut is
recommended for this union. When the stack temperature exceeds 210
deg.C (410 deg.F), a one-piece glass nozzle/liner assembly must be
used.
6.1.2 Probe Liner. Same as Method 5, Section 6.1.1.2, except metal
liners shall not be used. Water-cooling of the stainless steel sheath is
recommended at temperatures exceeding 500 deg.C (932 deg.F). Teflon
may be used in limited applications where the minimum stack temperature
exceeds 120 deg.C (250 deg.F) but never exceeds the temperature where
Teflon is estimated to become unstable [approximately 210 deg.C (410
deg.F)].
6.1.3 Pitot Tube, Differential Pressure Gauge, Filter Heating
System, Metering System, Barometer, Gas Density Determination Equipment.
Same as Method 5, Sections 6.1.1.3, 6.1.1.4, 6.1.1.6, 6.1.1.9, 6.1.2,
and 6.1.3.
6.1.4 Cyclone (Optional). Glass or Teflon. Use of the cyclone is
required only when the sample gas stream is saturated with moisture;
however, the cyclone is recommended to protect the filter from any
liquid droplets present.
6.1.5 Filter Holder. Borosilicate or quartz glass, or Teflon filter
holder, with a Teflon filter support and a sealing gasket. The sealing
gasket shall be constructed of Teflon or equivalent materials. The
holder design shall provide a positive seal against leakage at

[[Page 558]]

any point along the filter circumference. The holder shall be attached
immediately to the outlet of the cyclone.
6.1.6 Impinger Train. The following system shall be used to
determine the stack gas moisture content and to collect the hydrogen
halides and halogens: five or six impingers connected in series with
leak-free ground glass fittings or any similar leak-free
noncontaminating fittings. The first impinger shown in Figure 26A-1
(knockout or condensate impinger) is optional and is recommended as a
water knockout trap for use under high moisture conditions. If used,
this impinger should be constructed as described below for the alkaline
impingers, but with a shortened stem, and should contain 50 ml of 0.1 N
H2SO4. The following two impingers (acid impingers
which each contain 100 ml of 0.1 N H2SO4) shall be
of the Greenburg-Smith design with the standard tip (Method 5, Section
6.1.1.8). The next two impingers (alkaline impingers which each contain
100 ml of 0.1 N NaOH) and the last impinger (containing silica gel)
shall be of the modified Greenburg-Smith design (Method 5, Section
6.1.1.8). The condensate, acid, and alkaline impingers shall contain
known quantities of the appropriate absorbing reagents. The last
impinger shall contain a known weight of silica gel or equivalent
desiccant. Teflon impingers are an acceptable alternative.
6.1.7 Heating System. Any heating system capable of maintaining a
temperature around the probe and filter holder greater than 120 deg.C
(248 deg.F) during sampling, or such other temperature as specified by
an applicable subpart of the standards or approved by the Administrator
for a particular application.
6.1.8 Ambient Air Conditioning Tube (Optional). Tube tightly packed
with approximately 150 g of fresh 8 to 20 mesh sodium hydroxide-coated
silica, or equivalent, (Ascarite II has been found suitable) to dry and
remove acid gases from the ambient air used to remove moisture from the
filter and cyclone, when the cyclone is used. The inlet and outlet ends
of the tube should be packed with at least 1-cm thickness of glass wool
or filter material suitable to prevent escape of fines. Fit one end with
flexible tubing, etc. to allow connection to probe nozzle following the
test run.
6.2 Sample Recovery.
6.2.1 Probe-Liner and Probe-Nozzle Brushes, Wash Bottles, Glass
Sample Storage Containers, Petri Dishes, Graduated Cylinder and/or
Balance, and Rubber Policeman. Same as Method 5, Sections 6.2.1, 6.2.2,
6.2.3, 6.2.4, 6.2.5, and 6.2.7.
6.2.2 Plastic Storage Containers. Screw-cap polypropylene or
polyethylene containers to store silica gel. High-density polyethylene
bottles with Teflon screw cap liners to store impinger reagents, 1-
liter.
6.2.3 Funnels. Glass or high-density polyethylene, to aid in sample
recovery.
6.3 Sample Preparation and Analysis.
6.3.1 Volumetric Flasks. Class A, various sizes.
6.3.2 Volumetric Pipettes. Class A, assortment. To dilute samples
to calibration range of the ion chromatograph (IC).
6.3.3 Ion Chromatograph (IC). Suppressed or nonsuppressed, with a
conductivity detector and electronic integrator operating in the peak
area mode. Other detectors, a strip chart recorder, and peak heights may
be used.

7.0 Reagents and Standards

Note: Unless otherwise indicated, all reagents must conform to the
specifications established by the Committee on Analytical Reagents of
the American Chemical Society (ACS reagent grade). When such
specifications are not available, the best available grade shall be
used.
7.1 Sampling.
7.1.1 Filter. Teflon mat (e.g., Pallflex TX40HI45) filter. When the
stack gas temperature exceeds 210 deg.C (410 deg.F) a quartz fiber
filter may be used.
7.1.2 Water. Deionized, distilled water that conforms to American
Society of Testing and Materials (ASTM) Specification D 1193-77 or 91,
Type 3 (incorporated by reference--see Sec. 60.17).
7.1.3 Acidic Absorbing Solution, 0.1 N Sulfuric Acid
(H2SO4). To prepare 1 L, slowly add 2.80 ml of
concentrated 17.9 M H2SO4 to about 900 ml of water while stirring, and
adjust the final volume to 1 L using additional water. Shake well to mix
the solution.
7.1.4 Silica Gel, Crushed Ice, and Stopcock Grease. Same as Method
5, Sections 7.1.2, 7.1.4, and 7.1.5, respectively.
7.1.5 Alkaline Absorbing Solution, 0.1 N Sodium Hydroxide (NaOH).
To prepare 1 L, dissolve 4.00 g of solid NaOH in about 900 ml of water
and adjust the final volume to 1 L using additional water. Shake well to
mix the solution.
7.1.6 Sodium Thiosulfate,
(Na2S2O33^.5 H2O).
7.2 Sample Preparation and Analysis.
7.2.1 Water. Same as in Section 7.1.2.
7.2.2 Absorbing Solution Blanks. A separate blank solution of each
absorbing reagent should be prepared for analysis with the field
samples. Dilute 200 ml of each absorbing solution (250 ml of the acidic
absorbing solution, if a condensate impinger is used) to the same final
volume as the field samples using the blank sample of rinse water. If a
particulate determination is conducted, collect a blank sample of
acetone.
7.2.3 Halide Salt Stock Standard Solutions. Prepare concentrated
stock solutions from reagent grade sodium chloride (NaCl), sodium
bromide (NaBr), and sodium fluoride (NaF). Each must be dried at 110
deg.C (230 deg.F)

[[Page 559]]

for two or more hours and then cooled to room temperature in a
desiccator immediately before weighing. Accurately weigh 1.6 to 1.7 g of
the dried NaCl to within 0.1 mg, dissolve in water, and dilute to 1
liter. Calculate the exact Cl^-concentration using Equation
26A-1 in Section 12.2. In a similar manner, accurately weigh and
solubilize 1.2 to 1.3 g of dried NaBr and 2.2 to 2.3 g of NaF to make 1-
liter solutions. Use Equations 26A-2 and 26A-3 in Section 12.2, to
calculate the Br^-and F^-concentrations.
Alternately, solutions containing a nominal certified concentration of
1000 mg/L NaCl are commercially available as convenient stock solutions
from which standards can be made by appropriate volumetric dilution.
Refrigerate the stock standard solutions and store no longer than one
month.
7.2.4 Chromatographic Eluent. Same as Method 26, Section 7.2.4.
7.2.5 Water. Same as Section 7.1.1.
7.2.6 Acetone. Same as Method 5, Section 7.2.
7.3 Quality Assurance Audit Samples. When making compliance
determinations, and upon availability, audit samples may be obtained
from the appropriate EPA regional Office or from the responsible
enforcement authority.

Note: The responsible enforcement authority should be notified at
least 30 days prior to the test date to allow sufficient time for sample
delivery.

8.0 Sample Collection, Preservation, Storage, and Transport

Note: Because of the complexity of this method, testers and analysts
should be trained and experienced with the procedures to ensure reliable
results.

8.1 Sampling.
8.1.1 Pretest Preparation. Follow the general procedure given in
Method 5, Section 8.1, except the filter need only be desiccated and
weighed if a particulate determination will be conducted.
8.1.2 Preliminary Determinations. Same as Method 5, Section 8.2.
8.1.3 Preparation of Sampling Train. Follow the general procedure
given in Method 5, Section 8.1.3, except for the following variations:
Add 50 ml of 0.1 N H2SO4 to the condensate
impinger, if used. Place 100 ml of 0.1 N H2SO4 in
each of the next two impingers. Place 100 ml of 0.1 N NaOH in each of
the following two impingers. Finally, transfer approximately 200-300 g
of preweighed silica gel from its container to the last impinger. Set up
the train as in Figure 26A-1. When used, the optional cyclone is
inserted between the probe liner and filter holder and located in the
heated filter box.
8.1.4 Leak-Check Procedures. Follow the leak-check procedures given
in Method 5, Sections 8.4.2 (Pretest Leak-Check), 8.4.3 (Leak-Checks
During the Sample Run), and 8.4.4 (Post-Test Leak-Check).
8.1.5 Sampling Train Operation. Follow the general procedure given
in Method 5, Section 8.5. It is important to maintain a temperature
around the probe, filter (and cyclone, if used) of greater than 120
deg.C (248 deg.F) since it is extremely difficult to purge acid gases
off these components. (These components are not quantitatively recovered
and hence any collection of acid gases on these components would result
in potential undereporting these emissions. The applicable subparts may
specify alternative higher temperatures.) For each run, record the data
required on a data sheet such as the one shown in Method 5, Figure 5-3.
If the condensate impinger becomes too full, it may be emptied,
recharged with 50 ml of 0.1 N H2SO4, and replaced
during the sample run. The condensate emptied must be saved and included
in the measurement of the volume of moisture collected and included in
the sample for analysis. The additional 50 ml of absorbing reagent must
also be considered in calculating the moisture. Before the sampling
train integrity is compromised by removing the impinger, conduct a leak-
check as described in Method 5, Section 8.4.2.
8.1.6 Post-Test Moisture Removal (Optional). When the optional
cyclone is included in the sampling train or when liquid is visible on
the filter at the end of a sample run even in the absence of a cyclone,
perform the following procedure. Upon completion of the test run,
connect the ambient air conditioning tube at the probe inlet and operate
the train with the filter heating system at least 120 deg.C (248
deg.F) at a low flow rate (e.g., H = 1 in. H2O) to
vaporize any liquid and hydrogen halides in the cyclone or on the filter
and pull them through the train into the impingers. After 30 minutes,
turn off the flow, remove the conditioning tube, and examine the cyclone
and filter for any visible liquid. If liquid is visible, repeat this
step for 15 minutes and observe again. Keep repeating until the cyclone
is dry.
Note: It is critical that this is repeated until the cyclone is
completely dry.
8.2 Sample Recovery. Allow the probe to cool. When the probe can be
handled safely, wipe off all the external surfaces of the tip of the
probe nozzle and place a cap loosely over the tip to prevent gaining or
losing particulate matter. Do not cap the probe tip tightly while the
sampling train is cooling down because this will create a vacuum in the
filter holder, drawing water from the impingers into the holder. Before
moving the sampling train to the cleanup site, remove the probe from the
sample train, wipe off any silicone grease, and cap the open outlet of
the impinger train, being careful not to lose any condensate that might
be present. Wipe off any silicone grease and cap the filter or cyclone
inlet. Remove the umbilical cord from

[[Page 560]]

the last impinger and cap the impinger. If a flexible line is used
between the first impinger and the filter holder, disconnect it at the
filter holder and let any condensed water drain into the first impinger.
Wipe off any silicone grease and cap the filter holder outlet and the
impinger inlet. Ground glass stoppers, plastic caps, serum caps, Teflon
tape, Parafilm, or aluminum foil may be used to close these openings.
Transfer the probe and filter/impinger assembly to the cleanup area.
This area should be clean and protected from the weather to minimize
sample contamination or loss. Inspect the train prior to and during
disassembly and note any abnormal conditions. Treat samples as follows:
8.2.1 Container No. 1 (Optional; Filter Catch for Particulate
Determination). Same as Method 5, Section 8.7.6.1, Container No. 1.
8.2.2 Container No. 2 (Optional; Front-Half Rinse for Particulate
Determination). Same as Method 5, Section 8.7.6.2, Container No. 2.
8.2.3 Container No. 3 (Knockout and Acid Impinger Catch for
Moisture and Hydrogen Halide Determination). Disconnect the impingers.
Measure the liquid in the acid and knockout impingers to 1
ml by using a graduated cylinder or by weighing it to 0.5 g
by using a balance. Record the volume or weight of liquid present. This
information is required to calculate the moisture content of the
effluent gas. Quantitatively transfer this liquid to a leak-free sample
storage container. Rinse these impingers and connecting glassware
including the back portion of the filter holder (and flexible tubing, if
used) with water and add these rinses to the storage container. Seal the
container, shake to mix, and label. The fluid level should be marked so
that if any sample is lost during transport, a correction proportional
to the lost volume can be applied. Retain rinse water and acidic
absorbing solution blanks to be analyzed with the samples.
8.2.4 Container No. 4 (Alkaline Impinger Catch for Halogen and
Moisture Determination). Measure and record the liquid in the alkaline
impingers as described in Section 8.2.3. Quantitatively transfer this
liquid to a leak-free sample storage container. Rinse these two
impingers and connecting glassware with water and add these rinses to
the container. Add 25 mg of sodium thiosulfate per ppm halogen
anticipated to be in the stack gas multiplied by the volume (dscm) of
stack gas sampled (0.7 mg/ppm-dscf). Seal the container, shake to mix,
and label; mark the fluid level. Retain alkaline absorbing solution
blank to be analyzed with the samples.
Note: 25 mg per sodium thiosulfate per ppm halogen anticipated to be
in the stack includes a safety factor of approximately 5 to assure
complete reaction with the hypohalous acid to form a second
Cl^- ion in the alkaline solution.
8.2.5 Container No. 5 (Silica Gel for Moisture Determination). Same
as Method 5, Section 8.7.6.3, Container No. 3.
8.2.6 Container Nos. 6 through 9 (Reagent Blanks). Save portions of
the absorbing reagents (0.1 N H2SO4 and 0.1 N
NaOH) equivalent to the amount used in the sampling train; dilute to the
approximate volume of the corresponding samples using rinse water
directly from the wash bottle being used. Add the same ratio of sodium
thiosulfate solution used in container No. 4 to the 0.1 N NaOH absorbing
reagent blank. Also, save a portion of the rinse water alone and a
portion of the acetone equivalent to the amount used to rinse the front
half of the sampling train. Place each in a separate, prelabeled sample
container.
8.2.7 Prior to shipment, recheck all sample containers to ensure
that the caps are well-secured. Seal the lids of all containers around
the circumference with Teflon tape. Ship all liquid samples upright and
all particulate filters with the particulate catch facing upward.

9.0 Quality Control

9.1 Miscellaneous Quality Control Measures.

9.1 Volume Metering System Checks. Same as Method 5, Section 9.2.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.
10.1 Probe Nozzle, Pitot Tube Assembly, Dry Gas Metering System,
Probe Heater, Temperature Sensors, Leak-Check of Metering System, and
Barometer. Same as Method 5, Sections 10.1, 10.2, 10.3, 10.4, 10.5,
8.4.1, and 10.6, respectively.

10.2 Ion Chromatograph.
10.2.1 To prepare the calibration standards, dilute given amounts
(1.0 ml or greater)

[[Page 561]]

of the stock standard solutions to convenient volumes, using 0.1 N
H2SO4 or 0.1 N NaOH, as appropriate. Prepare at
least four calibration standards for each absorbing reagent containing
the three stock solutions such that they are within the linear range of
the field samples.
10.2.2 Using one of the standards in each series, ensure adequate
baseline separation for the peaks of interest.
10.2.3 Inject the appropriate series of calibration standards,
starting with the lowest concentration standard first both before and
after injection of the quality control check sample, reagent blanks, and
field samples. This allows compensation for any instrument drift
occurring during sample analysis. The values from duplicate injections
of these calibration samples should agree within 5 percent of their mean
for the analysis to be valid.
10.2.4 Determine the peak areas, or height, of the standards and
plot individual values versus halide ion concentrations in g/
ml.
10.2.5 Draw a smooth curve through the points. Use linear
regression to calculate a formula describing the resulting linear curve.

11.0 Analytical Procedures

Note: the liquid levels in the sample containers and confirm on the
analysis sheet whether or not leakage occurred during transport. If a
noticeable leakage has occurred, either void the sample or use methods,
subject to the approval of the Administrator, to correct the final
results.

11.1 Sample Analysis.
11.1.1 The IC conditions will depend upon analytical column type
and whether suppressed or non-suppressed IC is used. An example
chromatogram from a non-suppressed system using a 150-mm Hamilton PRP-
X100 anion column, a 2 ml/min flow rate of a 4 mM 4-hydroxy benzoate
solution adjusted to a pH of 8.6 using 1 N NaOH, a 50 l sample
loop, and a conductivity detector set on 1.0 S full scale is
shown in Figure 26-2.
11.1.2 Before sample analysis, establish a stable baseline. Next,
inject a sample of water, and determine if any Cl^-,
Br^-, or F^- appears in the chromatogram. If any of
these ions are present, repeat the load/injection procedure until they
are no longer present. Analysis of the acid and alkaline absorbing
solution samples requires separate standard calibration curves; prepare
each according to Section 10.2. Ensure adequate baseline separation of
the analyses.
11.1.3 Between injections of the appropriate series of calibration
standards, inject in duplicate the reagent blanks, quality control
sample, and the field samples. Measure the areas or heights of the
Cl^-, Br^-, and F^- peaks. Use the mean
response of the duplicate injections to determine the concentrations of
the field samples and reagent blanks using the linear calibration curve.
The values from duplicate injections should agree within 5 percent of
their mean for the analysis to be valid. If the values of duplicate
injections are not within 5 percent of the mean, the duplicator
injections shall be repeated and all four values used to determine the
average response. Dilute any sample and the blank with equal volumes of
water if the concentration exceeds that of the highest standard.
11.2 Container Nos. 1 and 2 and Acetone Blank (Optional;
Particulate Determination). Same as Method 5, Sections 11.2.1 and
11.2.2, respectively.
11.3 Container No. 5. Same as Method 5, Section 11.2.3 for silica
gel.
11.4 Audit Sample Analysis.
11.4.1 When the method is used to analyze samples to demonstrate
compliance with a source emission regulation, a set of two EPA audit
samples must be analyzed, subject to availability.
11.4.2 Concurrently analyze the audit samples and the compliance
samples in the same manner to evaluate the technique of the analyst and
the standards preparation.
11.4.3 The same analyst, analytical reagents, and analytical system
shall be used for the compliance samples and the EPA audit samples. If
this condition is met, duplicate auditing of subsequent compliance
analyses for the same enforcement agency within a 30-day period is
waived. An audit sample set may not be used to validate different sets
of compliance samples under the jurisdiction of separate enforcement
agencies, unless prior arrangements have been made with both enforcement
agencies.
11.5 Audit Sample Results.
11.5.1 Calculate the concentrations in mg/L of audit sample and
submit results following the instructions provided with the audit
samples.
11.5.2 Report the results of the audit samples and the compliance
determination samples along with their identification numbers, and the
analyst's name to the responsible enforcement authority. Include this
information with reports of any subsequent compliance analyses for the
same enforcement authority during the 30-day period.
11.5.3 The concentrations of the audit samples obtained by the
analyst shall agree within 10 percent of the actual concentrations. If
the 10 percent specification is not met, reanalyze the compliance and
audit samples, and include initial and reanalysis values in the test
report.
11.5.4 Failure to meet the 10 percent specification may require
retests until the audit problems are resolved. However, if the audit
results do not affect the compliance or noncompliance status of the
affected facility, the Administrator may waive the reanalysis

[[Page 562]]

requirement, further audits, or retests and accept the results of the
compliance test. While steps are being taken to resolve audit analysis
problems, the Administrator may also choose to use the data to determine
the compliance or noncompliance status of the affected facility.

12.0 Data Analysis and Calculations

Note: Retain at least one extra decimal figure beyond those
contained in the available data in intermediate calculations, and round
off only the final answer appropriately.

12.1 Nomenclature. Same as Method 5, Section 12.1. In addition:

BX- = Mass concentration of applicable absorbing solution
blank, g halide ion (Cl^-, Br^-,
F^-)/ml, not to exceed 1 g/ml which is 10
times the published analytical detection limit of 0.1
g/ml. (It is also approximately 5 percent of the mass
concentration anticipated to result from a one hour sample at
10 ppmv HCl.)
C = Concentration of hydrogen halide (HX) or halogen (X2),
dry basis, mg/dscm.
K = 10^-3 mg/g.
KHCl = 1.028 (g HCl/g-mole)/(g
Cl^-/g-mole).
KHBr = 1.013 (g HBr/g-mole)/(g
Br^-/g-mole).
KHF = 1.053 (g HF/g-mole)/(g
F^-/g-mole).
mHX = Mass of HCl, HBr, or HF in sample, ug.
mX2 = Mass of Cl2 or Br2 in sample, ug.
SX- = Analysis of sample, ug halide ion (Cl^-,
Br^-, F^-)/ml.
Vs = Volume of filtered and diluted sample, ml.

12.2 Calculate the exact Cl^-, Br^-, and
F^- concentration in the halide salt stock standard solutions
using the following equations.
[GRAPHIC] [TIFF OMITTED] TR17OC00.419

[GRAPHIC] [TIFF OMITTED] TR17OC00.420

12.3 Average Dry Gas Meter Temperature and Average Orifice Pressure
Drop. See data sheet (Figure 5-3 of Method 5).
12.4 Dry Gas Volume. Calculate Vm(std) and adjust for
leakage, if necessary, using the equation in Section 12.3 of Method 5.
12.5 Volume of Water Vapor and Moisture Content. Calculate the volume
of water vapor Vw(std) and moisture content Bws
from the data obtained in this method (Figure 5-3 of Method 5); use
Equations 5-2 and 5-3 of Method 5.
12.6 Isokinetic Variation and Acceptable Results. Use Method 5, Section
12.11.
12.7 Acetone Blank Concentration, Acetone Wash Blank Residue Weight,
Particulate Weight, and Particulate Concentration. For particulate
determination.
12.8 Total g HCl, HBr, or HF Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.421

12.9 Total g Cl2 or Br2 Per Sample.
[GRAPHIC] [TIFF OMITTED] TR17OC00.422

12.10 Concentration of Hydrogen Halide or Halogen in Flue Gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.423

12.11 Stack Gas Velocity and Volumetric Flow Rate. Calculate the
average stack gas velocity and volumetric flow rate, if needed, using
data obtained in this method and the equations in Sections 12.3 and 12.4
of Method 2.

3.0 Method Performance

13.1 Precision and Bias. The method has a possible measurable
negative bias below 20 ppm HCl perhaps due to reaction with small
amounts of moisture in the probe and filter. Similar bias for the other
hydrogen halides is possible.
13.2 Sample Stability. The collected Cl-samples can be stored for
up to 4 weeks for analysis for HCl and Cl2.
13.3 Detection Limit. A typical analytical detection limit for HCl
is 0.2 g/ml. Detection limits for the other analyses should be
similar. Assuming 300 ml of liquid recovered for the acidified impingers
and a similar amounts recovered from the basic impingers,

[[Page 563]]

and 1 dscm of stack gas sampled, the analytical detection limits in the
stack gas would be about 0.04 ppm for HCl and Cl2, respectively.

14.0 Pollution Prevention, [Reserved]

15.0 Waste Management, [Reserved]

16.0 References

1. Steinsberger, S. C. and J. H. Margeson. Laboratory and Field
Evaluation of a Methodology for Determination of Hydrogen Chloride
Emissions from Municipal and Hazardous Waste Incinerators. U.S.
Environmental Protection Agency, Office of Research and Development.
Publication No. 600/3-89/064. April 1989. Available from National
Technical Information Service, Springfield, VA 22161 as PB89220586/AS.
2. State of California Air Resources Board. Method 421--
Determination of Hydrochloric Acid Emissions from Stationary Sources.
March 18, 1987.
3. Cheney, J.L. and C.R. Fortune. Improvements in the Methodology
for Measuring Hydrochloric Acid in Combustion Source Emissions. J.
Environ. Sci. Health. A19(3): 337-350. 1984.
4. Stern, D.A., B.M. Myatt, J.F. Lachowski, and K.T. McGregor.
Speciation of Halogen and Hydrogen Halide Compounds in Gaseous
Emissions. In: Incineration and Treatment of Hazardous Waste:
Proceedings of the 9th Annual Research Symposium, Cincinnati, Ohio, May
2-4, 1983. Publication No. 600/9-84-015. July 1984. Available from
National Technical Information Service, Springfield, VA 22161 as PB84-
234525.
5. Holm, R.D. and S.A. Barksdale. Analysis of Anions in Combustion
Products. In: Ion Chromatographic Analysis of Environmental Pollutants,
E. Sawicki, J.D. Mulik, and E. Wittgenstein (eds.). Ann Arbor, Michigan,
Ann Arbor Science Publishers. 1978. pp. 99-110.

[[Page 564]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data
[GRAPHIC] [TIFF OMITTED] TR17OC00.424

Method 27--Determination of Vapor Tightness of Gasoline Delivery Tank
Using Pressure Vaccuum Test

1.0 Scope and Application

1.1 Applicability. This method is applicable for the determination
of vapor tightness of a gasoline delivery collection equipment.

2.0 Summary of Method

2.1 Pressure and vacuum are applied alternately to the compartments
of a gasoline delivery tank and the change in pressure or vacuum is
recorded after a specified period of time.

[[Page 565]]

3.0 Definitions

3.1 Allowable pressure change (p) means the allowable
amount of decrease in pressure during the static pressure test, within
the time period t, as specified in the appropriate regulation, in mm
H2O.
3.2 Allowable vacuum change (v) means the allowable amount
of decrease in vacuum during the static vacuum test, within the time
period t, as specified in the appropriate regulation, in mm
H2O.
3.3 Compartment means a liquid-tight division of a delivery tank.
3.4 Delivery tank means a container, including associated pipes and
fittings, that is attached to or forms a part of any truck, trailer, or
railcar used for the transport of gasoline.
3.5 Delivery tank vapor collection equipment means any piping,
hoses, and devices on the delivery tank used to collect and route
gasoline vapors either from the tank to a bulk terminal vapor control
system or from a bulk plant or service station into the tank.
3.6 Gasoline means a petroleum distillate or petroleum distillate/
alcohol blend having a Reid vapor pressure of 27.6 kilopascals or
greater which is used as a fuel for internal combustion engines.
3.7 Initial pressure (Pi) means the pressure applied to
the delivery tank at the beginning of the static pressure test, as
specified in the appropriate regulation, in mm H2O.
3.8 Initial vacuum (Vi) means the vacuum applied to the
delivery tank at the beginning of the static vacuum test, as specified
in the appropriate regulation, in mm H3.
3.9 Time period of the pressure or vacuum test (t) means the time
period of the test, as specified in the appropriate regulation, during
which the change in pressure or vacuum is monitored, in minutes.

4.0 Interferences [Reserved]

5.0 Safety

5.1 Gasoline contains several volatile organic compounds (e.g.
benzene and hexane) which presents a potential for fire and/or
explosions. It is advisable to take appropriate precautions when testing
a gasoline vessel's vapor tightness, such as refraining from smoking and
using explosion-proof equipment.
5.2 This method may involve hazardous materials, operations, and
equipment. This test method may not address all of the safety problems
associated with its use. It is the responsibility of the user of this
test method to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to
performing this test method

6.0 Equipment and Supplies

The following equipment and supplies are required for testing:
6.1 Pressure Source. Pump or compressed gas cylinder of air or
inert gas sufficient to pressurize the delivery tank to 500 mm (20 in.)
H2O above atmospheric pressure.
6.2 Regulator. Low pressure regulator for controlling
pressurization of the delivery tank.
6.3 Vacuum Source. Vacuum pump capable of evacuating the delivery
tank to 250 mm (10 in.) H2O below atmospheric pressure.
6.4 Pressure-Vacuum Supply Hose.
6.5 Manometer. Liquid manometer, or equivalent instrument, capable
of measuring up to 500 mm (20 in.) H2O gauge pressure with
2.5 mm (0.1 in.) H2O precision.
6.6 Pressure-Vacuum Relief Valves. The test apparatus shall be
equipped with an inline pressure-vacuum relief valve set to activate at
675 mm (26.6 in.) H2O above atmospheric pressure or 250 mm
(10 in.) H2O below atmospheric pressure, with a capacity equal to the
pressurizing or evacuating pumps.
6.7 Test Cap for Vapor Recovery Hose. This cap shall have a tap for
manometer connection and a fitting with shut-off valve for connection to
the pressure-vacuum supply hose.
6.8 Caps for Liquid Delivery Hoses.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Pretest Preparations.
8.1.1 Summary. Testing problems may occur due to the presence of
volatile vapors and/or temperature fluctuations inside the delivery
tank. Under these conditions, it is often difficult to obtain a stable
initial pressure at the beginning of a test, and erroneous test results
may occur. To help prevent this, it is recommended that prior to
testing, volatile vapors be removed from the tank and the temperature
inside the tank be allowed to stabilize. Because it is not always
possible to completely attain these pretest conditions, a provision to
ensure reproducible results is included. The difference in results for
two consecutive runs must meet the criteria in Sections 8.2.2.5 and
8.2.3.5.
8.1.2 Emptying of Tank. The delivery tank shall be emptied of all
liquid.
8.1.3 Purging of Vapor. As much as possible the delivery tank shall
be purged of all volatile vapors by any safe, acceptable method. One
method is to carry a load of non-volatile liquid fuel, such as diesel or
heating oil, immediately prior to the test, thus flushing out all the
volatile gasoline vapors. A second method is to remove the volatile
vapors by blowing ambient air into each tank compartment for at least 20
minutes. This second method is usually not as effective and

[[Page 566]]

often causes stabilization problems, requiring a much longer time for
stabilization during the testing.
8.1.4 Temperature Stabilization. As much as possible, the test
shall be conducted under isothermal conditions. The temperature of the
delivery tank should be allowed to equilibrate in the test environment.
During the test, the tank should be protected from extreme environmental
and temperature variability, such as direct sunlight.
8.2 Test Procedure.
8.2.1 Preparations.
8.2.1.1 Open and close each dome cover.
8.2.1.2 Connect static electrical ground connections to the tank.
Attach the liquid delivery and vapor return hoses, remove the liquid
delivery elbows, and plug the liquid delivery fittings.

Note: The purpose of testing the liquid delivery hoses is to detect
tears or holes that would allow liquid leakage during a delivery. Liquid
delivery hoses are not considered to be possible sources of vapor
leakage, and thus, do not have to be attached for a vapor leakage test.
Instead, a liquid delivery hose could be either visually inspected, or
filled with water to detect any liquid leakage.

8.2.1.3 Attach the test cap to the end of the vapor recovery hose.
8.2.1.4 Connect the pressure-vacuum supply hose and the pressure-
vacuum relief valve to the shut-off valve. Attach a manometer to the
pressure tap.
8.2.1.5 Connect compartments of the tank internally to each other
if possible. If not possible, each compartment must be tested
separately, as if it were an individual delivery tank.
8.2.2 Pressure Test.
8.2.2.1 Connect the pressure source to the pressure-vacuum supply
hose.
8.2.2.2 Open the shut-off valve in the vapor recovery hose cap.
Apply air pressure slowly, pressurize the tank to Pi, the
initial pressure specified in the regulation.
8.2.2.3 Close the shut-off and allow the pressure in the tank to
stabilize, adjusting the pressure if necessary to maintain pressure of
Pi. When the pressure stabilizes, record the time and initial
pressure.
8.2.2.4 At the end of the time period (t) specified in the
regulation, record the time and final pressure.
8.2.2.5 Repeat steps 8.2.2.2 through 8.2.2.4 until the change in
pressure for two consecutive runs agrees within 12.5 mm (0.5 in.)
H2O. Calculate the arithmetic average of the two results.
8.2.2.6 Compare the average measured change in pressure to the
allowable pressure change, p, specified in the regulation. If
the delivery tank does not satisfy the vapor tightness criterion
specified in the regulation, repair the sources of leakage, and repeat
the pressure test until the criterion is met.
8.2.2.7 Disconnect the pressure source from the pressure-vacuum
supply hose, and slowly open the shut-off valve to bring the tank to
atmospheric pressure.
8.2.3 Vacuum Test.
8.2.3.1 Connect the vacuum source to the pressure-vacuum supply
hose.
8.2.3.2 Open the shut-off valve in the vapor recovery hose cap.
Slowly evacuate the tank to Vi, the initial vacuum specified
in the regulation.
8.2.3.3 Close the shut-off valve and allow the pressure in the tank
to stabilize, adjusting the pressure if necessary to maintain a vacuum
of Vi. When the pressure stabilizes, record the time and
initial vacuum.
8.2.3.4 At the end of the time period specified in the regulation
(t), record the time and final vacuum.
8.2.3.5 Repeat steps 8.2.3.2 through 8.2.3.4 until the change in
vacuum for two consecutive runs agrees within 12.5 mm (0.5 in.)
H2O. Calculate the arithmetic average of the two results.
8.2.3.6 Compare the average measured change in vacuum to the
allowable vacuum change, v, as specified in the regulation. If
the delivery tank does not satisfy the vapor tightness criterion
specified in the regulation, repair the sources of leakage, and repeat
the vacuum test until the criterion is met.
8.2.3.7 Disconnect the vacuum source from the pressure-vacuum
supply hose, and slowly open the shut-off valve to bring the tank to
atmospheric pressure.
8.2.4 Post-Test Clean-up. Disconnect all test equipment and return
the delivery tank to its pretest condition.

9.0 Quality Control

------------------------------------------------------------------------
Quality control
Section(s) measure Effect
------------------------------------------------------------------------
8.2.2.5, 8.3.3.5.............. Repeat test Ensures data
procedures until precision.
change in
pressure or
vacuum for two
consecutive runs
agrees within

12.5 mm (0.5
in.) H2O.
------------------------------------------------------------------------

[[Page 567]]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedures [Reserved]

12.0 Data Analysis and Calculations [Reserved]

13.0 Method Performance

13.1 Precision. The vapor tightness of a gasoline delivery tank
under positive or negative pressure, as measured by this method, is
precise within 12.5 mm (0.5 in.) H2O
13.2 Bias. No bias has been identified.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 The pumping of water into the bottom of a delivery tank is an
acceptable alternative to the pressure source described above. Likewise,
the draining of water out of the bottom of a delivery tank may be
substituted for the vacuum source. Note that some of the specific step-
by-step procedures in the method must be altered slightly to accommodate
these different pressure and vacuum sources.
16.2 Techniques other than specified above may be used for purging
and pressurizing a delivery tank, if prior approval is obtained from the
Administrator. Such approval will be based upon demonstrated equivalency
with the above method.

17.0 References [Reserved]

18.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Method 28--Certification and Auditing of Wood Heaters

Note: This method does not include all of the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 1, Method 2, Method 3,
Method 4, Method 5, Method 5G, Method 5H, Method 6, Method 6C, and
Method 16A.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.
1.2 Applicability. This method is applicable for the certification
and auditing of wood heaters, including pellet burning wood heaters.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 Particulate matter emissions are measured from a wood heater
burning a prepared test fuel crib in a test facility maintained at a set
of prescribed conditions. Procedures for determining burn rates and
particulate emission rates and for reducing data are provided.

3.0 Definitions

3.1 2 x 4 or 4 x 4 means two inches by four inches or four
inches by four inches (50 mm by 100 mm or 100 mm by 100 mm), as nominal
dimensions for lumber.
3.2 Burn rate means the rate at which test fuel is consumed in a
wood heater. Measured in kilograms or lbs of wood (dry basis) per hour
(kg/hr or lb/hr).
3.3 Certification or audit test means a series of at least four
test runs conducted for certification or audit purposes that meets the
burn rate specifications in Section 8.4.
3.4 Firebox means the chamber in the wood heater in which the test
fuel charge is placed and combusted.
3.5 Height means the vertical distance extending above the loading
door, if fuel could reasonably occupy that space, but not more than 2
inches above the top (peak height) of the loading door, to the floor of
the firebox (i.e., below a permanent grate) if the grate allows a 1-inch
diameter piece of wood to pass through the grate, or, if not, to the top
of the grate. Firebox height is not necessarily uniform but must account
for variations caused by internal baffles, air channels, or other
permanent obstructions.
3.6 Length means the longest horizontal fire chamber dimension that
is parallel to a wall of the chamber.
3.7 Pellet burning wood heater means a wood heater which meets the
following criteria: (1) The manufacturer makes no reference to burning
cord wood in advertising or other literature, (2) the unit is safety
listed for pellet fuel only, (3) the unit operating and instruction
manual must state that the use of cordwood is prohibited by law, and (4)
the unit must be manufactured and sold including the hopper and auger
combination as integral parts.
3.8 Secondary air supply means an air supply that introduces air to
the wood heater such that the burn rate is not altered by more than 25
percent when the secondary air supply is adjusted during the test run.
The wood heater manufacturer can document this through design drawings
that show the secondary air is introduced only into a mixing chamber or
secondary chamber outside the firebox.
3.9 Test facility means the area in which the wood heater is
installed, operated, and sampled for emissions.

[[Page 568]]

3.10 Test fuel charge means the collection of test fuel pieces
placed in the wood heater at the start of the emission test run.
3.11 Test fuel crib means the arrangement of the test fuel charge
with the proper spacing requirements between adjacent fuel pieces.
3.12 Test fuel loading density means the weight of the as-fired
test fuel charge per unit volume of usable firebox.
3.13 Test fuel piece means the 2 x 4 or 4 x 4 wood piece cut to
the length required for the test fuel charge and used to construct the
test fuel crib.
3.14 Test run means an individual emission test which encompasses
the time required to consume the mass of the test fuel charge.
3.15 Usable firebox volume means the volume of the firebox
determined using its height, length, and width as defined in this
section.
3.16 Width means the shortest horizontal fire chamber dimension
that is parallel to a wall of the chamber.
3.17 Wood heater means an enclosed, woodburning appliance capable
of and intended for space heating or domestic water heating, as defined
in the applicable regulation.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Section 6.0 of either Method 5G or Method 5H, with the
addition of the following:
6.1 Insulated Solid Pack Chimney. For installation of wood heaters.
Solid pack insulated chimneys shall have a minimum of 2.5 cm (1 in.)
solid pack insulating material surrounding the entire flue and possess a
label demonstrating conformance to U.L. 103 (incorporated by reference--
see Sec. 60.17).
6.2 Platform Scale and Monitor. For monitoring of fuel load weight
change. The scale shall be capable of measuring weight to within 0.05 kg
(0.1 lb) or 1 percent of the initial test fuel charge weight, whichever
is greater.
6.3 Wood Heater Temperature Monitors. Seven, each capable of
measuring temperature to within 1.5 percent of expected absolute
temperatures.
6.4 Test Facility Temperature Monitor. A thermocouple located
centrally in a vertically oriented 150 mm (6 in.) long, 50 mm (2 in.)
diameter pipe shield that is open at both ends, capable of measuring
temperature to within 1.5 percent of expected temperatures.
6.5 Balance (optional). Balance capable of weighing the test fuel
charge to within 0.05 kg (0.1 lb).
6.6 Moisture Meter. Calibrated electrical resistance meter for
measuring test fuel moisture to within 1 percent moisture content.
6.7 Anemometer. Device capable of detecting air velocities less
than 0.10 m/sec (20 ft/min), for measuring air velocities near the test
appliance.
6.8 Barometer. Mercury, aneroid or other barometer capable of
measuring atmospheric pressure to within 2.5 mm Hg (0.1 in. Hg).
6.9 Draft Gauge. Electromanometer or other device for the
determination of flue draft or static pressure readable to within 0.50
Pa (0.002 in. H2O).
6.10 Humidity Gauge. Psychrometer or hygrometer for measuring room
humidity.
6.11 Wood Heater Flue.
6.11.1 Steel flue pipe extending to 2.6 0.15 m (8.5
0.5 ft) above the top of the platform scale, and above this
level, insulated solid pack type chimney extending to 4.6
0.3 m (15 1 ft) above the platform scale, and of the size
specified by the wood heater manufacturer. This applies to both
freestanding and insert type wood heaters.
6.11.2 Other chimney types (e.g., solid pack insulated pipe) may be
used in place of the steel flue pipe if the wood heater manufacturer's
written appliance specifications require such chimney for home
installation (e.g., zero clearance wood heater inserts). Such
alternative chimney or flue pipe must remain and be sealed with the wood
heater following the certification test.
6.12 Test Facility. The test facility shall meet the following
requirements during testing:
6.12.1 The test facility temperature shall be maintained between 18
and 32 deg.C (65 and 90 deg.F) during each test run.
6.12.2 Air velocities within 0.6 m (2 ft) of the test appliance and
exhaust system shall be less than 0.25 m/sec (50 ft/min) without fire in
the unit.
6.12.3 The flue shall discharge into the same space or into a space
freely communicating with the test facility. Any hood or similar device
used to vent combustion products shall not induce a draft greater than
1.25 Pa (0.005 in. H2O) on the wood heater measured when the
wood heater is not operating.
6.12.4 For test facilities with artificially induced barometric
pressures (e.g., pressurized chambers), the barometric pressure in the
test facility shall not exceed 775 mm Hg (30.5 in. Hg) during any test
run.

[[Page 569]]

7.0 Reagents and Standards

Same as Section 6.0 of either Method 5G or Method 5H, with the
addition of the following:
7.1 Test Fuel. The test fuel shall conform to the following
requirements:
7.1.1 Fuel Species. Untreated, air-dried, Douglas fir lumber. Kiln-
dried lumber is not permitted. The lumber shall be certified C grade
(standard) or better Douglas fir by a lumber grader at the mill of
origin as specified in the West Coast Lumber Inspection Bureau Standard
No. 16 (incorporated by reference--see Sec. 60.17).
7.1.2 Fuel Moisture. The test fuel shall have a moisture content
range between 16 to 20 percent on a wet basis (19 to 25 percent dry
basis). Addition of moisture to previously dried wood is not allowed. It
is recommended that the test fuel be stored in a temperature and
humidity-controlled room.
7.1.3 Fuel Temperature. The test fuel shall be at the test facility
temperature of 18 to 32 deg.C (65 to 90 deg.F).
7.1.4 Fuel Dimensions. The dimensions of each test fuel piece shall
conform to the nominal measurements of 2 x 4 and 4 x 4 lumber. Each
piece of test fuel (not including spacers) shall be of equal length,
except as necessary to meet requirements in Section 8.8, and shall
closely approximate \5/6\ the dimensions of the length of the usable
firebox. The fuel piece dimensions shall be determined in relation to
the appliance's firebox volume according to guidelines listed below:
7.1.4.1 If the usable firebox volume is less than or equal to 0.043
m³ (1.5 ft³), use 2 x 4 lumber.
7.1.4.2 If the usable firebox volume is greater than 0.043
m³ (1.5 ft³) and less than or equal to 0.085
m³ (3.0 ft³), use 2 x 4 and 4 x 4 lumber. About
half the weight of the test fuel charge shall be 2 x 4 lumber, and the
remainder shall be 4 x 4 lumber.
7.1.4.3 If the usable firebox volume is greater than 0.085
m³ (3.0 ft³), use 4 x 4 lumber.
7.2 Test Fuel Spacers. Air-dried, Douglas fir lumber meeting the
requirements outlined in Sections 7.1.1 through 7.1.3. The spacers shall
be 130 x 40 x 20 mm (5 x 1.5 x 0.75 in.).

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Test Run Requirements.
8.1.1 Burn Rate Categories. One emission test run is required in
each of the following burn rate categories:

Burn Rate Categories
[Average kg/hr (lb/hr), dry basis]
----------------------------------------------------------------------------------------------------------------
Category 1 Category 2 Category 3 Category 4
----------------------------------------------------------------------------------------------------------------
0.80................................. 0.80 to 1.25........... 1.25 to 1.90........... Maximum.
(1.76)............................... (1.76 to 2.76)......... (2.76 to 4.19)......... burn rate.
----------------------------------------------------------------------------------------------------------------

8.1.1.1 Maximum Burn Rate. For Category 4, the wood heater shall be
operated with the primary air supply inlet controls fully open (or, if
thermostatically controlled, the thermostat shall be set at maximum heat
output) during the entire test run, or the maximum burn rate setting
specified by the manufacturer's written instructions.
8.1.1.2 Other Burn Rate Categories. For burn rates in Categories 1
through 3, the wood heater shall be operated with the primary air supply
inlet control, or other mechanical control device, set at a
predetermined position necessary to obtain the average burn rate
required for the category.
8.1.1.3 Alternative Burn Rates for Burn Rate Categories 1 and 2.
8.1.1.3.1 If a wood heater cannot be operated at a burn rate below
0.80 kg/hr (1.76 lb/hr), two test runs shall be conducted with burn
rates within Category 2. If a wood heater cannot be operated at a burn
rate below 1.25 kg/hr (2.76 lb/hr), the flue shall be dampered or the
air supply otherwise controlled in order to achieve two test runs within
Category 2.
8.1.1.3.2 Evidence that a wood heater cannot be operated at a burn
rate less than 0.80 kg/hr shall include documentation of two or more
attempts to operate the wood heater in burn rate Category 1 and fuel
combustion has stopped, or results of two or more test runs
demonstrating that the burn rates were greater than 0.80 kg/hr when the
air supply controls were adjusted to the lowest possible position or
settings. Stopped fuel combustion is evidenced when an elapsed time of
30 minutes or more has occurred without a measurable ( 0.05 kg (0.1 lb)
or 1.0 percent, whichever is greater) weight change in the test fuel
charge. See also Section 8.8.3. Report the evidence and the reasoning
used to determine that a test in burn rate Category 1 cannot be
achieved; for example, two unsuccessful attempts to operate at a burn
rate of 0.4 kg/hr are not sufficient evidence that burn rate Category 1
cannot be achieved.
Note: After July 1, 1990, if a wood heater cannot be operated at a
burn rate less than 0.80 kg/hr, at least one test run with an average
burn rate of 1.00 kg/hr or less shall be conducted. Additionally, if
flue dampering must be used to achieve burn rates below 1.25

[[Page 570]]

kg/hr (or 1.0 kg/hr), results from a test run conducted at burn rates
below 0.90 kg/hr need not be reported or included in the test run
average provided that such results are replaced with results from a test
run meeting the criteria above.

8.2 Catalytic Combustor and Wood Heater Aging. The catalyst-
equipped wood heater or a wood heater of any type shall be aged before
the certification test begins. The aging procedure shall be conducted
and documented by a testing laboratory accredited according to
procedures in Sec. 60.535 of 40 CFR part 60.
8.2.1 Catalyst-equipped Wood Heater. Operate the catalyst-equipped
wood heater using fuel meeting the specifications outlined in Sections
7.1.1 through 7.1.3, or cordwood with a moisture content between 15 and
25 percent on a wet basis. Operate the wood heater at a medium burn rate
(Category 2 or 3) with a new catalytic combustor in place and in
operation for at least 50 hours. Record and report hourly catalyst exit
temperature data (Section 8.6.2) and the hours of operation.
8.2.2 Non-Catalyst Wood Heater. Operate the wood heater using the
fuel described in Section 8.4.1 at a medium burn rate for at least 10
hours. Record and report the hours of operation.
8.3 Pretest Recordkeeping. Record the test fuel charge dimensions
and weights, and wood heater and catalyst descriptions as shown in the
example in Figure 28-1.
8.4 Wood Heater Installation. Assemble the wood heater appliance
and parts in conformance with the manufacturer's written installation
instructions. Place the wood heater centrally on the platform scale and
connect the wood heater to the flue described in Section 6.11. Clean the
flue with an appropriately sized, wire chimney brush before each
certification test.
8.5 Wood Heater Temperature Monitors.
8.5.1 For catalyst-equipped wood heaters, locate a temperature
monitor (optional) about 25 mm (1 in.) upstream of the catalyst at the
centroid of the catalyst face area, and locate a temperature monitor
(mandatory) that will indicate the catalyst exhaust temperature. This
temperature monitor is centrally located within 25 mm (1 in.) downstream
at the centroid of catalyst face area. Record these locations.
8.5.2 Locate wood heater surface temperature monitors at five
locations on the wood heater firebox exterior surface. Position the
temperature monitors centrally on the top surface, on two sidewall
surfaces, and on the bottom and back surfaces. Position the monitor
sensing tip on the firebox exterior surface inside of any heat shield,
air circulation walls, or other wall or shield separated from the
firebox exterior surface. Surface temperature locations for unusual
design shapes (e.g., spherical, etc.) shall be positioned so that there
are four surface temperature monitors in both the vertical and
horizontal planes passing at right angles through the centroid of the
firebox, not including the fuel loading door (total of five temperature
monitors).
8.6 Test Facility Conditions.
8.6.1 Locate the test facility temperature monitor on the
horizontal plane that includes the primary air intake opening for the
wood heater. Locate the temperature monitor 1 to 2 m (3 to 6 ft) from
the front of the wood heater in the 90 deg. sector in front of the wood
heater.
8.6.2 Use an anemometer to measure the air velocity. Measure and
record the room air velocity before the pretest ignition period (Section
8.7) and once immediately following the test run completion.
8.6.3 Measure and record the test facility's ambient relative
humidity, barometric pressure, and temperature before and after each
test run.
8.6.4 Measure and record the flue draft or static pressure in the
flue at a location no greater than 0.3 m (1 ft) above the flue connector
at the wood heater exhaust during the test run at the recording
intervals (Section 8.8.2).
8.7 Wood Heater Firebox Volume.
8.7.1 Determine the firebox volume using the definitions for
height, width, and length in Section 3. Volume adjustments due to
presence of firebrick and other permanent fixtures may be necessary.
Adjust width and length dimensions to extend to the metal wall of the
wood heater above the firebrick or permanent obstruction if the
firebrick or obstruction extending the length of the side(s) or back
wall extends less than one-third of the usable firebox height. Use the
width or length dimensions inside the firebrick if the firebrick extends
more than one-third of the usable firebox height. If a log retainer or
grate is a permanent fixture and the manufacturer recommends that no
fuel be placed outside the retainer, the area outside of the retainer is
excluded from the firebox volume calculations.
8.7.2 In general, exclude the area above the ash lip if that area
is less than 10 percent of the usable firebox volume. Otherwise, take
into account consumer loading practices. For instance, if fuel is to be
loaded front-to-back, an ash lip may be considered usable firebox
volume.
8.7.3 Include areas adjacent to and above a baffle (up to two
inches above the fuel loading opening) if four inches or more horizontal
space exist between the edge of the baffle and a vertical obstruction
(e.g., sidewalls or air channels).
8.8 Test Fuel Charge.
8.8.1 Prepare the test fuel pieces in accordance with the
specifications outlined in Sections 7.1 and 7.2. Determine the test fuel
moisture content with a calibrated electrical

[[Page 571]]

resistance meter or other equivalent performance meter. If necessary,
convert fuel moisture content values from dry basis (%Md) to
wet basis (%Mw) in Section 12.2 using Equation 28-1.
Determine fuel moisture for each fuel piece (not including spacers) by
averaging at least three moisture meter readings, one from each of three
sides, measured parallel to the wood grain. Average all the readings for
all the fuel pieces in the test fuel charge. If an electrical resistance
type meter is used, penetration of insulated electrodes shall be one-
fourth the thickness of the test fuel piece or 19 mm (0.75 in.),
whichever is greater. Measure the moisture content within a 4-hour
period prior to the test run. Determine the fuel temperature by
measuring the temperature of the room where the wood has been stored for
at least 24 hours prior to the moisture determination.
8.8.2 Attach the spacers to the test fuel pieces with uncoated,
ungalvanized nails or staples as illustrated in Figure 28-2. Attachment
of spacers to the top of the test fuel piece(s) on top of the test fuel
charge is optional.
8.8.3 To avoid stacking difficulties, or when a whole number of
test fuel pieces does not result, all piece lengths shall be adjusted
uniformly to remain within the specified loading density. The shape of
the test fuel crib shall be geometrically similar to the shape of the
firebox volume without resorting to special angular or round cuts on the
individual fuel pieces.
8.8.4 The test fuel loading density shall be 112 11.2
kg/m³ (7 0.7 lb/ft³) of usable
firebox volume on a wet basis.
8.9 Sampling Equipment. Prepare the sampling equipment as defined
by the selected method (i.e., either Method 5G or Method 5H). Collect
one particulate emission sample for each test run.
8.10 Secondary Air Adjustment Validation.
8.10.1 If design drawings do not show the introduction of secondary
air into a chamber outside the firebox (see ``secondary air supply''
under Section 3.0, Definitions), conduct a separate test of the wood
heater's secondary air supply. Operate the wood heater at a burn rate in
Category 1 (Section 8.1.1) with the secondary air supply operated
following the manufacturer's written instructions. Start the secondary
air validation test run as described in Section 8.8.1, except no
emission sampling is necessary and burn rate data shall be recorded at
5-minute intervals.
8.10.2 After the start of the test run, operate the wood heater
with the secondary air supply set as per the manufacturer's
instructions, but with no adjustments to this setting. After 25 percent
of the test fuel has been consumed, adjust the secondary air supply
controls to another setting, as per the manufacturer's instructions.
Record the burn rate data (5-minute intervals) for 20 minutes following
the air supply adjustment.
8.10.3 Adjust the air supply control(s) to the original
position(s), operate at this condition for at least 20 minutes, and
repeat the air supply adjustment procedure above. Repeat the procedure
three times at equal intervals over the entire burn period as defined in
Section 8.8. If the secondary air adjustment results in a burn rate
change of more than an average of 25 percent between the 20-minute
periods before and after the secondary adjustments, the secondary air
supply shall be considered a primary air supply, and no adjustment to
this air supply is allowed during the test run.
8.10.4 The example sequence below describes a typical secondary air
adjustment validation check. The first cycle begins after at least 25
percent of the test fuel charge has been consumed.

Cycle 1
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min
Cycle 2
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min
Cycle 3
Part 1, sec air adjusted to final position--20 min
Part 2, sec air adjusted to final position--20 min
Part 3, sec air adjusted to final position--20 min

Note that the cycles may overlap; that is, Part 3 of Cycle 1 may
coincide in part or in total with Part 1 of Cycle 2. The calculation of
the secondary air percent effect for this example is as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.425

[[Page 572]]

8.11 Pretest Ignition. Build a fire in the wood heater in
accordance with the manufacturer's written instructions.
8.11.1 Pretest Fuel Charge. Crumpled newspaper loaded with kindling
may be used to help ignite the pretest fuel. The pretest fuel, used to
sustain the fire, shall meet the same fuel requirements prescribed in
Section 7.1. The pretest fuel charge shall consist of whole 2 x 4's that
are no less than \1/3\ the length of the test fuel pieces. Pieces of
4 x 4 lumber in approximately the same weight ratio as for the test fuel
charge may be added to the pretest fuel charge.
8.11.2 Wood Heater Operation and Adjustments. Set the air inlet
supply controls at any position that will maintain combustion of the
pretest fuel load. At least one hour before the start of the test run,
set the air supply controls at the approximate positions necessary to
achieve the burn rate desired for the test run. Adjustment of the air
supply controls, fuel addition or subtractions, and coalbed raking shall
be kept to a minimum but are allowed up to 15 minutes prior to the start
of the test run. For the purposes of this method, coalbed raking is the
use of a metal tool (poker) to stir coals, break burning fuel into
smaller pieces, dislodge fuel pieces from positions of poor combustion,
and check for the condition of uniform charcoalization. Record all
adjustments made to the air supply controls, adjustments to and
additions or subtractions of fuel, and any other changes to wood heater
operations that occur during pretest ignition period. Record fuel weight
data and wood heater temperature measurements at 10-minute intervals
during the hour of the pretest ignition period preceding the start of
the test run. During the 15-minute period prior to the start of the test
run, the wood heater loading door shall not be open more than a total of
1 minute. Coalbed raking is the only adjustment allowed during this
period.

Note: One purpose of the pretest ignition period is to achieve
uniform charcoalization of the test fuel bed prior to loading the test
fuel charge. Uniform charcoalization is a general condition of the test
fuel bed evidenced by an absence of large pieces of burning wood in the
coal bed and the remaining fuel pieces being brittle enough to be broken
into smaller charcoal pieces with a metal poker. Manipulations to the
fuel bed prior to the start of the test run should be done to achieve
uniform charcoalization while maintaining the desired burn rate. In
addition, some wood heaters (e.g., high mass units) may require extended
pretest burn time and fuel additions to reach an initial average surface
temperature sufficient to meet the thermal equilibrium criteria in
Section 8.3.

8.11.3 The weight of pretest fuel remaining at the start of the
test run is determined as the difference between the weight of the wood
heater with the remaining pretest fuel and the tare weight of the
cleaned, dry wood heater with or without dry ash or sand added
consistent with the manufacturer's instructions and the owner's manual.
The tare weight of the wood heater must be determined with the wood
heater (and ash, if added) in a dry condition.
8.12 Test Run. Complete a test run in each burn rate category, as
follows:
8.12.1 Test Run Start.
8.12.1.1 When the kindling and pretest fuel have been consumed to
leave a fuel weight between 20 and 25 percent of the weight of the test
fuel charge, record the weight of the fuel remaining and start the test
run. Record and report any other criteria, in addition to those
specified in this section, used to determine the moment of the test run
start (e.g., firebox or catalyst temperature), whether such criteria are
specified by the wood heater manufacturer or the testing laboratory.
Record all wood heater individual surface temperatures, catalyst
temperatures, any initial sampling method measurement values, and begin
the particulate emission sampling. Within 1 minute following the start
of the test run, open the wood heater door, load the test fuel charge,
and record the test fuel charge weight. Recording of average, rather
than individual, surface temperatures is acceptable for tests conducted
in accordance with Sec. 60.533(o)(3)(i) of 40 CFR part 60.
8.12.1.2 Position the fuel charge so that the spacers are parallel
to the floor of the firebox, with the spacer edges abutting each other.
If loading difficulties result, some fuel pieces may be placed on edge.
If the usable firebox volume is between 0.043 and 0.085 m³
(1.5 and 3.0 ft³), alternate the piece sizes in vertical
stacking layers to the extent possible. For example, place 2 x 4's on
the bottom layer in direct contact with the coal bed and 4 x 4's on
the next layer, etc. (See Figure 28-3). Position the fuel pieces
parallel to each other and parallel to the longest wall of the firebox
to the extent possible within the specifications in Section 8.8.
8.12.1.3 Load the test fuel in appliances having unusual or
unconventional firebox design maintaining air space intervals between
the test fuel pieces and in conformance with the manufacturer's written
instructions. For any appliance that will not accommodate the loading
arrangement specified in the paragraph above, the test facility
personnel shall contact the Administrator for an alternative loading
arrangement.
8.12.1.4 The wood heater door may remain open and the air supply
controls adjusted up to five minutes after the start of the test run in
order to make adjustments to the test fuel charge and to ensure ignition
of the test fuel charge has occurred. Within the five minutes after the
start of the test run, close the wood heater door and adjust the air
supply controls to the position determined to produce

[[Page 573]]

the desired burn rate. No other adjustments to the air supply controls
or the test fuel charge are allowed (except as specified in Sections
8.12.3 and 8.12.4) after the first five minutes of the test run. Record
the length of time the wood heater door remains open, the adjustments to
the air supply controls, and any other operational adjustments.
8.12.2 Data Recording. Record on a data sheet similar to that shown
in Figure 28-4, at intervals no greater than 10 minutes, fuel weight
data, wood heater individual surface and catalyst temperature
measurements, other wood heater operational data (e.g., draft), test
facility temperature and sampling method data.
8.12.3 Test Fuel Charge Adjustment. The test fuel charge may be
adjusted (i.e., repositioned) once during a test run if more than 60
percent of the initial test fuel charge weight has been consumed and
more than 10 minutes have elapsed without a measurable (0.05 kg (0.1 lb)
or 1.0 percent, whichever is greater) weight change. The time used to
make this adjustment shall be less than 15 seconds.
8.12.4 Air Supply Adjustment. Secondary air supply controls may be
adjusted once during the test run following the manufacturer's written
instructions (see Section 8.10). No other air supply adjustments are
allowed during the test run. Recording of wood heater flue draft during
the test run is optional for tests conducted in accordance with
Sec. 60.533(o)(3)(i) of 40 CFR part 60.
8.12.5 Auxiliary Wood Heater Equipment Operation. Heat exchange
blowers sold with the wood heater shall be operated during the test run
following the manufacturer's written instructions. If no manufacturer's
written instructions are available, operate the heat exchange blower in
the ``high'' position. (Automatically operated blowers shall be operated
as designed.) Shaker grates, by-pass controls, or other auxiliary
equipment may be adjusted only one time during the test run following
the manufacturer's written instructions.
Record all adjustments on a wood heater operational written record.

Note: If the wood heater is sold with a heat exchange blower as an
option, test the wood heater with the heat exchange blower operating as
described in Sections 8.1 through 8.12 and report the results. As an
alternative to repeating all test runs without the heat exchange blower
operating, one additional test run may be without the blower operating
as described in Section 8.12.5 at a burn rate in Category 2 (Section
8.1.1). If the emission rate resulting from this test run without the
blower operating is equal to or less than the emission rate plus 1.0 g/
hr (0.0022 lb/hr) for the test run in burn rate Category 2 with the
blower operating, the wood heater may be considered to have the same
average emission rate with or without the blower operating. Additional
test runs without the blower operating are unnecessary.

8.13 Test Run Completion. Continue emission sampling and wood
heater operation for 2 hours. The test run is completed when the
remaining weight of the test fuel charge is 0.00 kg (0.0 lb). End the
test run when the scale has indicated a test fuel charge weight of 0.00
kg (0.0 lb) or less for 30 seconds. At the end of the test run, stop the
particulate sampling, and record the final fuel weight, the run time,
and all final measurement values.
8.14 Wood Heater Thermal Equilibrium. The average of the wood
heater surface temperatures at the end of the test run shall agree with
the average surface temperature at the start of the test run to within
70 deg.C (126 deg.F).
8.15 Consecutive Test Runs. Test runs on a wood heater may be
conducted consecutively provided that a minimum one-hour interval occurs
between test runs.
8.16 Additional Test Runs. The testing laboratory may conduct more
than one test run in each of the burn rate categories specified in
Section 8.1.1. If more than one test run is conducted at a specified
burn rate, the results from at least two-thirds of the test runs in that
burn rate category shall be used in calculating the weighted average
emission rate (see Section 12.2). The measurement data and results of
all test runs shall be reported regardless of which values are used in
calculating the weighted average emission rate (see Note in Section
8.1).

9.0 Quality Control

Same as Section 9.0 of either Method 5G or Method 5H.

10.0 Calibration and Standardizations

Same as Section 10.0 of either Method 5G or Method 5H, with the
addition of the following:
10.1 Platform Scale. Perform a multi-point calibration (at least
five points spanning the operational range) of the platform scale before
its initial use. The scale manufacturer's calibration results are
sufficient for this purpose. Before each certification test, audit the
scale with the wood heater in place by weighing at least one calibration
weight (Class F) that corresponds to between 20 percent and 80 percent
of the expected test fuel charge weight. If the scale cannot reproduce
the value of the calibration weight within 0.05 kg (0.1 lb) or 1 percent
of the expected test fuel charge weight, whichever is greater,
recalibrate the scale before use with at least five calibration weights
spanning the operational range of the scale.
10.2 Balance (optional). Calibrate as described in Section 10.1.

[[Page 574]]

10.3 Temperature Monitor. Calibrate as in Method 2, Section 4.3,
before the first certification test and semiannually thereafter.
10.4 Moisture Meter. Calibrate as per the manufacturer's
instructions before each certification test.
10.5 Anemometer. Calibrate the anemometer as specified by the
manufacturer's instructions before the first certification test and
semiannually thereafter.
10.6 Barometer. Calibrate against a mercury barometer before the
first certification test and semiannually thereafter.
10.7 Draft Gauge. Calibrate as per the manufacturer's instructions;
a liquid manometer does not require calibration.
10.8 Humidity Gauge. Calibrate as per the manufacturer's
instructions before the first certification test and semiannually
thereafter.

11.0 Analytical Procedures

Same as Section 11.0 of either Method 5G or Method 5H.

12.0 Data Analysis and Calculations

Same as Section 12.0 of either Method 5G or Method 5H, with the
addition of the following:
12.1 Nomenclature.

BR = Dry wood burn rate, kg/hr (lb/hr)
Ei = Emission rate for test run, i, from Method 5G or 5H, g/
hr (lb/hr)
Ew = Weighted average emission rate, g/hr (lb/hr)
ki = Test run weighting factor = Pi+1 -
Pi-1
%Md = Fuel moisture content, dry basis, percent.
%Mw = Average moisture in test fuel charge, wet basis,
percent.
n = Total number of test runs.
Pi = Probability for burn rate during test run, i, obtained
from Table 28-1. Use linear interpolation to determine
probability values for burn rates between those listed on the
table.
Wwd = Total mass of wood burned during the test run, kg (lb).

12.2 Wet Basis Fuel Moisture Content.
[GRAPHIC] [TIFF OMITTED] TR17OC00.426

12.3 Weighted Average Emission Rate. Calculate the weighted average
emission rate (Ew) using Equation 28-1:
[GRAPHIC] [TIFF OMITTED] TR17OC00.427

Note: Po always equals 0, P(n+1) always equals
1, P1 corresponds to the probability of the lowest recorded
burn rate, P2 corresponds to the probability of the next
lowest burn rate, etc. An example calculation is in Section 12.3.1.

12.3.1 Example Calculation of Weighted Average Emission Rate.

------------------------------------------------------------------------
Burn rate Emissions
Burn rate category Test No. (Dry-kg/hr) (g/hr)
------------------------------------------------------------------------
1................................ 1 0.65 5.0
2\1\............................. 2 0.85 6.7
2................................ 3 0.90 4.7
2................................ 4 1.00 5.3
3................................ 5 1.45 3.8
4................................ 6 2.00 5.1
------------------------------------------------------------------------
\1\ As permitted in Section 6.6, this test run may be omitted from the
calculation of the weighted average emission rate because three runs
were conducted for this burn rate category.

----------------------------------------------------------------------------------------------------------------
Test No. Burn rate Pi Ei Ki
----------------------------------------------------------------------------------------------------------------
0........................................................... ........... 0.000 ........... ...........
1........................................................... 0.65 0.121 5.0 0.300
2........................................................... 0.90 0.300 4.7 0.259
3........................................................... 1.00 0.380 5.3 0.422
4........................................................... 1.45 0.722 3.8 0.532
5........................................................... 2.00 0.912 5.1 0.278
6........................................................... ........... 1.000 ........... ...........
----------------------------------------------------------------------------------------------------------------
K1 = P2 - P0 = 0.300 - 0 = 0.300
K2 = P3 - P1 = 0.381 - 0.121 = 0.259
K3 = P4 - P2 = 0.722 - 0.300 = 0.422
K4 = P5 - P3 = 0.912 - 0.380 = 0.532
K5 = P6 - P4 = 1.000 - 0.722 = 0.278

[[Page 575]]

Weighted Average Emission Rate, Ew, Calculation
[GRAPHIC] [TIFF OMITTED] TR17OC00.428

12.4 Average Wood Heater Surface Temperatures. Calculate the average of
the wood heater surface temperatures for the start of the test run
(Section 8.12.1) and for the test run completion (Section 8.13). If the
two average temperatures do not agree within 70 deg.C (125 deg.F),
report the test run results, but do not include the test run results in
the test average. Replace such test run results with results from
another test run in the same burn rate category.
12.5 Burn Rate. Calculate the burn rate (BR) using Equation 28-3:
[GRAPHIC] [TIFF OMITTED] TR17OC00.429

12.6 Reporting Criteria. Submit both raw and reduced test data for
wood heater tests.
12.6.1 Suggested Test Report Format.
12.6.1.1 Introduction.
12.6.1.1.1 Purpose of test-certification, audit, efficiency,
research and development.
12.6.1.1.2 Wood heater identification-manufacturer, model number,
catalytic/noncatalytic, options.
12.6.1.1.3 Laboratory-name, location (altitude), participants.
12.6.1.1.4 Test information-date wood heater received, date of
tests, sampling methods used, number of test runs.
12.6.1.2 Summary and Discussion of Results
12.6.1.2.1 Table of results (in order of increasing burn rate)-test
run number, burn rate, particulate emission rate, efficiency (if
determined), averages (indicate which test runs are used).
12.6.1.2.2 Summary of other data-test facility conditions, surface
temperature averages, catalyst temperature averages, pretest fuel
weights, test fuel charge weights, run times.
12.6.1.2.3 Discussion-Burn rate categories achieved, test run
result selection, specific test run problems and solutions.
12.6.1.3 Process Description.
12.6.1.3.1 Wood heater dimensions-volume, height, width, lengths
(or other linear dimensions), weight, volume adjustments.
12.6.1.3.2 Firebox configuration-air supply locations and
operation, air supply introduction location, refractory location and
dimensions, catalyst location, baffle and by-pass location and operation
(include line drawings or photographs).
12.6.1.3.3 Process operation during test-air supply settings and
adjustments, fuel bed adjustments, draft.
12.6.1.3.4 Test fuel-test fuel properties (moisture and
temperature), test fuel crib description (include line drawing or
photograph), test fuel loading density.
12.6.1.4 Sampling Locations.
12.6.1.4.1 Describe sampling location relative to wood heater.
Include drawing or photograph.
12.6.1.5 Sampling and Analytical Procedures
12.6.1.5.1 Sampling methods-brief reference to operational and
sampling procedures and optional and alternative procedures used.
12.6.1.5.2 Analytical methods-brief description of sample recovery
and analysis procedures.
12.6.1.6 Quality Control and Assurance Procedures and Results
12.6.1.6.1 Calibration procedures and results-certification
procedures, sampling and analysis procedures.
12.6.1.6.2 Test method quality control procedures-leak-checks,
volume meter checks, stratification (velocity) checks, proportionality
results.
12.6.1.7 Appendices
12.6.1.7.1 Results and Example Calculations. Complete summary
tables and accompanying examples of all calculations.
12.6.1.7.2 Raw Data. Copies of all uncorrected data sheets for
sampling measurements, temperature records and sample recovery data.
Copies of all pretest burn rate and wood heater temperature data.
12.6.1.7.3 Sampling and Analytical Procedures. Detailed description
of procedures followed by laboratory personnel in conducting

[[Page 576]]

the certification test, emphasizing particular parts of the procedures
differing from the methods (e.g., approved alternatives).
12.6.1.7.4 Calibration Results. Summary of all calibrations,
checks, and audits pertinent to certification test results with dates.
12.6.1.7.5 Participants. Test personnel, manufacturer
representatives, and regulatory observers.
12.6.1.7.6 Sampling and Operation Records. Copies of uncorrected
records of activities not included on raw data sheets (e.g., wood heater
door open times and durations).
12.6.1.7.7 Additional Information. Wood heater manufacturer's
written instructions for operation during the certification test.
12.6.2.1 Wood Heater Identification. Report wood heater
identification information. An example data form is shown in Figure 28-
4.
12.6.2.2 Test Facility Information. Report test facility
temperature, air velocity, and humidity information. An example data
form is shown on Figure 28-4.
12.6.2.3 Test Equipment Calibration and Audit Information. Report
calibration and audit results for the platform scale, test fuel balance,
test fuel moisture meter, and sampling equipment including volume
metering systems and gaseous analyzers.
12.6.2.4 Pretest Procedure Description. Report all pretest
procedures including pretest fuel weight, burn rates, wood heater
temperatures, and air supply settings. An example data form is shown on
Figure 28-4.
12.6.2.5 Particulate Emission Data. Report a summary of test
results for all test runs and the weighted average emission rate. Submit
copies of all data sheets and other records collected during the
testing. Submit examples of all calculations.

13.0 Method Performance, [Reserved]

14.0 Pollution Prevention, [Reserved]

15.0 Waste Management, [Reserved]

16.0 Alternative Procedures

16.1 Pellet Burning Heaters. Certification testing requirements and
procedures for pellet burning wood heaters are identical to those for
other wood heaters, with the following exceptions:
16.1.1 Test Fuel Properties. The test fuel shall be all wood
pellets with a moisture content no greater than 20 percent on a wet
basis (25 percent on a dry basis). Determine the wood moisture content
with either ASTM D 2016-74 or 83, (Method A), ASTM D 4444-92, or ASTM D
4442-84 or 92 (all noted ASTM standards are incorporated by reference--
see Sec. 60.17).
16.1.2 Test Fuel Charge Specifications. The test fuel charge size
shall be as per the manufacturer's written instructions for maintaining
the desired burn rate.
16.1.3 Wood Heater Firebox Volume. The firebox volume need not be
measured or determined for establishing the test fuel charge size. The
firebox dimensions and other heater specifications needed to identify
the heater for certification purposes shall be reported.
16.1.4 Heater Installation. Arrange the heater with the fuel supply
hopper on the platform scale as described in Section 8.6.1.
16.1.5 Pretest Ignition. Start a fire in the heater as directed by
the manufacturer's written instructions, and adjust the heater controls
to achieve the desired burn rate. Operate the heater at the desired burn
rate for at least 1 hour before the start of the test run.
16.1.6 Test Run. Complete a test run in each burn rate category as
follows:
16.1.6.1 Test Run Start. When the wood heater has operated for at
least 1 hour at the desired burn rate, add fuel to the supply hopper as
necessary to complete the test run, record the weight of the fuel in the
supply hopper (the wood heater weight), and start the test run. Add no
additional fuel to the hopper during the test run.
Record all the wood heater surface temperatures, the initial
sampling method measurement values, the time at the start of the test,
and begin the emission sampling. Make no adjustments to the wood heater
air supply or wood supply rate during the test run.
16.1.6.2 Data Recording. Record the fuel (wood heater) weight data,
wood heater temperature and operational data, and emission sampling data
as described in Section 8.12.2.
16.1.6.3 Test Run Completion. Continue emission sampling and wood
heater operation for 2 hours. At the end of the test run, stop the
particulate sampling, and record the final fuel weight, the run time,
and all final measurement values, including all wood heater individual
surface temperatures.
16.1.7 Calculations. Determine the burn rate using the difference
between the initial and final fuel (wood heater) weights and the
procedures described in Section 12.4. Complete the other calculations as
described in Section 12.0.

17.0 References

Same as Method 5G, with the addition of the following:

1. Radian Corporation. OMNI Environmental Services, Inc., Cumulative
Probability for a Given Burn Rate Based on Data Generated in the CONEG
and BPA Studies. Package of materials submitted to the Fifth Session of
the Regulatory Negotiation Committee, July 16-17, 1986.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 577]]

Table 28-1.--Burn Rate Weighted Probabilities for Calculating Weighted Average Emission Rates
----------------------------------------------------------------------------------------------------------------
Cumulative Cumulative Cumulative
Burn rate (kg/hr-dry) probability Burn rate (kg/ probability Burn rate (kg/ probability
(P) hr-dry) (P) hr-dry) (P)
----------------------------------------------------------------------------------------------------------------
0.00............................ 0.000 1.70 0.840 3.40 0.989
0.05............................ 0.002 1.75 0.857 3.45 0.989
0.10............................ 0.007 1.80 0.875 3.50 0.990
0.15............................ 0.012 1.85 0.882 3.55 0.991
0.20............................ 0.016 1.90 0.895 3.60 0.991
0.25............................ 0.021 1.95 0.906 3.65 0.992
0.30............................ 0.028 2.00 0.912 3.70 0.992
0.35............................ 0.033 2.05 0.920 3.75 0.992
0.40............................ 0.041 2.10 0.925 3.80 0.993
0.45............................ 0.054 2.15 0.932 3.85 0.994
0.50............................ 0.065 2.20 0.936 3.90 0.994
0.55............................ 0.086 2.25 0.940 3.95 0.994
0.60............................ 0.100 2.30 0.945 4.00 0.994
0.65............................ 0.121 2.35 0.951 4.05 0.995
0.70............................ 0.150 2.40 0.956 4.10 0.995
0.75............................ 0.185 2.45 0.959 4.15 0.995
0.80............................ 0.220 2.50 0.964 4.20 0.995
0.85............................ 0.254 2.55 0.968 4.25 0.995
0.90............................ 0.300 2.60 0.972 4.30 0.996
0.95............................ 0.328 2.65 0.975 4.35 0.996
1.00............................ 0.380 2.70 0.977 4.40 0.996
1.05............................ 0.407 2.75 0.979 4.45 0.996
1.10............................ 0.460 2.80 0.980 4.50 0.996
1.15............................ 0.490 2.85 0.981 4.55 0.996
1.20............................ 0.550 2.90 0.982 4.60 0.996
1.25............................ 0.572 2.95 0.984 4.65 0.996
1.30............................ 0.620 3.00 0.984 4.70 0.996
1.35............................ 0.654 3.05 0.985 4.75 0.997
1.40............................ 0.695 3.10 0.986 4.80 0.997
1.45............................ 0.722 3.15 0.987 4.85 0.997
1.50............................ 0.750 3.20 0.987 4.90 0.997
1.55............................ 0.779 3.25 0.988 4.95 0.997
1.60............................ 0.800 3.30 0.988 5.0 1.000
0
1.65............................ 0.825 3.35 0.989 .............. ..............
----------------------------------------------------------------------------------------------------------------

[[Page 578]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.430

[[Page 579]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.431

[[Page 580]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.432

Method 28A--Measurement of Air- to-Fuel Ratio and Mimimum Achievable
Burn Rates for Wood-Fired Appliances

Note: This method does not include all or the specifications (e.g.,
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should also have a thorough knowledge of at
least the following additional test methods: Method 3, Method 3A, Method
5H, Method 6C, and Method 28.

1.0 Scope and Application

1.1 Analyte. Particulate matter (PM). No CAS number assigned.

[[Page 581]]

1.2 Applicability. This method is applicable for the measurement of
air-to-fuel ratios and minimum achievable burn rates, for determining
whether a wood-fired appliance is an affected facility, as specified in
40 CFR 60.530.
1.3 Data Quality Objectives. Adherence to the requirements of this
method will enhance the quality of the data obtained from air pollutant
sampling methods.

2.0 Summary of Method

2.1 A gas sample is extracted from a location in the stack of a
wood-fired appliance while the appliance is operating at a prescribed
set of conditions. The gas sample is analyzed for carbon dioxide
(CO2), oxygen (O2), and carbon monoxide (CO).
These stack gas components are measured for determining the dry
molecular weight of the exhaust gas. Total moles of exhaust gas are
determined stoichiometrically. Air-to-fuel ratio is determined by
relating the mass of dry combustion air to the mass of dry fuel
consumed.

3.0 Definitions

Same as Method 28, Section 3.0, with the addition of the following:
3.1 Air-to-fuel ratio means the ratio of the mass of dry combustion
air introduced into the firebox to the mass of dry fuel consumed (grams
of dry air per gram of dry wood burned).

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

6.1 Test Facility. Insulated Solid Pack Chimney, Platform Scale and
Monitor, Test Facility Temperature Monitor, Balance, Moisture Meter,
Anemometer, Barometer, Draft Gauge, Humidity Gauge, Wood Heater Flue,
and Test Facility. Same as Method 28, Sections 6.1, 6.2, and 6.4 to
6.12, respectively.
6.2 Sampling System. Probe, Condenser, Valve, Pump, Rate Meter,
Flexible Bag, Pressure Gauge, and Vacuum Gauge. Same as Method 3,
Sections 6.2.1 to 6.2.8, respectively. Alternatively, the sampling
system described in Method 5H, Section 6.1 may be used.
6.3 Exhaust Gas Analysis. Use one or both of the following:
6.3.1 Orsat Analyzer. Same as Method 3, Section 6.1.3
6.3.2 Instrumental Analyzers. Same as Method 5H, Sections 6.1.3.4
and 6.1.3.5, for CO2 and CO analyzers, except use a CO
analyzer with a range of 0 to 5 percent and use a CO2
analyzer with a range of 0 to 5 percent. Use an O2 analyzer
capable of providing a measure of O2 in the range of 0 to 25
percent by volume at least once every 10 minutes.

7.0 Reagents and Standards

7.1 Test Fuel and Test Fuel Spacers. Same as Method 28, Sections
7.1 and 7.2, respectively.
7.2 Cylinder Gases. For each of the three analyzers, use the same
concentration as specified in Sections 7.2.1, 7.2.2, and 7.2.3 of Method
6C.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Wood Heater Air Supply Adjustments.
8.1.1 This section describes how dampers are to be set or adjusted
and air inlet ports closed or sealed during Method 28A tests. The
specifications in this section are intended to ensure that affected
facility determinations are made on the facility configurations that
could reasonably be expected to be employed by the user. They are also
intended to prevent circumvention of the standard through the addition
of an air port that would often be blocked off in actual use. These
specifications are based on the assumption that consumers will remove
such items as dampers or other closure mechanism stops if this can be
done readily with household tools; that consumers will block air inlet
passages not visible during normal operation of the appliance using
aluminum tape or parts generally available at retail stores; and that
consumers will cap off any threaded or flanged air inlets. They also
assume that air leakage around glass doors, sheet metal joints or
through inlet grilles visible during normal operation of the appliance
would not be further blocked or taped off by a consumer.
8.1.2 It is not the intention of this section to cause an appliance
that is clearly designed, intended, and, in most normal installations,
used as a fireplace to be converted into a wood heater for purposes of
applicability testing. Such a fireplace would be identifiable by such
features as large or multiple glass doors or panels that are not
gasketed, relatively unrestricted air inlets intended, in large part, to
limit smoking and fogging of glass surfaces, and other aesthetic
features not normally included in wood heaters.
8.1.3 Adjustable Air Supply Mechanisms. Any commercially available
flue damper, other adjustment mechanism or other air

[[Page 582]]

inlet port that is designed, intended or otherwise reasonably expected
to be adjusted or closed by consumers, installers, or dealers and which
could restrict air into the firebox shall be set so as to achieve
minimum air into the firebox (i.e., closed off or set in the most closed
position).
8.1.3.1 Flue dampers, mechanisms and air inlet ports which could
reasonably be expected to be adjusted or closed would include:
8.1.3.1.1 All internal or externally adjustable mechanisms
(including adjustments that affect the tightness of door fittings) that
are accessible either before and/or after installation.
8.1.3.1.2 All mechanisms, other inlet ports, or inlet port stops
that are identified in the owner's manual or in any dealer literature as
being adjustable or alterable. For example, an inlet port that could be
used to provide access to an outside air duct but which is identified as
being closable through use of additional materials whether or not they
are supplied with the facility.
8.1.3.1.3 Any combustion air inlet port or commercially available
flue damper or mechanism stop, which would readily lend itself to
closure by consumers who are handy with household tools by the removal
of parts or the addition of parts generally available at retail stores
(e.g., addition of a pipe cap or plug, addition of a small metal plate
to an inlet hole on a nondecorative sheet metal surface, or removal of
riveted or screwed damper stops).
8.1.3.1.4 Any flue damper, other adjustment mechanisms or other air
inlet ports that are found and documented in several (e.g., a number
sufficient to reasonably conclude that the practice is not unique or
uncommon) actual installations as having been adjusted to a more closed
position, or closed by consumers, installers, or dealers.
8.1.4 Air Supply Adjustments During Test. The test shall be
performed with all air inlets identified under this section in the
closed or most closed position or in the configuration which otherwise
achieves the lowest air inlet (i.e., greatest blockage).

Note: For the purposes of this section, air flow shall not be
minimized beyond the point necessary to maintain combustion or beyond
the point that forces smoke into the room.

8.1.5 Notwithstanding Section 8.1.1, any flue damper, adjustment
mechanism, or air inlet port (whether or not equipped with flue dampers
or adjusting mechanisms) that is visible during normal operation of the
appliance and which could not reasonably be closed further or blocked
except through means that would significantly degrade the aesthetics of
the facility (e.g., through use of duct tape) will not be closed further
or blocked.
8.2 Sampling System.
8.2.1 Sampling Location. Same as Method 5H, Section 8.1.2.
8.2.2 Sampling System Set Up. Set up the sampling equipment as
described in Method 3, Section 8.1.
8.3 Wood Heater Installation, Test Facility Conditions, Wood Heater
Firebox Volume, and Test Fuel Charge. Same as Method 28, Sections 8.4
and 8.6 to 8.8, respectively.
8.4 Pretest Ignition. Same as Method 28, Section 8.11. Set the wood
heater air supply settings to achieve a burn rate in Category 1 or the
lowest achievable burn rate (see Section 8.1).
8.5 Test Run. Same as Method 28, Section 8.12. Begin sample
collection at the start of the test run as defined in Method 28, Section
8.12.1.
8.5.1 Gas Analysis.
8.5.1.1 If Method 3 is used, collect a minimum of two bag samples
simultaneously at a constant sampling rate for the duration of the test
run. A minimum sample volume of 30 liters (1.1 ft³) per bag
is recommended.
8.5.1.2 If instrumental gas concentration measurement procedures
are used, conduct the gas measurement system performance tests, analyzer
calibration, and analyzer calibration error check outlined in Method 6C,
Sections 8.2.3, 8.2.4, 8.5, and 10.0, respectively. Sample at a constant
rate for the duration of the test run.
8.5.2 Data Recording. Record wood heater operational data, test
facility temperature, sample train flow rate, and fuel weight data at
intervals of no greater than 10 minutes.
8.5.3 Test Run Completion. Same as Method 28, Section 8.13.

9.0 Quality Control

9.1 Data Validation. The following quality control procedure is
suggested to provide a check on the quality of the data.
9.1.1 Calculate a fuel factor, Fo, using Equation 28A-1
in Section 12.2.
9.1.2 If CO is present in quantities measurable by this method,
adjust the O2 and CO2 values before performing the
calculation for Fo as shown in Section 12.3 and 12.4.
9.1.3 Compare the calculated Fo factor with the expected
Fo range for wood (1.000--1.120). Calculated Fo
values beyond this acceptable range should be investigated before
accepting the test results. For example, the strength of the solutions
in the gas analyzer and the analyzing technique should be checked by
sampling and analyzing a known concentration, such as air. If no
detectable or correctable measurement error can be identified, the test
should be repeated. Alternatively, determine a range of air-to-fuel
ratio results that could include the correct value by using an
Fo value of 1.05 and calculating a potential range of
CO2 and O2 values. Acceptance of such results will
be based on whether the calculated range includes the

[[Page 583]]

exemption limit and the judgment of the Administrator.
9.2 Method 3 Analyses. Compare the results of the analyses of the
two bag samples. If all the gas components (O2, CO, and
CO2) values for the two analyses agree within 0.5 percent
(e.g., 6.0 percent O2 for bag 1 and 6.5 percent O2
for bag 2, agree within 0.5 percent), the results of the bag analyses
may be averaged for the calculations in Section 12. If the analysis
results do not agree within 0.5 percent for each component, calculate
the air-to-fuel ratio using both sets of analyses and report the
results.

10.0 Calibration and Standardization, [Reserved]

11.0 Analytical Procedures

11.1 Method 3 Integrated Bag Samples. Within 4 hours after the
sample collection, analyze each bag sample for percent CO2,
O2, and CO using an Orsat analyzer as described in Method 3,
Section 11.0.
11.2 Instrumental Analyzers. Average the percent CO2,
CO, and O2 values for the test run.

12.0 Data Analyses and Calculations

Carry out calculations, retaining at least one extra significant
figure beyond that of the acquired data. Round off figure after the
final calculation. Other forms of the equations may be used as long as
they give equivalent results.
12.1 Nomenclature.

Md = Dry molecular weight, g/g-mole (lb/lb-mole).
NT = Total gram-moles of dry exhaust gas per kg of wood
burned (lb-moles/lb).
%CO2 = Percent CO2 by volume (dry basis).
%CO = Percent CO by volume (dry basis).
%N2 = Percent N2 by volume (dry basis).
%O2 = Percent O2 by volume (dry basis).
YHC = Assumed mole fraction of HC (dry as CH4) =
0.0088 for catalytic wood heaters; = 0.0132 for noncatalytic
wood heaters. = 0.0080 for pellet-fired wood heaters.
YCO = Measured mole fraction of CO (e.g., 1 percent CO = .01
mole fraction), g/g-mole (lb/lb-mole).
YCO2 = Measured mole fraction of COCO2 (e.g., 10
percent CO2 = .10 mole fraction), g/g-mole (lb/lb-
mole).
0.280 = Molecular weight of N2 or CO, divided by 100.
0.320 = Molecular weight of O2 divided by 100.
0.440 = Molecular weight of CO2 divided by 100.
20.9 = Percent O2 by volume in ambient air.
42.5 = Gram-moles of carbon in 1 kg of dry wood assuming 51 percent
carbon by weight dry basis (.0425 lb/lb-mole).
510 = Grams of carbon in exhaust gas per kg of wood burned.
1,000 = Grams in 1 kg.

12.2 Fuel Factor. Use Equation 28A-1 to calculate the fuel factor.
[GRAPHIC] [TIFF OMITTED] TR17OC00.433

12. 3 Adjusted %CO2. Use Equation 28A-2 to adjust
CO2 values if measurable CO is present.
[GRAPHIC] [TIFF OMITTED] TR17OC00.434

12.4 Adjusted %O2. Use Equation 28A-3 to adjust
O2 value if measurable CO is present.
[GRAPHIC] [TIFF OMITTED] TR17OC00.435

12.5 Dry Molecular Weight. Use Equation 28A-4 to calculate the dry
molecular weight of the stack gas.
[GRAPHIC] [TIFF OMITTED] TR17OC00.436

Note: The above equation does not consider argon in air (about 0.9
percent, molecular weight of 39.9). A negative error of about 0.4
percent is introduced. Argon may

[[Page 584]]

be included in the analysis using procedures subject to approval of the
Administrator.

12.6 Dry Moles of Exhaust Gas. Use Equation 28A-5 to calculate the
total moles of dry exhaust gas produced per kilogram of dry wood burned.
[GRAPHIC] [TIFF OMITTED] TR17OC00.437

12.7 Air-to-Fuel Ratio. Use Equation 28A-6 to calculate the air-to-
fuel ratio on a dry mass basis.
[GRAPHIC] [TIFF OMITTED] TR17OC00.438

12.8 Burn Rate. Calculate the fuel burn rate as in Method 28,
Section 12.4.

13.0 Method Performance, [Reserved]

14.0 Pollution Prevention, [Reserved]

15.0 Waste Management, [Reserved]

16.0 References

Same as Section 16.0 of Method 3 and Section 17 of Method 5G.

17.0 Tables, Diagrams, Flowcharts, and Validation Data, [Reserved]

Method 29--Determination of Metals Emissions From Stationary Sources

Note: This method does not include all of the specifications (e.g.
equipment and supplies) and procedures (e.g., sampling and analytical)
essential to its performance. Some material is incorporated by reference
from other methods in this part. Therefore, to obtain reliable results,
persons using this method should have a thorough knowledge of at least
the following additional test methods: Method 5 and Method 12.

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Antimony (Sb)........................................... 7440-36-0
Arsenic (As)............................................ 7440-38-2
Barium (Ba)............................................. 7440-39-3
Beryllium (Be).......................................... 7440-41-7
Cadmium (Cd)............................................ 7440-43-9
Chromium (Cr)........................................... 7440-47-3
Cobalt (Co)............................................. 7440-48-4
Copper (Cu)............................................. 7440-50-8
Lead (Pb)............................................... 7439-92-1
Manganese (Mn).......................................... 7439-96-5
Mercury (Hg)............................................ 7439-97-6
Nickel (Ni)............................................. 7440-02-0
Phosphorus (P).......................................... 7723-14-0
Selenium (Se)........................................... 7782-49-2
Silver (Ag)............................................. 7440-22-4
Thallium (Tl)........................................... 7440-28-0
Zinc (Zn)............................................... 7440-66-6
------------------------------------------------------------------------

1.2 Applicability. This method is applicable to the determination
of metals emissions from stationary sources. This method may be used to
determine particulate emissions in addition to the metals emissions if
the prescribed procedures and precautions are followed.
1.2.1 Hg emissions can be measured, alternatively, using EPA Method
101A of Appendix B, 40 CFR Part 61. Method 101-A measures only Hg but it
can be of special interest to sources which need to measure both Hg and
Mn emissions.

2.0 Summary of Method

2.1 Principle. A stack sample is withdrawn isokinetically from the
source, particulate emissions are collected in the probe and on a heated
filter, and gaseous emissions are then collected in an aqueous acidic
solution of hydrogen peroxide (analyzed for all metals including Hg) and
an aqueous acidic solution of potassium permanganate (analyzed only for
Hg). The recovered samples are digested, and appropriate fractions are
analyzed for Hg by cold vapor atomic absorption spectroscopy (CVAAS) and
for Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Ni, P, Se, Ag, Tl, and Zn by
inductively coupled argon plasma emission spectroscopy (ICAP) or atomic
absorption spectroscopy (AAS). Graphite furnace atomic absorption
spectroscopy (GFAAS) is used for analysis of Sb, As, Cd, Co, Pb, Se, and
Tl if these elements require greater analytical sensitivity than can be
obtained by ICAP. If one so chooses, AAS may be used for analysis of all
listed metals if the resulting in-stack method detection limits meet the
goal of the testing program. Similarly, inductively coupled plasma-mass
spectroscopy (ICP-MS) may be used for analysis of Sb, As, Ba, Be, Cd,
Cr, Co, Cu, Pb, Mn, Ni, Ag, Tl and Zn.

3.0 Definitions. [Reserved]

4.0 Interferences

4.1 Iron (Fe) can be a spectral interference during the analysis of
As, Cr, and Cd by ICAP. Aluminum (Al) can be a spectral interference
during the analysis of As and Pb by ICAP. Generally, these interferences
can be reduced by diluting the analytical sample, but such dilution
raises the in-stack detection limits. Background and overlap corrections
may be used to adjust for spectral interferences. Refer to Method 6010
of Reference 2 in Section 16.0 or the other analytical methods used for
details on potential interferences to this method. For all GFAAS
analyses, use matrix modifiers to limit interferences, and matrix match
all standards.

[[Page 585]]

5.0 Safety

5.1 Disclaimer. This method may involve hazardous materials,
operations, and equipment. This test method may not address all of the
safety problems associated with its use. It is the responsibility of the
user of this test method to establish appropriate safety and health
practices and to determine the applicability of regulatory limitations
prior to performing this test method.
5.2 Corrosive Reagents. The following reagents are hazardous.
Personal protective equipment and safe procedures are useful in
preventing chemical splashes. If contact occurs, immediately flush with
copious amounts of water at least 15 minutes. Remove clothing under
shower and decontaminate. Treat residual chemical burn as thermal burn.
5.2.1 Nitric Acid (HNO3). Highly corrosive to eyes,
skin, nose, and lungs. Vapors cause bronchitis, pneumonia, or edema of
lungs. Reaction to inhalation may be delayed as long as 30 hours and
still be fatal. Provide ventilation to limit exposure. Strong oxidizer.
Hazardous reaction may occur with organic materials such as solvents.
5.2.2 Sulfuric Acid (H2SO4). Rapidly
destructive to body tissue. Will cause third degree burns. Eye damage
may result in blindness. Inhalation may be fatal from spasm of the
larynx, usually within 30 minutes. May cause lung tissue damage with
edema. 1 mg/m\3\ for 8 hours will cause lung damage or, in higher
concentrations, death. Provide ventilation to limit inhalation. Reacts
violently with metals and organics.
5.2.3 Hydrochloric Acid (HC1). Highly corrosive liquid with toxic
vapors. Vapors are highly irritating to eyes, skin, nose, and lungs,
causing severe damage. May cause bronchitis, pneumonia, or edema of
lungs. Exposure to concentrations of 0.13 to 0.2 percent can be lethal
to humans in a few minutes. Provide ventilation to limit exposure.
Reacts with metals, producing hydrogen gas.
5.2.4 Hydrofluoric Acid (HF). Highly corrosive to eyes, skin, nose,
throat, and lungs. Reaction to exposure may be delayed by 24 hours or
more. Provide ventilation to limit exposure.
5.2.5 Hydrogen Peroxide (H2O2). Irritating to
eyes, skin, nose, and lungs. 30% H2O2 is a strong
oxidizing agent. Avoid contact with skin, eyes, and combustible
material. Wear gloves when handling.
5.2.6 Potassium Permanganate (KMnO4). Caustic, strong
oxidizer. Avoid bodily contact with.
5.2.7 Potassium Persulfate. Strong oxidizer. Avoid bodily contact
with. Keep containers well closed and in a cool place.
5.3 Reaction Pressure. Due to the potential reaction of the
potassium permanganate with the acid, there could be pressure buildup in
the acidic KMnO4 absorbing solution storage bottle. Therefore
these bottles shall not be fully filled and shall be vented to relieve
excess pressure and prevent explosion potentials. Venting is required,
but not in a manner that will allow contamination of the solution. A No.
70-72 hole drilled in the container cap and Teflon liner has been used.

6.0 Equipment and Supplies

6.1 Sampling. A schematic of the sampling train is shown in Figure
29-1. It has general similarities to the Method 5 train.
6.1.1 Probe Nozzle (Probe Tip) and Borosilicate or Quartz Glass
Probe Liner. Same as Method 5, Sections 6.1.1.1 and 6.1.1.2, except that
glass nozzles are required unless alternate tips are constructed of
materials that are free from contamination and will not interfere with
the sample. If a probe tip other than glass is used, no correction to
the sample test results to compensate for the nozzle's effect on the
sample is allowed. Probe fittings of plastic such as Teflon,
polypropylene, etc. are recommended instead of metal fittings to prevent
contamination. If one chooses to do so, a single glass piece consisting
of a combined probe tip and probe liner may be used.
6.1.2 Pitot Tube and Differential Pressure Gauge. Same as Method 2,
Sections 6.1 and 6.2, respectively.
6.1.3 Filter Holder. Glass, same as Method 5, Section 6.1.1.5,
except use a Teflon filter support or other non-metallic, non-
contaminating support in place of the glass frit.
6.1.4 Filter Heating System. Same as Method 5, Section 6.1.1.6.
6.1.5 Condenser. Use the following system for condensing and
collecting gaseous metals and determining the moisture content of the
stack gas. The condensing system shall consist of four to seven
impingers connected in series with leak-free ground glass fittings or
other leak-free, non-contaminating fittings. Use the first impinger as a
moisture trap. The second impinger (which is the first HNO3/
H2O2 impinger) shall be identical to the first
impinger in Method 5. The third impinger (which is the second
HNO3/H2O2 impinger) shall be a
Greenburg Smith impinger with the standard tip as described for the
second impinger in Method 5, Section 6.1.1.8. The fourth (empty)
impinger and the fifth and sixth (both acidified KMnO4)
impingers are the same as the first impinger in Method 5. Place a
temperature sensor capable of measuring to within 1 deg.C (2 deg.F) at
the outlet of the last impinger. If no Hg analysis is planned, then the
fourth, fifth, and sixth impingers are not used.
6.1.6 Metering System, Barometer, and Gas Density Determination
Equipment. Same as Method 5, Sections 6.1.1.9, 6.1.2, and 6.1.3,
respectively.
6.1.7 Teflon Tape. For capping openings and sealing connections, if
necessary, on the sampling train.

[[Page 586]]

6.2 Sample Recovery. Same as Method 5, Sections 6.2.1 through 6.2.8
(Probe-Liner and Probe-Nozzle Brushes or Swabs, Wash Bottles, Sample
Storage Containers, Petri Dishes, Glass Graduated Cylinder, Plastic
Storage Containers, Funnel and Rubber Policeman, and Glass Funnel),
respectively, with the following exceptions and additions:
6.2.1 Non-metallic Probe-Liner and Probe-Nozzle Brushes or Swabs.
Use non-metallic probe-liner and probe-nozzle brushes or swabs for
quantitative recovery of materials collected in the front-half of the
sampling train.
6.2.2 Sample Storage Containers. Use glass bottles (see Section 8.1
of this Method) with Teflon-lined caps that are non-reactive to the
oxidizing solutions, with capacities of 1000- and 500-ml, for storage of
acidified KMnO4--containing samples and blanks. Glass or
polyethylene bottles may be used for other sample types.
6.2.3 Graduated Cylinder. Glass or equivalent.
6.2.4 Funnel. Glass or equivalent.
6.2.5 Labels. For identifying samples.
6.2.6 Polypropylene Tweezers and/or Plastic Gloves. For recovery of
the filter from the sampling train filter holder.
6.3 Sample Preparation and Analysis.
6.3.1 Volumetric Flasks, 100-ml, 250-ml, and 1000-ml. For
preparation of standards and sample dilutions.
6.3.2 Graduated Cylinders. For preparation of reagents.
6.3.3 Parr Bombs or Microwave Pressure Relief Vessels with Capping
Station (CEM Corporation model or equivalent). For sample digestion.
6.3.4 Beakers and Watch Glasses. 250-ml beakers, with watch glass
covers, for sample digestion.
6.3.5 Ring Stands and Clamps. For securing equipment such as
filtration apparatus.
6.3.6 Filter Funnels. For holding filter paper.
6.3.7 Disposable Pasteur Pipets and Bulbs.
6.3.8 Volumetric Pipets.
6.3.9 Analytical Balance. Accurate to within 0.1 mg.
6.3.10 Microwave or Conventional Oven. For heating samples at fixed
power levels or temperatures, respectively.
6.3.11 Hot Plates.
6.3.12 Atomic Absorption Spectrometer (AAS). Equipped with a
background corrector.
6.3.12.1 Graphite Furnace Attachment. With Sb, As, Cd, Co, Pb, Se,
and Tl hollow cathode lamps (HCLs) or electrodeless discharge lamps
(EDLs). Same as Reference 2 in Section 16.0. Methods 7041 (Sb), 7060
(As), 7131 (Cd), 7201 (Co), 7421 (Pb), 7740 (Se), and 7841 (Tl).
6.3.12.2 Cold Vapor Mercury Attachment. With a mercury HCL or EDL,
an air recirculation pump, a quartz cell, an aerator apparatus, and a
heat lamp or desiccator tube. The heat lamp shall be capable of raising
the temperature at the quartz cell by 10 deg.C above ambient, so that
no condensation forms on the wall of the quartz cell. Same as Method
7470 in Reference 2 in Section 16.0. See Note 2: Section 11.1.3 for
other acceptable approaches for analysis of Hg in which analytical
detection limits of 0.002 ng/ml were obtained.
6.3.13 Inductively Coupled Argon Plasma Spectrometer. With either a
direct or sequential reader and an alumina torch. Same as EPA Method
6010 in Reference 2 in Section 16.0.
6.3.14 Inductively Coupled Plasma-Mass Spectrometer.
Same as EPA Method 6020 in Reference 2 in Section 16.0.

7.0 Reagents and Standards

7.1 Unless otherwise indicated, it is intended that all reagents
conform to the specifications established by the Committee on Analytical
Reagents of the American Chemical Society, where such specifications are
available. Otherwise, use the best available grade.
7.2 Sampling Reagents.
7.2.1 Sample Filters. Without organic binders. The filters shall
contain less than 1.3 g/in.\2\ of each of the metals to be
measured. Analytical results provided by filter manufacturers stating
metals content of the filters are acceptable. However, if no such
results are available, analyze filter blanks for each target metal prior
to emission testing. Quartz fiber filters meeting these requirements are
recommended. However, if glass fiber filters become available which meet
these requirements, they may be used. Filter efficiencies and
unreactiveness to sulfur dioxide (SO2) or sulfur trioxide
(SO3) shall be as described in Section 7.1.1 of Method 5.
7.2.2 Water. To conform to ASTM Specification D1193-77 or 91, Type
II (incorporated by reference--see Sec. 60.17). If necessary, analyze
the water for all target metals prior to field use. All target metals
should be less than 1 ng/ml.
7.2.3 HNO3, Concentrated. Baker Instra-analyzed or
equivalent.
7.2.4 HCl, Concentrated. Baker Instra-analyzed or equivalent.
7.2.5 H2O2, 30 Percent (V/V).
7.2.6 KMnO4.
7.2.7 H2SO4, Concentrated.
7.2.8 Silica Gel and Crushed Ice. Same as Method 5, Sections 7.1.2
and 7.1.4, respectively.
7.3 Pretest Preparation of Sampling Reagents.
7.3.1 HNO3/H2O2 Absorbing
Solution, 5 Percent HNO3/10 Percent
H2O2. Add carefully with stirring 50 ml of
concentrated HNO3 to a 1000-ml volumetric flask containing
approximately 500 ml of water, and then add

[[Page 587]]

carefully with stirring 333 ml of 30 percent H2O2.
Dilute to volume with water. Mix well. This reagent shall contain less
than 2 ng/ml of each target metal.
7.3.2 Acidic KMnO4 Absorbing Solution, 4 Percent
KMnO4 (W/V), 10 Percent H2SO4 (V/V).
Prepare fresh daily. Mix carefully, with stirring, 100 ml of
concentrated H2SO4 into approximately 800 ml of
water, and add water with stirring to make a volume of 1 liter: this
solution is 10 percent H2SO4 (V/V). Dissolve, with
stirring, 40 g of KMnO4 into 10 percent
H2SO4 (V/V) and add 10 percent
H2SO4 (V/V) with stirring to make a volume of 1
liter. Prepare and store in glass bottles to prevent degradation. This
reagent shall contain less than 2 ng/ml of Hg.
Precaution: To prevent autocatalytic decomposition of the
permanganate solution, filter the solution through Whatman 541 filter
paper.
7.3.3 HNO3, 0.1 N. Add with stirring 6.3 ml of
concentrated HNO3 (70 percent) to a flask containing
approximately 900 ml of water. Dilute to 1000 ml with water. Mix well.
This reagent shall contain less than 2 ng/ml of each target metal.
7.3.4 HCl, 8 N. Carefully add with stirring 690 ml of concentrated
HCl to a flask containing 250 ml of water. Dilute to 1000 ml with water.
Mix well. This reagent shall contain less than 2 ng/ml of Hg.
7.4 Glassware Cleaning Reagents.
7.4.1 HNO3, Concentrated. Fisher ACS grade or
equivalent.
7.4.2 Water. To conform to ASTM Specifications D1193, Type II.
7.4.3 HNO3, 10 Percent (V/V). Add with stirring 500 ml
of concentrated HNO3 to a flask containing approximately 4000
ml of water. Dilute to 5000 ml with water. Mix well. This reagent shall
contain less than 2 ng/ml of each target metal.
7.5 Sample Digestion and Analysis Reagents. The metals standards,
except Hg, may also be made from solid chemicals as described in
Reference 3 in Section 16.0. Refer to References 1, 2, or 5 in Section
16.0 for additional information on Hg standards. The 1000 g/ml
Hg stock solution standard may be made according to Section 7.2.7 of
Method 101A.
7.5.1 HCl, Concentrated.
7.5.2 HF, Concentrated.
7.5.3 HNO3, Concentrated. Baker Instra-analyzed or
equivalent.
7.5.4 HNO3, 50 Percent (V/V). Add with stirring 125 ml
of concentrated HNO3 to 100 ml of water. Dilute to 250 ml
with water. Mix well. This reagent shall contain less than 2 ng/ml of
each target metal.
7.5.5 HNO3, 5 Percent (V/V). Add with stirring 50 ml of
concentrated HNO3 to 800 ml of water. Dilute to 1000 ml with
water. Mix well. This reagent shall contain less than 2 ng/ml of each
target metal.
7.5.6 Water. To conform to ASTM Specifications D1193, Type II.
7.5.7 Hydroxylamine Hydrochloride and Sodium Chloride Solution. See
Reference 2 In Section 16.0 for preparation.
7.5.8 Stannous Chloride. See Reference 2 in Section 16.0 for
preparation.
7.5.9 KMnO4, 5 Percent (W/V). See Reference 2 in Section
16.0 for preparation.
7.5.10 H2SO4, Concentrated.
7.5.11 Potassium Persulfate, 5 Percent (W/V). See Reference 2 in
Section 16.0 for preparation.
7.5.12 Nickel Nitrate, Ni(N03) 2
6H20.
7.5.13 Lanthanum Oxide, La203.
7.5.14 Hg Standard (AAS Grade), 1000 g/ml.
7.5.15 Pb Standard (AAS Grade), 1000 g/ml.
7.5.16 As Standard (AAS Grade), 1000 g/ml.
7.5.17 Cd Standard (AAS Grade), 1000 g/ml.
7.5.18 Cr Standard (AAS Grade), 1000 g/ml.
7.5.19 Sb Standard (AAS Grade), 1000 g/ml.
7.5.20 Ba Standard (AAS Grade), 1000 g/ml.
7.5.21 Be Standard (AAS Grade), 1000 g/ml.
7.5.22 Co Standard (AAS Grade), 1000 g/ml.
7.5.23 Cu Standard (AAS Grade), 1000 g/ml.
7.5.24 Mn Standard (AAS Grade), 1000 g/ml.
7.5.25 Ni Standard (AAS Grade), 1000 g/ml.
7.5.26 P Standard (AAS Grade), 1000 g/ml.
7.5.27 Se Standard (AAS Grade), 1000 g/ml.
7.5.28 Ag Standard (AAS Grade), 1000 g/ml.
7.5.29 Tl Standard (AAS Grade), 1000 g/ml.
7.5.30 Zn Standard (AAS Grade), 1000 g/ml.
7.5.31 Al Standard (AAS Grade), 1000 g/ml.
7.5.32 Fe Standard (AAS Grade), 1000 g/ml.
7.5.33 Hg Standards and Quality Control Samples. Prepare fresh
weekly a 10 g/ml intermediate Hg standard by adding 5 ml of
1000 g/ml Hg stock solution prepared according to Method 101A
to a 500-ml volumetric flask; dilute with stirring to 500 ml by first
carefully adding 20 ml of 15 percent HNO3 and then adding
water to the 500-ml volume. Mix well. Prepare a 200 ng/ml working Hg
standard solution fresh daily: add 5 ml of the 10 g/ml
intermediate standard to a 250-ml volumetric flask, and dilute to 250 ml
with 5 ml of 4 percent KMnO4, 5 ml of 15 percent
HNO3, and then water. Mix well. Use at least five separate
aliquots of the working

[[Page 588]]

Hg standard solution and a blank to prepare the standard curve. These
aliquots and blank shall contain 0.0, 1.0, 2.0, 3.0, 4.0, and 5.0 ml of
the working standard solution containing 0, 200, 400, 600, 800, and 1000
ng Hg, respectively. Prepare quality control samples by making a
separate 10 g/ml standard and diluting until in the calibration
range.
7.5.34 ICAP Standards and Quality Control Samples. Calibration
standards for ICAP analysis can be combined into four different mixed
standard solutions as follows:

Mixed Standard Solutions for ICAP Analysis
------------------------------------------------------------------------
Solution Elements
------------------------------------------------------------------------
I................................. As, Be, Cd, Mn, Pb, Se, Zn.
II................................ Ba, Co, Cu, Fe.
III............................... Al, Cr, Ni.
IV................................ Ag, P, Sb, Tl.
------------------------------------------------------------------------

Prepare these standards by combining and diluting the appropriate
volumes of the 1000 g/ml solutions with 5 percent
HNO3. A minimum of one standard and a blank can be used to
form each calibration curve. However, prepare a separate quality control
sample spiked with known amounts of the target metals in quantities in
the mid-range of the calibration curve. Suggested standard levels are 25
g/ml for Al, Cr and Pb, 15 g/ml for Fe, and 10
g/ml for the remaining elements. Prepare any standards
containing less than 1 g/ml of metal on a daily basis.
Standards containing greater than 1 g/ml of metal should be
stable for a minimum of 1 to 2 weeks. For ICP-MS, follow Method 6020 in
EPA Publication SW-846 Third Edition (November 1986) including updates
I, II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i).
7.5.35 GFAAS Standards. Sb, As, Cd, Co, Pb, Se, and Tl. Prepare a
10 g/ml standard by adding 1 ml of 1000 g/ml standard
to a 100-ml volumetric flask. Dilute with stirring to 100 ml with 10
percent HNO3. For GFAAS, matrix match the standards. Prepare
a 100 ng/ml standard by adding 1 ml of the 10 g/ml standard to
a 100-ml volumetric flask, and dilute to 100 ml with the appropriate
matrix solution. Prepare other standards by diluting the 100 ng/ml
standards. Use at least five standards to make up the standard curve.
Suggested levels are 0, 10, 50, 75, and 100 ng/ml. Prepare quality
control samples by making a separate 10 g/ml standard and
diluting until it is in the range of the samples. Prepare any standards
containing less than 1 g/ml of metal on a daily basis.
Standards containing greater than 1 g/ml of metal should be
stable for a minimum of 1 to 2 weeks.
7.5.36 Matrix Modifiers.
7.5.36.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of
Ni(N03)26H20 or other nickel
compound suitable for preparation of this matrix modifier in
approximately 50 ml of water in a 100-ml volumetric flask. Dilute to 100
ml with water.
7.5.36.2 Nickel Nitrate, 0.1 Percent (V/V). Dilute 10 ml of 1
percent nickel nitrate solution to 100 ml with water. Inject an equal
amount of sample and this modifier into the graphite furnace during
GFAAS analysis for As.
7.5.36.3 Lanthanum. Carefully dissolve 0.5864 g of
La203 in 10 ml of concentrated HN03,
and dilute the solution by adding it with stirring to approximately 50
ml of water. Dilute to 100 ml with water, and mix well. Inject an equal
amount of sample and this modifier into the graphite furnace during
GFAAS analysis for Pb.
7.5.37 Whatman 40 and 541 Filter Papers (or equivalent). For
filtration of digested samples.

8.0 Sample Collection, Preservation, Transport, and Storage

8.1 Sampling. The complexity of this method is such that, to obtain
reliable results, both testers and analysts must be trained and
experienced with the test procedures, including source sampling; reagent
preparation and handling; sample handling; safety equipment and
procedures; analytical calculations; reporting; and the specific
procedural descriptions throughout this method.
8.1.1 Pretest Preparation. Follow the same general procedure given
in Method 5, Section 8.1, except that, unless particulate emissions are
to be determined, the filter need not be desiccated or weighed. First,
rinse all sampling train glassware with hot tap water and then wash in
hot soapy water. Next, rinse glassware three times with tap water,
followed by three additional rinses with water. Then soak all glassware
in a 10 percent (V/V) nitric acid solution for a minimum of 4 hours,
rinse three times with water, rinse a final time with acetone, and allow
to air dry. Cover all glassware openings where contamination can occur
until the sampling train is assembled for sampling.
8.1.2 Preliminary Determinations. Same as Method 5, Section 8.1.2.
8.1.3 Preparation of Sampling Train.
8.1.3.1 Set up the sampling train as shown in Figure 29-1. Follow
the same general procedures given in Method 5, Section 8.3, except place
100 ml of the HNO3/H2O2 solution
(Section 7.3.1 of this method) in each of the second and third impingers
as shown in Figure 29-1. Place 100 ml of the acidic KMnO4
absorbing solution (Section 7.3.2 of this method) in each of the fifth
and sixth impingers as shown in Figure 29-1, and transfer approximately
200 to 300 g of pre-weighed silica gel from its container to the last
impinger. Alternatively, the silica gel may be weighed directly in the
impinger just prior to final train assembly.

[[Page 589]]

8.1.3.2 Based on the specific source sampling conditions, the use
of an empty first impinger can be eliminated if the moisture to be
collected in the impingers will be less than approximately 100 ml.
8.1.3.3 If Hg analysis will not be performed, the fourth, fifth,
and sixth impingers as shown in Figure 29-1 are not required.
8.1.3.4 To insure leak-free sampling train connections and to
prevent possible sample contamination problems, use Teflon tape or other
non-contaminating material instead of silicone grease.
Precaution: Exercise extreme care to prevent contamination within
the train. Prevent the acidic KMnO4 from contacting any
glassware that contains sample material to be analyzed for Mn. Prevent
acidic H2O2 from mixing with the acidic
KMnO4.
8.1.4 Leak-Check Procedures. Follow the leak-check procedures given
in Method 5, Section 8.4.2 (Pretest Leak-Check), Section 8.4.3 (Leak-
Checks During the Sample Run), and Section 8.4.4 (Post-Test Leak-
Checks).
8.1.5 Sampling Train Operation. Follow the procedures given in
Method 5, Section 8.5. When sampling for Hg, use a procedure analogous
to that described in Section 8.1 of Method 101A, 40 CFR Part 61,
Appendix B, if necessary to maintain the desired color in the last
acidified permanganate impinger. For each run, record the data required
on a data sheet such as the one shown in Figure 5-3 of Method 5.
8.1.6 Calculation of Percent Isokinetic. Same as Method 5, Section
12.11.
8.2 Sample Recovery.
8.2.1 Begin cleanup procedures as soon as the probe is removed from
the stack at the end of a sampling period. The probe should be allowed
to cool prior to sample recovery. When it can be safely handled, wipe
off all external particulate matter near the tip of the probe nozzle and
place a rinsed, non-contaminating cap over the probe nozzle to prevent
losing or gaining particulate matter. Do not cap the probe tip tightly
while the sampling train is cooling; a vacuum can form in the filter
holder with the undesired result of drawing liquid from the impingers
onto the filter.
8.2.2 Before moving the sampling train to the cleanup site, remove
the probe from the sampling train and cap the open outlet. Be careful
not to lose any condensate that might be present. Cap the filter inlet
where the probe was fastened. Remove the umbilical cord from the last
impinger and cap the impinger. Cap the filter holder outlet and impinger
inlet. Use non-contaminating caps, whether ground-glass stoppers,
plastic caps, serum caps, or Teflon tape to close these
openings.
8.2.3 Alternatively, the following procedure may be used to
disassemble the train before the probe and filter holder/oven are
completely cooled: Initially disconnect the filter holder outlet/
impinger inlet and loosely cap the open ends. Then disconnect the probe
from the filter holder or cyclone inlet and loosely cap the open ends.
Cap the probe tip and remove the umbilical cord as previously described.
8.2.4 Transfer the probe and filter-impinger assembly to a cleanup
area that is clean and protected from the wind and other potential
causes of contamination or loss of sample. Inspect the train before and
during disassembly and note any abnormal conditions. Take special
precautions to assure that all the items necessary for recovery do not
contaminate the samples. The sample is recovered and treated as follows
(see schematic in Figures 29-2a and 29-2b):
8.2.5 Container No. 1 (Sample Filter). Carefully remove the filter
from the filter holder and place it in its labeled petri dish container.
To handle the filter, use either acid-washed polypropylene or Teflon
coated tweezers or clean, disposable surgical gloves rinsed with water
and dried. If it is necessary to fold the filter, make certain the
particulate cake is inside the fold. Carefully transfer the filter and
any particulate matter or filter fibers that adhere to the filter holder
gasket to the petri dish by using a dry (acid-cleaned) nylon bristle
brush. Do not use any metal-containing materials when recovering this
train. Seal the labeled petri dish.
8.2.6 Container No. 2 (Acetone Rinse). Perform this procedure only
if a determination of particulate emissions is to be made.
Quantitatively recover particulate matter and any condensate from the
probe nozzle, probe fitting, probe liner, and front half of the filter
holder by washing these components with a total of 100 ml of acetone,
while simultaneously taking great care to see that no dust on the
outside of the probe or other surfaces gets in the sample. The use of
exactly 100 ml is necessary for the subsequent blank correction
procedures. Distilled water may be used instead of acetone when approved
by the Administrator and shall be used when specified by the
Administrator; in these cases, save a water blank and follow the
Administrator's directions on analysis.
8.2.6.1 Carefully remove the probe nozzle, and clean the inside
surface by rinsing with acetone from a wash bottle while brushing with a
non-metallic brush. Brush until the acetone rinse shows no visible
particles, then make a final rinse of the inside surface with acetone.
8.2.6.2 Brush and rinse the sample exposed inside parts of the
probe fitting with acetone in a similar way until no visible particles
remain. Rinse the probe liner with acetone by tilting and rotating the
probe while squirting acetone into its upper end so that all inside
surfaces will be wetted with acetone. Allow the acetone to drain from
the lower end into the sample container. A funnel may be used to aid in
transferring liquid washings

[[Page 590]]

to the container. Follow the acetone rinse with a non-metallic probe
brush. Hold the probe in an inclined position, squirt acetone into the
upper end as the probe brush is being pushed with a twisting action
three times through the probe. Hold a sample container underneath the
lower end of the probe, and catch any acetone and particulate matter
which is brushed through the probe until no visible particulate matter
is carried out with the acetone or until none remains in the probe liner
on visual inspection. Rinse the brush with acetone, and quantitatively
collect these washings in the sample container. After the brushing, make
a final acetone rinse of the probe as described above.
8.2.6.3 It is recommended that two people clean the probe to
minimize sample losses. Between sampling runs, keep brushes clean and
protected from contamination. Clean the inside of the front-half of the
filter holder by rubbing the surfaces with a non-metallic brush and
rinsing with acetone. Rinse each surface three times or more if needed
to remove visible particulate. Make a final rinse of the brush and
filter holder. After all acetone washings and particulate matter have
been collected in the sample container, tighten the lid so that acetone
will not leak out when shipped to the laboratory. Mark the height of the
fluid level to determine whether or not leakage occurred during
transport. Clearly label the container to identify its contents.
8.2.7 Container No. 3 (Probe Rinse). Keep the probe assembly clean
and free from contamination during the probe rinse. Rinse the probe
nozzle and fitting, probe liner, and front-half of the filter holder
thoroughly with a total of 100 ml of 0.1 N HNO3, and place
the wash into a sample storage container. Perform the rinses as
applicable and generally as described in Method 12, Section 8.7.1.
Record the volume of the rinses. Mark the height of the fluid level on
the outside of the storage container and use this mark to determine if
leakage occurs during transport. Seal the container, and clearly label
the contents. Finally, rinse the nozzle, probe liner, and front-half of
the filter holder with water followed by acetone, and discard these
rinses.

Note: The use of a total of exactly 100 ml is necessary for the
subsequent blank correction procedures.
8.2.8 Container No. 4 (Impingers 1 through 3, Moisture Knockout
Impinger, when used, HNO3/H2O2
Impingers Contents and Rinses). Due to the potentially large quantity of
liquid involved, the tester may place the impinger solutions from
impingers 1 through 3 in more than one container, if necessary. Measure
the liquid in the first three impingers to within 0.5 ml using a
graduated cylinder. Record the volume. This information is required to
calculate the moisture content of the sampled flue gas. Clean each of
the first three impingers, the filter support, the back half of the
filter housing, and connecting glassware by thoroughly rinsing with 100
ml of 0.1 N HNO3 using the procedure as applicable in Method
12, Section 8.7.3.

Note: The use of exactly 100 ml of 0.1 N HNO3 rinse is
necessary for the subsequent blank correction procedures. Combine the
rinses and impinger solutions, measure and record the final total
volume. Mark the height of the fluid level, seal the container, and
clearly label the contents.

8.2.9 Container Nos. 5A (0.1 N HNO3), 5B
(KMnO4/H2SO4 absorbing solution), and
5C (8 N HCl rinse and dilution).
8.2.9.1 When sampling for Hg, pour all the liquid from the impinger
(normally impinger No. 4) that immediately preceded the two permanganate
impingers into a graduated cylinder and measure the volume to within 0.5
ml. This information is required to calculate the moisture content of
the sampled flue gas. Place the liquid in Container No. 5A. Rinse the
impinger with exactly 100 ml of 0.1 N HNO3 and place this
rinse in Container No. 5A.
8.2.9.2 Pour all the liquid from the two permanganate impingers
into a graduated cylinder and measure the volume to within 0.5 ml. This
information is required to calculate the moisture content of the sampled
flue gas. Place this acidic KMnO4 solution into Container No.
5B. Using a total of exactly 100 ml of fresh acidified KMnO4
solution for all rinses (approximately 33 ml per rinse), rinse the two
permanganate impingers and connecting glassware a minimum of three
times. Pour the rinses into Container No. 5B, carefully assuring
transfer of all loose precipitated materials from the two impingers.
Similarly, using 100 ml total of water, rinse the permanganate impingers
and connecting glass a minimum of three times, and pour the rinses into
Container 5B, carefully assuring transfer of any loose precipitated
material. Mark the height of the fluid level, and clearly label the
contents. Read the Precaution: in Section 7.3.2.

Note: Due to the potential reaction of KMnO4 with acid,
pressure buildup can occur in the sample storage bottles. Do not fill
these bottles completely and take precautions to relieve excess
pressure. A No. 70-72 hole drilled in the container cap and Teflon liner
has been used successfully.

8.2.9.3 If no visible deposits remain after the water rinse, no
further rinse is necessary. However, if deposits remain on the impinger
surfaces, wash them with 25 ml of 8 N HCl, and place the wash in a
separate sample container labeled No. 5C containing 200 ml of water.
First, place 200 ml of water in the container. Then wash the impinger
walls and stem with the HCl by turning the impinger on its side and
rotating it so that

[[Page 591]]

the HCl contacts all inside surfaces. Use a total of only 25 ml of 8 N
HCl for rinsing both permanganate impingers combined. Rinse the first
impinger, then pour the actual rinse used for the first impinger into
the second impinger for its rinse. Finally, pour the 25 ml of 8 N HCl
rinse carefully into the container. Mark the height of the fluid level
on the outside of the container to determine if leakage occurs during
transport.
8.2.10 Container No. 6 (Silica Gel). Note the color of the
indicating silica gel to determine whether it has been completely spent
and make a notation of its condition. Transfer the silica gel from its
impinger to its original container and seal it. The tester may use a
funnel to pour the silica gel and a rubber policeman to remove the
silica gel from the impinger. The small amount of particles that might
adhere to the impinger wall need not be removed. Do not use water or
other liquids to transfer the silica gel since weight gained in the
silica gel impinger is used for moisture calculations. Alternatively, if
a balance is available in the field, record the weight of the spent
silica gel (or silica gel plus impinger) to the nearest 0.5 g.
8.2.11 Container No. 7 (Acetone Blank). If particulate emissions
are to be determined, at least once during each field test, place a 100-
ml portion of the acetone used in the sample recovery process into a
container labeled No. 7. Seal the container.
8.2.12 Container No. 8A (0.1 N HNO3 Blank). At least
once during each field test, place 300 ml of the 0.1 N HNO3
solution used in the sample recovery process into a container labeled
No. 8A. Seal the container.
8.2.13 Container No. 8B (Water Blank). At least once during each
field test, place 100 ml of the water used in the sample recovery
process into a container labeled No. 8B. Seal the container.
8.2.14 Container No. 9 (5 Percent HNO3/10 Percent
H2O2 Blank). At least once during each field test,
place 200 ml of the 5 Percent HNO3/10 Percent
H2O2 solution used as the nitric acid impinger
reagent into a container labeled No. 9. Seal the container.
8.2.15 Container No. 10 (Acidified KMnO4 Blank). At
least once during each field test, place 100 ml of the acidified
KMnO4 solution used as the impinger solution and in the
sample recovery process into a container labeled No. 10. Prepare the
container as described in Section 8.2.9.2. Read the Precaution: in
Section 7.3.2 and read the NOTE in Section 8.2.9.2.
8.2.16 Container No. 11 (8 N HCl Blank). At least once during each
field test, place 200 ml of water into a sample container labeled No.
11. Then carefully add with stirring 25 ml of 8 N HCl. Mix well and seal
the container.
8.2.17 Container No. 12 (Sample Filter Blank). Once during each
field test, place into a petri dish labeled No. 12 three unused blank
filters from the same lot as the sampling filters. Seal the petri dish.
8.3 Sample Preparation. Note the level of the liquid in each of the
containers and determine if any sample was lost during shipment. If a
noticeable amount of leakage has occurred, either void the sample or use
methods, subject to the approval of the Administrator, to correct the
final results. A diagram illustrating sample preparation and analysis
procedures for each of the sample train components is shown in Figure
29-3.
8.3.1 Container No. 1 (Sample Filter).
8.3.1.1 If particulate emissions are being determined, first
desiccate the filter and filter catch without added heat (do not heat
the filters to speed the drying) and weigh to a constant weight as
described in Section 11.2.1 of Method 5.
8.3.1.2 Following this procedure, or initially, if particulate
emissions are not being determined in addition to metals analysis,
divide the filter with its filter catch into portions containing
approximately 0.5 g each. Place the pieces in the analyst's choice of
either individual microwave pressure relief vessels or Parr Bombs. Add 6
ml of concentrated HNO3 and 4 ml of concentrated HF to each
vessel. For microwave heating, microwave the samples for approximately
12 to 15 minutes total heating time as follows: heat for 2 to 3 minutes,
then turn off the microwave for 2 to 3 minutes, then heat for 2 to 3
minutes, etc., continue this alternation until the 12 to 15 minutes
total heating time are completed (this procedure should comprise
approximately 24 to 30 minutes at 600 watts). Microwave heating times
are approximate and are dependent upon the number of samples being
digested simultaneously. Sufficient heating is evidenced by sorbent
reflux within the vessel. For conventional heating, heat the Parr Bombs
at 140 deg.C (285 deg.F) for 6 hours. Then cool the samples to room
temperature, and combine with the acid digested probe rinse as required
in Section 8.3.3.
8.3.1.3 If the sampling train includes an optional glass cyclone in
front of the filter, prepare and digest the cyclone catch by the
procedures described in Section 8.3.1.2 and then combine the digestate
with the digested filter sample.
8.3.2 Container No. 2 (Acetone Rinse). Note the level of liquid in
the container and confirm on the analysis sheet whether or not leakage
occurred during transport. If a noticeable amount of leakage has
occurred, either void the sample or use methods, subject to the approval
of the Administrator, to correct the final results. Measure the liquid
in this container either volumetrically within 1 ml or gravimetrically
within 0.5 g. Transfer the contents to an acid-cleaned, tared 250-ml
beaker and evaporate to dryness at ambient temperature and pressure. If
particulate emissions are being determined, desiccate

[[Page 592]]

for 24 hours without added heat, weigh to a constant weight according to
the procedures described in Section 11.2.1 of Method 5, and report the
results to the nearest 0.1 mg. Redissolve the residue with 10 ml of
concentrated HNO3. Quantitatively combine the resultant
sample, including all liquid and any particulate matter, with Container
No. 3 before beginning Section 8.3.3.
8.3.3 Container No. 3 (Probe Rinse). Verify that the pH of this
sample is 2 or lower. If it is not, acidify the sample by careful
addition with stirring of concentrated HNO3 to pH 2. Use
water to rinse the sample into a beaker, and cover the beaker with a
ribbed watch glass. Reduce the sample volume to approximately 20 ml by
heating on a hot plate at a temperature just below boiling. Digest the
sample in microwave vessels or Parr Bombs by quantitatively transferring
the sample to the vessel or bomb, carefully adding the 6 ml of
concentrated HNO3, 4 ml of concentrated HF, and then
continuing to follow the procedures described in Section 8.3.1.2. Then
combine the resultant sample directly with the acid digested portions of
the filter prepared previously in Section 8.3.1.2. The resultant
combined sample is referred to as ``Sample Fraction 1''. Filter the
combined sample using Whatman 541 filter paper. Dilute to 300 ml (or the
appropriate volume for the expected metals concentration) with water.
This diluted sample is ``Analytical Fraction 1''. Measure and record the
volume of Analytical Fraction 1 to within 0.1 ml. Quantitatively remove
a 50-ml aliquot and label as ``Analytical Fraction 1B''. Label the
remaining 250-ml portion as ``Analytical Fraction 1A''. Analytical
Fraction 1A is used for ICAP or AAS analysis for all desired metals
except Hg. Analytical Fraction 1B is used for the determination of
front-half Hg.
8.3.4 Container No. 4 (Impingers 1-3). Measure and record the total
volume of this sample to within 0.5 ml and label it ``Sample Fraction
2''. Remove a 75- to 100-ml aliquot for Hg analysis and label the
aliquot ``Analytical Fraction 2B''. Label the remaining portion of
Container No. 4 as ``Sample Fraction 2A''. Sample Fraction 2A defines
the volume of Analytical Fraction 2A prior to digestion. All of Sample
Fraction 2A is digested to produce ``Analytical Fraction 2A''.
Analytical Fraction 2A defines the volume of Sample Fraction 2A after
its digestion and the volume of Analytical Fraction 2A is normally 150
ml. Analytical Fraction 2A is analyzed for all metals except Hg. Verify
that the pH of Sample Fraction 2A is 2 or lower. If necessary, use
concentrated HNO3 by careful addition and stirring to lower
Sample Fraction 2A to pH 2. Use water to rinse Sample Fraction 2A into a
beaker and then cover the beaker with a ribbed watchglass. Reduce Sample
Fraction 2A to approximately 20 ml by heating on a hot plate at a
temperature just below boiling. Then follow either of the digestion
procedures described in Sections 8.3.4.1 or 8.3.4.2.
8.3.4.1 Conventional Digestion Procedure. Add 30 ml of 50 percent
HNO3, and heat for 30 minutes on a hot plate to just below
boiling. Add 10 ml of 3 percent H2O2 and heat for
10 more minutes. Add 50 ml of hot water, and heat the sample for an
additional 20 minutes. Cool, filter the sample, and dilute to 150 ml (or
the appropriate volume for the expected metals concentrations) with
water. This dilution produces Analytical Fraction 2A. Measure and record
the volume to within 0.1 ml.
8.3.4.2 Microwave Digestion Procedure. Add 10 ml of 50 percent
HNO3 and heat for 6 minutes total heating time in
alternations of 1 to 2 minutes at 600 Watts followed by 1 to 2 minutes
with no power, etc., similar to the procedure described in Section
8.3.1. Allow the sample to cool. Add 10 ml of 3 percent
H2O2 and heat for 2 more minutes. Add 50 ml of hot
water, and heat for an additional 5 minutes. Cool, filter the sample,
and dilute to 150 ml (or the appropriate volume for the expected metals
concentrations) with water. This dilution produces Analytical Fraction
2A. Measure and record the volume to within 0.1 ml.

Note: All microwave heating times given are approximate and are
dependent upon the number of samples being digested at a time. Heating
times as given above have been found acceptable for simultaneous
digestion of up to 12 individual samples. Sufficient heating is
evidenced by solvent reflux within the vessel.

8.3.5 Container No. 5A (Impinger 4), Container Nos. 5B and 5C
(Impingers 5 and 6). Keep the samples in Containers Nos. 5A, 5B, and 5C
separate from each other. Measure and record the volume of 5A to within
0.5 ml. Label the contents of Container No. 5A to be Analytical Fraction
3A. To remove any brown MnO2 precipitate from the contents of
Container No. 5B, filter its contents through Whatman 40 filter paper
into a 500 ml volumetric flask and dilute to volume with water. Save the
filter for digestion of the brown MnO2 precipitate. Label the
500 ml filtrate from Container No. 5B to be Analytical Fraction 3B.
Analyze Analytical Fraction 3B for Hg within 48 hours of the filtration
step. Place the saved filter, which was used to remove the brown
MnO2 precipitate, into an appropriately sized vented
container, which will allow release of any gases including chlorine
formed when the filter is digested. In a laboratory hood which will
remove any gas produced by the digestion of the MnO2, add 25
ml of 8 N HCl to the filter and allow to digest for a minimum of 24
hours at room temperature. Filter the contents of Container No. 5C
through a Whatman 40 filter into a 500-ml volumetric flask. Then filter
the result of the digestion of the brown MnO2

[[Page 593]]

from Container No. 5B through a Whatman 40 filter into the same 500-ml
volumetric flask, and dilute and mix well to volume with water. Discard
the Whatman 40 filter. Mark this combined 500-ml dilute HCl solution as
Analytical Fraction 3C.
8.3.6 Container No. 6 (Silica Gel). Weigh the spent silica gel (or
silica gel plus impinger) to the nearest 0.5 g using a balance.

9.0 Quality Control

9.1 Field Reagent Blanks, if analyzed. Perform the digestion and
analysis of the blanks in Container Nos. 7 through 12 that were produced
in Sections 8.2.11 through 8.2.17, respectively. For Hg field reagent
blanks, use a 10 ml aliquot for digestion and analysis.
9.1.1 Digest and analyze one of the filters from Container No. 12
per Section 8.3.1, 100 ml from Container No. 7 per Section 8.3.2, and
100 ml from Container No. 8A per Section 8.3.3. This step produces
blanks for Analytical Fractions 1A and 1B.
9.1.2 Combine 100 ml of Container No. 8A with 200 ml from Container
No. 9, and digest and analyze the resultant volume per Section 8.3.4.
This step produces blanks for Analytical Fractions 2A and 2B.
9.1.3 Digest and analyze a 100-ml portion of Container No. 8A to
produce a blank for Analytical Fraction 3A.
9.1.4 Combine 100 ml from Container No. 10 with 33 ml from
Container No. 8B to produce a blank for Analytical Fraction 3B. Filter
the resultant 133 ml as described for Container No. 5B in Section 8.3.5,
except do not dilute the 133 ml. Analyze this blank for Hg within 48 hr
of the filtration step, and use 400 ml as the blank volume when
calculating the blank mass value. Use the actual volumes of the other
analytical blanks when calculating their mass values.
9.1.5 Digest the filter that was used to remove any brown
MnO2 precipitate from the blank for Analytical Fraction 3B by
the same procedure as described in Section 8.3.5 for the similar sample
filter. Filter the digestate and the contents of Container No. 11
through Whatman 40 paper into a 500-ml volumetric flask, and dilute to
volume with water. These steps produce a blank for Analytical Fraction
3C.
9.1.6 Analyze the blanks for Analytical Fraction Blanks 1A and 2A
per Section 11.1.1 and/or Section 11.1.2. Analyze the blanks for
Analytical Fractions 1B, 2B, 3A, 3B, and 3C per Section 11.1.3. Analysis
of the blank for Analytical Fraction 1A produces the front-half reagent
blank correction values for the desired metals except for Hg; Analysis
of the blank for Analytical Fraction 1B produces the front-half reagent
blank correction value for Hg. Analysis of the blank for Analytical
Fraction 2A produces the back-half reagent blank correction values for
all of the desired metals except for Hg, while separate analyses of the
blanks for Analytical Fractions 2B, 3A, 3B, and 3C produce the back-half
reagent blank correction value for Hg.
9.2 Quality Control Samples. Analyze the following quality control
samples.
9.2.1 ICAP and ICP-MS Analysis. Follow the respective quality
control descriptions in Section 8 of Methods 6010 and 6020 in EPA
Publication SW-846 Third Edition (November 1986) including updates I,
II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i). For
the purposes of a source test that consists of three sample runs, modify
those requirements to include the following: two instrument check
standard runs, two calibration blank runs, one interference check sample
at the beginning of the analysis (analyze by Method of Standard
Additions unless within 25 percent), one quality control sample to check
the accuracy of the calibration standards (required to be within 25
percent of calibration), and one duplicate analysis (required to be
within 20 percent of average or repeat all analyses).
9.2.2 Direct Aspiration AAS and/or GFAAS Analysis for Sb, As, Ba,
Be, Cd, Cu, Cr, Co, Pb, Ni, Mn, Hg, P, Se, Ag, Tl, and Zn. Analyze all
samples in duplicate. Perform a matrix spike on at least one front-half
sample and one back-half sample, or one combined sample. If recoveries
of less than 75 percent or greater than 125 percent are obtained for the
matrix spike, analyze each sample by the Method of Standard Additions.
Analyze a quality control sample to check the accuracy of the
calibration standards. If the results are not within 20 percent, repeat
the calibration.
9.2.3 CVAAS Analysis for Hg. Analyze all samples in duplicate.
Analyze a quality control sample to check the accuracy of the
calibration standards (if not within 15 percent, repeat calibration).
Perform a matrix spike on one sample (if not within 25 percent, analyze
all samples by the Method of Standard Additions). Additional information
on quality control can be obtained from Method 7470 in EPA Publication
SW-846 Third Edition (November 1986) including updates I, II, IIA, IIB
and III, as incorporated by reference in Sec. 60.17(i), or in Standard
Methods for Water and Wastewater Method 303F.

10.0 Calibration and Standardization

Note: Maintain a laboratory log of all calibrations.

10.1 Sampling Train Calibration. Calibrate the sampling train
components according to the indicated sections of Method 5: Probe Nozzle
(Section 10.1); Pitot Tube (Section 10.2); Metering System (Section
10.3); Probe Heater (Section 10.4); Temperature Sensors (Section 10.5);
Leak-Check of the Metering System (Section 8.4.1); and Barometer
(Section 10.6).

[[Page 594]]

10.2 Inductively Coupled Argon Plasma Spectrometer Calibration.
Prepare standards as outlined in Section 7.5. Profile and calibrate the
instrument according to the manufacturer's recommended procedures using
those standards. Check the calibration once per hour. If the instrument
does not reproduce the standard concentrations within 10 percent,
perform the complete calibration procedures. Perform ICP-MS analysis by
following Method 6020 in EPA Publication SW-846 Third Edition (November
1986) including updates I, II, IIA, IIB and III, as incorporated by
reference in Sec. 60.17(i).
10.3 Atomic Absorption Spectrometer--Direct Aspiration AAS, GFAAS,
and CVAAS analyses. Prepare the standards as outlined in Section 7.5 and
use them to calibrate the spectrometer. Calibration procedures are also
outlined in the EPA methods referred to in Table 29-2 and in Method 7470
in EPA Publication SW-846 Third Edition (November 1986) including
updates I, II, IIA, IIB and III, as incorporated by reference in
Sec. 60.17(i), or in Standard Methods for Water and Wastewater Method
303F (for Hg). Run each standard curve in duplicate and use the mean
values to calculate the calibration line. Recalibrate the instrument
approximately once every 10 to 12 samples.

11.0 Analytical Procedure

11.1 Sample Analysis. For each sampling train sample run, seven
individual analytical samples are generated; two for all desired metals
except Hg, and five for Hg. A schematic identifying each sample
container and the prescribed analytical preparation and analysis scheme
is shown in Figure 29-3. The first two analytical samples, labeled
Analytical Fractions 1A and 1B, consist of the digested samples from the
front-half of the train. Analytical Fraction 1A is for ICAP, ICP-MS or
AAS analysis as described in Sections 11.1.1 and 11.1.2, respectively.
Analytical Fraction 1B is for front-half Hg analysis as described in
Section 11.1.3. The contents of the back-half of the train are used to
prepare the third through seventh analytical samples. The third and
fourth analytical samples, labeled Analytical Fractions 2A and 2B,
contain the samples from the moisture removal impinger No. 1, if used,
and HNO3/H2O2 impingers Nos. 2 and 3.
Analytical Fraction 2A is for ICAP, ICP-MS or AAS analysis for target
metals, except Hg. Analytical Fraction 2B is for analysis for Hg. The
fifth through seventh analytical samples, labeled Analytical Fractions
3A, 3B, and 3C, consist of the impinger contents and rinses from the
empty impinger No. 4 and the H2SO4/
KMnO4 Impingers Nos. 5 and 6. These analytical samples are
for analysis for Hg as described in Section 11.1.3. The total back-half
Hg catch is determined from the sum of Analytical Fractions 2B, 3A, 3B,
and 3C. Analytical Fractions 1A and 2A can be combined proportionally
prior to analysis.
11.1.1 ICAP and ICP-MS Analysis. Analyze Analytical Fractions 1A
and 2A by ICAP using Method 6010 or Method 200.7 (40 CFR 136, Appendix
C). Calibrate the ICAP, and set up an analysis program as described in
Method 6010 or Method 200.7. Follow the quality control procedures
described in Section 9.2.1. Recommended wavelengths for analysis are as
shown in Table 29-2. These wavelengths represent the best combination of
specificity and potential detection limit. Other wavelengths may be
substituted if they can provide the needed specificity and detection
limit, and are treated with the same corrective techniques for spectral
interference. Initially, analyze all samples for the target metals
(except Hg) plus Fe and Al. If Fe and Al are present, the sample might
have to be diluted so that each of these elements is at a concentration
of less than 50 ppm so as to reduce their spectral interferences on As,
Cd, Cr, and Pb. Perform ICP-MS analysis by following Method 6020 in EPA
Publication SW-846 Third Edition (November 1986) including updates I,
II, IIA, IIB and III, as incorporated by reference in Sec. 60.17(i).

Note: When analyzing samples in a HF matrix, an alumina torch should
be used; since all front-half samples will contain HF, use an alumina
torch.
11.1.2 AAS by Direct Aspiration and/or GFAAS. If analysis of metals
in Analytical Fractions 1A and 2A by using GFAAS or direct aspiration
AAS is needed, use Table 29-3 to determine which techniques and
procedures to apply for each target metal. Use Table 29-3, if necessary,
to determine techniques for minimization of interferences. Calibrate the
instrument according to Section 10.3 and follow the quality control
procedures specified in Section 9.2.2.
11.1.3 CVAAS Hg analysis. Analyze Analytical Fractions 1B, 2B, 3A,
3B, and 3C separately for Hg using CVAAS following the method outlined
in Method 7470 in EPA Publication SW-846 Third Edition (November 1986)
including updates I, II, IIA, IIB and III, as incorporated by reference
in Sec. 60.17(i), or in Standard Methods for Water and Wastewater
Analysis, 15th Edition, Method 303F, or, optionally using Note No. 2 at
the end of this section. Set up the calibration curve (zero to 1000 ng)
as described in Method 7470 or similar to Method 303F using 300-ml BOD
bottles instead of Erlenmeyers. Perform the following for each Hg
analysis. From each original sample, select and record an aliquot in the
size range from 1 ml to 10 ml. If no prior knowledge of the expected
amount of Hg in the sample exists, a 5 ml aliquot is suggested for the
first dilution to 100 ml (see Note No. 1 at end of this section). The
total amount of Hg in the aliquot shall be less than 1 g and
within the range (zero to 1000

[[Page 595]]

ng) of the calibration curve. Place the sample aliquot into a separate
300-ml BOD bottle, and add enough water to make a total volume of 100
ml. Next add to it sequentially the sample digestion solutions and
perform the sample preparation described in the procedures of Method
7470 or Method 303F. (See Note No. 2 at the end of this section). If the
maximum readings are off-scale (because Hg in the aliquot exceeded the
calibration range; including the situation where only a 1-ml aliquot of
the original sample was digested), then dilute the original sample (or a
portion of it) with 0.15 percent HNO3 (1.5 ml concentrated
HNO3 per liter aqueous solution) so that when a 1- to 10-ml
aliquot of the ``0.15 HNO3 percent dilution of the original
sample'' is digested and analyzed by the procedures described above, it
will yield an analysis within the range of the calibration curve.

Note No. 1: When Hg levels in the sample fractions are below the in-
stack detection limit given in Table 29-1, select a 10 ml aliquot for
digestion and analysis as described.
Note No. 2: Optionally, Hg can be analyzed by using the CVAAS
analytical procedures given by some instrument manufacturer's
directions. These include calibration and quality control procedures for
the Leeman Model PS200, the Perkin Elmer FIAS systems, and similar
models, if available, of other instrument manufacturers. For digestion
and analyses by these instruments, perform the following two steps: (1),
Digest the sample aliquot through the addition of the aqueous
hydroxylamine hydrochloride/sodium chloride solution the same as
described in this section: (The Leeman, Perkin Elmer, and similar
instruments described in this note add automatically the necessary
stannous chloride solution during the automated analysis of Hg.); (2),
Upon completion of the digestion described in (1), analyze the sample
according to the instrument manufacturer's directions. This approach
allows multiple (including duplicate) automated analyses of a digested
sample aliquot.

12.0 Data Analysis and Calculations

12.1 Nomenclature.

A = Analytical detection limit, g/ml.
B = Liquid volume of digested sample prior to aliquotting for analysis,
ml.
C = Stack sample gas volume, dsm\3\.
Ca1 = Concentration of metal in Analytical Fraction 1A as
read from the standard curve, g/ml.
Ca2 = Concentration of metal in Analytical Fraction 2A as
read from the standard curve, (g/ml).
Cs = Concentration of a metal in the stack gas, mg/dscm.
D = In-stack detection limit, g/m\3\.
Fa = Aliquot factor, volume of Sample Fraction 2 divided by
volume of Sample Fraction 2A (see Section 8.3.4.)
Fd = Dilution factor (Fd = the inverse of the
fractional portion of the concentrated sample in the solution
actually used in the instrument to produce the reading
Ca1. For example, if a 2 ml aliquot of Analytical
Fraction 1A is diluted to 10 ml to place it in the calibration
range, Fd = 5).
Hgbh = Total mass of Hg collected in the back-half of the
sampling train, g.
Hgbh2 = Total mass of Hg collected in Sample Fraction 2,
g.
Hgbh3(A,B,C) = Total mass of Hg collected separately in
Fraction 3A, 3B, or 3C, g.
Hgbhb = Blank correction value for mass of Hg detected in
back-half field reagent blanks, g.
Hgfh = Total mass of Hg collected in the front-half of the
sampling train (Sample Fraction 1), g.
Hgfhb = Blank correction value for mass of Hg detected in
front-half field reagent blank, g.
Hgt = Total mass of Hg collected in the sampling train,
g.
Mbh = Total mass of each metal (except Hg) collected in the
back-half of the sampling train (Sample Fraction 2),
g.
Mbhb = Blank correction value for mass of metal detected in
back-half field reagent blank, g.
Mfh = Total mass of each metal (except Hg) collected in the
front half of the sampling train (Sample Fraction 1),
g.
Mfhb = Blank correction value for mass of metal detected in
front-half field reagent blank, g.
Mt = Total mass of each metal (separately stated for each
metal) collected in the sampling train, g.
Mt = Total mass of that metal collected in the sampling
train, g; (substitute Hgt for
Mt for the Hg calculation).
Qbh2 = Quantity of Hg, g, TOTAL in the ALIQUOT of
Analytical Fraction 2B selected for digestion and analysis .
NOTE: For example, if a 10 ml aliquot of Analytical Fraction
2B is taken and digested and analyzed (according to Section
11.1.3 and its NOTES Nos. 1 and 2), then calculate and use the
total amount of Hg in the 10 ml aliquot for Qbh2.
Qbh3(A,B,C) = Quantity of Hg, g, TOTAL, separately,
in the ALIQUOT of Analytical Fraction 3A, 3B, or 3C selected
for digestion and analysis (see NOTES in Sections 12.7.1 and
12.7.2 describing the quantity ``Q'' and calculate similarly).
Qfh = Quantity of Hg, g, TOTAL in the ALIQUOT of
Analytical Fraction 1B selected for digestion and analysis.
NOTE: For example, if a 10 ml aliquot of Analytical Fraction
1B is taken and digested and analyzed (according to Section
11.1.3 and its NOTES Nos. 1 and 2), then calculate

[[Page 596]]

and use the total amount of Hg in the 10 ml aliquot for
Qfh.
Va = Total volume of digested sample solution (Analytical
Fraction 2A), ml (see Section 8.3.4.1 or 8.3.4.2, as
applicable).
Vf1B = Volume of aliquot of Analytical Fraction 1B analyzed,
ml. NOTE: For example, if a 1 ml aliquot of Analytical
Fraction 1B was diluted to 50 ml with 0.15 percent
HNO3 as described in Section 11.1.3 to bring it
into the proper analytical range, and then 1 ml of that 50-ml
was digested according to Section 11.1.3 and analyzed,
Vf1B would be 0.02 ml.
Vf2B = Volume of Analytical Fraction 2B analyzed, ml. NOTE:
For example, if 1 ml of Analytical Fraction 2B was diluted to
10 ml with 0.15 percent HNO3 as described in
Section 11.1.3 to bring it into the proper analytical range,
and then 5 ml of that 10 ml was analyzed, Vf2B
would be 0.5 ml.
Vf3(A,B,C) = Volume, separately, of Analytical Fraction 3A,
3B, or 3C analyzed, ml (see previous notes in Sections 12.7.1
and 12.7.2, describing the quantity ``V'' and calculate
similarly).
Vm(std) = Volume of gas sample as measured by the dry gas
meter, corrected to dry standard conditions, dscm.
Vsoln,1 = Total volume of digested sample solution
(Analytical Fraction 1), ml.
Vsoln,1 = Total volume of Analytical Fraction 1, ml.
Vsoln,2 = Total volume of Sample Fraction 2, ml.
Vsoln,3(A,B,C) = Total volume, separately, of Analytical
Fraction 3A, 3B, or 3C, ml.
K4 = 10^-\3\ mg/g.

12.2 Dry Gas Volume. Using the data from this test, calculate
Vm(std), the dry gas sample volume at standard conditions as
outlined in Section 12.3 of Method 5.
12.3 Volume of Water Vapor and Moisture Content. Using the total
volume of condensate collected during the source sampling, calculate the
volume of water vapor Vw(std) and the moisture content
Bws of the stack gas. Use Equations 5-2 and 5-3 of Method 5.
12.4 Stack Gas Velocity. Using the data from this test and Equation
2-9 of Method 2, calculate the average stack gas velocity.
12.5 In-Stack Detection Limits. Calculate the in-stack method
detection limits shown in Table 29-4 using the conditions described in
Section 13.3.1 as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.439

12.6 Metals (Except Hg) in Source Sample.
12.6.1 Analytical Fraction 1A, Front-Half, Metals (except Hg).
Calculate separately the amount of each metal collected in Sample
Fraction 1 of the sampling train using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.440

Note: If Analytical Fractions 1A and 2A are combined, use
proportional aliquots. Then make appropriate changes in Equations 29-2
through 29-4 to reflect this approach.

12.6.2 Analytical Fraction 2A, Back-Half, Metals (except Hg).
Calculate separately the amount of each metal collected in Fraction 2 of
the sampling train using the following equation:
[GRAPHIC] [TIFF OMITTED] TR17OC00.441

12.6.3 Total Train, Metals (except Hg). Calculate the total amount
of each of the quantified metals collected in the sampling train as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.442

Note: If the measured blank value for the front half
(Mfhb) is in the range 0.0 to ``A'' g (where ``A''
g equals the value determined by multiplying 1.4 g/
in.² times the actual area in in.² of the sample
filter), use Mfhb to correct the emission sample value
(Mfh); if Mfhb exceeds ``A'' g, use the
greater of I or II:
I. ``A'' g.
II. The lesser of (a) Mfhb, or (b) 5 percent of
Mfh. If the measured blank value for the back-half
(Mbhb) is in the range 0.0 to 1 g, use
Mbhb to correct the emission sample value (Mbh);
if Mbhb exceeds 1 g, use the greater of I or II:
I. 1 g.
II. The lesser of (a) Mbhb, or (b) 5 percent of
Mbh.

12.7 Hg in Source Sample.
12.7.1 Analytical Fraction 1B; Front-Half Hg. Calculate the amount
ofHg collected in the front-half, Sample Fraction 1, of the sampling
train by using Equation 29-5:
[GRAPHIC] [TIFF OMITTED] TR17OC00.443

12.7.2 Analytical Fractions 2B, 3A, 3B, and 3C; Back Half Hg.
12.7.2.1 Calculate the amount of Hg collected in Sample Fraction 2
by using Equation 29-6:

[[Page 597]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.444

12.7.2.2 Calculate each of the back-half Hg values for Analytical
Fractions 3A, 3B, and 3C by using Equation 29-7:
[GRAPHIC] [TIFF OMITTED] TR17OC00.445

12.7.2.3 Calculate the total amount of Hg collected in the back-
half of the sampling train by using Equation 29-8:
[GRAPHIC] [TIFF OMITTED] TR17OC00.446

12.7.3 Total Train Hg Catch. Calculate the total amount of Hg
collected in the sampling train by using Equation 29-9:
[GRAPHIC] [TIFF OMITTED] TR17OC00.447

Note: If the total of the measured blank values (Hgfhb +
Hgbhb) is in the range of 0.0 to 0.6 g, then use the
total to correct the sample value (Hgfh + Hgbh);
if it exceeds 0.6 g, use the greater of I. or II:
I. 0.6 g.
II. The lesser of (a) (Hgfhb + Hgbhb), or (b)
5 percent of the sample value (Hgfh + Hgbh).

12.8 Individual Metal Concentrations in Stack Gas. Calculate the
concentration of each metal in the stack gas (dry basis, adjusted to
standard conditions) by using Equation 29-10:
[GRAPHIC] [TIFF OMITTED] TR17OC00.448

12.9 Isokinetic Variation and Acceptable Results. Same as Method 5,
Sections 12.11 and 12.12, respectively.

13.0 Method Performance

13.1 Range. For the analysis described and for similar analyses,
the ICAP response is linear over several orders of magnitude. Samples
containing metal concentrations in the nanograms per ml (ng/ml) to
micrograms per ml (g/ml) range in the final analytical solution
can be analyzed using this method. Samples containing greater than
approximately 50 g/ml As, Cr, or Pb should be diluted to that
level or lower for final analysis. Samples containing greater than
approximately 20 g/ml of Cd should be diluted to that level
before analysis.
13.2 Analytical Detection Limits.

Note: See Section 13.3 for the description of in-stack detection
limits.

13.2.1 ICAP analytical detection limits for the sample solutions
(based on SW-846, Method 6010) are approximately as follows: Sb (32 ng/
ml), As (53 ng/ml), Ba (2 ng/ml), Be (0.3 ng/ml), Cd (4 ng/ml), Cr (7
ng/ml), Co (7 ng/ml), Cu (6 ng/ml), Pb (42 ng/ml), Mn (2 ng/ml), Ni (15
ng/ml), P (75 ng/ml), Se (75 ng/ml), Ag (7 ng/ml), Tl (40 ng/ml), and Zn
(2 ng/ml). ICP-MS analytical detection limits (based on SW-846, Method
6020) are lower generally by a factor of ten or more. Be is lower by a
factor of three. The actual sample analytical detection limits are
sample dependent and may vary due to the sample matrix.
13.2.2 The analytical detection limits for analysis by direct
aspiration AAS (based on SW-846, Method 7000 series) are approximately
as follows: Sb (200 ng/ml), As (2 ng/ml), Ba (100 ng/ml), Be (5 ng/ml),
Cd (5 ng/ml), Cr (50 ng/ml), Co (50 ng/ml), Cu (20 ng/ml), Pb (100 ng/
ml), Mn (10 ng/ml), Ni (40 ng/ml), Se (2 ng/ml), Ag (10 ng/ml), Tl (100
ng/ml), and Zn (5 ng/ml).
13.2.3 The detection limit for Hg by CVAAS (on the resultant volume
of the digestion of the aliquots taken for Hg analyses) can be
approximately 0.02 to 0.2 ng/ml,

[[Page 598]]

depending upon the type of CVAAS analytical instrument used. 13.2.4 The
use of GFAAS can enhance the detection limits compared to direct
aspiration AAS as follows: Sb (3 ng/ml), As (1 ng/ml), Be (0.2 ng/ml),
Cd (0.1 ng/ml), Cr (1 ng/ml), Co (1 ng/ml), Pb (1 ng/ml), Se (2 ng/ml),
and Tl (1 ng/ml).
13.3 In-stack Detection Limits.
13.3.1 For test planning purposes in-stack detection limits can be
developed by using the following information: (1) The procedures
described in this method, (2) the analytical detection limits described
in Section 13.2 and in SW-846,(3) the normal volumes of 300 ml
(Analytical Fraction 1) for the front-half and 150 ml (Analytical
Fraction 2A) for the back-half samples, and (4) a stack gas sample
volume of 1.25 m³. The resultant in-stack method detection
limits for the above set of conditions are presented in Table 29-1 and
were calculated by using Eq. 29-1 shown in Section 12.5.
13.3.2 To ensure optimum precision/resolution in the analyses, the
target concentrations of metals in the analytical solutions should be at
least ten times their respective analytical detection limits. Under
certain conditions, and with greater care in the analytical procedure,
these concentrations can be as low as approximately three times the
respective analytical detection limits without seriously impairing the
precision of the analyses. On at least one sample run in the source
test, and for each metal analyzed, perform either repetitive analyses,
Method of Standard Additions, serial dilution, or matrix spike addition,
etc., to document the quality of the data.
13.3.3 Actual in-stack method detection limits are based on actual
source sampling parameters and analytical results as described above. If
required, the method in-stack detection limits can be improved over
those shown in Table 29-1 for a specific test by either increasing the
sampled stack gas volume, reducing the total volume of the digested
samples, improving the analytical detection limits, or any combination
of the three. For extremely low levels of Hg only, the aliquot size
selected for digestion and analysis can be increased to as much as 10
ml, thus improving the in-stack detection limit by a factor of ten
compared to a 1 ml aliquot size.
13.3.3.1 A nominal one hour sampling run will collect a stack gas
sampling volume of about 1.25 m³. If the sampling time is
increased to four hours and 5 m³ are collected, the in-stack
method detection limits would be improved by a factor of four compared
to the values shown in Table 29-1.
13.3.3.2 The in-stack detection limits assume that all of the
sample is digested and the final liquid volumes for analysis are the
normal values of 300 ml for Analytical Fraction 1, and 150 ml for
Analytical Fraction 2A. If the volume of Analytical Fraction 1 is
reduced from 300 to 30 ml, the in-stack detection limits for that
fraction of the sample would be improved by a factor of ten. If the
volume of Analytical Fraction 2A is reduced from 150 to 25 ml, the in-
stack detection limits for that fraction of the sample would be improved
by a factor of six. Matrix effect checks are necessary on sample
analyses and typically are of much greater significance for samples that
have been concentrated to less than the normal original sample volume.
Reduction of Analytical Fractions 1 and 2A to volumes of less than 30
and 25 ml, respectively, could interfere with the redissolving of the
residue and could increase interference by other compounds to an
intolerable level.
13.3.3.3 When both of the modifications described in Sections
13.3.3.1 and 13.3.3.2 are used simultaneously on one sample, the
resultant improvements are multiplicative. For example, an increase in
stack gas volume by a factor of four and a reduction in the total liquid
sample digested volume of both Analytical Fractions 1 and 2A by a factor
of six would result in an improvement by a factor of twenty-four of the
in-stack method detection limit.
13.4 Precision. The precision (relative standard deviation) for
each metal detected in a method development test performed at a sewage
sludge incinerator were found to be as follows:

Sb (12.7 percent), As (13.5 percent), Ba (20.6 percent), Cd (11.5
percent), Cr (11.2 percent), Cu (11.5 percent), Pb (11.6 percent), P
(14.6 percent), Se (15.3 percent), Tl (12.3 percent), and Zn (11.8
percent). The precision for Ni was 7.7 percent for another test
conducted at a source simulator. Be, Mn, and Ag were not detected in the
tests. However, based on the analytical detection limits of the ICAP for
these metals, their precisions could be similar to those for the other
metals when detected at similar levels.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

1. Method 303F in Standard Methods for the Examination of Water
Wastewater, 15th Edition, 1980. Available from the American Public
Health Association, 1015 18th Street N.W., Washington, D.C. 20036.
2. EPA Methods 6010, 6020, 7000, 7041, 7060, 7131, 7421, 7470, 7740,
and 7841, Test Methods for Evaluating Solid Waste: Physical/Chemical
Methods. SW-846, Third Edition, November 1986, with updates I, II, IIA,
IIB and III. Office of Solid Waste and Emergency Response, U. S.
Environmental Protection Agency, Washington, DC 20460.
3. EPA Method 200.7, Code of Federal Regulations, Title 40, Part
136, Appendix C. July 1, 1987.

[[Page 599]]

4. EPA Methods 1 through 5, Code of Federal Regulations, Title 40,
Part 60, Appendix A, July 1, 1991.
5. EPA Method 101A, Code of Federal Regulations, Title 40, Part 61,
Appendix B, July 1, 1991.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Table 29-1.--In Stack Method Detection Limits (ug/m³) for the Front-Half, the Back Half, and the Total Sampling
Train Using ICAP, GFAAS, and CVAAS
----------------------------------------------------------------------------------------------------------------
Front-half: Back-half:
Metal probe and Back-half: impringers 4- Total train
filter impinters 1-3 6 ^a
----------------------------------------------------------------------------------------------------------------
Antimony........................................ ¹ 7.7 (0.7) ¹ 3.8 (0.4) .............. ¹ 11.5 (1.1)
Arsenic......................................... ¹ 12.7 (0.3) ¹ 6.4 (0.1) .............. ¹ 19.1 (0.4)
Barium.......................................... 0.5 0.3 .............. 0.8
Beryllium....................................... ¹ 0.07 (0.05) ¹ 0.04 (0.03) .............. ¹ 0.11 (0.08)
Cadmium......................................... ¹ 1.0 (0.02) ¹ 0.5 (0.01) .............. ¹ 1.5 (0.03)
Chromium........................................ ¹ 1.7 (0.2) ¹ 0.8 (0.1) .............. ¹ 2.5 (0.3)
Cobalt.......................................... ¹ 1.7 (0.2) ¹ 0.8 (0.1) .............. ¹ 2.5 (0.3)
Copper.......................................... 1.4 0.7 .............. 2.1
Lead............................................ ¹ 10.1 (0.2) ¹ 5.0 (0.1) .............. ¹ 15.1 (0.3)
Manganese....................................... ¹ 0.5 (0.2) ¹ 0.2 (0.1) .............. ¹ 0.7 (0.3)
Mercury......................................... ² 0.06 ² 0.3 ² 0.2 ² 0.56
Nickel.......................................... 3.6 1.8 .............. 5.4
Phosphorus...................................... 18 9 .............. 27
Selenium........................................ ¹ 18 (0.5) ¹ 9 (0.3) .............. ¹ 27 (0.8)
Silver.......................................... 1.7 0.9 (0.7) .............. 2.6
Thallium........................................ ¹ 9.6 (0.2) ¹ 4.8 (0.1) .............. ¹ 14.4 (0.3)
Zinc............................................ 0.5 0.3 .............. 0.8
----------------------------------------------------------------------------------------------------------------
\a\ Mercury analysis only.
\1\ Detection limit when analyzed by ICAP or GFAAS as shown in parentheses (see Section 11.1.2).
\2\ Detection limit when anaylzed by CVAAS, estimated for Back-half and Total Train. See Sections 13.2 and
11.1.3. Note: Actual method in-stack detection limits may vary from these values, as described in Section
13.3.3.

Table 29-2.--Recommended Wavelengths for ICAP Analysis
------------------------------------------------------------------------
Wavelength
Analyte (nm)
------------------------------------------------------------------------
Aluminum (Al)........................................... 308.215
Antimony (Sb)........................................... 206.833
Arsenic (As)............................................ 193.696
Barium (Ba)............................................. 455.403
Beryllium (Be).......................................... 313.042
Cadmium (Cd)............................................ 226.502
Chromium (Cr)........................................... 267.716
Cobalt (Co)............................................. 228.616
Copper (Cu)............................................. 328.754
Iron (Fe)............................................... 259.940
Lead (Pb)............................................... 220.353
Manganese (Mn).......................................... 257.610
Nickel (Ni)............................................. 231.604
Phosphorus (P).......................................... 214.914
Selenium (Se)........................................... 196.026
Silver (Ag)............................................. 328.068
Thallium (T1)........................................... 190,864
Zinc (Zn)............................................... 213,856
------------------------------------------------------------------------

[[Page 600]]

Table 29-3.--Applicable Techniques, Methods and Minimization of Interferences for AAS Analysis
----------------------------------------------------------------------------------------------------------------
Interferences
Metal Technique SW-846 \1\ Wavelength ----------------------------------------------
Methods No. (nm) Cause Minimization
----------------------------------------------------------------------------------------------------------------
Fe............... Aspiration.......... 7380 248.3 Contamination...... Great care taken to
avoid contamination.
Pb............... Aspiration.......... 7420 283.3 217.0 nm alternate. Background correction
required.
Pb............... Furnace............. 7421 283.3 Poor recoveries.... Matrix modifier, add 10
l of
phosphorus acid to 1 ml
of prepared sample in
sampler cup.
Mn............... Aspiration.......... 7460 279.5 403.1 nm alternate. Background correction
required.
Ni............... Aspiration.......... 7520 232.0 352.4 nm alternate Background correction
Fe, Co, and Cr. required. Matrix
Nonlinear response. matching or nitrous-
oxide/acetylene flame
Sample dilution or use
352.3 nm line
Se............... Furnace............. 7740 196.0 Volatility......... Spike samples and
reference materials and
add nickel nitrate to
minimize
volatilization.
Adsorption & Background correction is
scatter. required and Zeeman
background correction
can be useful.
Ag............... Aspiration.......... 7760 328.1 Adsorption & Background correction is
scatter AgCl required. Avoid
insoluble. hydrochloric acid
unless silver is in
solution as a chloride
complex. Sample and
standards monitored for
aspiration rate.
Tl............... Aspiration.......... 7840 276.8 Background correction is
required. Hydrochloric
acid should not be
used.
Tl............... Furnace............. 7841 276.8 Hydrochloric acid Background correction is
or chloride. required. Verify that
losses are not
occurring for
volatilization by
spiked samples or
standard addition;
Palladium is a suitable
matrix modifier. 4
Zn............... Aspiration.......... 7950 213.9 High Si, Cu, & P Strontium removes Cu and
Contamination. phosphate.
Great care taken to
avoid contamination.
Sb............... Aspiration.......... 7040 217.6 1000 mg/ml Pb, Ni, Use secondary wavelength
Cu, or acid. of 231.1 nm; match
sample & standards acid
concentration or use
nitrous oxide/acetylene
flame.
Sb............... Furnace............. 7041 217.6 High Pb............ Secondary wavelength or
Zeeman correction.
As............... Furnace............. 7060 193.7 Arsenic Spike samples and add
Volatilization nickel nitrate solution
Aluminum. to digestates prior to
analysis. Use Zeeman
background correction.
Ba............... Aspiration.......... 7080 553.6
Calcium............
Barium Ionization.. High hollow cathode
current and narrow band
set.
2 ml of KCl per 100 m1
of sample.
Be............... Aspiration.......... 7090 234.9 500 ppm Al. High Mg Add 0.1% fluoride.
and Si.
Be............... Furnace............. 7091 234.9 Be in optical path. Optimize parameters to
minimize effects.
Cd............... Aspiration.......... 7130 228.8 Absorption and Background correction is
light scattering. required.
Cd............... Furnace............. 7131 228.8 As above........... As above.
Excess Chloride.... Ammonium phosphate used
................. as a matrix modifier.
Pipet Tips......... Use cadmium-free tips.
Cr............... Aspiration.......... 7190 357.9 Alkali metal....... KCl ionization
suppressant in samples
and standards--Consult
mfgs' literature.
Co............... Furnace............. 7201 240.7 Excess chloride.... Use Method of Standard
Additions.
Cr............... Furnace............. 7191 357.9 200 mg/L Ca and P.. All calcium nitrate for
a know constant effect
and to eliminate effect
of phosphate.

[[Page 601]]

Cu............... Aspiration.......... 7210 324.7 Absorption and Consult manufacturer's
Scatter. manual.
----------------------------------------------------------------------------------------------------------------
\1\ Refer to EPA publication SW-846 (Reference 2 in Section 16.0).

[[Page 602]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.449

[[Page 603]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.450

[[Page 604]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.451

[[Page 605]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.452

[36 FR 24877, Dec. 23, 1971]

Editorial Note: For Federal Register citations affecting part 60,
appendix A see the List of CFR Sections Affected, which appears in the
Finding Aids section of the printed volume and on GPO Access.

Appendix B to Part 60--Performance Specifications

Performance Specification 1--Specifications and test procedures for
continuous opacity monitoring systems in stationary sources
Performance Specification 2--Specifications and Test Procedures for
SO2 and NOX

[[Page 606]]

Continuous Emission Monitoring Systems in Stationary
Sources
Performance Specification 3--Specifications and Test Procedures for
O2 and CO2 Continuous Emission
Monitoring Systems in Stationary Sources
Performance Specification 4--Specifications and Test Procedures for
Carbon Monoxide Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 4A--Specifications and Test Procedures for
Carbon Monoxide Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 4B--Specifications and Test Procedures for
Carbon Monoxide and Oxygen Continuous Monitoring Systems in
Stationary Sources
Performance Specification 5--Specifications and Test Procedures for TRS
Continuous Emission Monitoring Systems in Stationary Sources
Performance Specification 6--Specifications and Test Procedures for
Continuous Emission Rate Monitoring Systems in Stationary
Sources
Performance Specification 7--Specifications and Test Procedures for
Hydrogen Sulfide Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 8--Performance Specifications for Volatile
Organic Compound Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 8A--Specifications and Test Procedures for
Total Hydrocarbon Continuous Monitoring Systems in Stationary
Sources
Performance Specification 9--Specifications and Test Procedures for Gas
Chromatographic Continuous Emission Monitoring Systems in
Stationary Sources
Performance Specification 15--Performance Specification for Extractive
FTIR Continuous Emissions Monitor Systems in Stationary
Sources

Performance Specification 1--Specifications and Test Procedures for
Continuous Opacity Monitoring Systems in Stationary Sources

1.0 What Is the Purpose and Applicability of Performance Specification
1?

Performance Specification 1 (PS-1) provides (1) requirements for the
design, performance, and installation of a continuous opacity monitoring
system (COMS) and (2) data computation procedures for evaluating the
acceptability of a COMS. It specifies activities for two groups (1) the
owner or operator and (2) the opacity monitor manufacturer.
1.1 Measurement Parameter. PS-1 covers the instrumental measurement
of opacity caused by attenuation of projected light due to absorption
and scatter of the light by particulate matter in the effluent gas
stream.
1.2 What COMS must comply with PS-1? If you are an owner or
operator of a facility with a COMS as a result of this Part, then PS-1
applies to your COMS if one of the following is true:
(1) Your facility has a new COMS installed after February 6, 2001;
or
(2) Your COMS is replaced, relocated, or substantially refurbished
(in the opinion of the regulatory authority) after February 6, 2001; or
(3) Your COMS was installed before February 6, 2001 and is
specifically required by regulatory action other than the promulgation
of PS-1 to be recertified.
If you are an opacity monitor manufacturer, then paragraph 8.2
applies to you.
1.3 Does PS-1 apply to a facility with an applicable opacity limit
less than 10 percent? If you are an owner or operator of a facility with
a COMS as a result of this Part and the applicable opacity limit is less
than 10 percent, then PS-1 applies to your COMS as described in section
1.2; taking into account (through statistical procedures or otherwise)
the uncertainties associated with opacity measurements, and following
the conditions for attenuators selection for low opacity applications as
outlined in Section 8.1(3)(ii). At your option, you, the source owner or
operator, may select to establish a reduced full scale range of no less
than 50 percent opacity instead of the 80 percent as prescribed in
section 3.5, if the applicable opacity limit for your facility is less
than 10 percent. The EPA recognizes that reducing the range of the
analyzer to 50 percent does not necessarily result in any measurable
improvement in measurement accuracy at opacity levels less than 10
percent; however, it may allow improved chart recorder interpretation.
1.4 What data uncertainty issues apply to COMS data? The
measurement uncertainties associated with COMS data result from several
design and performance factors including limitations on the availability
of calibration attenuators for opacities less than about 6 percent (3
percent for single-pass instruments), calibration error tolerances, zero
and upscale drift tolerances, and allowance for dust compensation that
are significant relative to low opacity levels. The full scale
requirements of this PS may also contribute to measurement uncertainty
for opacity measurements where the applicable limits are below 10
percent opacity.

2.0 What Are the Basic Requirements of PS-1?

PS-1 requires (1) opacity monitor manufacturers comply with a
comprehensive series of design and performance specifications and test
procedures to certify opacity monitoring equipment before shipment to
the end

[[Page 607]]

user, (2) the owner or operator to follow installation guidelines, and
(3) the owner or operator to conduct a set of field performance tests
that confirm the acceptability of the COMS after it is installed.
2.1 ASTM D 6216-98 is the reference for design specifications,
manufacturer's performance specifications, and test procedures. The
opacity monitor manufacturer must periodically select and test an
opacity monitor, that is representative of a group of monitors produced
during a specified period or lot, for conformance with the design
specifications in ASTM D 6216-98. The opacity monitor manufacturer must
test each opacity monitor for conformance with the manufacturer's
performance specifications in ASTM D 6216-98.
2.2 Section 8.1(2) provides guidance for locating an opacity
monitor in vertical and horizontal ducts. You are encouraged to seek
approval for the opacity monitor location from the appropriate
regulatory authority prior to installation.
2.3 After the COMS is installed and calibrated, the owner or
operator must test the COMS for conformance with the field performance
specifications in PS-1.

3.0 What Special Definitions Apply to PS-1?

3.1 All definitions and discussions from section 3 of ASTM D 6216-
98 are applicable to PS-1.
3.2 Centroid Area. A concentric area that is geometrically similar
to the stack or duct cross-section and is no greater than 1 percent of
the stack or duct cross-sectional area.
3.3 Data Recorder. That portion of the installed COMS that provides
a permanent record of the opacity monitor output in terms of opacity.
The data recorder may include automatic data reduction capabilities.
3.4 External Audit Device. The inherent design, equipment, or
accommodation of the opacity monitor allowing the independent assessment
of the COMS's calibration and operation.
3.5 Full Scale. The maximum data display output of the COMS. For
purposes of recordkeeping and reporting, full scale will be greater than
80 percent opacity.
3.6 Operational Test Period. A period of time (168 hours) during
which the COMS is expected to operate within the established performance
specifications without any unscheduled maintenance, repair, or
adjustment.
3.7 Primary Attenuators. Those devices (glass or grid filter that
reduce the transmission of light) calibrated according to procedures in
section 7.1.
3.8 Secondary Attenuators. Those devices (glass or grid filter that
reduce the transmission of light) calibrated against primary attenuators
according to procedures in section 7.2.
3.9 System Response Time. The amount of time the COMS takes to
display 95 percent of a step change in opacity on the COMS data
recorder.

4.0 Interferences. Water Droplets

5.0 What Do I Need To Know To Ensure the Safety of Persons Using PS-1?

The procedures required under PS-1 may involve hazardous materials,
operations, and equipment. PS-1 does not purport to address all of the
safety problems associated with these procedures. Before performing
these procedures, you must establish appropriate safety and health
practices, and you must determine the applicable regulatory limitations.
You should consult the COMS user's manual for specific precautions to
take.

6.0 What Equipment and Supplies Do I Need?

6.1 Continuous Opacity Monitoring System. You, as owner or
operator, are responsible for purchasing an opacity monitor that meets
the specifications of ASTM D 6216-98, including a suitable data recorder
or automated data acquisition handling system. Example data recorders
include an analog strip chart recorder or more appropriately an
electronic data acquisition and reporting system with an input signal
range compatible with the analyzer output.
6.2 Calibration Attenuators. You, as owner or operator, are
responsible for purchasing a minimum of three calibration attenuators
that meet the requirements of PS-1. Calibration attenuators are optical
filters with neutral spectral characteristics. Calibration attenuators
must meet the requirements in section 7 and must be of sufficient size
to attenuate the entire light beam received by the detector of the COMS.
For transmissometers operating over a narrow bandwidth (e.g., laser), a
calibration attenuator's value is determined for the actual operating
wavelengths of the transmissometer. Some filters may not be uniform
across the face. If errors result in the daily calibration drift or
calibration error test, you may want to examine the across-face
uniformity of the filter.
6.3 Calibration Spectrophotometer. Whoever calibrates the
attenuators must have a spectrophotometer that meets the following
minimum design specifications:

------------------------------------------------------------------------
Parameter Specification
------------------------------------------------------------------------
Wavelength range.......................... 300-800 nm.
Detector angle of view.................... 10 deg..
Accuracy.................................. 0.5% transmittance, NIST
traceable calibration.
------------------------------------------------------------------------

7.0 What Reagents and Standards Do I Need?

You will need to use attenuators (i.e., neutral density filters) to
check the daily calibration drift and calibration error of a

[[Page 608]]

COMS. Attenuators are designated as either primary or secondary based on
how they are calibrated.
7.1 Attenuators are designated primary in one of two ways:
(1) They are calibrated by NIST; or
(2) They are calibrated on a 6-month frequency through the
assignment of a luminous transmittance value in the following manner:
(i) Use a spectrophotometer meeting the specifications of section
6.3 to calibrate the required filters. Verify the spectrophotometer
calibration through use of a NIST 930D Standard Reference Material
(SRM). A SRM 930D consists of three neutral density glass filters and a
blank, each mounted in a cuvette. The wavelengths and temperature to be
used in the calibration are listed on the NIST certificate that
accompanies the reported values. Determine and record a transmittance of
the SRM values at the NIST wavelengths (three filters at five
wavelengths each for a total of 15 determinations). Calculate a percent
difference between the NIST certified values and the spectrophotometer
response. At least 12 of the 15 differences (in percent) must be within
0.5 percent of the NIST SRM values. No difference can be
greater than 1.0 percent. Recalibrate the SRM or service the
spectrophotometer if the calibration results fail the criteria.
(ii) Scan the filter to be tested and the NIST blank from wavelength
380 to 780 nm, and record the spectrophotometer percent transmittance
responses at 10 nm intervals. Test in this sequence: blank filter,
tested filter, tested filter rotated 90 degrees in the plane of the
filter, blank filter. Calculate the average transmittance at each 10 nm
interval. If any pair of the tested filter transmittance values (for the
same filter and wavelength) differ by more than 0.25
percent, rescan the tested filter. If the filter fails to achieve this
tolerance, do not use the filter in the calibration tests of the COMS.
(iii) Correct the tested filter transmittance values by dividing the
average tested filter transmittance by the average blank filter
transmittance at each 10 nm interval.
(iv) Calculate the weighted (to the response of the human eye),
tested filter transmittance by multiplying the transmittance value by
the corresponding response factor shown in table 1-1, to obtain the
Source C Human Eye Response.
(v) Recalibrate the primary attenuators semi-annually if they are
used for the required calibration error test. Recalibrate the primary
attenuators annually if they are used only for calibration of secondary
attenuators.
7.2 Attenuators are designated secondary if the filter calibration
is done using a laboratory-based transmissometer. Conduct the secondary
attenuator calibration using a laboratory-based transmissometer
calibrated as follows:
(i) Use at least three primary filters of nominal luminous
transmittance 50, 70 and 90 percent, calibrated as specified in section
7.1(2)(i), to calibrate the laboratory-based transmissometer. Determine
and record the slope of the calibration line using linear regression
through zero opacity. The slope of the calibration line must be between
0.99 and 1.01, and the laboratory-based transmissometer reading for each
primary filter must not deviate by more than 2 percent from
the linear regression line. If the calibration of the laboratory-based
transmissometer yields a slope or individual readings outside the
specified ranges, secondary filter calibrations cannot be performed.
Determine the source of the variations (either transmissometer
performance or changes in the primary filters) and repeat the
transmissometer calibration before proceeding with the attenuator
calibration.
(ii) Immediately following the laboratory-based transmissometer
calibration, insert the secondary attenuators and determine and record
the percent effective opacity value per secondary attenuator from the
calibration curve (linear regression line).
(iii) Recalibrate the secondary attenuators semi-annually if they
are used for the required calibration error test.

8.0 What Performance Procedures Are Required To Comply With PS-1?

Procedures to verify the performance of the COMS are divided into
those completed by the owner or operator and those completed by the
opacity monitor manufacturer.
8.1 What procedures must I follow as the Owner or Operator?
(1) You must purchase an opacity monitor that complies with ASTM D
6216-98 and obtain a certificate of conformance from the opacity monitor
manufacturer.
(2) You must install the opacity monitor at a location where the
opacity measurements are representative of the total emissions from the
affected facility. You must meet this requirement by choosing a
measurement location and a light beam path as follows:
(i) Measurement Location. Select a measurement location that is (1)
at least 4 duct diameters downstream from all particulate control
equipment or flow disturbance, (2) at least 2 duct diameters upstream of
a flow disturbance, (3) where condensed water vapor is not present, and
(4) accessible in order to permit maintenance.
(ii) Light Beam Path. Select a light beam path that passes through
the centroidal area of the stack or duct. Also, you must follow these
additional requirements or modifications for these measurement
locations:

[[Page 609]]

------------------------------------------------------------------------
If your measurement location Then use a light
is in a: And is: beam path that is:
------------------------------------------------------------------------
1. Straight vertical section Less than 4 In the plane defined
of stack or duct. equivalent by the upstream
diameters bend (see figure 1-
downstream from a 1).
bend.
2. Straight vertical section Less than 4 In the plane defined
of stack or duct. equivalent by the downstream
diameters upstream bend (see figure 1-
from a bend. 2).
3. Straight vertical section Less than 4 In the plane defined
of stack or duct. equivalent by the upstream
diameters bend (see figure 1-
downstream and is 3).
also less than 1
diameter upstream
from a bend.
4. Horizontal section of At least 4 In the horizontal
stack or duct. equivalent plane that is
diameters between \1/3\ and
downstream from a \1/2\ the distance
vertical bend. up the vertical
axis from the
bottom of the duct
(see figure 1-4).
5. Horizontal section of Less than 4 In the horizontal
duct. equivalent plane that is
diameters between \1/2\ and
downstream from a \2/3\ the distance
vertical bend. up the vertical
axis from the
bottom of the duct
for upward flow in
the vertical
section, and is
between \1/3\ and
\1/2\ the distance
up the vertical
axis from the
bottom of the duct
for downward flow
(figure 1-5).
------------------------------------------------------------------------

(iii) Alternative Locations and Light Beam Paths. You may select
locations and light beam paths, other than those cited above, if you
demonstrate, to the satisfaction of the Administrator or delegated
agent, that the average opacity measured at the alternative location or
path is equivalent to the opacity as measured at a location meeting the
criteria of sections 8.1(2)(i) and 8.1(2)(ii). The opacity at the
alternative location is considered equivalent if (1) the average opacity
value measured at the alternative location is within 10
percent of the average opacity value measured at the location meeting
the installation criteria, and (2) the difference between any two
average opacity values is less than 2 percent opacity (absolute). You
use the following procedure to conduct this demonstration:
simultaneously measure the opacities at the two locations or paths for a
minimum period of time (e.g., 180-minutes) covering the range of normal
operating conditions and compare the results. The opacities of the two
locations or paths may be measured at different times, but must
represent the same process operating conditions. You may use alternative
procedures for determining acceptable locations if those procedures are
approved by the Administrator.
(3) Field Audit Performance Tests. After you install the COMS, you
must perform the following procedures and tests on the COMS.
(i) Optical Alignment Assessment. Verify and record that all
alignment indicator devices show proper alignment. A clear indication of
alignment is one that is objectively apparent relative to reference
marks or conditions.
(ii) Calibration Error Check. Conduct a three-point calibration
error test using three calibration attenuators that produce outlet
pathlength corrected, single-pass opacity values shown in ASTM D 6216-
98, section 7.5. If your applicable limit is less than 10 percent
opacity, use attenuators as described in ASTM D 6216-98, section 7.5 for
applicable standards of 10 to 19 percent opacity. Confirm the external
audit device produces the proper zero value on the COMS data recorder.
Separately, insert each calibration attenuators (low, mid, and high-
level) into the external audit device. While inserting each attenuator,
(1) ensure that the entire light beam passes through the attenuator, (2)
minimize interference from reflected light, and (3) leave the attenuator
in place for at least two times the shortest recording interval on the
COMS data recorder. Make a total of five nonconsecutive readings for
each attenuator. At the end of the test, correlate each attenuator
insertion to the corresponding value from the data recorder. Subtract
the single-pass calibration attenuator values corrected to the stack
exit conditions from the COMS responses. Calculate the arithmetic mean
difference, standard deviation, and confidence coefficient of the five
measurements value using equations 1-3, 1-4, and 1-5. Calculate the
calibration error as the sum of the absolute value of the mean
difference and the 95 percent confidence coefficient for each of the
three test attenuators using equation 1-6. Report the calibration error
test results for each of the three attenuators.
(iii) System Response Time Check. Using a high-level calibration
attenuator, alternately insert the filter five times and remove it from
the external audit device. For each filter insertion and removal,
measure the amount of time required for the COMS to display 95 percent
of the step change in opacity on the COMS data recorder. For the upscale
response time, measure the time from insertion to display of 95 percent
of the final, steady upscale reading. For the downscale response time,
measure the time from removal to display 5 percent of the initial
upscale reading. Calculate the mean of the five upscale response time
measurements and the mean of the five downscale response time
measurements. Report both the upscale and downscale response times.

[[Page 610]]

(iv) Averaging Period Calculation and Recording Check. After the
calibration error check, conduct a check of the averaging period
calculation (e.g., 6-minute integrated average). Consecutively insert
each of the calibration error check attenuators (low, mid, and high-
level) into the external audit device for a period of two times the
averaging period plus 1 minute (e.g., 13 minutes for a 6-minute
averaging period). Compare the path length corrected opacity value of
each attenuator to the valid average value calculated by the COMS data
recording device for that attenuator.
(4) Operational Test Period. Before conducting the operational
testing, you must have successfully completed the field audit tests
described in sections 8.1(3)(i) through 8.1(3)(iv). Then, you operate
the COMS for an initial 168-hour test period while the source is
operating under normal operating conditions. If normal operations
contain routine source shutdowns, include the source's down periods in
the 168-hour operational test period. However, you must ensure that the
following minimum source operating time is included in the operational
test period: (1) For a batch operation, the operational test period must
include at least one full cycle of batch operation during the 168-hour
period unless the batch operation is longer than 168 hours or (2) for
continuous operating processes, the unit must be operating for at least
50 percent of the 168-hour period. Except during times of instrument
zero and upscale calibration drift checks, you must analyze the effluent
gas for opacity and produce a permanent record of the COMS output.
During this period, you may not perform unscheduled maintenance, repair,
or adjustment to the COMS. Automatic zero and calibration adjustments
(i.e., intrinsic adjustments), made by the COMS without operator
intervention or initiation, are allowable at any time. At the end of the
operational test period, verify and record that the COMS optical
alignment is still correct. If the test period is interrupted because of
COMS failure, record the time when the failure occurred. After the
failure is corrected, you restart the 168-hour period and tests from the
beginning (0-hour). During the operational test period, perform the
following test procedures:
(i) Zero Calibration Drift Test. At the outset of the 168-hour
operational test period and at each 24-hour interval, the automatic
calibration check system must initiate the simulated zero device to
allow the zero drift to be determined. Record the COMS response to the
simulated zero device. After each 24-hour period, subtract the COMS zero
reading from the nominal value of the simulated zero device to calculate
the 24-hour zero drift (ZD). At the end of the 168-hour period,
calculate the arithmetic mean, standard deviation, and confidence
coefficient of the 24-hour ZDs using equations 1-3, 1-4, and 1-5.
Calculate the sum of the absolute value of the mean and the absolute
value of the confidence coefficient using equation 1-6, and report this
value as the 24-hour ZD error.
(ii) Upscale Calibration Drift Test. At each 24-hour interval after
the simulated zero device value has been checked, check and record the
COMS response to the upscale calibration device. After each 24-hour
period, subtract the COMS upscale reading from the nominal value of the
upscale calibration device to calculate the 24-hour calibration drift
(CD). At the end of the 168-hour period, calculate the arithmetic mean,
standard deviation, and confidence coefficient of the 24-hour CD using
equations 1-3, 1-4, and 1-5. Calculate the sum of the absolute value of
the mean and the absolute value of the confidence coefficient using
equation 1-6, and report this value as the 24-hour CD error.
(5) Retesting. If the COMS fails to meet the specifications for the
tests conducted under the operational test period, make the necessary
corrections and restart the operational test period. Depending on the
opinion of the enforcing agency, you may have to repeat some or all of
the field audit tests.
8.2 What are the responsibilities of the Opacity Monitor
Manufacturer?
You, the manufacturer, must carry out the following activities:
(1) Conduct the verification procedures for design specifications in
section 6 of ASTM D 6216-98.
(2) Conduct the verification procedures for performance
specifications in section 7 of ASTM D 6216-98.
(3) Provide to the owner or operator, a report of the opacity
monitor's conformance to the design and performance specifications
required in sections 6 and 7 of ASTM D 6216-98 in accordance with the
reporting requirements of section 9 in ASTM D 6216-98.

9.0 What quality control measures are required by PS-1?

Opacity monitor manufacturers must initiate a quality program
following the requirements of ASTM D 6216-98, section 8. The quality
program must include (1) a quality system and (2) a corrective action
program.

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure [Reserved]

12.0 What Calculations Are Needed for PS-1?

12.1 Desired Attenuator Values. Calculate the desired attenuator
value corrected to the emission outlet pathlength as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.008

Where:

[[Page 611]]

OP1 = Nominal opacity value of required low-, mid-, or high-
range calibration attenuators.
OP2 = Desired attenuator opacity value from ASTM D 6216-98,
section 7.5 at the opacity limit required by the applicable subpart.
L1 = Monitoring pathlength.
L2 = Emission outlet pathlength.
12.2 Luminous Transmittance Value of a Filter. Calculate the
luminous transmittance of a filter as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.009

Where:

LT = Luminous transmittance
Ti = Weighted tested filter transmittance.
12.3 Arithmetic Mean. Calculate the arithmetic mean of a data set
as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.010

Where:
[GRAPHIC] [TIFF OMITTED] TR10AU00.011

12.4 Standard Deviation. Calculate the standard deviation as
follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.012

Where:

Sd = Standard deviation of a data set.
12.5 Confidence Coefficient. Calculate the 2.5 percent error
confidence coefficient (one-tailed) as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.013

Where:

CC = Confidence coefficient
t0.975 = t - value (see table 1-2).
12.6 Calibration Error. Calculate the error (calibration error,
zero drift error, and calibration drift error) as follows:
[GRAPHIC] [TIFF OMITTED] TR10AU00.014

Where:

Er = Error.

12.7 Conversion of Opacity Values for Monitor Pathlength to
Emission Outlet Pathlength. When the monitor pathlength is different
from the emission outlet pathlength, use either of the following
equations to convert from one basis to the other (this conversion may be
automatically calculated by the monitoring system):
[GRAPHIC] [TIFF OMITTED] TR10AU00.015

[GRAPHIC] [TIFF OMITTED] TR10AU00.016

Where:

Op1 = Opacity of the effluent based upon L1.
Op2 = Opacity of the effluent based upon L2.
L1 = Monitor pathlength.
L2 = Emission outlet pathlength.
OD1 = Optical density of the effluent based upon
L1.
OD2 = Optical density of the effluent based upon
L2.

12.8 Mean Response Wavelength. Calculate the mean of the effective
spectral response curve from the individual responses at the specified
wavelength values as follows:

[[Page 612]]

[GRAPHIC] [TIFF OMITTED] TR10AU00.017

Where:

L = mean of the effective spectral response curve
Li = The specified wavelength at which the response
gi is calculated at 20 nm intervals.
gi = The individual response value at Li.

13.0 What Specifications Does a COMS Have To Meet for Certification?

A COMS must meet the following design, manufacturer's performance,
and field audit performance specifications:
13.1 Design Specifications. The opacity monitoring equipment must
comply with the design specifications of ASTM D 6216-98.
13.2 Manufacturer's Performance Specifications. The opacity monitor
must comply with the manufacturer's performance specifications of ASTM D
6216-98.
13.3 Field Audit Performance Specifications. The installed COMS
must comply with the following performance specifications:
(1) Optical Alignment. Objectively indicate proper alignment
relative to reference marks (e.g., bull's-eye) or conditions.
(2) Calibration Error. The calibration error must be 3
percent opacity for each of the three calibration attenuators.
(3) System Response Time. The COMS upscale and downscale response
times must be 10 seconds as measured at the COMS data
recorder.
(4) Averaging Period Calculation and Recording. The COMS data
recorder must average and record each calibration attenuator value to
within 2 percent opacity of the certified value of the
attenuator.
(5) Operational Test Period. The COMS must be able to measure and
record opacity and to perform daily calibration drift assessments for
168 hours without unscheduled maintenance, repair, or adjustment.
(6) Zero and Upscale Calibration Drift Error. The COMS zero and
upscale calibration drift error must not exceed 2 percent opacity over a
24 hour period.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Which references are relevant to this method?

1. Experimental Statistics. Department of Commerce. National Bureau
of Standards Handbook 91. Paragraph 3-3.1.4. 1963. 3-31 p.
2. Performance Specifications for Stationary Source Monitoring
Systems for Gases and Visible Emissions, EPA-650/2-74-013, January 1974,
U. S. Environmental Protection Agency, Research Triangle Park, NC.
3. Koontz, E.C., Walton, J. Quality Assurance Programs for Visible
Emission Evaluations. Tennessee Division of Air Pollution Control.
Nashville, TN. 78th Meeting of the Air Pollution Control Association.
Detroit, MI. June 16-21, 1985.
4. Evaluation of Opacity CEMS Reliability and Quality Assurance
Procedures. Volume 1. U. S. Environmental Protection Agency. Research
Triangle Park, NC. EPA-340/1-86-009a.
5. Nimeroff, I. ``Colorimetry Precision Measurement and
Calibration.'' NBS Special Publication 300. Volume 9. June 1972.
6. Technical Assistance Document: Performance Audit Procedures for
Opacity Monitors. U. S. Environmental Protection Agency. Research
Triangle Park, NC. EPA-600/8-87-025. April 1987.
7. Technical Assistance Document: Performance Audit Procedures for
Opacity Monitors. U. S. Environmental Protection Agency. Research
Triangle Park, NC. EPA-450/4-92-010. April 1992.
8. ASTM D 6216-98: Standard Practice for Opacity Monitor
Manufacturers to Certify Conformance with Design and Performance
Specifications. American Society for Testing and Materials (ASTM). April
1998.

17.0 What tables and diagrams are relevant to this method?

17.1 Reference Tables.

Table 1-1.--Source C, Human Eye Response Factor
----------------------------------------------------------------------------------------------------------------
Wavelength nanometers Weighting factor \a\ Wavelength nanometers Weighting factor \a\
----------------------------------------------------------------------------------------------------------------
380.................................. 0 590 6627
390.................................. 0 600 5316
400.................................. 2 610 4176
410.................................. 9 620 3153
420.................................. 37 630 2190
430.................................. 122 640 1443
440.................................. 262 650 886
450.................................. 443 660 504
460.................................. 694 670 259
470.................................. 1058 680 134

[[Page 613]]

480.................................. 1618 690 62
490.................................. 2358 700 29
500.................................. 3401 720 14
510.................................. 4833 720 6
520.................................. 6462 730 3
530.................................. 7934 740 2
540.................................. 9194 750 1
550.................................. 9832 760 1
560.................................. 9841 770 0
570.................................. 9147 780 0
580.................................. 7992 ....................... .......................
----------------------------------------------------------------------------------------------------------------
\1\ Total of weighting factors = 100,000.

Table 1-2 \T\ Values
----------------------------------------------------------------------------------------------------------------
n \a\ \t\ 0.975 n \a\ \t\ 0.975 n \a\ \t\ 0.975
----------------------------------------------------------------------------------------------------------------
2.............................................. 12.706 7 2.447 12 2.201
3.............................................. 4.303 8 2.365 13 2.179
4.............................................. 3.182 9 2.306 14 2.160
5.............................................. 2.776 10 2.262 15 2.145
6.............................................. 2.571 11 2.228 16 2.131
----------------------------------------------------------------------------------------------------------------
\a\ The values in this table are already corrected for n-1 degrees of freedom. Use n equal to the number of
individual values.

17.2 Diagrams.

[[Page 614]]

[GRAPHIC] [TIFF OMITTED] TR10AU00.018

[[Page 615]]

[GRAPHIC] [TIFF OMITTED] TR10AU00.019

[[Page 616]]

[GRAPHIC] [TIFF OMITTED] TR10AU00.020

[[Page 617]]

[GRAPHIC] [TIFF OMITTED] TR10AU00.021

[[Page 618]]

Performance Specification 2--Specifications and Test Procedures for
SO2 and NOX Continuous Emission Monitoring Systems
in Stationary Sources

1.0 Scope and Application

1.1 Analytes

------------------------------------------------------------------------
Analyte CAS Nos.
------------------------------------------------------------------------
Sulfur Dioxide (SO2).................................... 7449-09-5
Nitrogen Oxides (NOx)................................... 10102-44-0
(NO2), 10024-
97-2 (NO)
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This specification is for evaluating the acceptability of
SO2 and NOX continuous emission monitoring systems
(CEMS) at the time of installation or soon after and whenever specified
in the regulations. The CEMS may include, for certain stationary
sources, a diluent (O2 or CO2) monitor.
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time nor does it identify
specific calibration techniques and other auxiliary procedures to assess
the CEMS performance. The source owner or operator is responsible to
calibrate, maintain, and operate the CEMS properly. The Administrator
may require, under Section 114 of the Act, the operator to conduct CEMS
performance evaluations at other times besides the initial test to
evaluate the CEMS performance. See 40 CFR Part 60, Sec. 60.13(c).

2.0 Summary of Performance Specification

Procedures for measuring CEMS relative accuracy and calibration
drift are outlined. CEMS installation and measurement location
specifications, equipment specifications, performance specifications,
and data reduction procedures are included. Conformance of the CEMS with
the Performance Specification is determined.

3.0 Definitions

3.1 Calibration Drift (CD) means the difference in the CEMS output
readings from the established reference value after a stated period of
operation during which no unscheduled maintenance, repair, or adjustment
took place.
3.2 Centroidal Area means a concentric area that is geometrically
similar to the stack or duct cross section and is no greater than l
percent of the stack or duct cross-sectional area.
3.3 Continuous Emission Monitoring System means the total equipment
required for the determination of a gas concentration or emission rate.
The sample interface, pollutant analyzer, diluent analyzer, and data
recorder are the major subsystems of the CEMS.
3.4 Data Recorder means that portion of the CEMS that provides a
permanent record of the analyzer output. The data recorder may include
automatic data reduction capabilities.
3.5 Diluent Analyzer means that portion of the CEMS that senses the
diluent gas (i.e., CO2 or O2) and generates an
output proportional to the gas concentration.
3.6 Path CEMS means a CEMS that measures the gas concentration
along a path greater than 10 percent of the equivalent diameter of the
stack or duct cross section.
3.7 Point CEMS means a CEMS that measures the gas concentration
either at a single point or along a path equal to or less than 10
percent of the equivalent diameter of the stack or duct cross section.
3.8 Pollutant Analyzer means that portion of the CEMS that senses
the pollutant gas and generates an output proportional to the gas
concentration.
3.9 Relative Accuracy (RA) means the absolute mean difference
between the gas concentration or emission rate determined by the CEMS
and the value determined by the reference method (RM), plus the 2.5
percent error confidence coefficient of a series of tests, divided by
the mean of the RM tests or the applicable emission limit.
3.10 Sample Interface means that portion of the CEMS used for one
or more of the following: sample acquisition, sample delivery, sample
conditioning, or protection of the monitor from the effects of the stack
effluent.
3.11 Span Value means the concentration specified for the affected
source category in an applicable subpart of the regulations that is used
to set the calibration gas concentration and in determining calibration
drift.

4.0 Interferences. [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety and health practices and determine the applicable
regulatory limitations prior to performing these procedures. The CEMS
user's manual and materials recommended by the reference method should
be consulted for specific precautions to be taken.

6.0 Equipment and Supplies

6.1 CEMS Equipment Specifications.
6.1.1 Data Recorder Scale. The CEMS data recorder output range must
include zero and a high-level value. The high-level value is chosen by
the source owner or operator and is defined as follows:

[[Page 619]]

6.1.1.1 For a CEMS intended to measure an uncontrolled emission
(e.g., SO2 measurements at the inlet of a flue gas
desulfurization unit), the high-level value should be between 1.25 and 2
times the maximum potential emission level over the appropriate
averaging time, unless otherwise specified in an applicable subpart of
the regulations.
6.1.1.2 For a CEMS installed to measure controlled emissions or
emissions that are in compliance with an applicable regulation, the
high-level value between 1.5 times the pollutant concentration
corresponding to the emission standard level and the span value given in
the applicable regulations is adequate.
6.1.1.3 Alternative high-level values may be used, provided the
source can measure emissions which exceed the full-scale limit in
accordance with the requirements of applicable regulations.
6.1.1.4 If an analog data recorder is used, the data recorder
output must be established so that the high-level value would read
between 90 and 100 percent of the data recorder full scale. (This scale
requirement may not be applicable to digital data recorders.) The zero
and high level calibration gas, optical filter, or cell values should be
used to establish the data recorder scale.
6.1.2 The CEMS design should also allow the determination of
calibration drift at the zero and high-level values. If this is not
possible or practical, the design must allow these determinations to be
conducted at a low-level value (zero to 20 percent of the high-level
value) and at a value between 50 and 100 percent of the high-level
value. In special cases, the Administrator may approve a single-point
calibration-drift determination.
6.2 Other equipment and supplies, as needed by the applicable
reference method(s) (see Section 8.4.2 of this Performance
Specification), may be required.

7.0 Reagents and Standards

7.1 Reference Gases, Gas Cells, or Optical Filters. As specified by
the CEMS manufacturer for calibration of the CEMS (these need not be
certified).
7.2 Reagents and Standards. May be required as needed by the
applicable reference method(s) (see Section 8.4.2 of this Performance
Specification).
8.0 Performance Specification Test Procedure
8.1 Installation and Measurement Location Specifications.
8.1.1 CEMS Installation. Install the CEMS at an accessible location
where the pollutant concentration or emission rate measurements are
directly representative or can be corrected so as to be representative
of the total emissions from the affected facility or at the measurement
location cross section. Then select representative measurement points or
paths for monitoring in locations that the CEMS will pass the RA test
(see Section 8.4). If the cause of failure to meet the RA test is
determined to be the measurement location and a satisfactory correction
technique cannot be established, the Administrator may require the CEMS
to be relocated. Suggested measurement locations and points or paths
that are most likely to provide data that will meet the RA requirements
are listed below.
8.1.2 CEMS Measurement Location. It is suggested that the
measurement location be (1) at least two equivalent diameters downstream
from the nearest control device, the point of pollutant generation, or
other point at which a change in the pollutant concentration or emission
rate may occur and (2) at least a half equivalent diameter upstream from
the effluent exhaust or control device.
8.1.2.1 Point CEMS. It is suggested that the measurement point be
(1) no less than 1.0 meter (3.3 ft) from the stack or duct wall or (2)
within or centrally located over the centroidal area of the stack or
duct cross section.
8.1.2.2 Path CEMS. It is suggested that the effective measurement
path (1) be totally within the inner area bounded by a line 1.0 meter
(3.3 ft) from the stack or duct wall, or (2) have at least 70 percent of
the path within the inner 50 percent of the stack or duct cross-
sectional area, or (3) be centrally located over any part of the
centroidal area.
8.1.3 Reference Method Measurement Location and Traverse Points.
8.1.3.1 Select, as appropriate, an accessible RM measurement point
at least two equivalent diameters downstream from the nearest control
device, the point of pollutant generation, or other point at which a
change in the pollutant concentration or emission rate may occur, and at
least a half equivalent diameter upstream from the effluent exhaust or
control device. When pollutant concentration changes are due solely to
diluent leakage (e.g., air heater leakages) and pollutants and diluents
are simultaneously measured at the same location, a half diameter may be
used in lieu of two equivalent diameters. The CEMS and RM locations need
not be the same.
8.1.3.2 Select traverse points that assure acquisition of
representative samples over the stack or duct cross section. The minimum
requirements are as follows: Establish a ``measurement line'' that
passes through the centroidal area and in the direction of any expected
stratification. If this line interferes with the CEMS measurements,
displace the line up to 30 cm (12 in.) (or 5 percent of the equivalent
diameter of the cross section, whichever is less) from the centroidal
area. Locate three traverse points at 16.7, 50.0, and 83.3 percent of
the measurement line. If the

[[Page 620]]

measurement line is longer than 2.4 meters (7.8 ft) and pollutant
stratification is not expected, the three traverse points may be located
on the line at 0.4, 1.2, and 2.0 meters from the stack or duct wall.
This option must not be used after wet scrubbers or at points where two
streams with different pollutant concentrations are combined. If
stratification is suspected, the following procedure is suggested. For
rectangular ducts, locate at least nine sample points in the cross
section such that sample points are the centroids of similarly-shaped,
equal area divisions of the cross section. Measure the pollutant
concentration, and, if applicable, the diluent concentration at each
point using appropriate reference methods or other appropriate
instrument methods that give responses relative to pollutant
concentrations. Then calculate the mean value for all sample points. For
circular ducts, conduct a 12-point traverse (i.e., six points on each of
the two perpendicular diameters) locating the sample points as described
in 40 CFR 60, Appendix A, Method 1. Perform the measurements and
calculations as described above. Determine if the mean pollutant
concentration is more than 10% different from any single point. If so,
the cross section is considered to be stratified, and the tester may not
use the alternative traverse point locations (...0.4, 1.2, and 2.0
meters from the stack or duct wall.) but must use the three traverse
points at 16.7, 50.0, and 83.3 percent of the entire measurement line.
Other traverse points may be selected, provided that they can be shown
to the satisfaction of the Administrator to provide a representative
sample over the stack or duct cross section. Conduct all necessary RM
tests within 3 cm (1.2 in.) of the traverse points, but no closer than 3
cm (1.2 in.) to the stack or duct wall.
8.2 Pretest Preparation. Install the CEMS, prepare the RM test site
according to the specifications in Section 8.1, and prepare the CEMS for
operation according to the manufacturer's written instructions.
8.3 Calibration Drift Test Procedure.
8.3.1 CD Test Period. While the affected facility is operating at
more than 50 percent of normal load, or as specified in an applicable
subpart, determine the magnitude of the CD once each day (at 24-hour
intervals) for 7 consecutive days according to the procedure given in
Sections 8.3.2 through 8.3.4.
8.3.2 The purpose of the CD measurement is to verify the ability of
the CEMS to conform to the established CEMS calibration used for
determining the emission concentration or emission rate. Therefore, if
periodic automatic or manual adjustments are made to the CEMS zero and
calibration settings, conduct the CD test immediately before these
adjustments, or conduct it in such a way that the CD can be determined.
8.3.3 Conduct the CD test at the two points specified in Section
6.1.2. Introduce to the CEMS the reference gases, gas cells, or optical
filters (these need not be certified). Record the CEMS response and
subtract this value from the reference value (see example data sheet in
Figure 2-1).
8.4 Relative Accuracy Test Procedure.
8.4.1 RA Test Period. Conduct the RA test according to the
procedure given in Sections 8.4.2 through 8.4.6 while the affected
facility is operating at more than 50 percent of normal load, or as
specified in an applicable subpart. The RA test may be conducted during
the CD test period.
8.4.2 Reference Methods. Unless otherwise specified in an
applicable subpart of the regulations, Methods 3B, 4, 6, and 7, or their
approved alternatives, are the reference methods for diluent
(O2 and CO2), moisture, SO2, and
NOx, respectively.
8.4.3 Sampling Strategy for RM Tests. Conduct the RM tests in such
a way that they will yield results representative of the emissions from
the source and can be correlated to the CEMS data. It is preferable to
conduct the diluent (if applicable), moisture (if needed), and pollutant
measurements simultaneously. However, diluent and moisture measurements
that are taken within an hour of the pollutant measurements may be used
to calculate dry pollutant concentration and emission rates. In order to
correlate the CEMS and RM data properly, note the beginning and end of
each RM test period of each run (including the exact time of day) on the
CEMS chart recordings or other permanent record of output. Use the
following strategies for the RM tests:
8.4.3.1 For integrated samples (e.g., Methods 6 and Method 4), make
a sample traverse of at least 21 minutes, sampling for an equal time at
each traverse point (see Section 8.1.3.2 for discussion of traverse
points.
8.4.3.2 For grab samples (e.g., Method 7), take one sample at each
traverse point, scheduling the grab samples so that they are taken
simultaneously (within a 3-minute period) or at an equal interval of
time apart over the span of time the CEM pollutant is measured. A test
run for grab samples must be made up of at least three separate
measurements.

Note: At times, CEMS RA tests are conducted during new source
performance standards performance tests. In these cases, RM results
obtained during CEMS RA tests may be used to determine compliance as
long as the source and test conditions are consistent with the
applicable regulations.
8.4.4 Number of RM Tests. Conduct a minimum of nine sets of all
necessary RM test runs.

Note: More than nine sets of RM tests may be performed. If this
option is chosen, a maximum of three sets of the test results may be
rejected so long as the total number of test results used to determine
the RA is greater

[[Page 621]]

than or equal to nine. However, all data must be reported, including the
rejected data.

8.4.5 Correlation of RM and CEMS Data. Correlate the CEMS and the
RM test data as to the time and duration by first determining from the
CEMS final output (the one used for reporting) the integrated average
pollutant concentration or emission rate for each pollutant RM test
period. Consider system response time, if important, and confirm that
the pair of results are on a consistent moisture, temperature, and
diluent concentration basis. Then, compare each integrated CEMS value
against the corresponding average RM value. Use the following guidelines
to make these comparisons.
8.4.5.1 If the RM has an integrated sampling technique, make a
direct comparison of the RM results and CEMS integrated average value.
8.4.5.2 If the RM has a grab sampling technique, first average the
results from all grab samples taken during the test run, and then
compare this average value against the integrated value obtained from
the CEMS chart recording or output during the run. If the pollutant
concentration is varying with time over the run, the arithmetic average
of the CEMS value recorded at the time of each grab sample may be used.
8.4.6 Calculate the mean difference between the RM and CEMS values
in the units of the emission standard, the standard deviation, the
confidence coefficient, and the relative accuracy according to the
procedures in Section 12.0.
8.5 Reporting. At a minimum (check with the appropriate regional
office, State, or Local agency for additional requirements, if any),
summarize in tabular form the results of the CD tests and the RA tests
or alternative RA procedure, as appropriate. Include all data sheets,
calculations, charts (records of CEMS responses), cylinder gas
concentration certifications, and calibration cell response
certifications (if applicable) necessary to confirm that the performance
of the CEMS met the performance specifications.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this Performance
Specification (see Section 8.0). Refer to the RM for specific analytical
procedures.

12.0 Calculations and Data Analysis

Summarize the results on a data sheet similar to that shown in
Figure 2-2 (in Section 18.0).
12.1 All data from the RM and CEMS must be on a consistent dry
basis and, as applicable, on a consistent diluent basis and in the units
of the emission standard. Correct the RM and CEMS data for moisture and
diluent as follows:
12.1.1 Moisture Correction (as applicable). Correct each wet RM run
for moisture with the corresponding Method 4 data; correct each wet CEMS
run using the corresponding CEMS moisture monitor date using Equation 2-
1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.453

12.1.2 Correction to Units of Standard (as applicable). Correct each
dry RM run to the units of the emission standard with the corresponding
Method 3B data; correct each dry CEMS run using the corresponding CEMS
diluent monitor data as follows:
12.1.2.1 Correct to Diluent Basis. The following is an example of
concentration (ppm) correction to 7% oxygen.
[GRAPHIC] [TIFF OMITTED] TR17OC00.454

The following is an example of mass/gross calorific value (lbs/million
Btu) correction.

lbs/MMBtu = Conc(dry) (F-factor) (20.9/20.9-%02)

12.2 Arithmetic Mean. Calculate the arithmetic mean of the difference,
d, of a data set as follows:

[[Page 622]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.455

Where:

n = Number of data points.
[GRAPHIC] [TIFF OMITTED] TR17OC00.456

12.3 Standard Deviation. Calculate the standard deviation,
Sd, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.457

12.4 Confidence Coefficient. Calculate the 2.5 percent error
confidence coefficient (one-tailed), CC, as follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.458

Where:

t0.975 = t-value (see Table 2-1).

12.5 Relative Accuracy. Calculate the RA of a set of data as
follows:
[GRAPHIC] [TIFF OMITTED] TR17OC00.459

Where:

|d| = Absolute value of the mean differences (from Equation 2-3).
|CC| = Absolute value of the confidence coefficient (from Equation 2-3).
RM = Average RM value. In cases where the average emissions for the test
are less than 50 percent of the applicable standard,
substitute the emission standard value in the denominator of
Eq. 2-6 in place of RM. In all other cases, use RM.

13.0 Method Performance

13.1 Calibration Drift Performance Specification. The CEMS
calibration must not drift or deviate from the reference value of the
gas cylinder, gas cell, or optical filter by more than 2.5 percent of
the span value. If the CEMS includes pollutant and diluent monitors, the
CD must be determined separately for each in terms of concentrations
(See Performance Specification 3 for the diluent specifications), and
none of the CDs may exceed the specification.
13.2 Relative Accuracy Performance Specification. The RA of the
CEMS must be no greater than 20 percent when RM is used in the
denominator of Eq. 2-6 (average emissions during test are greater than
50 percent of the emission standard) or 10 percent when the applicable
emission standard is used in the denominator of Eq. 2-6 (average
emissions during test are less than 50 percent of the emission
standard).
13.3 For instruments that use common components to measure more
than one effluent gas constituent, all channels must simultaneously pass
the RA requirement, unless it can be demonstrated that any adjustments
made to one channel did not affect the others.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

Paragraphs 60.13(j)(1) and (2) of 40 CFR part 60 contain criteria
for which the reference method procedure for determining relative
accuracy (see Section 8.4 of this Performance Specification) may be
waived and the following procedure substituted.
16.1 Conduct a complete CEMS status check following the
manufacturer's written instructions. The check should include operation
of the light source, signal receiver, timing mechanism functions, data
acquisition and data reduction functions, data recorders, mechanically
operated functions (mirror movements, zero pipe operation, calibration
gas valve operations, etc.), sample filters, sample line heaters,
moisture traps, and other related functions of the CEMS, as applicable.
All parts of the CEMS shall be functioning properly before proceeding to
the alternative RA procedure.
16.2 Alternative RA Procedure.
16.2.1 Challenge each monitor (both pollutant and diluent, if
applicable) with cylinder gases of known concentrations or calibration
cells that produce known responses at two measurement points within the
ranges shown in Table 2-2 (Section 18).

[[Page 623]]

16.2.2 Use a separate cylinder gas (for point CEMS only) or
calibration cell (for path CEMS or where compressed gas cylinders can
not be used) for measurement points 1 and 2. Challenge the CEMS and
record the responses three times at each measurement point. The
Administrator may allow dilution of cylinder gas using the performance
criteria in Test Method 205, 40 CFR Part 51, Appendix M. Use the average
of the three responses in determining relative accuracy.
16.2.3 Operate each monitor in its normal sampling mode as nearly
as possible. When using cylinder gases, pass the cylinder gas through
all filters, scrubbers, conditioners, and other monitor components used
during normal sampling and as much of the sampling probe as practical.
When using calibration cells, the CEMS components used in the normal
sampling mode should not be by-passed during the RA determination. These
include light sources, lenses, detectors, and reference cells. The CEMS
should be challenged at each measurement point for a sufficient period
of time to assure adsorption-desorption reactions on the CEMS surfaces
have stabilized.
16.2.4 Use cylinder gases that have been certified by comparison to
National Institute of Standards and Technology (NIST) gaseous standard
reference material (SRM) or NIST/EPA approved gas manufacturer's
certified reference material (CRM) (See Reference 2 in Section 17.0)
following EPA Traceability Protocol Number 1 (See Reference 3 in Section
17.0). As an alternative to Protocol Number 1 gases, CRM's may be used
directly as alternative RA cylinder gases. A list of gas manufacturers
that have prepared approved CRM's is available from EPA at the address
shown in Reference 2. Procedures for preparation of CRM's are described
in Reference 2.
16.2.5 Use calibration cells certified by the manufacturer to
produce a known response in the CEMS. The cell certification procedure
shall include determination of CEMS response produced by the calibration
cell in direct comparison with measurement of gases of known
concentration. This can be accomplished using SRM or CRM gases in a
laboratory source simulator or through extended tests using reference
methods at the CEMS location in the exhaust stack. These procedures are
discussed in Reference 4 in Section 17.0. The calibration cell
certification procedure is subject to approval of the Administrator.
16.3 The differences between the known concentrations of the
cylinder gases and the concentrations indicated by the CEMS are used to
assess the accuracy of the CEMS. The calculations and limits of
acceptable relative accuracy are as follows:
16.3.1 For pollutant CEMS:
[GRAPHIC] [TIFF OMITTED] TR17OC00.460

Where:

d = Average difference between responses and the concentration/responses
(see Section 16.2.2).
AC = The known concentration/response of the cylinder gas or calibration
cell.

16.3.2 For diluent CEMS:

RA = |d| : O.7 percent O2 or CO2, as applicable.

Note: Waiver of the relative accuracy test in favor of the
alternative RA procedure does not preclude the requirements to complete
the CD tests nor any other requirements specified in an applicable
subpart for reporting CEMS data and performing CEMS drift checks or
audits.

17.0 References

1. Department of Commerce. Experimental Statistics. Handbook 91.
Washington, D.C. p. 3-31, paragraphs 3-3.1.4.
2. ``A Procedure for Establishing Traceability of Gas Mixtures to
Certain National Bureau of Standards Standard Reference Materials.''
Joint publication by NBS and EPA. EPA 600/7-81-010. Available from U.S.
Environmental Protection Agency, Quality Assurance Division (MD-77),
Research Triangle Park, North Carolina 27711.
3. ``Traceability Protocol for Establishing True Concentrations of
Gases Used for Calibration and Audits of Continuous Source Emission
Monitors. (Protocol Number 1).'' June 1978. Protocol Number 1 is
included in the Quality Assurance Handbook for Air Pollution Measurement
Systems, Volume III, Stationary Source Specific Methods. EPA-600/4-77-
027b. August 1977.
4. ``Gaseous Continuous Emission Monitoring Systems--Performance
Specification Guidelines for SO2, NOX,
CO2, O2, and TRS.'' EPA-450/3-82-026. Available
from the U.S. EPA, Emission Measurement Center, Emission Monitoring and
Data Analysis Division (MD-19), Research Triangle Park, North Carolina
27711.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 624]]

Table 2-1.--t-Values
----------------------------------------------------------------------------------------------------------------
n^a t0.975 n^a t0.975 n^a t0.975
----------------------------------------------------------------------------------------------------------------
2.............................................. 12.706 7 2.447 12 2.201
3.............................................. 4.303 8 2.365 13 2.179
4.............................................. 3.182 9 2.306 14 2.160
5.............................................. 2.776 10 2.262 15 2.145
6.............................................. 2.571 11 2.228 16 2.131
----------------------------------------------------------------------------------------------------------------
^a The values in this table are already corrected for n-1 degrees of freedom. Use n equal to the number of
individual values.

[[Page 625]]

Table 2-2.--Measurement Range
--------------------------------------------------------------------------------------------------------------------------------------------------------
Diluent monitor for
Measurement point Pollutant monitor -----------------------------------------------------------------------
CO2 O2
--------------------------------------------------------------------------------------------------------------------------------------------------------
1.................................. 20-30% of span value....................... 5-8% by volume.................... 4-6% by volume.
2.................................. 50-60% of span value....................... 10-14% by volume.................. 8-12% by volume.

------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Percent of span value (C-M)/
Day Date and time Calibration value (C) Monitor value (M) Difference (C-M) span value x 100
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Low-level........................ ........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
High-level....................... ........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
........... .......................... ................................. .......................... ..................... ..............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

Figure 2-1. Calibration Drift Determination

Figure 2-2. Relative Accuracy Determination.
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
SO2 NOXb CO2 or O2a SO2a NOXa
Run No. Date and ---------------------------------------------------------------------------------------------------------------------------------------------------
time RM CEMS Diff RM CEMS Diff RM CEMS RM CEMS Diff RM CEMS Diff
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
ppm^c
ppm^c %^c %^c mass/GCV
mass/GCV
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
1.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
2.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
3.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
4.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
5.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------

[[Page 626]]

6.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
7.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
8.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
9.............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
10............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
11............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
12............................
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Average
Confidence Interval
Accuracy
------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
^a For steam generators.
^b Average of three samples.
^c Make sure that RM and CEMS data are on a consistent basis, either wet or dry.

[[Page 627]]

Performance Specification 3--Specifications and Test Procedures for
O2 and CO2 Continuous Emission Monitoring Systems
in Stationary Sources

1.0 Scope and Application

1.1 Analytes.

1.2 Applicability.
1.2.1 This specification is for evaluating acceptability of
O2 and CO2 continuous emission monitoring systems
(CEMS) at the time of installation or soon after and whenever specified
in an applicable subpart of the regulations. This specification applies
to O2 or CO2 monitors that are not included under
Performance Specification 2 (PS 2).
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time, nor does it identify
specific calibration techniques and other auxiliary procedures to assess
the CEMS performance. The source owner or operator, is responsible to
calibrate, maintain, and operate the CEMS properly. The Administrator
may require, under Section 114 of the Act, the operator to conduct CEMS
performance evaluations at other times besides the initial test to
evaluate the CEMS performance. See 40 CFR part 60, Section 60.13(c).
1.2.3 The definitions, installation and measurement location
specifications, calculations and data analysis, and references are the
same as in PS 2, Sections 3, 8.1, 12, and 17, respectively, and also
apply to O2 and CO2 CEMS under this specification.
The performance and equipment specifications and the relative accuracy
(RA) test procedures for O2 and CO2 CEMS do not
differ from those for SO2 and NOx CEMS (see PS 2),
except as noted below.

2.0 Summary of Performance Specification

The RA and calibration drift (CD) tests are conducted to determine
conformance of the CEMS to the specification.

3.0 Definitions

Same as in Section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

This performance specification may involve hazardous materials,
operations, and equipment. This performance specification may not
address all of the safety problems associated with its use. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the applicable regulatory limitations prior to
performing this performance specification. The CEMS users manual should
be consulted for specific precautions to be taken with regard to the
analytical procedures.

6.0 Equipment and Supplies

Same as Section 6.0 of PS2.

7.0 Reagents and Standards

Same as Section 7.0 of PS2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Relative Accuracy Test Procedure. Sampling Strategy for
reference method (RM) Tests, Correlation of RM and CEMS Data, and Number
of RM Tests. Same as PS 2, Sections 8.4.3, 8.4.5, and 8.4.4,
respectively.
8.2 Reference Method. Unless otherwise specified in an applicable
subpart of the regulations, Method 3B or other approved alternative is
the RM for O2 or CO2.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analyses are concurrent for this performance
specification (see Section 8). Refer to the RM for specific analytical
procedures.

12.0 Calculations and Data Analysis

Summarize the results on a data sheet similar to that shown in
Figure 2.2 of PS2. Calculate the arithmetic difference between the RM
and the CEMS output for each run. The average difference of the nine (or
more) data sets constitute the RA.

13.0 Method Performance

13.1 Calibration Drift Performance Specification. The CEMS
calibration must not drift by more than 0.5 percent O2 or
CO2 from the reference value of the gas, gas cell, or optical
filter.
13.2 CEMS Relative Accuracy Performance Specification. The RA of
the CEMS must be no greater than 1.0 percent O2 or
CO2.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 References

Same as in Section 17.0 of PS 2.

[[Page 628]]

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Performance Specification 4--Specifications and Test Procedures for
Carbon Monoxide Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Carbon Monoxide (CO)................................... 630-08-0
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This specification is for evaluating the acceptability of
carbon monoxide (CO) continuous emission monitoring systems (CEMS) at
the time of installation or soon after and whenever specified in an
applicable subpart of the regulations. This specification was developed
primarily for CEMS having span values of 1,000 ppmv CO.
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time nor does it identify
specific calibration techniques and other auxiliary procedures to assess
CEMS performance. The source owner or operator, is responsible to
calibrate, maintain, and operate the CEMS. The Administrator may
require, under Section 114 of the Act, the source owner or operator to
conduct CEMS performance evaluations at other times besides the initial
test to evaluate the CEMS performance. See 40 CFR part 60, Section
60.13(c).
1.2.3 The definitions, performance specification test procedures,
calculations, and data analysis procedures for determining calibration
drift (CD) and relative accuracy (RA) of Performance Specification 2 (PS
2), Sections 3, 8.0, and 12, respectively, apply to this specification.

2.0 Summary of Performance Specification

The CD and RA tests are conducted to determine conformance of the
CEMS to the specification.

3.0 Definitions

Same as in Section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Section 6.0 of PS 2.

7.0 Reagents and Standards

Same as Section 7.0 of PS 2.

8.0 Sample Collection, Preservation, Storage, and Transport

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this performance
specification (see Section 8.0). Refer to the RM for specific analytical
procedures.

12.0 Calculations and Data Analysis

Same as Section 12.0 of PS 2.

13.0 Method Performance

13.1 Calibration Drift. The CEMS calibration must not drift or
deviate from the reference value of the calibration gas, gas cell, or
optical filter by more than 5 percent of the established span value for
6 out of 7 test days (e.g., the established span value is 1000 ppm for
Subpart J affected facilities).
13.2 Relative Accuracy. The RA of the CEMS must be no greater than
10 percent when the average RM value is used to calculate RA or 5
percent when the applicable emission standard is used to calculate RA.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures [Reserved]

17.0 References

1. Ferguson, B.B., R.E. Lester, and W.J. Mitchell. Field Evaluation
of Carbon Monoxide and Hydrogen Sulfide Continuous Emission Monitors at
an Oil Refinery. U.S. Environmental Protection Agency. Research

[[Page 629]]

Triangle Park, N.C. Publication No. EPA-600/4-82-054. August 1982. 100
p.
2. ``Gaseous Continuous Emission Monitoring Systems--Performance
Specification Guidelines for SO2, NOx,
CO2, O2, and TRS.'' EPA-450/3-82-026. U.S.
Environmental Protection Agency, Technical Support Division (MD-19),
Research Triangle Park, NC 27711.
3. Repp, M. Evaluation of Continuous Monitors for Carbon Monoxide in
Stationary Sources. U.S. Environmental Protection Agency. Research
Triangle Park, N.C. Publication No. EPA-600/2-77-063. March 1977. 155 p.
4. Smith, F., D.E. Wagoner, and R.P. Donovan. Guidelines for
Development of a Quality Assurance Program: Volume VIII--Determination
of CO Emissions from Stationary Sources by NDIR Spectrometry. U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA-650/4-74-005-h. February 1975. 96 p.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Same as Section 18.0 of PS 2.

Performance Specification 4A--Specifications and Test Procedures for
Carbon Monoxide Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Carbon Monoxide (CO)................................... 630-80-0
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This specification is for evaluating the acceptability of
carbon monoxide (CO) continuous emission monitoring systems (CEMS) at
the time of installation or soon after and whenever specified in an
applicable subpart of the regulations. This specification was developed
primarily for CEMS that comply with low emission standards (less than
200 ppmv).
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time nor does it identify
specific calibration techniques and other auxiliary procedures to assess
CEMS performance. The source owner or operator is responsible to
calibrate, maintain, and operate the CEMS. The Administrator may
require, under Section 114 of the Act, the source owner or operator to
conduct CEMS performance evaluations at other times besides the initial
test to evaluate CEMS performance. See 40 CFR Part 60, Section 60.13(c).
1.2.3 The definitions, performance specification, test procedures,
calculations and data analysis procedures for determining calibration
drifts (CD) and relative accuracy (RA), of Performance Specification 2
(PS 2), Sections 3, 8.0, and 12, respectively, apply to this
specification.

2.0 Summary of Performance Specification

The CD and RA tests are conducted to determine conformance of the
CEMS to the specification.

3.0 Definitions

Same as in Section 3.0 of PS 2.

4.0 Interferences. [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Section 6.0 of PS 2 with the following additions.
6.1 Data Recorder Scale.
6.1.1 This specification is the same as Section 6.1 of PS 2. The
CEMS shall be capable of measuring emission levels under normal
conditions and under periods of short-duration peaks of high
concentrations. This dual-range capability may be met using two separate
analyzers (one for each range) or by using dual-range units which have
the capability of measuring both levels with a single unit. In the
latter case, when the reading goes above the full-scale measurement
value of the lower range, the higher-range operation shall be started
automatically. The CEMS recorder range must include zero and a high-
level value. Under applications of consistent low emissions, a single-
range analyzer is allowed provided normal and spike emissions can be
quantified. In this case, set an appropriate high-level value to include
all emissions.
6.1.2 For the low-range scale of dual-range units, the high-level
value shall be between 1.5 times the pollutant concentration
corresponding to the emission standard level and the span value. For the
high-range scale, the high-level value shall be set at 2000 ppm, as a
minimum, and the range shall include the level of the span value. There
shall be no concentration gap between the low-and high-range scales.

7.0 Reagents and Standards

Same as Section 7.0 of PS 2.

[[Page 630]]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Relative Accuracy Test Procedure. Sampling Strategy for
reference method (RM) Tests, Number of RM Tests, and Correlation of RM
and CEMS Data are the same as PS 2, Sections 8.4.3, 8.4.4, and 8.4.5,
respectively.
8.2 Reference Methods. Unless otherwise specified in an applicable
subpart of the regulation, Methods 10, 10A, 10B, or other approved
alternative is the RM for this PS. When evaluating nondispersive
infrared CEMS using Method 10 as the RM, the alternative interference
trap specified in Section 16.0 of Method 10 shall be used.
8.3 Response Time Test Procedure. The response time test applies to
all types of CEMS, but will generally have significance only for
extractive systems.
8.3.1 Introduce zero gas into the analyzer. When the system output
has stabilized (no change greater than 1 percent of full scale for 30
sec), introduce an upscale calibration gas and wait for a stable value.
Record the time (upscale response time) required to reach 95 percent of
the final stable value. Next, reintroduce the zero gas and wait for a
stable reading before recording the response time (downscale response
time). Repeat the entire procedure three times and determine the mean
upscale and downscale response times. The slower or longer of the two
means is the system response time.
8.4 Interference Check. The CEMS must be shown to be free from the
effects of any interferences.

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardization. [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this performance
specification (see Section 8.0). Refer to the RM for specific analytical
procedures.

12.0 Calculations and Data Analysis. Same as Section 12.0 of PS 2

13.0 Method Performance

13.1 Calibration Drift. The CEMS calibration must not drift or
deviate from the reference value of the calibration gas, gas cell, or
optical filter by more than 5 percent of the established span value for
6 out of 7 test days.
13.2 Relative Accuracy. The RA of the CEMS must be no greater than
10 percent when the average RM value is used to calculate RA, 5 percent
when the applicable emission standard is used to calculate RA, or within
5 ppmv when the RA is calculated as the absolute average difference
between the RM and CEMS plus the 2.5 percent confidence coefficient.
13.3 Response Time. The CEMS response time shall not exceed 1.5 min
to achieve 95 percent of the final stable value.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

16.1 Under conditions where the average CO emissions are less than
10 percent of the standard and this is verified by Method 10, a cylinder
gas audit may be performed in place of the RA test to determine
compliance with these limits. In this case, the cylinder gas shall
contain CO in 12 percent carbon dioxide as an interference check. If
this option is exercised, Method 10 must be used to verify that emission
levels are less than 10 percent of the standard.

17.0 References

Same as Section 17 of PS 4.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Same as Section 18.0 of PS 2.

Performance Specification 4B--Specifications and Test Procedures for
Carbon Monoxide and Oxygen Continuous Monitoring Systems in Stationary
Sources

a. Applicability and Principle

1.1 Applicability. a. This specification is to be used for
evaluating the acceptability of carbon monoxide (CO) and oxygen
(O2) continuous emission monitoring systems (CEMS) at the
time of or soon after installation and whenever specified in the
regulations. The CEMS may include, for certain stationary sources, (a)
flow monitoring equipment to allow measurement of the dry volume of
stack effluent sampled, and (b) an automatic sampling system.
b. This specification is not designed to evaluate the installed
CEMS' performance over an extended period of time nor does it identify
specific calibration techniques and auxiliary procedures to assess the
CEMS' performance. The source owner or operator, however, is responsible
to properly calibrate, maintain, and operate the CEMS. To evaluate the
CEMS' performance, the Administrator may require, under section 114 of
the Act, the operator to conduct CEMS performance evaluations at times
other than the initial test.
c. The definitions, installation and measurement location
specifications, test procedures, data reduction procedures, reporting
requirements, and bibliography are the same as in PS 3 (for
O2) and PS 4A (for CO) except as otherwise noted below.

[[Page 631]]

1.2 Principle. Installation and measurement location
specifications, performance specifications, test procedures, and data
reduction procedures are included in this specification. Reference
method tests, calibration error tests, calibration drift tests, and
interferant tests are conducted to determine conformance of the CEMS
with the specification.

b. Definitions

2.1 Continuous Emission Monitoring System (CEMS). This definition
is the same as PS 2 Section 2.1 with the following addition. A
continuous monitor is one in which the sample to be analyzed passes the
measurement section of the analyzer without interruption.
2.2 Response Time. The time interval between the start of a step
change in the system input and when the pollutant analyzer output
reaches 95 percent of the final value.
2.3 Calibration Error (CE). The difference between the
concentration indicated by the CEMS and the known concentration
generated by a calibration source when the entire CEMS, including the
sampling interface is challenged. A CE test procedure is performed to
document the accuracy and linearity of the CEMS over the entire
measurement range.

3. Installation and Measurement Location Specifications

3.1 The CEMS Installation and Measurement Location. This
specification is the same as PS 2 Section 3.1 with the following
additions. Both the CO and O2 monitors should be installed at
the same general location. If this is not possible, they may be
installed at different locations if the effluent gases at both sample
locations are not stratified and there is no in-leakage of air between
sampling locations.
3.1.1 Measurement Location. Same as PS 2 Section 3.1.1.
3.1.2 Point CEMS. The measurement point should be within or
centrally located over the centroidal area of the stack or duct cross
section.
3.1.3 Path CEMS. The effective measurement path should: (1) Have at
least 70 percent of the path within the inner 50 percent of the stack or
duct cross sectional area, or (2) be centrally located over any part of
the centroidal area.
3.2 Reference Method (RM) Measurement Location and Traverse Points.
This specification is the same as PS 2 Section 3.2 with the following
additions. When pollutant concentration changes are due solely to
diluent leakage and CO and O2 are simultaneously measured at
the same location, one half diameter may be used in place of two
equivalent diameters.
3.3 Stratification Test Procedure. Stratification is defined as the
difference in excess of 10 percent between the average concentration in
the duct or stack and the concentration at any point more than 1.0 meter
from the duct or stack wall. To determine whether effluent
stratification exists, a dual probe system should be used to determine
the average effluent concentration while measurements at each traverse
point are being made. One probe, located at the stack or duct centroid,
is used as a stationary reference point to indicate change in the
effluent concentration over time. The second probe is used for sampling
at the traverse points specified in Method 1 (40 CFR part 60 appendix
A). The monitoring system samples sequentially at the reference and
traverse points throughout the testing period for five minutes at each
point.

d. Performance and Equipment Specifications

4.1 Data Recorder Scale. For O2, same as specified in PS
3, except that the span must be 25 percent. The span of the
O2 may be higher if the O2 concentration at the
sampling point can be greater than 25 percent. For CO, same as specified
in PS 4A, except that the low-range span must be 200 ppm and the high
range span must be 3000 ppm. In addition, the scale for both CEMS must
record all readings within a measurement range with a resolution of 0.5
percent.
4.2 Calibration Drift. For O2, same as specified in PS
3. For CO, the same as specified in PS 4A except that the CEMS
calibration must not drift from the reference value of the calibration
standard by more than 3 percent of the span value on either the high or
low range.
4.3 Relative Accuracy (RA). For O2, same as specified in
PS 3. For CO, the same as specified in PS 4A.
4.4 Calibration Error (CE). The mean difference between the CEMS
and reference values at all three test points (see Table I) must be no
greater than 5 percent of span value for CO monitors and 0.5 percent for
O2 monitors.
4.5 Response Time. The response time for the CO or O2
monitor must not exceed 2 minutes.

e. Performance Specification Test Procedure

5.1 Calibration Error Test and Response Time Test Periods. Conduct
the CE and response time tests during the CD test period.

F. The CEMS Calibration Drift and Response Time Test Procedures

The response time test procedure is given in PS 4A, and must be
carried out for both the CO and O2 monitors.

7. Relative Accuracy and Calibration Error Test Procedures

7.1 Calibration Error Test Procedure. Challenge each monitor (both
low and high range CO and O2) with zero gas and EPA Protocol

[[Page 632]]

1 cylinder gases at three measurement points within the ranges specified
in Table I.

Table I. Calibration Error Concentration Ranges
------------------------------------------------------------------------
CO Low
Measurement point range CO High O2 (%)
(ppm) range (ppm)
------------------------------------------------------------------------
1................................. 0-40 0-600 0-2
2................................. 60-80 900-1200 8-10
3................................. 140-160 2100-2400 14-16
------------------------------------------------------------------------

Operate each monitor in its normal sampling mode as nearly as possible.
The calibration gas must be injected into the sample system as close to
the sampling probe outlet as practical and should pass through all CEMS
components used during normal sampling. Challenge the CEMS three non-
consecutive times at each measurement point and record the responses.
The duration of each gas injection should be sufficient to ensure that
the CEMS surfaces are conditioned.
7.1.1 Calculations. Summarize the results on a data sheet. Average
the differences between the instrument response and the certified
cylinder gas value for each gas. Calculate the CE results according to:
[GRAPHIC] [TIFF OMITTED] TR30SE99.010

where d is the mean difference between the CEMS response and the known
reference concentration and FS is the span value.
7.2 Relative Accuracy Test Procedure. Follow the RA test procedures
in PS 3 (for O2) section 3 and PS 4A (for CO) section 4.
7.3 Alternative RA Procedure. Under some operating conditions, it
may not be possible to obtain meaningful results using the RA test
procedure. This includes conditions where consistent, very low CO
emission or low CO emissions interrupted periodically by short duration,
high level spikes are observed. It may be appropriate in these
circumstances to waive the RA test and substitute the following
procedure.
Conduct a complete CEMS status check following the manufacturer's
written instructions. The check should include operation of the light
source, signal receiver, timing mechanism functions, data acquisition
and data reduction functions, data recorders, mechanically operated
functions, sample filters, sample line heaters, moisture traps, and
other related functions of the CEMS, as applicable. All parts of the
CEMS must be functioning properly before the RA requirement can be
waived. The instrument must also successfully passed the CE and CD
specifications. Substitution of the alternate procedure requires
approval of the Regional Administrator.

8. Bibliography

1. 40 CFR Part 266, Appendix IX, Section 2, ``Performance
Specifications for Continuous Emission Monitoring Systems.''

Performance Specification 5--Specifications and Test Procedures for TRS
Continuous Emission Monitoring Systems in Stationary Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Total Reduced Sulfur (TRS)............................. NA
------------------------------------------------------------------------

1.2 Applicability. This specification is for evaluating the
applicability of TRS continuous emission monitoring systems (CEMS) at
the time of installation or soon after and whenever specified in an
applicable subpart of the regulations. The CEMS may include oxygen
monitors which are subject to Performance Specification 3 (PS 3).
1.3 The definitions, performance specification, test procedures,
calculations and data analysis procedures for determining calibration
drifts (CD) and relative accuracy (RA) of PS 2, Sections 3.0, 8.0, and
12.0, respectively, apply to this specification.

2.0 Summary of Performance Specification

The CD and RA tests are conducted to determine conformance of the
CEMS to the specification.

3.0 Definitions

Same as in Section 3.0 of PS 2.

4.0 Interferences [Reserved]

5.0 Safety

6.0 Equipment and Supplies

Same as Section 6.0 of PS 2.

7.0 Reagents and Standards

Same as Section 7.0 of PS 2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Relative Accuracy Test Procedure. Sampling Strategy for
reference method

[[Page 633]]

(RM) Tests, Number of RM Tests, and Correlation of RM and CEMS Data are
the same as PS 2, Sections 8.4.3, 8.4.4, and 8.4.5, respectively.

Note: For Method 16, a sample is made up of at least three separate
injects equally space over time. For Method 16A, a sample is collected
for at least 1 hour.
8.2 Reference Methods. Unless otherwise specified in the applicable
subpart of the regulations, Method 16, Method 16A, 16B or other approved
alternative is the RM for TRS.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this performance
specification (see Section 8.0). Refer to the reference method for
specific analytical procedures.

12.0 Calculations and Data Analysis

Same as Section 12.0 of PS 2.

13.0 Method Performance

13.1 Calibration Drift. The CEMS detector calibration must not drift
or deviate from the reference value of the calibration gas by more than
5 percent of the established span value for 6 out of 7 test days. This
corresponds to 1.5 ppm drift for Subpart BB sources where the span value
is 30 ppm. If the CEMS includes pollutant and diluent monitors, the CD
must be determined separately for each in terms of concentrations (see
PS 3 for the diluent specifications).
13.2 Relative Accuracy. The RA of the CEMS must be no greater than
20 percent when the average RM value is used to calculate RA or 10
percent when the applicable emission standard is used to calculate RA.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures [Reserved]

17.0 References

1. Department of Commerce. Experimental Statistics, National Bureau
of Standards, Handbook 91. 1963. Paragraphs 3-3.1.4, p. 3-31.
2. A Guide to the Design, Maintenance and Operation of TRS
Monitoring Systems. National Council for Air and Stream Improvement
Technical Bulletin No. 89. September 1977.
3. Observation of Field Performance of TRS Monitors on a Kraft
Recovery Furnace. National Council for Air and Stream Improvement
Technical Bulletin No. 91. January 1978.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

Same as Section 18.0 of PS 2.

Performance Specification 6--Specifications and Test Procedures for
Continuous Emission Rate Monitoring Systems in Stationary Sources

1.0 Scope and Application

1.1 Applicability. This specification is used for evaluating the
acceptability of continuous emission rate monitoring systems (CERMSs).
1.2 The installation and measurement location specifications,
performance specification test procedure, calculations, and data
analysis procedures, of Performance Specifications (PS 2), Sections 8.0
and 12, respectively, apply to this specification.

2.0 Summary of Performance Specification

The calibration drift (CD) and relative accuracy (RA) tests are
conducted to determine conformance of the CERMS to the specification.

3.0 Definitions

The definitions are the same as in Section 3 of PS 2, except this
specification refers to the continuous emission rate monitoring system
rather than the continuous emission monitoring system. The following
definitions are added:
3.1 Continuous Emission Rate Monitoring System (CERMS). The total
equipment required for the determining and recording the pollutant mass
emission rate (in terms of mass per unit of time).
3.2 Flow Rate Sensor. That portion of the CERMS that senses the
volumetric flow rate and generates an output proportional to that flow
rate. The flow rate sensor shall have provisions to check the CD for
each flow rate parameter that it measures individually (e.g., velocity,
pressure).

4.0 Interferences [Reserved]

5.0 Safety

This performance specification may involve hazardous materials,
operations, and equipment. This performance specification may not
address all of the safety problems associated with its use. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the applicable regulatory limitations prior to
performing this performance specification. The CERMS users manual should
be consulted for specific precautions to be taken with regard to the
analytical procedures.

6.0 Equipment and Supplies

Same as Section 6.0 of PS 2.

[[Page 634]]

7.0 Reagents and Standards

Same as Section 7.0 of PS 2.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Calibration Drift Test Procedure.
8.1.1 The CD measurements are to verify the ability of the CERMS to
conform to the established CERMS calibrations used for determining the
emission rate. Therefore, if periodic automatic or manual adjustments
are made to the CERMS zero and calibration settings, conduct the CD
tests immediately before these adjustments, or conduct them in such a
way that CD can be determined.
8.1.2 Conduct the CD tests for pollutant concentration at the two
values specified in Section 6.1.2 of PS 2. For other parameters that are
selectively measured by the CERMS (e.g., velocity, pressure, flow rate),
use two analogous values (e.g., Low: 0-20% of full scale, High: 50-100%
of full scale). Introduce to the CERMS the reference signals (these need
not be certified). Record the CERMS response to each and subtract this
value from the respective reference value (see example data sheet in
Figure 6-1).
8.2 Relative Accuracy Test Procedure.
8.2.1 Sampling Strategy for reference method (RM) Tests,
Correlation of RM and CERMS Data, and Number of RM Tests are the same as
PS 2, Sections 8.4.3, 8.4.5, and 8.4.4, respectively. Summarize the
results on a data sheet. An example is shown in Figure 6-1. The RA test
may be conducted during the CD test period.
8.2.2 Reference Methods. Unless otherwise specified in the
applicable subpart of the regulations, the RM for the pollutant gas is
the Appendix A method that is cited for compliance test purposes, or its
approved alternatives. Methods 2, 2A, 2B, 2C, or 2D, as applicable, are
the RMs for the determination of volumetric flow rate.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization [Reserved]

11.0 Analytical Procedure

Same as Section 11.0 of PS 2.

12.0 Calculations and Data Analysis

Same as Section 12.0 of PS 2.

13.0 Method Performance

13.1 Calibration Drift. Since the CERMS includes analyzers for
several measurements, the CD shall be determined separately for each
analyzer in terms of its specific measurement. The calibration for each
analyzer associated with the measurement of flow rate shall not drift or
deviate from each reference value of flow rate by more than 3 percent of
the respective high-level value. The CD specification for each analyzer
for which other PSs have been established (e.g., PS 2 for SO2
and NOX), shall be the same as in the applicable PS.
13.2 CERMS Relative Accuracy. The RA of the CERMS shall be no
greater than 20 percent of the mean value of the RM's test data in terms
of the units of the emission standard, or 10 percent of the applicable
standard, whichever is greater.

14.0 Pollution Prevention [Reserved]

15.0 Waste Management [Reserved]

16.0 Alternative Procedures

Same as in Section 16.0 of PS 2.

17.0 References

1. Brooks, E.F., E.C. Beder, C.A. Flegal, D.J. Luciani, and R.
Williams. Continuous Measurement of Total Gas Flow Rate from Stationary
Sources. U.S. Environmental Protection Agency. Research Triangle Park,
North Carolina. Publication No. EPA-650/2-75-020. February 1975. 248 p.

18.0 Tables, Diagrams, Flowcharts, and Validation Data

----------------------------------------------------------------------------------------------------------------
Emission rate (kg/hr)^a
--------------------------------------------------------------------
Run No. Date and time Difference (RMs-
CERMS RMs CERMS)
----------------------------------------------------------------------------------------------------------------
1 .....................
----------------------------------------------------------------------------------------------------------------
2 .....................
----------------------------------------------------------------------------------------------------------------
3 .....................
----------------------------------------------------------------------------------------------------------------
4 .....................
----------------------------------------------------------------------------------------------------------------
5 .....................
----------------------------------------------------------------------------------------------------------------
6 .....................
----------------------------------------------------------------------------------------------------------------

[[Page 635]]

7 .....................
----------------------------------------------------------------------------------------------------------------
8 .....................
----------------------------------------------------------------------------------------------------------------
9 .....................
----------------------------------------------------------------------------------------------------------------
\a\ The RMs and CERMS data as corrected to a consistent basis (i.e., moisture, temperature, and pressure
conditions).

Figure 6-1.--Emission Rate Determinations

Performance Specification 7--Specifications and Test Procedures for
Hydrogen Sulfide Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes.

------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Hydrogen Sulfide........................................ 7783-06-4
------------------------------------------------------------------------

1.2 Applicability.
1.2.1 This specification is to be used for evaluating the
acceptability of hydrogen sulfide (H2S) continuous emission
monitoring systems (CEMS) at the time of or soon after installation and
whenever specified in an applicable subpart of the regulations.
1.2.2 This specification is not designed to evaluate the installed
CEMS performance over an extended period of time nor does it identify
specific calibration techniques and other auxiliary procedures to assess
CEMS performance. The source owner or operator, however, is responsible
to calibrate, maintain, and operate the CEMS. To evaluate CEMS
performance, the Administrator may require, under Section 114 of the
Act, the source owner or operator to conduct CEMS performance
evaluations at other times besides the initial test. See Section
60.13(c).

2.0 Summary

Calibration drift (CD) and relative accuracy (RA) tests are
conducted to determine that the CEMS conforms to the specification.

3.0 Definitions

Same as Section 3.0 of PS 2.

4.0 Interferences. [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety problems associated with these procedures. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the application regulatory limitations prior to
performing these procedures. The CEMS user's manual and materials
recommended by the reference method should be consulted for specific
precautions to be taken.

6.0 Equipment and Supplies

6.1 Instrument Zero and Span. This specification is the same as
Section 6.1 of PS 2.
6.2 Calibration Drift. The CEMS calibration must not drift or
deviate from the reference value of the calibration gas or reference
source by more than 5 percent of the established span value for 6 out of
7 test days (e.g., the established span value is 300 ppm for Subpart J
fuel gas combustion devices).
6.3 Relative Accuracy. The RA of the CEMS must be no greater than
20 percent when the average reference method (RM) value is used to
calculate RA or 10 percent when the applicable emission standard is used
to calculate RA.

7.0 Reagents and Standards

Same as Section 7.0 of PS 2.

8.0 Sample Collection, Preservation, Storage, and Transport.

8.1 Installation and Measurement Location Specification. Same as
Section 8.1 of PS 2.
8.2 Pretest Preparation. Same as Section 8.2 of PS 2.
8.3 Calibration Drift Test Procedure. Same as Section 8.3 of PS 2.
8.4 Relative Accuracy Test Procedure.
8.4.1 Sampling Strategy for RM Tests, Correlation of RM and CEMS
Data, and Number of RM Tests. These are the same as that in PS 2,
Sections 8.4.3, 8.4.5, and 8.4.4, respectively.
8.4.2 Reference Methods. Unless otherwise specified in an
applicable subpart of the regulation, Method 11 is the RM for this PS.
8.5 Reporting. Same as Section 8.5 of PS 2.

[[Page 636]]

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardizations. [Reserved]

11.0 Analytical Procedures

Sample Collection and analysis are concurrent for this PS (see
Section 8.0). Refer to the RM for specific analytical procedures.

12.0 Data Analysis and Calculations

Same as Section 12.0 of PS 2.

13.0 Method Performance. [Reserved]

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

1. U.S. Environmental Protection Agency. Standards of Performance
for New Stationary Sources; Appendix B; Performance Specifications 2 and
3 for SO2, NOX, CO2, and O2
Continuous Emission Monitoring Systems; Final Rule. 48 CFR 23608.
Washington, D.C. U.S. Government Printing Office. May 25, 1983.
2. U.S. Government Printing Office. Gaseous Continuous Emission
Monitoring Systems--Performance Specification Guidelines for
SO2, NOX, CO2, O2, and TRS.
U.S. Environmental Protection Agency. Washington, D.C. EPA-450/3-82-026.
October 1982. 26 p.
3. Maines, G.D., W.C. Kelly (Scott Environmental Technology, Inc.),
and J.B. Homolya. Evaluation of Monitors for Measuring H2S in
Refinery Gas. Prepared for the U.S. Environmental Protection Agency.
Research Triangle Park, N.C. Contract No. 68-02-2707. 1978. 60 p.
4. Ferguson, B.B., R.E. Lester (Harmon Engineering and Testing), and
W.J. Mitchell. Field Evaluation of Carbon Monoxide and Hydrogen Sulfide
Continuous Emission Monitors at an Oil Refinery. Prepared for the U.S.
Environmental Protection Agency. Research Triangle Park, N.C.
Publication No. EPA-600/4-82-054. August 1982. 100 p.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

Same as Section 18.0 of PS 2.

Performance Specification 8--Performance Specifications for Volatile
Organic Compound Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Analytes. Volatile Organic Compounds (VOCs).
1.2 Applicability.
1.2.1 This specification is to be used for evaluating a continuous
emission monitoring system (CEMS) that measures a mixture of VOC's and
generates a single combined response value. The VOC detection principle
may be flame ionization (FI), photoionization (PI), non-dispersive
infrared absorption (NDIR), or any other detection principle that is
appropriate for the VOC species present in the emission gases and that
meets this performance specification. The performance specification
includes procedures to evaluate the acceptability of the CEMS at the
time of or soon after its installation and whenever specified in
emission regulations or permits. This specification is not designed to
evaluate the installed CEMS performance over an extended period of time,
nor does it identify specific calibration techniques and other auxiliary
procedures to assess the CEMS performance. The source owner or operator,
however, is responsible to calibrate, maintain, and operate the CEMS
properly. To evaluate the CEMS performance, the Administrator may
require, under Section 114 of the Act, the operator to conduct CEMS
performance evaluations in addition to the initial test. See Section
60.13(c).
1.2.2 In most emission circumstances, most VOC monitors can provide
only a relative measure of the total mass or volume concentration of a
mixture of organic gases, rather than an accurate quantification. This
problem is removed when an emission standard is based on a total VOC
measurement as obtained with a particular detection principle. In those
situations where a true mass or volume VOC concentration is needed, the
problem can be mitigated by using the VOC CEMS as a relative indicator
of total VOC concentration if statistical analysis indicates that a
sufficient margin of compliance exists for this approach to be
acceptable. Otherwise, consideration can be given to calibrating the
CEMS with a mixture of the same VOC's in the same proportions as they
actually occur in the measured source. In those circumstances where only
one organic species is present in the source, or where equal incremental
amounts of each of the organic species present generate equal CEMS
responses, the latter choice can be more easily achieved.

2.0 Summary of Performance Specification

2.1 Calibration drift and relative accuracy tests are conducted to
determine adherence of the CEMS with specifications given for those
items. The performance specifications include criteria for installation
and measurement location, equipment and performance, and procedures for
testing and data reduction.

3.0 Definitions.

Same as Section 3.0 of PS 2.

[[Page 637]]

4.0 Interferences. [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety problems associated with these procedures. It is the
responsibility of the user to establish appropriate safety and health
practices and determine the application regulatory limitations prior to
performing these procedures. The CEMS user's manual and materials
recommended by the reference method should be consulted for specific
precautions to be taken.

6.0 Equipment and Supplies

6.1 VOC CEMS Selection. When possible, select a VOC CEMS with the
detection principle of the reference method specified in the regulation
or permit (usually either FI, NDIR, or PI). Otherwise, use knowledge of
the source process chemistry, previous emission studies, or gas
chromatographic analysis of the source gas to select an appropriate VOC
CEMS. Exercise extreme caution in choosing and installing any CEMS in an
area with explosive hazard potential.
6.2 Data Recorder Scale. Same as Section 6.1 of PS 2.

7.0 Reagents and Standards. [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Installation and Measurement Location Specifications. Same as
Section 8.1 of PS 2.
8.2 Pretest Preparation. Same as Section 8.2 of PS 2.
8.3 Reference Method (RM). Use the method specified in the
applicable regulation or permit, or any approved alternative, as the RM.
8.4 Sampling Strategy for RM Tests, Correlation of RM and CEMS
Data, and Number of RM Tests. Follow PS 2, Sections 8.4.3, 8.4.5, and
8.4.4, respectively.
8.5 Reporting. Same as Section 8.5 of PS 2.

9.0 Quality Control. [Reserved]

10.0 Calibration and Standardization. [Reserved]

11.0 Analytical Procedure

Sample collection and analysis are concurrent for this PS (see
Section 8.0). Refer to the RM for specific analytical procedures.

12.0 Calculations and Data Analysis

Same as Section 12.0 of PS 2.

13.0 Method Performance

13.1 Calibration Drift. The CEMS calibration must not drift by more
than 2.5 percent of the span value.
13.2 CEMS Relative Accuracy. Unless stated otherwise in the
regulation or permit, the RA of the CEMS must not be greater than 20
percent of the mean value of the RM test data in terms of the units of
the emission standard, or 10 percent of the applicable standard,
whichever is greater.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References

Same as Section 17.0 of PS 2.

17.0 Tables, Diagrams, Flowcharts, and Validation Data. [Reserved]

Performance Specification 8A--Specifications and Test Procedures for
Total Hydrocarbon Continuous Monitoring Systems in Stationary Sources

1. Applicability and Principle

1.1 Applicability. These performance specifications apply to
hydrocarbon (HC) continuous emission monitoring systems (CEMS) installed
on stationary sources. The specifications include procedures which are
intended to be used to evaluate the acceptability of the CEMS at the
time of its installation or whenever specified in regulations or
permits. The procedures are not designed to evaluate CEMS performance
over an extended period of time. The source owner or operator is
responsible for the proper calibration, maintenance, and operation of
the CEMS at all times.
1.2 Principle. A gas sample is extracted from the source through a
heated sample line and heated filter to a flame ionization detector
(FID). Results are reported as volume concentration equivalents of
propane. Installation and measurement location specifications,
performance and equipment specifications, test and data reduction
procedures, and brief quality assurance guidelines are included in the
specifications. Calibration drift, calibration error, and response time
tests are conducted to determine conformance of the CEMS with the
specifications.

2. Definitions

2.1 Continuous Emission Monitoring System (CEMS). The total
equipment used to acquire data, which includes sample extraction and
transport hardware, analyzer, data recording and processing hardware,
and software. The

[[Page 638]]

system consists of the following major subsystems:
2.1.1 Sample Interface. That portion of the system that is used for
one or more of the following: Sample acquisition, sample transportation,
sample conditioning, or protection of the analyzer from the effects of
the stack effluent.
2.1.2 Organic Analyzer. That portion of the system that senses
organic concentration and generates an output proportional to the gas
concentration.
2.1.3 Data Recorder. That portion of the system that records a
permanent record of the measurement values. The data recorder may
include automatic data reduction capabilities.
2.2 Instrument Measurement Range. The difference between the
minimum and maximum concentration that can be measured by a specific
instrument. The minimum is often stated or assumed to be zero and the
range expressed only as the maximum.
2.3 Span or Span Value. Full scale instrument measurement range.
The span value must be documented by the CEMS manufacturer with
laboratory data.
2.4 Calibration Gas. A known concentration of a gas in an
appropriate diluent gas.
2.5 Calibration Drift (CD). The difference in the CEMS output
readings from the established reference value after a stated period of
operation during which no unscheduled maintenance, repair, or adjustment
takes place. A CD test is performed to demonstrate the stability of the
CEMS calibration over time.
2.6 Response Time. The time interval between the start of a step
change in the system input (e.g., change of calibration gas) and the
time when the data recorder displays 95 percent of the final value.
2.7 Accuracy. A measurement of agreement between a measured value
and an accepted or true value, expressed as the percentage difference
between the true and measured values relative to the true value. For
these performance specifications, accuracy is checked by conducting a
calibration error (CE) test.
2.8 Calibration Error (CE). The difference between the
concentration indicated by the CEMS and the known concentration of the
cylinder gas. A CE test procedure is performed to document the accuracy
and linearity of the monitoring equipment over the entire measurement
range.
2.9 Performance Specification Test (PST) Period. The period during
which CD, CE, and response time tests are conducted.
2.10 Centroidal Area. A concentric area that is geometrically
similar to the stack or duct cross section and is no greater than 1
percent of the stack or duct cross-sectional area.

3. Installation and Measurement Location Specifications

3.1 CEMS Installation and Measurement Locations. The CEMS must be
installed in a location in which measurements representative of the
source's emissions can be obtained. The optimum location of the sample
interface for the CEMS is determined by a number of factors, including
ease of access for calibration and maintenance, the degree to which
sample conditioning will be required, the degree to which it represents
total emissions, and the degree to which it represents the combustion
situation in the firebox (where applicable). The location should be as
free from in-leakage influences as possible and reasonably free from
severe flow disturbances. The sample location should be at least two
equivalent duct diameters downstream from the nearest control device,
point of pollutant generation, or other point at which a change in the
pollutant concentration or emission rate occurs and at least 0.5
diameter upstream from the exhaust or control device. The equivalent
duct diameter is calculated as per 40 CFR part 60, appendix A, method 1,
section 2.1. If these criteria are not achievable or if the location is
otherwise less than optimum, the possibility of stratification should be
investigated as described in section 3.2. The measurement point must be
within the centroidal area of the stack or duct cross section.
3.2 Stratification Test Procedure. Stratification is defined as a
difference in excess of 10 percent between the average concentration in
the duct or stack and the concentration at any point more than 1.0 meter
from the duct or stack wall. To determine whether effluent
stratification exists, a dual probe system should be used to determine
the average effluent concentration while measurements at each traverse
point are being made. One probe, located at the stack or duct centroid,
is used as a stationary reference point to indicate the change in
effluent concentration over time. The second probe is used for sampling
at the traverse points specified in 40 CFR part 60 appendix A, method 1.
The monitoring system samples sequentially at the reference and traverse
points throughout the testing period for five minutes at each point.

4. CEMS Performance and Equipment Specifications

If this method is applied in highly explosive areas, caution and
care must be exercised in choice of equipment and installation.
4.1 Flame Ionization Detector (FID) Analyzer. A heated FID analyzer
capable of meeting or exceeding the requirements of these
specifications. Heated systems must maintain the temperature of the
sample gas between 150 deg.C (300 deg.F) and 175 deg.C (350 deg.F)

[[Page 639]]

throughout the system. This requires all system components such as the
probe, calibration valve, filter, sample lines, pump, and the FID to be
kept heated at all times such that no moisture is condensed out of the
system. The essential components of the measurement system are described
below:
4.1.1 Sample Probe. Stainless steel, or equivalent, to collect a
gas sample from the centroidal area of the stack cross-section.
4.1.2 Sample Line. Stainless steel or Teflon tubing to transport
the sample to the analyzer.

Note: Mention of trade names or specific products does not
constitute endorsement by the Environmental Protection Agency.

4.1.3 Calibration Valve Assembly. A heated three-way valve assembly
to direct the zero and calibration gases to the analyzer is recommended.
Other methods, such as quick-connect lines, to route calibration gas to
the analyzers are applicable.
4.1.4 Particulate Filter. An in-stack or out-of-stack sintered
stainless steel filter is recommended if exhaust gas particulate loading
is significant. An out-of-stack filter must be heated.
4.1.5 Fuel. The fuel specified by the manufacturer (e.g., 40
percent hydrogen/60 percent helium, 40 percent hydrogen/60 percent
nitrogen gas mixtures, or pure hydrogen) should be used.
4.1.6 Zero Gas. High purity air with less than 0.1 parts per
million by volume (ppm) HC as methane or carbon equivalent or less than
0.1 percent of the span value, whichever is greater.
4.1.7 Calibration Gases. Appropriate concentrations of propane gas
(in air or nitrogen). Preparation of the calibration gases should be
done according to the procedures in EPA Protocol 1. In addition, the
manufacturer of the cylinder gas should provide a recommended shelf life
for each calibration gas cylinder over which the concentration does not
change by more than 2 percent from the certified value.
4.2 CEMS Span Value. 100 ppm propane. The span value must be
documented by the CEMS manufacturer with laboratory data.
4.3 Daily Calibration Gas Values. The owner or operator must choose
calibration gas concentrations that include zero and high-level
calibration values.
4.3.1 The zero level may be between zero and 0.1 ppm (zero and 0.1
percent of the span value).
4.3.2 The high-level concentration must be between 50 and 90 ppm
(50 and 90 percent of the span value).
4.4 Data Recorder Scale. The strip chart recorder, computer, or
digital recorder must be capable of recording all readings within the
CEMS' measurement range and must have a resolution of 0.5 ppm (0.5
percent of span value).
4.5 Response Time. The response time for the CEMS must not exceed 2
minutes to achieve 95 percent of the final stable value.
4.6 Calibration Drift. The CEMS must allow the determination of CD
at the zero and high-level values. The CEMS calibration response must
not differ by more than 3 ppm (3 percent of the
span value) after each 24-hour period of the 7-day test at both zero and
high levels.
4.7 Calibration Error. The mean difference between the CEMS and
reference values at all three test points listed below must be no
greater than 5 ppm (5 percent of the span value).
4.7.1 Zero Level. Zero to 0.1 ppm (0 to 0.1 percent of span value).
4.7.2 Mid-Level. 30 to 40 ppm (30 to 40 percent of span value).
4.7.3 High-Level. 70 to 80 ppm (70 to 80 percent of span value).
4.8 Measurement and Recording Frequency. The sample to be analyzed
must pass through the measurement section of the analyzer without
interruption. The detector must measure the sample concentration at
least once every 15 seconds. An average emission rate must be computed
and recorded at least once every 60 seconds.
4.9 Hourly Rolling Average Calculation. The CEMS must calculate
every minute an hourly rolling average, which is the arithmetic mean of
the 60 most recent 1-minute average values.
4.10 Retest. If the CEMS produces results within the specified
criteria, the test is successful. If the CEMS does not meet one or more
of the criteria, necessary corrections must be made and the performance
tests repeated.

5. Performance Specification Test (PST) Periods

5.1 Pretest Preparation Period. Install the CEMS, prepare the PTM
test site according to the specifications in section 3, and prepare the
CEMS for operation and calibration according to the manufacturer's
written instructions. A pretest conditioning period similar to that of
the 7-day CD test is recommended to verify the operational status of the
CEMS.
5.2 Calibration Drift Test Period. While the facility is operating
under normal conditions, determine the magnitude of the CD at 24-hour
intervals for seven consecutive days according to the procedure given in
section 6.1. All CD determinations must be made following a 24-hour
period during which no unscheduled maintenance, repair, or adjustment
takes place. If the combustion unit is taken out of service during the
test period, record the onset and duration of the downtime and continue
the CD test when the unit resumes operation.
5.3 Calibration Error Test and Response Time Test Periods. Conduct
the CE and response time tests during the CD test period.

[[Page 640]]

6. Performance Specification Test Procedures

6.1 Relative Accuracy Test Audit (RATA) and Absolute Calibration
Audits (ACA). The test procedures described in this section are in lieu
of a RATA and ACA.
6.2 Calibration Drift Test.
6.2.1 Sampling Strategy. Conduct the CD test at 24-hour intervals
for seven consecutive days using calibration gases at the two daily
concentration levels specified in section 4.3. Introduce the two
calibration gases into the sampling system as close to the sampling
probe outlet as practical. The gas must pass through all CEM components
used during normal sampling. If periodic automatic or manual adjustments
are made to the CEMS zero and calibration settings, conduct the CD test
immediately before these adjustments, or conduct it in such a way that
the CD can be determined. Record the CEMS response and subtract this
value from the reference (calibration gas) value. To meet the
specification, none of the differences may exceed 3 percent of the span
of the CEM.
6.2.2 Calculations. Summarize the results on a data sheet. An
example is shown in Figure 1. Calculate the differences between the CEMS
responses and the reference values.
6.3 Response Time. The entire system including sample extraction
and transport, sample conditioning, gas analyses, and the data recording
is checked with this procedure.
6.3.1 Introduce the calibration gases at the probe as near to the
sample location as possible. Introduce the zero gas into the system.
When the system output has stabilized (no change greater than 1 percent
of full scale for 30 sec), switch to monitor stack effluent and wait for
a stable value. Record the time (upscale response time) required to
reach 95 percent of the final stable value.
6.3.2 Next, introduce a high-level calibration gas and repeat the
above procedure. Repeat the entire procedure three times and determine
the mean upscale and downscale response times. The longer of the two
means is the system response time.
6.4 Calibration Error Test Procedure.
6.4.1 Sampling Strategy. Challenge the CEMS with zero gas and EPA
Protocol 1 cylinder gases at measurement points within the ranges
specified in section 4.7.
6.4.1.1 The daily calibration gases, if Protocol 1, may be used for
this test.

[[Page 641]]

[GRAPHIC] [TIFF OMITTED] TR30SE99.011

6.4.1.2 Operate the CEMS as nearly as possible in its normal
sampling mode. The calibration gas should be injected into the sampling
system as close to the sampling probe outlet as practical and must pass
through all filters, scrubbers, conditioners, and other monitor
components used during normal sampling. Challenge the CEMS three non-
consecutive times at each measurement point and record the responses.
The duration of each gas injection should be for a sufficient period of
time to ensure that the CEMS surfaces are conditioned.
6.4.2 Calculations. Summarize the results on a data sheet. An
example data sheet is shown in Figure 2. Average the differences between
the instrument response and the certified cylinder gas value for each
gas. Calculate three CE results according to Equation 1. No confidence
coefficient is used in CE calculations.

7. Equations

Calibration Error. Calculate CE using Equation 1.
[GRAPHIC] [TIFF OMITTED] TR30SE99.012

Where:

d= Mean difference between CEMS response and the known reference
concentration, determined using Equation 2.

[[Page 642]]

[GRAPHIC] [TIFF OMITTED] TR30SE99.013

Where:

di = Individual difference between CEMS response and the
known reference concentration.

8. Reporting

At a minimum, summarize in tabular form the results of the CD,
response time, and CE test, as appropriate. Include all data sheets,
calculations, CEMS data records, and cylinder gas or reference material
certifications.

[GRAPHIC] [TIFF OMITTED] TR30SE99.014

9. References

1. Measurement of Volatile Organic Compounds-Guideline Series. U.S.
Environmental Protection Agency, Research Triangle Park, North Carolina,
27711, EPA-450/2-78-041, June 1978.
2. Traceability Protocol for Establishing True Concentrations of
Gases Used for Calibration and Audits of Continuous Source Emission
Monitors (Protocol No. 1). U.S. Environmental Protection Agency ORD/
EMSL, Research Triangle Park, North Carolina, 27711, June 1978.
3. Gasoline Vapor Emission Laboratory Evaluation-Part 2. U.S.
Environmental Protection Agency, OAQPS, Research Triangle Park, North
Carolina, 27711, EMB Report No. 76-GAS-6, August 1975.

[[Page 643]]

Performance Specification 9--Specifications and Test Procedures for Gas
Chromatographic Continuous Emission Monitoring Systems in Stationary
Sources

1.0 Scope and Application

1.1 Applicability. These requirements apply to continuous emission
monitoring systems (CEMSs) that use gas chromatography (GC) to measure
gaseous organic compound emissions. The requirements include procedures
intended to evaluate the acceptability of the CEMS at the time of its
installation and whenever specified in regulations or permits. Quality
assurance procedures for calibrating, maintaining, and operating the
CEMS properly at all times are also given in this procedure.

2.0 Summary of Performance Specification

2.1 Calibration precision, calibration error, and performance audit
tests are conducted to determine conformance of the CEMS with these
specifications. Daily calibration and maintenance requirements are also
specified.

3.0 Definitions

3.1 Gas Chromatograph (GC). That portion of the system that
separates and detects organic analytes and generates an output
proportional to the gas concentration. The GC must be temperature
controlled.

Note: The term temperature controlled refers to the ability to
maintain a certain temperature around the column. Temperature-
programmable GC is not required for this performance specification, as
long as all other requirements for precision, linearity and accuracy
listed in this performance specification are met. It should be noted
that temperature programming a GC will speed up peak elution, thus
allowing increased sampling frequency.

3.1.1 Column. Analytical column capable of separating the analytes
of interest.
3.1.2 Detector. A detection system capable of detecting and
quantifying all analytes of interest.
3.1.3 Integrator. That portion of the system that quantifies the
area under a particular sample peak generated by the GC.
3.1.4 Data Recorder. A strip chart recorder, computer, or digital
recorder capable of recording all readings within the instrument's
calibration range.
3.2 Calibration Precision. The error between triplicate injections
of each calibration standard.

4.0 Interferences [Reserved]

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification does not purport to address all of the safety problems
associated with these procedures. It is the responsibility of the user
to establish appropriate safety problems associated with these
procedures. It is the responsibility of the user to establish
appropriate safety and health practices and determine the application
regulatory limitations prior to performing these procedures. The CEMS
user's manual and materials recommended by the reference method should
be consulted for specific precautions to be taken.

6.0 Equipment and Supplies

6.1 Presurvey Sample Analysis and GC Selection. Determine the
pollutants to be monitored from the applicable regulation or permit and
determine the approximate concentration of each pollutant (this
information can be based on past compliance test results). Select an
appropriate GC configuration to measure the organic compounds. The GC
components should include a heated sample injection loop (or other
sample introduction systems), separatory column, temperature-controlled
oven, and detector. If the source chooses dual column and/or dual
detector configurations, each column/detector is considered a separate
instrument for the purpose of this performance specification and thus
the procedures in this performance specification shall be carried out on
each system. If this method is applied in highly explosive areas,
caution should be exercised in selecting the equipment and method of
installation.
6.2 Sampling System. The sampling system shall be heat traced and
maintained at a minimum of 120 deg.C with no cold spots. All system
components shall be heated, including the probe, calibration valve,
sample lines, sampling loop (or sample introduction system), GC oven,
and the detector block (when appropriate for the type of detector being
utilized, e.g., flame ionization detector).

7.0 Reagents and Standards

7.1 Calibration Gases. Obtain three concentrations of calibration
gases certified by the manufacturer to be accurate to within 2 percent
of the value on the label. A gas dilution system may be used to prepare
the calibration gases from a high concentration certified standard if
the gas dilution system meets the requirements specified in Test Method
205, 40 CFR Part 51, Appendix M. The performance test specified in Test
Method 205 shall be repeated quarterly, and the results of the Method
205 test shall be included in the report. The calibration gas
concentration of each target analyte shall be as follows (measured
concentration is based on the

[[Page 644]]

presurvey concentration determined in Section 6.1).

Note: If the low level calibration gas concentration falls at or
below the limit of detection for the instrument for any target
pollutant, a calibration gas with a concentration at 4 to 5 times the
limit of detection for the instrument may be substituted for the low-
level calibration gas listed in Section 7.1.1.
7.1.1 Low-level. 40-60 percent of measured concentration.
7.1.2 Mid-level. 90-110 percent of measured concentration.
7.1.3 High-level. 140-160 percent of measured concentration, or
select highest expected concentration.
7.2 Performance Audit Gas. A certified EPA audit gas shall be used,
when possible. A gas mixture containing all the target compounds within
the calibration range and certified by EPA's Traceability Protocol for
Assay and Certification of Gaseous Calibration Standards may be used
when EPA performance audit materials are not available. The instrument
relative error shall be 10 percent of the certified value of
the audit gas.

8.0 Sample Collection, Preservation, Storage, and Transport

8.1 Installation and Measurement Location Specifications. Install
the CEMs in a location where the measurements are representative of the
source emissions. Consider other factors, such as ease of access for
calibration and maintenance purposes. The location should not be close
to air in-leakages. The sampling location should be at least two
equivalent duct diameters downstream from the nearest control device,
point of pollutant generation, or other point at which a change in the
pollutant concentration or emission rate occurs. The location should be
at least 0.5 diameter upstream from the exhaust or control device. To
calculate equivalent duct diameter, see Section 12.2 of Method 1 (40 CFR
Part 60, Appendix A). Sampling locations not conforming to the
requirements in this section may be used if necessary upon approval of
the Administrator.
8.2 Pretest Preparation Period. Using the procedures described in
Method 18
(40 CFR Part 60, Appendix A), perform initial tests to determine GC
conditions that provide good resolution and minimum analysis time for
compounds of interest. Resolution interferences that may occur can be
eliminated by appropriate GC column and detector choice or by shifting
the retention times through changes in the column flow rate and the use
of temperature programming.
8.3 7-Day Calibration Error (CE) Test Period. At the beginning of
each 24-hour period, set the initial instrument setpoints by conducting
a multi-point calibration for each compound. The multi-point calibration
shall meet the requirements in Section 13.3. Throughout the 24-hour
period, sample and analyze the stack gas at the sampling intervals
prescribed in the regulation or permit. At the end of the 24 hour
period, inject the three calibration gases for each compound in
triplicate and determine the average instrument response. Determine the
CE for each pollutant at each level using the equation in Section 9-2.
Each CE shall be 10 percent. Repeat this procedure six
more times for a total of 7 consecutive days.
8.4 Performance Audit Test Periods. Conduct the performance audit
once during the initial 7-day CE test and quarterly thereafter. Sample
and analyze the EPA audit gas(es) (or the gas mixture prepared by EPA's
traceability protocol if an EPA audit gas is not available) three times.
Calculate the average instrument response. Report the audit results as
part of the reporting requirements in the appropriate regulation or
permit (if using a gas mixture, report the certified cylinder
concentration of each pollutant).
8.5 Reporting. Follow the reporting requirements of the applicable
regulation or permit. If the reporting requirements include the results
of this performance specification, summarize in tabular form the results
of the CE tests. Include all data sheets, calculations, CEMS data
records, performance audit results, and calibration gas concentrations
and certifications.

9.0 Quality Control [Reserved]

10.0 Calibration and Standardization

10.1 Initial Multi-Point Calibration. After initial startup of the
GC, after routine maintenance or repair, or at least once per month,
conduct a multi-point calibration of the GC for each target analyte. The
multi-point calibration for each analyte shall meet the requirements in
Section 13.3.
10.2 Daily Calibration. Once every 24 hours, analyze the mid-level
calibration standard for each analyte in triplicate. Calculate the
average instrument response for each analyte. The average instrument
response shall not vary more than 10 percent from the certified
concentration value of the cylinder for each analyte. If the difference
between the analyzer response and the cylinder concentration for any
target compound is greater than 10 percent, immediately inspect the
instrument making any necessary adjustments, and conduct an initial
multi-point calibration as described in Section 10.1.

[[Page 645]]

11.0 Analytical Procedure. Sample Collection and Analysis Are
Concurrent for This Performance Specification (See Section 8.0)

12.0 Calculations and Data Analysis

12.1 Nomenclature.

Cm = average instrument response, ppm.
Ca = cylinder gas value, ppm.
F = Flow rate of stack gas through sampling system, in Liters/min.
n = Number of measurement points.
r² = Coefficient of determination.
V = Sample system volume, in Liters, which is the volume inside the
sample probe and tubing leading from the stack to the sampling
loop.
x = CEMS response.
y = Actual value of calibration standard.
12.2 Coefficient of Determination. Calculate r² using
linear regression analysis and the average concentrations obtained at
three calibration points as shown in Equation 9-1.
[GRAPHIC] [TIFF OMITTED] TR17OC00.461

12.3 Calibration Error Determination. Determine the percent calibration
error (CE) at each concentration for each pollutant using the following
equation.
[GRAPHIC] [TIFF OMITTED] TR17OC00.462

12.4 Sampling System Time Constant (T).
[GRAPHIC] [TIFF OMITTED] TR17OC00.463

13.0 Method Performance

13.1 Calibration Error (CE). The CEMS must allow the determination
of CE at all three calibration levels. The average CEMS calibration
response must not differ by more than 10 percent of calibration gas
value at each level after each 24-hour period of the initial test.
13.2 Calibration Precision and Linearity. For each triplicate
injection at each concentration level for each target analyte, any one
injection shall not deviate more than 5 percent from the average
concentration measured at that level. The linear regression curve for
each organic compound at all three levels shall have an r²
0.995 (using Equation 9-1).
13.3 Measurement Frequency. The sample to be analyzed shall flow
continuously through the sampling system. The sampling system time
constant shall be 5 minutes or the sampling frequency
specified in the applicable regulation, whichever is less. Use Equation
9-3 to determine T. The analytical system shall be capable of measuring
the effluent stream at the frequency specified in the appropriate
regulation or permit.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 References. [Reserved]

17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]

Performance Specification 15--Performance Specification for Extractive
FTIR Continuous Emissions Monitor Systems in Stationary Sources

1.0 Scope and Application

1.1 Analytes. This performance specification is applicable for
measuring all hazardous air pollutants (HAPs) which absorb in the
infrared region and can be quantified using Fourier Transform Infrared
Spectroscopy (FTIR), as long as the performance criteria of this
performance specification are met. This specification is to be used for
evaluating FTIR continuous emission monitoring systems for measuring
HAPs regulated under Title III of the 1990 Clean Air Act Amendments.
This specification also applies to the use of FTIR CEMs for measuring
other volatile organic or inorganic species.
1.2 Applicability. A source which can demonstrate that the
extractive FTIR system meets the criteria of this performance
specification for each regulated pollutant may use the FTIR system to
continuously monitor for the regulated pollutants.

2.0 Summary of Performance Specification

For compound-specific sampling requirements refer to FTIR sampling
methods (e.g., reference 1). For data reduction procedures

[[Page 646]]

and requirements refer to the EPA FTIR Protocol (reference 2), hereafter
referred to as the ``FTIR Protocol.'' This specification describes
sampling and analytical procedures for quality assurance. The infrared
spectrum of any absorbing compound provides a distinct signature. The
infrared spectrum of a mixture contains the superimposed spectra of each
mixture component. Thus, an FTIR CEM provides the capability to
continuously measure multiple components in a sample using a single
analyzer. The number of compounds that can be speciated in a single
spectrum depends, in practice, on the specific compounds present and the
test conditions.

3.0 Definitions

For a list of definitions related to FTIR spectroscopy refer to
Appendix A of the FTIR Protocol. Unless otherwise specified,
spectroscopic terms, symbols and equations in this performance
specification are taken from the FTIR Protocol or from documents cited
in the Protocol. Additional definitions are given below.
3.1 FTIR Continuous Emission Monitoring System (FTIR CEM).
3.1.1 FTIR System. Instrument to measure spectra in the mid-
infrared spectral region (500 to 4000 cm^-1). It contains an
infrared source, interferometer, sample gas containment cell, infrared
detector, and computer. The interferometer consists of a beam splitter
that divides the beam into two paths, one path a fixed distance and the
other a variable distance. The computer is equipped with software to run
the interferometer and store the raw digitized signal from the detector
(interferogram). The software performs the mathematical conversion (the
Fourier transform) of the interferogram into a spectrum showing the
frequency dependent sample absorbance. All spectral data can be stored
on computer media.
3.1.2 Gas Cell. A gas containment cell that can be evacuated. It
contains the sample as the infrared beam passes from the interferometer,
through the sample, and to the detector. The gas cell may have multi-
pass mirrors depending on the required detection limit(s) for the
application.
3.1.3 Sampling System. Equipment used to extract sample from the
test location and transport the gas to the FTIR analyzer. Sampling
system components include probe, heated line, heated non-reactive pump,
gas distribution manifold and valves, flow measurement devices and any
sample conditioning systems.
3.2 Reference CEM. An FTIR CEM, with sampling system, that can be
used for comparison measurements.
3.3 Infrared Band (also Absorbance Band or Band). Collection of
lines arising from rotational transitions superimposed on a vibrational
transition. An infrared absorbance band is analyzed to determine the
analyte concentration.
3.4 Sample Analysis. Interpreting infrared band shapes,
frequencies, and intensities to obtain sample component concentrations.
This is usually performed by a software routine using a classical least
squares (cls), partial least squares (pls), or K- or P- matrix method.
3.5 (Target) Analyte. A compound whose measurement is required,
usually to some established limit of detection and analytical
uncertainty.
3.6 Interferant. A compound in the sample matrix whose infrared
spectrum overlaps at least part of an analyte spectrum complicating the
analyte measurement. The interferant may not prevent the analyte
measurement, but could increase the analytical uncertainty in the
measured concentration. Reference spectra of interferants are used to
distinguish the interferant bands from the analyte bands. An interferant
for one analyte may not be an interferant for other analytes.
3.7 Reference Spectrum. Infrared spectra of an analyte, or
interferant, prepared under controlled, documented, and reproducible
laboratory conditions (see Section 4.6 of the FTIR Protocol). A suitable
library of reference spectra can be used to measure target analytes in
gas samples.
3.8 Calibration Spectrum. Infrared spectrum of a compound suitable
for characterizing the FTIR instrument configuration (Section 4.5 in the
FTIR Protocol).
3.9 One hundred percent line. A double beam transmittance spectrum
obtained by combining two successive background single beam spectra.
Ideally, this line is equal to 100 percent transmittance (or zero
absorbance) at every point in the spectrum. The zero absorbance line is
used to measure the RMS noise of the system.
3.10 Background Deviation. Any deviation (from 100 percent) in the
one hundred percent line (or from zero absorbance). Deviations greater
than 5 percent in any analytical region are unacceptable.
Such deviations indicate a change in the instrument throughput relative
to the single-beam background.
3.11 Batch Sampling. A gas cell is alternately filled and
evacuated. A Spectrum of each filled cell (one discreet sample) is
collected and saved.
3.12 Continuous Sampling. Sample is continuously flowing through a
gas cell. Spectra of the flowing sample are collected at regular
intervals.
3.13 Continuous Operation. In continuous operation an FTIR CEM
system, without user intervention, samples flue gas, records spectra of
samples, saves the spectra to a disk, analyzes the spectra for the
target analytes, and prints concentrations of target

[[Page 647]]

analytes to a computer file. User intervention is permitted for initial
set-up of sampling system, initial calibrations, and periodic
maintenance.
3.14 Sampling Time. In batch sampling--the time required to fill
the cell with flue gas. In continuous sampling--the time required to
collect the infrared spectrum of the sample gas.
3.15 PPM-Meters. Sample concentration expressed as the
concentration-path length product, ppm (molar) concentration multiplied
by the path length of the FTIR gas cell. Expressing concentration in
these units provides a way to directly compare measurements made using
systems with different optical configurations. Another useful expression
is (ppm-meters)/K, where K is the absolute temperature of the sample in
the gas cell.
3.16 CEM Measurement Time Constant. The Time Constant (TC, minutes
for one cell volume to flow through the cell) determines the minimum
interval for complete removal of an analyte from the FTIR cell. It
depends on the sampling rate (Rs in Lpm), the FTIR cell
volume (Vcell in L) and the chemical and physical properties
of an analyte.
[GRAPHIC] [TIFF OMITTED] TR17OC00.464

For example, if the sample flow rate (through the FTIR cell) is 5 Lpm
and the cell volume is 7 liters, then TC is equal to 1.4 minutes (0.71
cell volumes per minute). This performance specification defines 5 * TC
as the minimum interval between independent samples.
3.17 Independent Measurement. Two independent measurements are
spectra of two independent samples. Two independent samples are
separated by, at least 5 cell volumes. The interval between independent
measurements depends on the cell volume and the sample flow rate
(through the cell). There is no mixing of gas between two independent
samples. Alternatively, estimate the analyte residence time empirically:
(1) Fill cell to ambient pressure with a (known analyte concentration)
gas standard, (2) measure the spectrum of the gas standard, (3) purge
the cell with zero gas at the sampling rate and collect a spectrum every
minute until the analyte standard is no longer detected
spectroscopically. If the measured time corresponds to less than 5 cell
volumes, use 5 * TC as the minimum interval between independent
measurements. If the measured time is greater than 5 * TC, then use this
time as the minimum interval between independent measurements.
3.18 Test Condition. A period of sampling where all process, and
sampling conditions, and emissions remain constant and during which a
single sampling technique and a single analytical program are used. One
Run may include results for more than one test condition. Constant
emissions means that the composition of the emissions remains
approximately stable so that a single analytical program is suitable for
analyzing all of the sample spectra. A greater than two-fold change in
analyte or interferant concentrations or the appearance of additional
compounds in the emissions, may constitute a new test condition and may
require modification of the analytical program.
3.19 Run. A single Run consists of spectra (one spectrum each) of
at least 10 independent samples over a minimum of one hour. The
concentration results from the spectra can be averaged together to give
a run average for each analyte measured in the test run.

4.0 Interferences

Several compounds, including water, carbon monoxide, and carbon
dioxide, are known interferences in the infrared region in which the
FTIR instrument operates. Follow the procedures in the FTIR protocol for
subtracting or otherwise dealing with these and other interferences.

5.0 Safety

The procedures required under this performance specification may
involve hazardous materials, operations, and equipment. This performance
specification may not address all of the safety problems associated with
these procedures. It is the responsibility of the user to establish
appropriate safety and health practices and determine the applicable
regulatory limitations prior to performing these procedures. The CEMS
users manual and materials recommended by this performance specification
should be consulted for specific precautions to be taken.

6.0 Equipment and Supplies

6.1 Installation of sampling equipment should follow requirements
of FTIR test Methods such as references 1 and 3 and the EPA FTIR
Protocol (reference 2). Select test points where the gas stream
composition is representative of the process emissions. If comparing to
a reference method, the probe tips for the FTIR CEM and the RM should be
positioned close together using the same sample port if possible.
6.2 FTIR Specifications. The FTIR CEM must be equipped with
reference spectra bracketing the range of path length-concentrations
(absorbance intensities) to be measured for each analyte. The effective
concentration range of the analyzer can be adjusted by changing the path
length of the gas cell or by diluting the sample. The optical
configuration of the FTIR system must be such that maximum absorbance of
any target analyte is no greater than 1.0 and the

[[Page 648]]

minimum absorbance of any target analyte is at least 10 times the RMSD
noise in the analytical region. For example, if the measured RMSD in an
analytical region is equal to 10^-3, then the peak analyte
absorbance is required to be at least 0.01. Adequate measurement of all
of the target analytes may require changing path lengths during a run,
conducting separate runs for different analytes, diluting the sample, or
using more than one gas cell.
6.3 Data Storage Requirements. The system must have sufficient
capacity to store all data collected in one week of routine sampling.
Data must be stored to a write-protected medium, such as write-once-
read-many (WORM) optical storage medium or to a password protected
remote storage location. A back-up copy of all data can be temporarily
saved to the computer hard drive. The following items must be stored
during testing.
At least one sample interferogram per sampling Run or one
interferogram per hour, whichever is greater. This assumes that no
sampling or analytical conditions have changed during the run.
All sample absorbance spectra (about 12 per hr, 288 per
day).
All background spectra and interferograms (variable, but
about 5 per day).
All CTS spectra and interferograms (at least 2 each 24 hour
period).
Documentation showing a record of resolution, path length,
apodization, sampling time, sampling conditions, and test conditions for
all sample, CTS, calibration, and background spectra.
Using a resolution of 0.5 cm^-1, with analytical range of
3500 cm^-1, assuming about 65 Kbytes per spectrum and 130 Kb
per interferogram, the storage requirement is about 164 Mb for one week
of continuous sampling. Lower spectral resolution requires less storage
capacity. All of the above data must be stored for at least two weeks.
After two weeks, storage requirements include: (1) all analytical
results (calculated concentrations), (2) at least 1 sample spectrum with
corresponding background and sample interferograms for each test
condition, (3) CTS and calibration spectra with at least one
interferogram for CTS and all interferograms for calibrations, (4) a
record of analytical input used to produce results, and (5) all other
documentation. These data must be stored according to the requirements
of the applicable regulation.

7.0 Reagents and Standards [Reserved]

8.0 Sample Collection, Preservation, Storage, and Transport [Reserved]

9.0 Quality Control

These procedures shall be used for periodic quarterly or semiannual
QA/QC checks on the operation of the FTIR CEM. Some procedures test only
the analytical program and are not intended as a test of the sampling
system.
9.1 Audit Sample. This can serve as a check on both the sampling
system and the analytical program.
9.1.1 Sample Requirements. The audit sample can be a mixture or a
single component. It must contain target analyte(s) at approximately the
expected flue gas concentration(s). If possible, each mixture component
concentration should be NIST traceable ( 2 percent
accuracy). If a cylinder mixture standard(s) cannot be obtained, then,
alternatively, a gas phase standard can be generated from a condensed
phase analyte sample. Audit sample contents and concentrations are not
revealed to the FTIR CEM operator until after successful completion of
procedures in 5.3.2.
9.1.2 Test Procedure. An audit sample is obtained from the
Administrator. Spike the audit sample using the analyte spike procedure
in Section 11. The audit sample is measured directly by the FTIR system
(undiluted) and then spiked into the effluent at a known dilution ratio.
Measure a series of spiked and unspiked samples using the same
procedures as those used to analyze the stack gas. Analyze the results
using Sections 12.1 and 12.2. The measured concentration of each analyte
must be within 5 percent of the expected concentration
(plus the uncertainty), i.e., the calculated correction factor must be
within 0.93 and 1.07 for an audit with an analyte uncertainty of
2 percent.
9.2 Audit Spectra. Audit spectra can be used to test the analytical
program of the FTIR CEM, but provide no test of the sampling system.
9.2.1 Definition and Requirements. Audit spectra are absorbance
spectra that; (1) have been well characterized, and (2) contain
absorbance bands of target analyte(s) and potential interferants at
intensities equivalent to what is expected in the source effluent. Audit
spectra are provided by the administrator without identifying
information. Methods of preparing Audit spectra include; (1)
mathematically adding sample spectra or adding reference and interferant
spectra, (2) obtaining sample spectra of mixtures prepared in the
laboratory, or (3) they may be sample spectra collected previously at a

[[Page 649]]

similar source. In the last case it must be demonstrated that the
analytical results are correct and reproducible. A record associated
with each Audit spectrum documents its method of preparation. The
documentation must be sufficient to enable an independent analyst to
reproduce the Audit spectra.
9.2.2 Test Procedure. Audit spectra concentrations are measured
using the FTIR CEM analytical program. Analytical results must be within
5 percent of the certified audit concentration for each
analyte (plus the uncertainty in the audit concentration). If the
condition is not met, demonstrate how the audit spectra are
unrepresentative of the sample spectra. If the audit spectra are
representative, modify the FTIR CEM analytical program until the test
requirement is met. Use the new analytical program in subsequent FTIR
CEM analyses of effluent samples.
9.3 Submit Spectra For Independent Analysis. This procedure tests
only the analytical program and not the FTIR CEM sampling system. The
analyst can submit FTIR CEM spectra for independent analysis by EPA.
Requirements for submission include; (1) three representative absorbance
spectra (and stored interferograms) for each test period to be reviewed,
(2) corresponding CTS spectra, (3) corresponding background spectra and
interferograms, (4) spectra of associated spiked samples if applicable,
and (5) analytical results for these sample spectra. The analyst will
also submit documentation of process times and conditions, sampling
conditions associated with each spectrum, file names and sampling times,
method of analysis and reference spectra used, optical configuration of
FTIR CEM including cell path length and temperature, spectral resolution
and apodization used for every spectrum. Independent analysis can also
be performed on site in conjunction with the FTIR CEM sampling and
analysis. Sample spectra are stored on the independent analytical system
as they are collected by the FTIR CEM system. The FTIR CEM and the
independent analyses are then performed separately. The two analyses
will agree to within 120 percent for each analyte using the
procedure in Section 12.3. This assumes both analytical routines have
properly accounted for differences in optical path length, resolution,
and temperature between the sample spectra and the reference spectra.

10.0 Calibration and Standardization

10.1 Calibration Transfer Standards. For CTS requirements see
Section 4.5 of the FTIR Protocol. A well characterized absorbance band
in the CTS gas is used to measure the path length and line resolution of
the instrument. The CTS measurements made at the beginning of every 24
hour period must agree to within 5 percent after correction
for differences in pressure.
Verify that the frequency response of the instrument and CTS
absorbance intensity are correct by comparing to other CTS spectra or by
referring to the literature.
10.2 Analyte Calibration. If EPA library reference spectra are not
available, use calibration standards to prepare reference spectra
according to Section 6 of the FTIR Protocol. A suitable set of analyte
reference data includes spectra of at least 2 independent samples at
each of at least 2 different concentrations. The concentrations bracket
a range that includes the expected analyte absorbance intensities. The
linear fit of the reference analyte band areas must have a fractional
calibration uncertainty (FCU in Appendix F of the FTIR Protocol) of no
greater than 10 percent. For requirements of analyte standards refer to
Section 4.6 of the FTIR Protocol.
10.3 System Calibration. The calibration standard is introduced at
a point on the sampling probe. The sampling system is purged with the
calibration standard to verify that the absorbance measured in this way
is equal to the absorbance in the analyte calibration. Note that the
system calibration gives no indication of the ability of the sampling
system to transport the target analyte(s) under the test conditions.
10.4 Analyte Spike. The target analyte(s) is spiked at the outlet
of the sampling probe, upstream of the particulate filter, and combined
with effluent at a ratio of about 1 part spike to 9 parts effluent. The
measured absorbance of the spike is compared to the expected absorbance
of the spike plus the analyte concentration already in the effluent.
This measures sampling system bias, if any, as distinguished from
analyzer bias. It is important that spiked sample pass through all of
the sampling system components before analysis.
10.5 Signal-to-Noise Ratio (S/N). The measure of S/N in this
performance specification is the root-mean-square (RMS) noise level as
given in Appendix C of the FTIR Protocol. The RMS noise level of a
contiguous segment of a spectrum is defined as the RMS difference (RMSD)
between the n contiguous absorbance values (Ai) which form
the segment and the mean value (AM) of that segment.
[GRAPHIC] [TIFF OMITTED] TR17OC00.465

A decrease in the S/N may indicate a loss in optical throughput, or
detector or interferometer malfunction.
10.6 Background Deviation. The 100 percent baseline must be between
95 and 105 percent transmittance (absorbance of 0.02 to -0.02) in every
analytical region. When

[[Page 650]]

background deviation exceeds this range, a new background spectrum must
be collected using nitrogen or other zero gas.
10.7 Detector Linearity. Measure the background and CTS at three
instrument aperture settings; one at the aperture setting to be used in
the testing, and one each at settings one half and twice the test
aperture setting. Compare the three CTS spectra. CTS band areas should
agree to within the uncertainty of the cylinder standard. If test
aperture is the maximum aperture, collect CTS spectrum at maximum
aperture, then close the aperture to reduce the IR through-put by half.
Collect a second background and CTS at the smaller aperture setting and
compare the spectra as above. Instead of changing the aperture neutral
density filters can be used to attenuate the infrared beam. Set up the
FTIR system as it will be used in the test measurements. Collect a CTS
spectrum. Use a neutral density filter to attenuate the infrared beam
(either immediately after the source or the interferometer) to
approximately \1/2\ its original intensity. Collect a second CTS
spectrum. Use another filter to attenuate the infrared beam to
approximately \1/4\ its original intensity. Collect a third background
and CTS spectrum. Compare the CTS spectra as above. Another check on
linearity is to observe the single beam background in frequency regions
where the optical configuration is known to have a zero response. Verify
that the detector response is ``flat'' and equal to zero in these
regions. If detector response is not linear, decrease aperture, or
attenuate the infrared beam. Repeat the linearity check until system
passes the requirement.

11.0 Analytical Procedure

11.1 Initial Certification. First, perform the evaluation
procedures in Section 6.0 of the FTIR Protocol. The performance of an
FTIR CEM can be certified upon installation using EPA Method 301 type
validation (40 CFR, Part 63, Appendix A), or by comparison to a
reference Method if one exists for the target analyte(s). Details of
each procedure are given below. Validation testing is used for initial
certification upon installation of a new system. Subsequent performance
checks can be performed with more limited analyte spiking. Performance
of the analytical program is checked initially, and periodically as
required by EPA, by analyzing audit spectra or audit gases.
11.1.1 Validation. Use EPA Method 301 type sampling (reference 4,
Section 5.3 of Method 301) to validate the FTIR CEM for measuring the
target analytes. The analyte spike procedure is as follows: (1) a known
concentration of analyte is mixed with a known concentration of a non-
reactive tracer gas, (2) the undiluted spike gas is sent directly to the
FTIR cell and a spectrum of this sample is collected, (3) pre-heat the
spiked gas to at least the sample line temperature, (4) introduce spike
gas at the back of the sample probe upstream of the particulate filter,
(5) spiked effluent is carried through all sampling components
downstream of the probe, (6) spike at a ratio of roughly 1 part spike to
9 parts flue gas (or more dilute), (7) the spike-to-flue gas ratio is
estimated by comparing the spike flow to the total sample flow, and (8)
the spike ratio is verified by comparing the tracer concentration in
spiked flue gas to the tracer concentration in undiluted spike gas. The
analyte flue gas concentration is unimportant as long as the spiked
component can be measured and the sample matrix (including
interferences) is similar to its composition under test conditions.
Validation can be performed using a single FTIR CEM analyzing sample
spectra collected sequentially. Since flue gas analyte (unspiked)
concentrations can vary, it is recommended that two separate sampling
lines (and pumps) are used; one line to carry unspiked flue gas and the
other line to carry spiked flue gas. Even with two sampling lines the
variation in unspiked concentration may be fast compared to the interval
between consecutive measurements. Alternatively, two FTIR CEMs can be
operated side-by-side, one measuring spiked sample, the other unspiked
sample. In this arrangement spiked and unspiked measurements can be
synchronized to minimize the affect of temporal variation in the
unspiked analyte concentration. In either sampling arrangement, the
interval between measured concentrations used in the statistical
analysis should be, at least, 5 cell volumes (5 * TC in equation 1). A
validation run consists of, at least, 24 independent analytical results,
12 spiked and 12 unspiked samples. See Section 3.17 for definition of an
``independent'' analytical result. The results are analyzed using
Sections 12.1 and 12.2 to determine if the measurements passed the
validation requirements. Several analytes can be spiked and measured in
the same sampling run, but a separate statistical analysis is performed
for each analyte. In lieu of 24 independent measurements, averaged
results can be used in the statistical analysis. In this procedure, a
series of consecutive spiked measurements are combined over a sampling
period to give a single average result. The related unspiked
measurements are averaged in the same way. The minimum 12 spiked and 12
unspiked result averages are obtained by averaging measurements over
subsequent sampling periods of equal duration. The averaged results are
grouped together and statistically analyzed using Section 12.2.
11.1.1.1 Validation with a Single Analyzer and Sampling Line. If
one sampling line is used, connect the sampling system components and
purge the entire sampling system

[[Page 651]]

and cell with at least 10 cell volumes of sample gas. Begin sampling by
collecting spectra of 2 independent unspiked samples. Introduce the
spike gas into the back of the probe, upstream of the particulate
filter. Allow 10 cell volumes of spiked flue gas to purge the cell and
sampling system. Collect spectra of 2 independent spiked samples. Turn
off the spike flow and allow 10 cell volumes of unspiked flue gas to
purge the FTIR cell and sampling system. Repeat this procedure 6 times
until the 24 samples are collected. Spiked and unspiked samples can also
be measured in groups of 4 instead of in pairs. Analyze the results
using Sections 12.1 and 12.2. If the statistical analysis passes the
validation criteria, then the validation is completed. If the results do
not pass the validation, the cause may be that temporal variations in
the analyte sample gas concentration are fast relative to the interval
between measurements. The difficulty may be avoided by: (1) Averaging
the measurements over long sampling periods and using the averaged
results in the statistical analysis, (2) modifying the sampling system
to reduce TC by, for example, using a smaller volume cell or increasing
the sample flow rate, (3) using two sample lines (4) use two analyzers
to perform synchronized measurements. This performance specification
permits modifications in the sampling system to minimize TC if the other
requirements of the validation sampling procedure are met.
11.1.1.2 Validation With a Single Analyzer and Two Sampling Lines.
An alternative sampling procedure uses two separate sample lines, one
carrying spiked flue gas, the other carrying unspiked gas. A valve in
the gas distribution manifold allows the operator to choose either
sample. A short heated line connects the FTIR cell to the 3-way valve in
the manifold. Both sampling lines are continuously purged. Each sample
line has a rotameter and a bypass vent line after the rotameter,
immediately upstream of the valve, so that the spike and unspiked sample
flows can each be continuously monitored. Begin sampling by collecting
spectra of 2 independent unspiked samples. Turn the sampling valve to
close off the unspiked gas flow and allow the spiked flue gas to enter
the FTIR cell. Isolate and evacuate the cell and fill with the spiked
sample to ambient pressure. (While the evacuated cell is filling,
prevent air leaks into the cell by making sure that the spike sample
rotameter always indicates that a portion of the flow is directed out
the by-pass vent.) Open the cell outlet valve to allow spiked sample to
continuously flow through the cell. Measure spectra of 2 independent
spiked samples. Repeat this procedure until at least 24 samples are
collected.
11.1.1.3 Synchronized Measurements With Two Analyzers. Use two FTIR
analyzers, each with its own cell, to perform synchronized spiked and
unspiked measurements. If possible, use a similar optical configuration
for both systems. The optical configurations are compared by measuring
the same CTS gas with both analyzers. Each FTIR system uses its own
sampling system including a separate sampling probe and sampling line. A
common gas distribution manifold can be used if the samples are never
mixed. One sampling system and analyzer measures spiked effluent. The
other sampling system and analyzer measures unspiked flue gas. The two
systems are synchronized so that each measures spectra at approximately
the same times. The sample flow rates are also synchronized so that both
sampling rates are approximately the same (TC1 ~
TC2 in equation 1). Start both systems at the same time.
Collect spectra of at least 12 independent samples with each (spiked and
unspiked) system to obtain the minimum 24 measurements. Analyze the
analytical results using Sections 12.1 and 12.2. Run averages can be
used in the statistical analysis instead of individual measurements.
11.1.1.4 Compare to a Reference Method (RM). Obtain EPA approval
that the method qualifies as an RM for the analyte(s) and the source to
be tested. Follow the published procedures for the RM in preparing and
setting up equipment and sampling system, performing measurements, and
reporting results. Since FTIR CEMS have multicomponent capability, it is
possible to perform more than one RM simultaneously, one for each target
analyte. Conduct at least 9 runs where the FTIR CEM and the RM are
sampling simultaneously. Each Run is at least 30 minutes long and
consists of spectra of at least 5 independent FTIR CEM samples and the
corresponding RM measurements. If more than 9 runs are conducted, the
analyst may eliminate up to 3 runs from the analysis if at least 9 runs
are used.
11.1.1.4.1 RMs Using Integrated Sampling. Perform the RM and FTIR
CEM sampling simultaneously. The FTIR CEM can measure spectra as
frequently as the analyst chooses (and should obtain measurements as
frequently as possible) provided that the measurements include spectra
of at least 5 independent measurements every 30 minutes. Concentration
results from all of the FTIR CEM spectra within a run may be averaged
for use in the statistical comparison even if all of the measurements
are not independent. When averaging the FTIR CEM concentrations within a
run, it is permitted to exclude some measurements from the average
provided the minimum of 5 independent measurements every 30 minutes are
included: The Run average of the FTIR CEM measurements depends on both
the sample flow rate and the measurement frequency (MF). The run average
of the RM using the integrated sampling method depends primarily on its
sampling rate. If the target analyte concentration

[[Page 652]]

fluctuates significantly, the contribution to the run average of a large
fluctuation depends on the sampling rate and measurement frequency, and
on the duration and magnitude of the fluctuation. It is, therefore,
important to carefully select the sampling rate for both the FTIR CEM
and the RM and the measurement frequency for the FTIR CEM. The minimum
of 9 run averages can be compared according to the relative accuracy
test procedure in Performance Specification 2 for SO2 and
NOx CEMs (40 CFR, Part 60, App. B).
11.1.1.4.2 RMs Using a Grab Sampling Technique. Synchronize the RM
and FTIR CEM measurements as closely as possible. For a grab sampling RM
record the volume collected and the exact sampling period for each
sample. Synchronize the FTIR CEM so that the FTIR measures a spectrum of
a similar cell volume at the same time as the RM grab sample was
collected. Measure at least 5 independent samples with both the FTIR CEM
and the RM for each of the minimum 9 Runs. Compare the Run concentration
averages by using the relative accuracy analysis procedure in 40 CFR,
Part 60, App. B.
11.1.1.4.3 Continuous Emission Monitors (CEMs) as RMs. If the RM is
a CEM, synchronize the sampling flow rates of the RM and the FTIR CEM.
Each run is at least 1-hour long and consists of at least 10 FTIR CEM
measurements and the corresponding 10 RM measurements (or averages). For
the statistical comparison use the relative accuracy analysis procedure
in 40 CFR, Part 60, App. B. If the RM time constant is \1/2\ the FTIR
CEM time constant, brief fluctuations in analyte concentrations which
are not adequately measured with the slower FTIR CEM time constant can
be excluded from the run average along with the corresponding RM
measurements. However, the FTIR CEM run average must still include at
least 10 measurements over a 1-hr period.

12.0 Calculations and Data Analysis

12.1 Spike Dilution Ratio, Expected Concentration. The Method 301
bias is calculated as follows.
[GRAPHIC] [TIFF OMITTED] TR17OC00.466

Where:

B = Bias at the spike level
Sm = Mean of the observed spiked sample concentrations
Mm = Mean of the observed unspiked sample concentrations
CS = Expected value of the spiked concentration.

The CS is determined by comparing the SF6 tracer
concentration in undiluted spike gas to the SF6 tracer
concentrations in the spiked samples;
[GRAPHIC] [TIFF OMITTED] TR17OC00.467

The expected concentration (CS) is the measured concentration of the
analyte in undiluted spike gas divided by the dilution factor
[GRAPHIC] [TIFF OMITTED] TR17OC00.468

Where:

[anal]dir=The analyte concentration in undiluted spike gas
measured directly by filling the FTIR cell with the spike gas.

If the bias is statistically significant (Section 12.2), Method 301
requires that a correction factor, CF, be multiplied by the analytical
results, and that 0.7 CF 1.3.
[GRAPHIC] [TIFF OMITTED] TR17OC00.469

12.2 Statistical Analysis of Validation Measurements. Arrange the
independent measurements (or measurement averages) as in Table 1. More
than 12 pairs of measurements can be analyzed. The statistical analysis
follows EPA Method 301, Section 6.3. Section 12.1 of this performance
specification shows the calculations for the bias, expected spike
concentration, and correction factor. This Section shows the
determination of the statistical significance of the bias. Determine the
statistical significance of the bias at the 95 percent confidence level
by calculating the t-value for the set of measurements. First, calculate
the differences, di, for each pair of spiked and each pair of
unspiked measurements. Then calculate the standard deviation of the
spiked pairs of measurements.

[[Page 653]]

[GRAPHIC] [TIFF OMITTED] TR17OC00.470

Where:

di = The differences between pairs of spiked measurements.
SDs = The standard deviation in the di values.
n = The number of spiked pairs, 2n=12 for the minimum of 12 spiked and
12 unspiked measurements.

Calculate the relative standard deviation, RSD, using SDs and
the mean of the spiked concentrations, Sm. The RSD must be
50%.
[GRAPHIC] [TIFF OMITTED] TR17OC00.471

Repeat the calculations in equations 7 and 8 to determine SDu
and RSD, respectively, for the unspiked samples. Calculate the standard
deviation of the mean using SDs and SDu from
equation 7.
[GRAPHIC] [TIFF OMITTED] TR17OC00.472

The t-statistic is calculated as follows to test the bias for
statistical significance;
[GRAPHIC] [TIFF OMITTED] TR17OC00.473

where the bias, B, and the correction factor, CF, are given in Section
12.1. For 11 degrees of freedom, and a one-tailed distribution, Method
301 requires that t 2.201. If the t-statistic indicates the
bias is statistically significant, then analytical measurements must be
multiplied by the correction factor. There is no limitation on the
number of measurements, but there must be at least 12 independent spiked
and 12 independent unspiked measurements. Refer to the t-distribution
(Table 2) at the 95 percent confidence level and appropriate degrees of
freedom for the critical t-value.

16.0 References

1. Method 318, 40 CFR, Part 63, Appendix A (Draft), ``Measurement of
Gaseous Formaldehyde, Phenol and Methanol Emissions by FTIR
Spectroscopy,'' EPA Contract No. 68D20163, Work Assignment 2-18,
February, 1995.
2. ``EPA Protocol for the Use of Extractive Fourier Transform
Infrared (FTIR) Spectrometry in Analyses of Gaseous Emissions from
Stationary Industrial Sources,'' February, 1995.
3. ``Measurement of Gaseous Organic and Inorganic Emissions by
Extractive FTIR Spectroscopy,'' EPA Contract No. 68-D2-0165, Work
Assignment 3-08.
4. ``Method 301--Field Validation of Pollutant Measurement Methods
from Various Waste Media,'' 40 CFR 63, App A.

17.0 Tables, Diagrams, Flowcharts, and Validation Data

[[Page 654]]

Table 1.--Arrangement of Validation Measurements for Statistical Analysis
----------------------------------------------------------------------------------------------------------------
Measurement (or average) Time Spiked (ppm) di spiked Unspiked (ppm) di unspiked
----------------------------------------------------------------------------------------------------------------
1........................... S1 U1
-------------------------------------------------------------- -----------------
2........................... S2 S2-S1 U2 U2-U1
----------------------------------------------------------------------------------------------------------------
3........................... S3 U3
-------------------------------------------------------------- -----------------
4........................... S4 S4-S3 U4 U4-U3
----------------------------------------------------------------------------------------------------------------
5........................... S5 U5
-------------------------------------------------------------- -----------------
6........................... S6 S6-S5 U6 U6-U5
----------------------------------------------------------------------------------------------------------------
7........................... S7 U7
-------------------------------------------------------------- -----------------
8........................... S8 S8-S7 U8 U8-U7
----------------------------------------------------------------------------------------------------------------
9........................... S9 U9
-------------------------------------------------------------- -----------------
10.......................... S10 S10-S9 U10 U10-U9
----------------------------------------------------------------------------------------------------------------
11.......................... S11 U11
-------------------------------------------------------------- -----------------
12.......................... S12 S12-S11 U12 U12-U11
----------------------------------------------------------------------------------------------------------------
Average ->.................. Sm Mm
----------------------------------------------------------------------------------------------------------------

[[Page 655]]

Table 2.--t=Values
--------------------------------------------------------------------------------------------------------------------------------------------------------
n-1^a t-value n-1^a t-value n-1^a t-value n-1^a t-value
--------------------------------------------------------------------------------------------------------------------------------------------------------
11 2.201 17 2.110 23 2.069 29 2.045
12 2.179 18 2.101 24 2.064 30 2.042
13 2.160 19 2.093 25 2.060 40 2.021
14 2.145 20 2.086 26 2.056 60 2.000
15 2.131 21 2.080 27 2.052 120 1.980
16 2.120 22 2.074 28 2.048 8 1.960
--------------------------------------------------------------------------------------------------------------------------------------------------------
^(a)n is the number of independent pairs of measurements (a pair consists of one spiked and its corresponding unspiked measurement). Either discreet
(independent) measurements in a single run, or run averages can be used.

[[Page 656]]

[48 FR 13327, Mar. 30, 1983 and 48 FR 23611, May 25, 1983, as amended at
48 FR 32986, July 20, 1983; 51 FR 31701, Aug. 5, 1985; 52 FR 17556, May
11, 1987; 52 FR 30675, Aug. 18, 1987; 52 FR 34650, Sept. 14, 1987; 53 FR
7515, Mar. 9, 1988; 53 FR 41335, Oct. 21, 1988; 55 FR 18876, May 7,
1990; 55 FR 40178, Oct. 2, 1990; 55 FR 47474, Nov. 14, 1990; 56 FR 5526,
Feb. 11, 1991; 59 FR 64593, Dec. 15, 1994; 64 FR 53032, Sept. 30, 1999;
65 FR 62130, 62144, Oct. 17, 2000; 65 FR 48920, Aug. 10, 2000]

Appendix C to Part 60--Determination of Emission Rate Change

1. Introduction.

1.1 The following method shall be used to determine whether a
physical or operational change to an existing facility resulted in an
increase in the emission rate to the atmosphere. The method used is the
Student's t test, commonly used to make inferences from small samples.

2. Data.

2.1 Each emission test shall consist of n runs (usually three) which
produce n emission rates. Thus two sets of emission rates are generated,
one before and one after the change, the two sets being of equal size.
2.2 When using manual emission tests, except as provided in
Sec. 60.8(b) of this part, the reference methods of appendix A to this
part shall be used in accordance with the procedures specified in the
applicable subpart both before and after the change to obtain the data.
2.3 When using continuous monitors, the facility shall be operated
as if a manual emission test were being performed. Valid data using the
averaging time which would be required if a manual emission test were
being conducted shall be used.

3. Procedure.

3.1 Subscripts a and b denote prechange and postchange respectively.
3.2 Calculate the arithmetic mean emission rate, E, for each set of
data using Equation 1.
[GRAPHIC] [TIFF OMITTED] TC01JN92.292

Where:
Ei=Emission rate for the i th run.
n=number of runs.

3.3 Calculate the sample variance, S², for each set of
data using Equation 2.
[GRAPHIC] [TIFF OMITTED] TC01JN92.293

3.4 Calculate the pooled estimate, Sp, using Equation 3.
[GRAPHIC] [TIFF OMITTED] TC01JN92.294

3.5 Calculate the test statistic, t, using Equation 4.
[GRAPHIC] [TIFF OMITTED] TC01JN92.295

4. Results.

4.1 If Eb>,Ea and t^>t', where t' is
the critical value of t obtained from Table 1, then with 95% confidence
the difference between Eb and Ea is significant,
and an increase in emission rate to the atmosphere has occurred.

Table 1
------------------------------------------------------------------------
t' (95
percent
Degrees of freedom (na=nb-2) confidence
level)
------------------------------------------------------------------------
2.......................................................... 2.920
3.......................................................... 2.353
4.......................................................... 2.132
5.......................................................... 2.015
6.......................................................... 1.943
7.......................................................... 1.895
8.......................................................... 1.860
------------------------------------------------------------------------

For greater than 8 degrees of freedom, see any standard statistical
handbook or text.
5.1 Assume the two performance tests produced the following set of
data:

------------------------------------------------------------------------
Test a Test b
------------------------------------------------------------------------
Run 1. 100.................................................. 115
Run 2. 95................................................... 120
Run 3. 110.................................................. 125
------------------------------------------------------------------------

5.2 Using Equation 1--
Ea=100+95+110/3=102
Eb=115+120+125/3=120
5.3 Using Equation 2--
Sa2=(100-102)²+(95-102)²+(110-102)²
/3-1=58.5
Sb2=(115-120)²+(120-120)²+(125-120)²
/3-1=25
5.4 Using Equation 3--
Sp=[(3-1)(58.5)+(3+1)(25)/3+3-2] \1/2\=6.46
5.5 Using Equation 4--
[GRAPHIC] [TIFF OMITTED] TC01JN92.296

5.6 Since (n\1\+n\2\-2)=4, t'=2.132 (from Table 1). Thus since
t^>t' the difference in the values of Ea and
Eb is significant, and there has been an increase in emission
rate to the atmosphere.

6. Continuous Monitoring Data.

6.1 Hourly averages from continuous monitoring devices, where
available, should be

[[Page 657]]

used as data points and the above procedure followed.

[40 FR 58420, Dec. 16, 1975]

Appendix D to Part 60--Required Emission Inventory Information

(a) Completed NEDS point source form(s) for the entire plant
containing the designated facility, including information on the
applicable criteria pollutants. If data concerning the plant are already
in NEDS, only that information must be submitted which is necessary to
update the existing NEDS record for that plant. Plant and point
identification codes for NEDS records shall correspond to those
previously assigned in NEDS; for plants not in NEDS, these codes shall
be obtained from the appropriate Regional Office.
(b) Accompanying the basic NEDS information shall be the following
information on each designated facility:
(1) The state and county identification codes, as well as the
complete plant and point identification codes of the designated facility
in NEDS. (The codes are needed to match these data with the NEDS data.)
(2) A description of the designated facility including, where
appropriate:
(i) Process name.
(ii) Description and quantity of each product (maximum per hour and
average per year).
(iii) Description and quantity of raw materials handled for each
product (maximum per hour and average per year).
(iv) Types of fuels burned, quantities and characteristics (maximum
and average quantities per hour, average per year).
(v) Description and quantity of solid wastes generated (per year)
and method of disposal.
(3) A description of the air pollution control equipment in use or
proposed to control the designated pollutant, including:
(i) Verbal description of equipment.
(ii) Optimum control efficiency, in percent. This shall be a
combined efficiency when more than one device operates in series. The
method of control efficiency determination shall be indicated (e.g.,
design efficiency, measured efficiency, estimated efficiency).
(iii) Annual average control efficiency, in percent, taking into
account control equipment down time. This shall be a combined efficiency
when more than one device operates in series.
(4) An estimate of the designated pollutant emissions from the
designated facility (maximum per hour and average per year). The method
of emission determination shall also be specified (e.g., stack test,
material balance, emission factor).

[40 FR 53349, Nov. 17, 1975]

Appendix E to Part 60 [Reserved]

Appendix F to Part 60--Quality Assurance Procedures

Procedure 1. Quality Assurance Requirements for Gas Continuous Emission
Monitoring Systems Used for Compliance Determination

1. Applicability and Principle
1.1 Applicability. Procedure 1 is used to evaluate the
effectiveness of quality control (QC) and quality assurance (QA)
procedures and the quality of data produced by any continuous emission
monitoring system (CEMS) that is used for determining compliance with
the emission standards on a continuous basis as specified in the
applicable regulation. The CEMS may include pollutant (e.g.,
S02 and N0x) and diluent (e.g., 02 or
C02) monitors.
This procedure specifies the minimum QA requirements necessary for
the control and assessment of the quality of CEMS data submitted to the
Environmental Protection Agency (EPA). Source owners and operators
responsible for one or more CEMS's used for compliance monitoring must
meet these minimum requirements and are encouraged to develop and
implement a more extensive QA program or to continue such programs where
they already exist.
Data collected as a result of QA and QC measures required in this
procedure are to be submitted to the Agency. These data are to be used
by both the Agency and the CEMS operator in assessing the effectiveness
of the CEMS QC and QA procedures in the maintenance of acceptable CEMS
operation and valid emission data.
Appendix F, Procedure 1 is applicable December 4, 1987. The first
CEMS accuracy assessment shall be a relative accuracy test audit (RATA)
(see section 5) and shall be completed by March 4, 1988 or the date of
the initial performance test required by the applicable regulation,
whichever is later.
1.2 Principle. The QA procedures consist of two distinct and
equally important functions. One function is the assessment of the
quality of the CEMS data by estimating accuracy. The other function is
the control and improvement of the quality of the CEMS data by
implementing QC policies and corrective actions. These two functions
form a control loop: When the assessment function indicates that the
data quality is inadequate, the control effort must be increased until
the data quality is acceptable. In order to provide uniformity in the
assessment and reporting of data quality, this procedure explicitly
specifies the assessment methods for response drift and accuracy. The
methods are based on procedures included in the applicable performance
specifications (PS's) in appendix B of 40 CFR part 60. Procedure 1 also
requires the analysis of the EPA audit

[[Page 658]]

samples concurrent with certain reference method (RM) analyses as
specified in the applicable RM's.
Because the control and corrective action function encompasses a
variety of policies, specifications, standards, and corrective measures,
this procedure treats QC requirements in general terms to allow each
source owner or operator to develop a QC system that is most effective
and efficient for the circumstances.

2. Definitions
2.1 Continuous Emission Monitoring System. The total equipment
required for the determination of a gas concentration or emission rate.
2.2 Diluent Gas. A major gaseous constituent in a gaseous pollutant
mixture. For combustion sources, CO2 and O2 are
the major gaseous constituents of interest.
2.3 Span Value. The upper limit of a gas concentration measurement
range that is specified for affected source categories in the applicable
subpart of the regulation.
2.4 Zero, Low-Level, and High-Level Values. The CEMS response values
related to the source specific span value. Determination of zero, low-
level, and high-level values is defined in the appropriate PS in
appendix B of this part.
2.5 Calibration Drift (CD). The difference in the CEMS output
reading from a reference value after a period of operation during which
no unscheduled maintenance, repair or adjustment took place. The
reference value may be supplied by a cylinder gas, gas cell, or optical
filter and need not be certified.
2.6 Relative Accuracy (RA). The absolute mean difference between the
gas concentration or emission rate determined by the CEMS and the value
determined by the RM's plus the 2.5 percent error confidence coefficient
of a series of tests divided by the mean of the RM tests or the
applicable emission limit.

3. QC Requirements
Each source owner or operator must develop and implement a QC
program. As a minimum, each QC program must include written procedures
which should describe in detail, complete, step-by-step procedures and
operations for each of the following activities:
1. Calibration of CEMS.
2. CD determination and adjustment of CEMS.
3. Preventive maintenance of CEMS (including spare parts inventory).
4. Data recording, calculations, and reporting.
5. Accuracy audit procedures including sampling and analysis
methods.
6. Program of corrective action for malfunctioning CEMS.
As described in Section 5.2, whenever excessive inaccuracies occur
for two consecutive quarters, the source owner or operator must revise
the current written procedures or modify or replace the CEMS to correct
the deficiency causing the excessive inaccuracies.
These written procedures must be kept on record and available for
inspection by the enforcement agency.

4. CD Assessment
4.1 CD Requirement. As described in 40 CFR 60.13(d), source owners
and operators of CEMS must check, record, and quantify the CD at two
concentration values at least once daily (approximately 24 hours) in
accordance with the method prescribed by the manufacturer. The CEMS
calibration must, as minimum, be adjusted whenever the daily zero (or
low-level) CD or the daily high-level CD exceeds two times the limits of
the applicable PS's in appendix B of this regulation.
4.2 Recording Requirement for Automatic CD Adjusting Monitors.
Monitors that automatically adjust the data to the corrected calibration
values (e.g., microprocessor control) must be programmed to record the
unadjusted concentration measured in the CD prior to resetting the
calibration, if performed, or record the amount of adjustment.
4.3 Criteria for Excessive CD. If either the zero (or low-level) or
high-level CD result exceeds twice the applicable drift specification in
appendix B for five, consecutive, daily periods, the CEMS is out-of-
control. If either the zero (or low-level) or high-level CD result
exceeds four times the applicable drift specification in appendix B
during any CD check, the CEMS is out-of-control. If the CEMS is out-of-
control, take necessary corrective action. Following corrective action,
repeat the CD checks.
4.3.1 Out-Of-Control Period Definition. The beginning of the out-
of-control period is the time corresponding to the completion of the
fifth, consecutive, daily CD check with a CD in excess of two times the
allowable limit, or the time corresponding to the completion of the
daily CD check preceding the daily CD check that results in a CD in
excess of four times the allowable limit. The end of the out-of-control
period is the time corresponding to the completion of the CD check
following corrective action that results in the CD's at both the zero
(or low-level) and high-level measurement points being within the
corresponding allowable CD limit (i.e., either two times or four times
the allowable limit in appendix B).
4.3.2 CEMS Data Status During Out-of-Control Period. During the
period the CEMS is out-of-control, the CEMS data may not be used in
calculating emission compliance nor be counted towards meeting minimum
data availability as required and described in the applicable subpart
[e.g., Sec. 60.47a(f)].
4.4 Data Recording and Reporting. As required in Sec. 60.7(d) of
this regulation (40 CFR part 60), all measurements from the CEMS

[[Page 659]]

must be retained on file by the source owner for at least 2 years.
However, emission data obtained on each successive day while the CEMS is
out-of-control may not be included as part of the minimum daily data
requirement of the applicable subpart [e.g., Sec. 60.47a(f)] nor be used
in the calculation of reported emissions for that period.

5. Data Accuracy Assessment
5.1 Auditing Requirements. Each CEMS must be audited at least once
each calendar quarter. Successive quarterly audits shall occur no closer
than 2 months. The audits shall be conducted as follows:
5.1.1 Relative Accuracy Test Audit (RATA). The RATA must be
conducted at least once every four calendar quarters. Conduct the RATA
as described for the RA test procedure in the applicable PS in appendix
B (e.g., PS 2 for SO2 and NOX). In addition,
analyze the appropriate performance audit samples received from EPA as
described in the applicable sampling methods (e.g., Methods 6 and 7).
5.1.2 Cylinder Gas Audit (CGA). If applicable, a CGA may be
conducted in three of four calendar quarters, but in no more than three
quarters in succession.
To conduct a CGA: (1) Challenge the CEMS (both pollutant and diluent
portions of the CEMS, if applicable) with an audit gas of known
concentration at two points within the following ranges:

------------------------------------------------------------------------
Audit range
-------------------------------------------------------------
Audit Diluent monitors for--
point Pollutant monitors ----------------------------------------
CO2 O2
------------------------------------------------------------------------
1......... 20 to 30% of span 5 to 8% by volume.. 4 to 6% by volume.
value.
2......... 50 to 60% of span 10 to 14% by volume 8 to 12% by
value. volume.
------------------------------------------------------------------------

Challenge the CEMS three times at each audit point, and use the
average of the three responses in determining accuracy.
Use of separate audit gas cylinder for audit points 1 and 2. Do not
dilute gas from audit cylinder when challenging the CEMS.
The monitor should be challenged at each audit point for a
sufficient period of time to assure adsorption-desorption of the CEMS
sample transport surfaces has stabilized.
(2) Operate each monitor in its normal sampling mode, i.e., pass the
audit gas through all filters, scrubbers, conditioners, and other
monitor components used during normal sampling, and as much of the
sampling probe as is practical. At a minimum, the audit gas should be
introduced at the connection between the probe and the sample line.
(3) Use audit gases that have been certified by comparision to
National Bureau of Standards (NBS) gaseous Standard Reference Materials
(SRM's) or NBS/EPA approved gas manufacturer's Certified Reference
Materials (CRM's) (See Citation 1) following EPA Traceability Protocol
No. 1 (See Citation 2). As an alternative to Protocol No. 1 audit gases,
CRM's may be used directly as audit gases. A list of gas manufacturers
that have prepared approved CRM's is available from EPA at the address
shown in Citation 1. Procedures for preparation of CRM's are described
in Citation 1. Procedures for preparation of EPA Traceability Protocol 1
materials are described in Citation 2.
The difference between the actual concentration of the audit gas and
the concentration indicated by the monitor is used to assess the
accuracy of the CEMS.
5.1.3 Relative Accuracy Audit (RAA). The RAA may be conducted three
of four calendar quarters, but in no more than three quarters in
succession. To conduct a RAA, follow the procedure described in the
applicable PS in appendix B for the relative accuracy test, except that
only three sets of measurement data are required. Analyses of EPA
performance audit samples are also required.
The relative difference between the mean of the RM values and the
mean of the CEMS responses will be used to assess the accuracy of the
CEMS.
5.1.4 Other Alternative Audits. Other alternative audit procedures
may be used as approved by the Administrator for three of four calendar
quarters. One RATA is required at least once every four calendar
quarters.
5.2 Excessive Audit Inaccuracy. If the RA, using the RATA, CGA, or
RAA exceeds the criteria in section 5.2.3, the CEMS is out-of-control.
If the CEMS is out-of-control, take necessary corrective action to
eliminate the problem. Following corrective action, the source owner or
operator must audit the CEMS with a RATA, CGA, or RAA to determine if
the CEMS is operating within the specifications. A RATA must always be
used following an out-of-control period resulting from a RATA. The audit
following corrective action does not require analysis of EPA performance
audit samples. If audit results show the CEMS to be out-of-control, the
CEMS operator shall report both the audit showing the CEMS to be out-of-
control and the results of the audit following corrective action showing
the CEMS to be operating within specifications.
5.2.1 Out-Of-Control Period Definition. The beginning of the out-of-
control period is the time corresponding to the completion of the
sampling for the RATA, RAA, or CGA. The end of the out-of-control period
is the time corresponding to the completion of the sampling of the
subsequent successful audit.
5.2.2 CEMS Data Status During Out-Of-Control Period. During the
period the monitor is out-of-control, the CEMS data may

[[Page 660]]

not be used in calculating emission compliance nor be counted towards
meeting minimum data availabilty as required and described in the
applicable subpart [e.g., Sec. 60.47a(f)].
5.2.3 Criteria for Excessive Audit Inaccuracy. Unless specified
otherwise in the applicable subpart, the criteria for excessive
inaccuracy are:
(1) For the RATA, the allowable RA in the applicable PS in appendix
B.
(2) For the CGA, 15 percent of the average audit value
or 5 ppm, whichever is greater.
(3) For the RAA, 15 percent of the three run average or
7.5 percent of the applicable standard, whichever is
greater.
5.3 Criteria for Acceptable QC Procedure. Repeated excessive
inaccuracies (i.e., out-of-control conditions resulting from the
quarterly audits) indicates the QC procedures are inadequate or that the
CEMS is incapable of providing quality data. Therefore, whenever
excessive inaccuracies occur for two consective quarters, the source
owner or operator must revise the QC procedures (see Section 3) or
modify or replace the CEMS.

6. Calculations for CEMS Data Accuracy
6.1 RATA RA Calculation. Follow the equations described in Section 8
of appendix B, PS 2 to calculate the RA for the RATA. The RATA must be
calculated in units of the applicable emission standard (e.g., ng/J).
6.2 RAA Accuracy Calculation. Use Equation 1-1 to calculate the
accuracy for the RAA. The RAA must be calculated in units of the
applicable emission standard (e.g., ng/J).
6.3 CGA Accuracy Calculation. Use Equation 1-1 to calculate the
accuracy for the CGA, which is calculated in units of the appropriate
concentration (e.g., ppm SO2 or percent O2). Each
component of the CEMS must meet the acceptable accuracy requirement.
[GRAPHIC] [TIFF OMITTED] TC16NO91.240

where:
A = Accuracy of the CEMS, percent.
Cm = Average CEMS response during audit in units of
applicable standard or appropriate concentration.
Ca = Average audit value (CGA certified value or three-
run average for RAA) in units of applicable standard or appropriate
concentration.
6.4 Example Accuracy Calculations. Example calculations for the
RATA, RAA, and CGA are available in Citation 3.

7. Reporting Requirements
At the reporting interval specified in the applicable regulation,
report for each CEMS the accuracy results from Section 6 and the CD
assessment results from Section 4. Report the drift and accuracy
information as a Data Assessment Report (DAR), and include one copy of
this DAR for each quarterly audit with the report of emissions required
under the applicable subparts of this part.
As a minimum, the DAR must contain the following information:
1. Source owner or operator name and address.
2. Identification and location of monitors in the CEMS.
3. Manufacturer and model number of each monitor in the CEMS.
4. Assessment of CEMS data accuracy and date of assessment as
determined by a RATA, RAA, or CGA described in Section 5 including the
RA for the RATA, the A for the RAA or CGA, the RM results, the cylinder
gases certified values, the CEMS responses, and the calculations results
as defined in Section 6. If the accuracy audit results show the CEMS to
be out-of-control, the CEMS operator shall report both the audit results
showing the CEMS to be out-of-control and the results of the audit
following corrective action showing the CEMS to be operating within
specifications.
5. Results from EPA performance audit samples described in Section 5
and the applicable RM's.
6. Summary of all corrective actions taken when CEMS was determined
out-of-control, as described in Sections 4 and 5.
An example of a DAR format is shown in Figure 1.

8. Bibliography
1. ``A Procedure for Establishing Traceability of Gas Mixtures to
Certain National Bureau of Standards Standard Reference Materials.''
Joint publication by NBS and EPA-600/7-81-010. Available from the U.S.
Environmental Protection Agency. Quality Assurance Division (MD-77).
Research Triangle Park, NC 27711.
2. ``Traceability Protocol for Establishing True Concentrations of
Gases Used for Calibration and Audits of Continuous Source Emission
Monitors (Protocol Number 1)'' June 1978. Section 3.0.4 of the Quality
Assurance Handbook for Air Pollution Measurement Systems. Volume III.
Stationary Source Specific Methods. EPA-600/4-77-027b. August 1977. U.S.
Environmental Protection Agency. Office of Research and Development
Publications, 26 West St. Clair Street, Cincinnati, OH 45268.
3. Calculation and Interpretation of Accuracy for Continuous
Emission Monitoring Systems (CEMS). Section 3.0.7 of the Quality
Assurance Handbook for Air Pollution Measurement Systems, Volume III,
Stationary Source Specific Methods. EPA-600/4-77-027b. August 1977. U.S.
Environmental Protection Agency. Office of Research and Development
Publications, 26 West St. Clair Street, Cincinnati, OH 45268.

[[Page 661]]

Figure 1--Example Format for Data Assessment Report

Period ending date______________________________________________________
Year____________________________________________________________________
Company name____________________________________________________________
Plant name______________________________________________________________
Source unit no._________________________________________________________
CEMS manufacturer_______________________________________________________
Model no._______________________________________________________________
CEMS serial no._________________________________________________________
CEMS type (e.g., in situ)_______________________________________________
CEMS sampling location (e.g., control device outlet)____________________
CEMS span values as per the applicable regulation: ____________ (e.g.,
SO2 ________ ppm, NOx ________ ppm).
________________
I. Accuracy assessment results (Complete A, B, or C below for each
CEMS or for each pollutant and diluent analyzer, as applicable.) If the
quarterly audit results show the CEMS to be out-of-control, report the
results of both the quarterly audit and the audit following corrective
action showing the CEMS to be operating properly.

A. Relative accuracy test audit (RATA) for ________ (e.g.,
SO2 in ng/J).

1. Date of audit ________.
2. Reference methods (RM's) used ________ (e.g., Methods 3 and 6).
3. Average RM value ________ (e.g., ng/J, mg/dsm\3\, or percent
volume).
4. Average CEMS value ________.
5. Absolute value of mean difference [d] ________.
6. Confidence coefficient [CC] ________.
7. Percent relative accuracy (RA) ________ percent.
8. EPA performance audit results:
a. Audit lot number (1) ________ (2) ________
b. Audit sample number (1) ________ (2) ________
c. Results (mg/dsm\3\) (1) ________ (2) ________
d. Actual value (mg/dsm\3\)* (1) ________ (2) ________
e. Relative error* (1) ________ (2) ________

B. Cylinder gas audit (CGA) for ________ (e.g., SO2 in
ppm).

------------------------------------------------------------------------
Audit Audit
point point
1 2
------------------------------------------------------------------------
1. Date of audit................... ...... ......
2. Cylinder ID number.............. ...... ......
3. Date of certification........... ...... ......
4. Type of certification........... ...... ...... (e.g., EPA Protocol
1 or CRM).
5. Certified audit value........... ...... ...... (e.g., ppm).
6. CEMS response value............. ...... ...... (e.g., ppm).
7. Accuracy........................ ...... ...... percent.
------------------------------------------------------------------------

C. Relative accuracy audit (RAA) for ________ (e.g., SO2
in ng/J).

1. Date of audit ________.
2. Reference methods (RM's) used ________ (e.g., Methods 3 and 6).
3. Average RM value ________ (e.g., ng/J).
4. Average CEMS value ________.
5. Accuracy ________ percent.
6. EPA performance audit results:
a. Audit lot number (1) ________ (2) ________
b. Audit sample number (1) ________ (2) ________
c. Results (mg/dsm\3\) (1) ________ (2) ________
d. Actual value (mg/dsm\3\) *(1) ________ (2)
e. Relative error* (1) ________ (2) ________
---------------------------------------------------------------------------

* To be completed by the Agency.
---------------------------------------------------------------------------

D. Corrective action for excessive inaccuracy.

1. Out-of-control periods.
a. Date(s) ________.
b. Number of days ________.
2. Corrective action taken____________________________________________
3. Results of audit following corrective action. (Use format of A,
B, or C above, as applicable.)

II. Calibration drift assessment.

A. Out-of-control periods.
1. Date(s) ________.
2. Number of days ________.

B. Corrective action taken____________________________________________
_______________________________________________________________________

[52 FR 21008, June 4, 1987; 52 FR 27612, July 22, 1987, as amended at 56
FR 5527, Feb. 11, 1991]

Appendix G to Part 60--Provisions for an Alternative Method of
Demonstrating Compliance With 40 CFR 60.43 for the Newton Power Station
of Central Illinois Public Service Company

1. Designation of Affected Facilities
1.1 The affected facilities to which this alternative compliance
method applies are the Unit 1 and 2 coal-fired steam generating units
located at the Central Illinois Public Service Company's (CIPS) Newton
Power Station in Jasper County, Illinois. Each of these units is subject
to the Standards of Performance for Fossil-Fuel-Fired Steam Generators
for Which Construction Commenced After August 17, 1971 (subpart D).
2. Definitions
2.1 All definitions in subparts D and Da of part 60 apply to this
provision except that:
24-hour period means the period of time between 12:00 midnight and
the following midnight.
Boiler operating day means a 24-hour period during which any fossil
is combusted in either the Unit 1 or Unit 2 steam generating unit and
during which the provisions of Sec. 60.43(e) are applicable.
CEMs means continuous emission monitoring system.

[[Page 662]]

Coal bunker means a single or group of coal trailers, hoppers, silos
or other containers that:
(1) are physically attached to the affected facility; and
(2) provide coal to the coal pulverizers.
DAFGDS means the dual alkali flue gas desulfurization system for the
Newton Unit 1 steam generating unit.
3. Compliance Provisions
3.1 If the owner or operator of the affected facility elects to
comply with the 470 ng/J (1.1 lbs/MMBTU) of combined heat input emission
limit under Sec. 60.43(e), he shall notify the Regional Administrator,
of the United States Environmental Protection Agency (USEPA), Region 5
and the Director, of the Illinois Environmental Protection Agency (IEPA)
at least 30 days in advance of the date such election is to take effect,
stating the date such operation is to commence. When the owner or
operator elects to comply with this limit after one or more periods of
reverting to the 520 ng/J heat input (1.2 lbs/MMBTU) limit of
Sec. 60.43(a)(2), as provided under 3.4, he shall notify the Regional
Administrator of the USEPA, Region 5 and the Director of the (IEPA) in
writing at least ten (10) days in advance of the date such election is
to take effect.
3.2 Compliance with the sulfur dioxide emission limit under
Sec. 60.43(e) is determined on a continuous basis by performance testing
using CEMs. Within 60 days after the initial operation of Units 1 and 2
subject to the combined emission limit in Sec. 60.43(e), the owner or
operator shall conduct an initial performance test, as required by
Sec. 60.8, to determine compliance with the combined emission limit.
This initial performance test is to be scheduled so that the thirtieth
boiler operating day of the 30 successive boiler operating days is
completed within 60 days after initial operation subject to the 470 ng/J
(1.1 lbs/MMBTU) combined emission limit. Following the initial
performance test, a separate performance test is completed at the end of
each boiler operating day Unit 1 and Unit 2 are subject to
Sec. 60.43(e), and a new 30 day average emission rate calculated.
3.2.1 Following the initial performance test, a new 30 day average
emission rate is calculated for each boiler operating day the affected
facility is subject to Sec. 60.43(e). If the owner or operator of the
affected facility elects to comply with Sec. 60.43(e) after one or more
periods of reverting to the 520 ng/J heat input (1.2 lbs/MMBTU) limit
under Sec. 60.43(a)(2), as provided under 3.4, the 30 day average
emission rate under Sec. 60.43(e) is calculated using emissions data of
the current boiler operating day and data for the previous 29 boiler
operating days when the affected facility was subject to Sec. 60.43(e).
Periods of operation of the affected facility under Sec. 60.43(a)(2) are
not considered boiler operating days. Emissions data collected during
operation under Sec. 60.43(a)(2) are not considered relative to 4.6 and
emissions data are not included in calculations of emission under
Sec. 60.43(e).
3.2.2 When the affected facility is operated under the provisions
of Sec. 60.43(e), the Unit 1 DAFGDS bypass damper must be fully closed.
The DAFGDS bypass may be opened only during periods of DAFGDS startup,
shutdown, malfunction or testing as described under Sections 3.5.1,
3.5.2, 3.5.3, 3.5.4, and 4.8.2.
3.3 Compliance with the sulfur dioxide emission limit set forth in
Sec. 60.43(e) is based on the average combined hourly emission rate from
Units 1 and 2 for 30 successive boiler operating days determined as
follows:
[GRAPHIC] [TIFF OMITTED] TC15NO91.206

where:

n=the number of available hourly combined emission rate values in the 30
successive boiler operating day period where Unit 1 and Unit 2
are subject to Sec. 60.43(e).
E30=average emission rate for 30 successive boiler operating days where
Unit 1 and Unit 2 are subject to Sec. 60.43(e).
EC=the hourly combined emission rate from Units 1 and 2, in ng/J or lbs/
MMBTU.
3.3.1 The average hourly combined emission rate for Units 1 and
2for each hour of operation of either Unit 1 or 2, or both, is
determined as follows:

EC=[(E1)+(E2)]/[H1+H2]

where:

EC=the hourly combined SO2 emission rate, lbs/MMBTU, from
Units 1 and 2 when Units 1 and 2 are subject to Sec. 60.43(e).
E1=the hourly SO2 mass emission, lb/hr, from Unit 1 as
determined from CEMs data using the calculation procedures in
section 4 of this appendix.
E2=the hourly SO2 mass emission, lb/hr, from Unit 2 as
determined from CEMs data using the calculation procedures in
section 4 of this appendix.
H1=the hourly heat input, MMBTU/HR to Unit 1 as determined in section 4
of this appendix.
H2=the hourly heat input, MMBTU/HR, to Unit 2 as determined by section 4
of this appendix.
3.3.2 If data for any of the four hourly parameters (E1, E2, H1and
H2, under 3.3.1 are unavailable during an hourly period, the combined
emission rate (EC) is not calculated and the period is counted as
missing data under 4.6.1., except as provided under 3.5. and 4.4.2.
3.4 After the date of initial operation subject to the combined
emission limit, Units 1 and 2 shall remain subject to the combined
emission limit and the owner or operator

[[Page 663]]

shall remain subject to the requirements of this Appendix until the
initial performance test as required by 3.2 is completed and the owner
or operator of the affected facility elects and provides notice to
revert on a certain date to the 520 ng/J heat input (1.2 lbs/MMBTU)
limit of Sec. 60.43(a)(2) applicable separately at each unit. The
Regional Administrator of the USEPA, Region 5 and the Director, of the
IEPA shall be given written notification from CIPS as soon as possible
of CIPs' decision to revert to the 520 ng/J heat input (1.2 lbs/MMBTU)
limit of Sec. 60.43(a)(2) separately at each unit, but no later than 10
days in advance of the date such election is to take effect.
3.5 Emission monitoring data for Unit 1 may be excluded from
calculations of the 30 day rolling average only during the following
times:
3.5.1 Periods of DAFGDS startup.
3.5.2 Periods of DAFGDS shutdown.
3.5.3 Periods of DAFGDS malfunction during system emergencies as
defined in Sec. 60.41a.
3.5.4 The first 250 hours per calendar year of DAFGDS malfunctions
of Unit 1 DAFGDS provided that efforts are made to minimize emissions
from Unit 1 in accordance with Sec. 60.11(d), and if, after 16 hours but
not more than 24 hours of DAFGDS malfunction, the owner or operator of
the affected facility begins (following the customary loading
procedures) loading into the Unit 1 coal bunker, coal with a potential
SO2 emission rate equal to or less than the emission rate of
Unit 2 recorded at the beginning of the DAFGDS malfunction. Malfunction
periods under 3.5.3 are not counted toward the 250 hour/yr limit under
this section.
3.5.4.1 The malfunction exemption in 3.5.4 is limited to the first
250 hours per calendar year of DAFGDS malfunction.
3.5.4.2 For malfunctions of the DAFGDS after the 250 hours per
calendar year limit (cumulative), other than those defined in 3.5.3, the
owner or operator of the affected facility shall combust lower sulfur
coal or use any other method to comply with the 470 ng/J (1.1 lbs/MMBTU)
combined emission limit.
3.5.4.3 During the first 250 hours of DAFGDS malfunction per year
or during periods of DAFGDS startup, or DAFGDS shutdown, CEMs emissions
data from Unit 2 shall continue to be included in the daily calculation
of the combined 30 day rolling average emission rate; that is, the load
on Unit 1 is assumed to be zero (H1 and E1=O; EC=E2/H2).
3.5.5--3.5.7 [Reserved]
3.6 The provision for excluding CEMs data from Unit 1 during the
first 250 hours of DAFGDS malfunctions from combined hourly emissions
calculations supersedes the provisions of Sec. 60.11(d). However, the
general purpose contained in Sec. 60.11(d) (i.e., following good control
practices to minimize air pollution emission during malfunctions) has
not been superseded.

4. Continuous Emission Monitoring

4.1 The CEMs required under Section 3.2 are operated and data are
recorded for all periods of operation of the affected facility including
periods of the DAFGDS startup, shutdown and malfunction except for CEMs
breakdowns, repairs, calibration checks, and zero and span adjustment.
All provisions of Sec. 60.45 apply except as follows:
4.2 The owner or operator shall install, calibrate, maintain, and
operate CEMs and monitoring devices for measuring the following:
4.2.1 For Unit 1:
4.2.1.1 Sulfur dioxide, oxygen or carbon dioxide, and volumetric
flow rate for the Unit 1 DAFGDS stack.
4.2.1.2 Sulfur dioxide, oxygen or carbon dioxide, and volumetric
flow rate for the Unit 1 DAFGDS bypass stack.
4.2.1.3 Moisture content of the flue gas must be determined
continuously for the Unit 1 DAFGDS stack and the Unit 1 DAFGDS bypass
stack, if the sulfur dioxide concentration in each stack is measured on
a dry basis.
4.2.2 For Unit 2, sulfur dioxide, oxygen or carbon dioxide, and
volumetric flow rate.
4.2.2.1 Moisture content of the flue gas must be determined
continuously for the Unit 2 stack, if the sulfur dioxide concentration
in the stack is measured on a dry basis.
4.2.3 For Units 1 and 2, the hourly heat input, the hourly steam
production rate, or the hourly gross electrical power output from each
unit.
4.3 For the Unit 1 bypass stack and the Unit 2 stack, the span
value of the sulfur dioxide analyzer shall be equivalent to 200 percent
of the maximum estimated hourly potential sulfur dioxide emissions of
the fuel fired in parts per million sulfur dioxide. For the Unit 1
DAFGDS stack, the span value of the sulfur dioxide analyzer shall be
equivalent to 100 percent of the maximum estimated hourly potential
emissions of the fuel fired in parts per million sulfur dioxide. The
span value for volumetric flow monitors shall be equivalent to 125
percent of the maximum estimated hourly flow in standard cubic meters/
minute (standard cubic feet per minute). The span value of the
continuous moisture monitors, if required by 4.2.1.3 and 4.2.2.1, shall
be equivalent to 100 percent by volume. The span value of the oxygen or
carbon dioxide analyzers shall be equivalent to 25 percent by volume.
4.3.1--4.3.2 [Reserved]
4.4 The monitoring devices required in 4.2 shall be installed,
calibrated, and maintained as follows:
4.4.1 Each volumetric flow rate monitoring device specified in 4.2
shall be installed at approximately the same location

[[Page 664]]

as the sulfur dioxide emission monitoring sample location.
4.4.2 Hourly steam production rate and hourly electrical power
output monitoring devices for Unit 1 and Unit 2 shall be calibrated and
maintained according to manufacturer's specifications. The data from
either of these devices may be used in the calculation of the combined
emission rate in Section 3.3.1, only when the hourly heat input for Unit
1 (H1) or the hourly heat input for Unit 2 (H2) cannot be determined
from CEM data, and the hourly heat input to steam production or hourly
heat input to electrical power output efficiency over a given segment of
each boiler or generator operating range, respectively, varies by less
than 5 percent within the specified operating range, or the efficiencies
of the boiler/generator units differ by less than 5 percent. The hourly
heat input for Unit 1 (H1) or the hourly heat input for Unit 2 (H2) in
Section 3.3.1 may also be calculated based on the fuel firing rates and
fuel analysis.
4.4.3--4.4.5 [Reserved]
4.5 The hourly mass emissions from Unit 1 (E1) and Unit 2 (E2) and
the hourly heat inputs from Unit 1 (H1) and Unit 2 (H2) used to
determine the hourly combined emission rate for Units 1 and 2 (EC) in
Section 3.3.1 are calculated using CEM data for each respective stack as
follows:
4.5.1 The hourly SO2 mass emission from each respective
stack is determined as follows:

E=(C) (F) (D) (K)

Where:

E=SO2 mass emission from the respective stack in lb per hour
C=SO2 concentration from the respective stack ppm
F=flue gas flow rate from the respective stack in scfm
D=density of SO2 in lb per standard cubic feet
K=time conversion, 60 mins./hr
4.5.2 The hourly heat input from each respective stack is
determined as follows:

H=[(F) (C) (K)/(Fc)

where:

H=heat input from the respective stack in MMBTU per hour
C=CO2 or O2 concentration from the respective
stack as a decimal
F=flue gas flow rate from the respective stack in scfm
K=time conversion, 60 mins./hr
Fc=fuel constant for the appropriate diluent in scf/MMBTU as
per Secs. 60.45(f) (4) and (5)
4.5.3 The hourly SO2 mass emission for Unit 1 in pounds
per hour (E1) is calculated as follows, when leakage or diversion of any
DAFGDS inlet gas to the bypass stack occurs:

E1=(EF)+(EB)

Where:

EF=Hourly SO2 mass emission measured in DAFGDS stack, lb/hr,
using the calculation in Section 4.5.1.
EB=Hourly SO2 mass emission measured in bypass stack, lb/hr,
using the calculation in Section 4.5.1.
Other than during conditions under 3.5.1, 3.5.2, 3.5.3, 3.5.4, or 4.8.2,
the DAFGDS bypass damper must be fully closed and any leakage
will be indicated by the bypass stack volumetric flow and
SO2 measurements, and when no leakage through the
bypass damper is indicated:

E1=EF
4.5.4 The hourly heat input for Unit 1 in MMBTU per hour (H1) is
calculated as follows, when leakage or diversion of any DAFGDS inlet gas
to the bypass stack occurs:

H1=(HF)+(HB)

where:

HF=Hourly heat input as determined from the DAFGDS stack CEMs, in MMBTU
per hour, using the calculation in Section 4.5.2
HB=Hourly heat input as determined from the DAFGDS bypass stack CEMs, in
MMBTU per hour, using the calculation in Section 4.5.2
4.6 For the CEMs required for Unit 1 and Unit 2, the owner or
operator of the affected facility shall maintain and operate the CEMs
and obtain combined emission data values (EC) for at least 75 percent of
the boiler operting hours per day for at least 26 out of each 30
successive boiler operating days.
4.6.1 When hourly SO2 emission data are not obtained by
the CEMs because of CEMs breakdowns, repairs, calibration checks and
zero and span adjustment, hourly emission data required by 4.6 are
obtained by using Methods 6 or 6C and 3 or 3A, 6A, or 8 and 3, or by
other alternative methods approved by the Regional Administrator of the
USEPA, Region 5 and the Director, of the IEPA. Failure to obtain the
minimum data requirements of 4.6 by CEMs, or by CEMs supplemented with
alternative methods of this section, is a violation of performance
testing requirements.
4.6.2 Independent of complying with the minimum data requirements
of 4.6, all valid emissions data collected are used to calculate
combined hourly emission rates (EC) and 30-day rolling average emission
rates (E30) are calculated and used to judge compliance with 60.43(e).
4.7 For each continuous emission monitoring system, a quality
control plan shall be prepared by CIPS and submitted to the Regional
Administrator of the USEPA, Region 5 and the Director, of the IEPA. The
plan is to be submitted to the Regional Administrator of the USEPA,
Region 5 and the

[[Page 665]]

Director, of the IEPA 45 days before initiation of the initial
performance test. At a minimum, the plan shall contain the following
quality control elements:
4.7.1 Calibration of continuous emission monitoring systems (CEMs)
and volumetric flow measurement devices.
4.7.2 Calibration drift determination and adjustment of CEMs and
volumetric flow measurement devices.
4.7.3 Periodic CEMs, volumetric flow measurement devices and
relative accuracy determinations.
4.7.4 Preventive maintenance of CEMs and volumetric flow
measurement devices (including spare parts inventory).
4.7.5 Data recording and reporting.
4.7.6 Program of corrective action for malfunctioning CEMs and
volumetric flow measurement devices.
4.7.7 Criteria for determining when the CEMs and volumetric flow
measurement devices are not producing valid data.
4.7.8 Calibration and periodic checks of monitoring devices
identified in 4.4.2.
4.8 For the purpose of conducting the continuous emission
monitoring system performance specification tests as required by
Sec. 60.13 and appendix B, the following conditions apply:
4.8.1 The calibration drift specification of Performance
Specification 2, appendix B shall be determined separately for each of
the Unit 1 SO2 CEMs and the Unit 2 SO2 CEMs. The
calibration drift specification of Performance Specification 3, appendix
B shall be determined separately for each of the Unit 1 diluent CEMs and
Unit 2 diluent CEMs.
4.8.2 The relative accuracy of the combined SO2 emission
rate for Unit 1 and Unit 2, as calculated from CEMs and volumetric flow
data using the procedures in 3.3.1, 4.5.1, 4.5.2 and 4.5.3 shall be no
greater than 20 percent of the mean value of the combined emission rate,
as determined from testing conducted simultaneously on the DAFGDS stack,
the DAFGDS bypass stack and the Unit 2 stack using reference methods 2,
3, or 3A and 6 or 6C, or shall be no greater than 10 percent of the
emission limit in Sec. 60.43(e), whichever criteria is less stringent.
The relative accuracy shall be computed from at least nine comparisons
of the combined emission rate values using the procedures in section 7
and the equations in section 8, Performance Specification 2, appendix B.
Throughout, but only during, the relative accuracy test period the
DAFGDS bypass damper shall be partially opened such that there is a
detectable flow.
4.8.3--4.8.3.4 [Reserved]
4.9 The total monitoring system required by 4.2 shall be subject
only to an annual relative accuracy test audit (RATA) in accordance with
the quality assurance requirements of section 5.1.1 of 40 CFR part 60,
appendix F. Each SO2 and diluent CEMs shall be subject to
cylinder gas audits (OGA) in accordance with the quality assurance
requirements of section 5.1.2 of appendix F with the exception that any
SO2 or diluent CEMs without any type of probe or sample line
shall be exempt from the OGA requirements.

5. Recordkeeping Requirements

5.1 The plant owner or operator shall keep a record of each hourly
emission rate, each hourly SO2 CEMs value and hourly flow
rate value, and each hourly Btu heat input rate, hourly steam rate, or
hourly electrical power output, and a record of each hourly weighted
average emission rate. These records shall be kept for all periods of
operation of Unit 1 or 2 under provisions of Sec. 60.43(e), including
operations of Unit 1 (E1) during periods of DAFGDS startup, shutdown,
and malfunction when H1 and E1 are assumed to be zero (0) (see 4.5).
5.2 The plant owner or operator shall keep a record of each hourly
gas flow rate through the DAFGDS stack, each hourly stack gas flow rate
through the bypass stack during any periods that the DAFGDS bypass
damper is opened or flow is indicated, and reason for bypass operation.

6. Reporting Requirements

6.1 The owner or operator of any affected facility shall submit the
written reports required under 6.2 of this section and subpart A to the
Regional Administrator of the USEPA, Region 5 and the Director, of the
IEPA for every calendar quarter. All quarterly reports shall be
submitted by the 30th day following the end of each calendar quarter.
6.2 For sulfur dioxide, the following data resubmitted to the
Regional Administrator of the USEPA, Region 5 and the Director, of the
IEPA for each 24-hour period:
6.2.1 Calendar date
6.2.2 The combined average sulfur dioxide emission rate (ng/J or
lb/million Btu) for the past 30 successive boiler operating days (ending
with the last 30-day period in the quarter); and, for any noncompliance
periods, reasons for noncompliance with the emission standards and
description of corrective action taken.
6.2.3 Identification of the boiler operating days for which valid
sulfur dioxide emissions data required by 4.6 have not been obtained for
75 percent of the boiler operating hours; reasons for not obtaining
sufficient data; and description of corrective actions taken to prevent
recurrence.
6.2.4 Identification of the time periods (hours) when Unit 1 or
Unit 2 were operated but combined hourly emission rates (EC) were not
calculated because of the unavailability of parameters E1, E2, H1, or H2
as described in 3.2.

[[Page 666]]

6.2.5 Identification of the time periods (hours) when Unit 1 and
Unit 2 were operated and where the combined hourly emission rate (EC)
equalled Unit 2 (E2/H2) emissions because of the Unit 1 malfunction
provisions under 3.5.3, and 3.5.4.
6.2.6 Identification of the time periods (hours) when emissions
from the Unit 1 DAFGDS have been excluded from the calculation of
average sulfur dioxide emission rates because of Unit 1 DAFGDS startup,
shutdown, malfunction, or other reasons; and justification for excluding
data for reasons other than startup or shutdown. Reporting of hourly
emission rate of Unit 1 (E1/H2) during each hour of the DAFGDS startup,
malfunction under 3.5.1, 3.5.2, 3.5.3, and 3.5.4 (see 4.5).
6.2.7 Identification of the number of days in the calendar quarter
that the affected facility was operated (any fuel fired).
6.2.8 Identify any periods where Unit 1 DAFGDS malfunctions
occurred and the cumulative hours of Unit 1 DAFGDS malfunction for the
quarter.
6.2.9 Identify any periods of time that any exhaust gases were
discharged to the DAFGDS bypass stack and the hourly gas flow rate
through the DAFGDS stack and through the DAFGDS bypass stack during such
periods and reason for bypass operation.
6.2.10 [Reserved]

[52 FR 28955, Aug. 4, 1987, as amended at 58 FR 28785, May 17, 1993; 59
FR 8135, Feb. 18, 1994]

Appendix H to Part 60 [Reserved]

Appendix I to Part 60--Removable Label and Owner's Manual

1. Introduction

The purpose of this appendix is to provide guidance to the
manufacturer for compliance with the temporary labeling and owner's
manual provisions of subpart AAA. Section 2 provides guidance for the
content and presentation of information on the temporary labels. Section
3 provides guidance for the contents of the owner's manual.

2. Temporary Labels

2.1 General

Temporary labels shall be printed on 90 pound bond paper and shall
measure 5 inches wide by 7 inches long. All labels shall be printed in
black ink on one side of the label only. The type font that shall be
used for all printing is helvetica. Specific instructions for drafting
labels are provided below depending upon the compliance status of the
wood heater model. Figures 1 through 7 illustrate the various label
types that may apply.

2.2 Certified Wood Heaters

The design and content of certified wood heaters vary according to
the following:
Catalyst or noncatalyst,
Measured or default thermal efficiency value, and
Compliance with 1988 or 1990 emission limit.
There are five parts of a label. These include:
Identification and compliance status,
Emission value,
Efficiency value,
Heat output value, and
Caveats.
Instructions for drafting each of these five parts are discussed
below in terms of the three variables listed above. Figures 1 and 2
illustrate the variations in label design. Figure 1 is a temporary label
for a hypothetical catalyst wood heater that meets the 1990 standard,
has a certification test emission composite value of 3.5 g/h, and has a
default efficiency of 72 percent. The label in Figure 2 is for a
hypothetical noncatalyst wood heater with a certification test emission
composite value of 7.8 g/h and a measured efficiency of 68 percent. It
meets the 1988 but not the 1990 standard. All labels for wood heaters
that have been certified and tested should conform as much as possible
to the general layout, the type font and type size illustrated in
Figures 1 and 2.

2.2.1 Identification and Compliance Status

The top 1.5 inches of the label should contain the following items
(and location on the label):
Manufacturer name (upper left hand corner,
Model name/number (upper left hand corner,
The words ``U.S. ENVIRONMENTAL PROTECTION AGENCY''
(centered at top and enclosed in a box with rounded edges),
For catalytic wood heaters, in large bold print the words
``CATALYST EQUIPPED'' (centered below the words ``U.S. ENVIRONMENTAL
PROTECTION AGENCY''),
Text indicating compliance status for catalytic wood
heaters. For those catalytic wood heaters which comply with the 1988
emission limits, but not the 1990 emission limits, the words: ``Meets
EPA particulate matter (smoke) control requirements for catalytic wood
heaters built on or after July 1, 1988, and before July 1, 1990.'' For
those catalytic wood heaters which comply with the 1990 emission limits,
the words: ``Meets EPA particulate matter (smoke) control requirements
for catalytic wood heaters built on or after July 1, 1990.'' Finally,
for all catalytic wood heaters, the following text should be included:
``See catalyst warranty. Illegal to operate when catalyst is not
working. See

[[Page 667]]

owner's manual for operation and maintenance.''
Text indicating compliance status for noncatalytic wood
heaters. For those noncatalytic wood heaters that comply with the 1988
emission limits but not the 1990 emission limits, the words: ``Meets EPA
particulate matter (smoke) control requirements for NONCATALYTIC wood
heaters built on or after July 1, 1988, and before July 1, 1990.'' For
those noncatalytic wood heaters that comply with 1990 emission limits,
the words: ``Meets EPA particulate matter (smoke) control requirements
for NONCATALYTIC wood heaters built on or after July 1, 1990.''

2.2.2 Emission Value

Between 1.5 and 3.0 inches down from the top of the label is the
part that graphically illustrates the particulate matter, or smoke,
emission value. This part consists of the word ``SMOKE'' in large bold
print and a 3.0 inch line with words ``(grams per hour)'' centered
beneath the line. A blunt end arrow with a base (blunt end) that spans 2
g/hr shall be centered over the point on the emissions line that
represents the composite emission value for the model as measured in the
certification test.
For catalyst equipped wood heaters the 3.0 inch line shall be
labeled ``0'' on the left end of the line (centered below the end) and
``5.5'' on the right end (centered below the end). To find where to
center the large blunt end arrow, measure 0.55 inches from the left end
for each g/h of the composite emission value. Thus, a 4 g/h value would
be 2.2 inches from the left end. The base of the blunt end should always
be 1.1 inches wide (2 g/hr). The words ``This Model'' should be centered
above or within the blunt end arrow.
For noncatalyst equipped wood heaters, the 3.0 inch line should be
labeled ``0'' on the left end of the line (centered below the end) and
``8.5'' on the right end of the line (centered below the end). To find
where to center the large blunt end arrow, measure 0.35 inches from the
left end for each g/h of the composite emission value. Thus, a 4 g/h
value would be 1.4 inches from the left end. The base of the blunt end
should always be 0.7 inches wide (2 g/h). The words ``This Model''
should be centered above or within the blunt end arrow.

2.2.3 Efficiency Value

Between 3.0 and 4.75 inches down from the top of the label is the
part that illustrates overall thermal efficiency value. The efficiency
value may either be a measured value or a calculated or default value as
provided in Sec. 60.536(i)(3) of the regulation. Regardless of how the
efficiency is derived, the words ``EFFICIENCY'' shall be centered above
a 4 inch line. The 4 inch line should be divided into 5 equal lengths
(each 0.8 inches) and labeled ``50%,'' ``60%,'' * * * ``100%'' as
indicated in Figures 1 and 2. As with the smoke line in 2.2.2, a blunt
end arrow shall be centered over the point on the line where the
efficiency value would be located. The base of the blunt end arrow shall
be 0.48 inches wide (6 percentage points). To find where to center the
blunt end arrow, measure 0.08 inches for each percentage point to the
right of the nearest labeled value. For example, a value of 82 percent
would be 0.16 inches to the right of the ``80%'' mark.
For default efficiency values, an asterisk shall follow the word
``EFFICIENCY'' as in Figure 1. The asterisk refers to a note in
parentheses that shall say ``Not tested for efficiency. Value indicated
is for similar catalyst equipped (or noncatalytic, as appropriate) wood
heaters.''
For measured efficiency values measured with the method in appendix
J, the words ``Tested Efficiency'' shall be centered above the blunt end
arrow as in Figure 2.
The last item required for this part is a sentence that says ``Wood
heaters with higher efficiencies cost less to operate.''

2.2.4 Heat Output Value

Between 4.75 and 6.0 inches down from the top of the label is the
heat output part. The words ``HEAT OUTPUT'' in large bold print are
centered above the Heat Output range numbers in Btu/hr, as derived from
the certification test. The words ``Use this to choose the right size
appliance for your needs. ASK DEALER FOR HELP'' should follow the heat
output range numbers as in Figures 1 and 2. (Note that ``ASK DEALER FOR
HELP'' is a single line, centered in the label.) The low end of the burn
rate range indicated on the label should reflect the low end of the burn
rate range achievable by the wood heater as sold and not as tested in
the laboratory (see Sec. 60.536(i)(4)).

2.2.5 Caveats

In the lower 0.75 inch of the label, the following text shall be
presented:
``This wood heater will achieve low smoke output and high efficiency
only if properly operated and maintained. See owner's manual.''

2.3 Coal-Only Heaters

For those heaters which meet the definition of ``coal only heater''
in Sec. 60.531, the temporary label should contain the identical
material (same layout and print font and size) as that illustrated in
Figure 3, except that the hypothetical manufacturer and model name
should be replaced with the appropriate actual names.

[[Page 668]]

2.4 Small Manufacturer Exempted Wood Heaters

For those wood heaters exempted under Sec. 60.530(d), the small
manufacturer exemption, the temporary label should contain the identical
material (same layout and print font and size) as that illustrated in
Figure 4, except that the hypothetical manufacturer and model name
should be replaced with the appropriate actual names.

2.5 Wood Heaters that Are Not Certified

For those wood heaters that do not meet applicable emission limits
under Sec. 60.532 and are not otherwise exempted, the temporary label
should contain the identical material (same layout and print font and
size) as those illustrated in Figures 5, 6, and 7, as appropriate. The
hypothetical manufacturer and model names should be replaced with the
appropriate actual names.
There are three kinds of wood heaters which fall into this category
of ``not certified.'' Each requires a separate label. If a wood heater
is tested but fails to meet the applicable limits, the label in Figure 5
applies. Such a label should be printed on red rather than white paper.
If a wood heater is tested and does meet the emission limit but is not
subsequently certified, the label in Figure 6 applies. (An example would
be a one-of-a-kind wood heater which is not part of a model line.
Because of the costs of testing, this circumstance is not expected to
arise often, if at all.) If a wood heater is not tested and is not
certified, it should bear the label illustrated in Figure 7. As with
Figure 5, this label should be printed on red paper.

3.0 Guidance for Preparation of Wood Heater Owner's Manuals

3.1 Introduction

Although the owner's manuals do not require premarket approval, EPA
will monitor the contents to ensure that sufficient information is
included to provide heater operation and maintenance information
affecting emissions to consumers. The purpose of this section is to
provide guidance to manufacturers in complying with the owner's manual
provisions of Sec. 60.536(1). A checklist of topics and illustrative
language is provided as a guideline. Owner's manuals should be tailored
to specific wood heater models, as appropriate.

3.2 Topics Required To Be Addressed in Owner's Manual

Wood heater description and compliance status,
Tamper warning,
Catalyst information and warranty (if catalyst equipped),
Fuel selection,
Achieving and maintaining catalyst light-off (if catalyst
equipped),
Catalyst monitoring (if catalyst equipped),
Troubleshooting catalytic equipped heaters (if catalyst
equipped),
Catalyst replacement (if catalyst equipped),
Wood heater operation and maintenance, and
Wood heater installation: achieving proper draft.

3.3 Sample Text/Descriptions

The following are example texts and/or further descriptions
illustrating the topics identified above. Although the regulation
requires manufacturers to address (where applicable) the ten topics
identified above, the exact language is not specified. Manuals should be
written specific to the model and design of the wood heater. The
following guidance is composed of generic descriptions and texts. If
manufacturers choose to use the language provided in the example, the
portion in italics should be revised as appropriate. Any manufacturer
electing to use the EPA example language shall be in compliance with
owner's manual requirements provided that the particular language is
printed in full with only such changes as are necessary to ensure
accuracy. Example language is not provided for certain topics, since
these areas are generally heater specific. For these topics,
manufacturers should develop text that is specific to the operation and
maintenance of their particular products.

3.3.1 Wood Heater Description and Compliance Status

Owner's Manuals shall include:
A. Manufacturer and model,
B. Compliance status (exempt, 1988 std., 1990 std., etc.), and
C. Heat output range (as indicated on temporary label).
Example Text covering A, B, and C above:

``This manual describes the installation and operation of the Brand X,
Model 0 catalytic equipped wood heater. This heater meets the U.S.
Environmental Protection Agency's emission limits for wood heaters sold
between July 1, 1990, and July 1, 1992. Under specific test conditions
this heater has been shown to deliver heat at rates ranging from 8,000
to 35,000 Btu/hr.''

3.3.2 Tamper Warning

This consists of the following statement which must be included in
the owner's manual for catalyst equipped units:
Example Text covering legal prohibition on tampering:
``This wood heater contains a catalytic combustor, which needs
periodic inspection and replacement for proper operation. It is

[[Page 669]]

against the law to operate this wood heater in a manner inconsistent
with operating instructions in this manual, or if the catalytic element
is deactivated or removed.''

3.3.3 Catalyst Information

Included with or supplied in the owner's and warranty manuals shall
be the following information:
A. Catalyst manufacturer, model,
B. Catalyst warranty details, and
C. Instructions for warranty claims.
Example Text covering A, B, and C:
``The combustor supplied with this heater is a Brand Z, Long Life
Combustor. Consult the catalytic combustor warranty also supplied with
this wood heater. Warranty claims should be addressed to:

Stove or Catalyst Manufacturer__________________________________________
Address_________________________________________________________________
Phone _________________________________________________________________

This section should also provide clear guidance on how to exercise the
warranty (how to package for return shipment, etc.).

3.3.4 Fuel Selection

Owner's manuals shall include:
A. Instructions on acceptable fuels, and
B. Warning against inappropriate fuels.
Example Text covering A and B:
``This heater is designed to burn natural wood only. Higher
efficiencies and lower emissions generally result when burning air dried
seasoned hardwoods, as compared to softwoods or to green or freshly cut
hardwoods.
DO NOT BURN:
Treated Wood.
Coal.
Garbage.
Cardboard.
Solvents.
Colored Paper.
Trash.
Burning treated wood, garbage, solvents, colored paper or trash may
result in release of toxic fumes and may poison or render ineffective
the catalytic combustor.
Burning coal, cardboard, or loose paper can produce soot, or large
flakes of char or fly ash that can coat the combustor, causing smoke
spillage into the room, and rendering the combustor ineffective.''

3.3.5 Achieving and Maintaining Catalyst Light-Off

Owner's manuals shall describe in detail proper procedures for:
A. Operation of catalyst bypass (stove specific),
B. Achieving catalyst light-off from a cold start, and
C. Achieving catalyst light-off when refueling.
No example text is supplied for describing operation of catalyst
bypass mechanisms (Item A) since these are typically stove-specific.
Manufacturers however must provide instructions specific to their model
describing:
1. Bypass position during start-up,
2. Bypass position during normal operation, and
3. Bypass position during reloading.
Example Text for item B:
``The temperature in the stove and the gases entering the combustor
must be raised to between 500 deg. to 700 deg.F for catalytic activity
to be initiated. During the start-up of a cold stove, a medium to high
firing rate must be maintained for about 20 minutes. This ensures that
the stove, catalyst, and fuel are all stabilized at proper operating
temperatures. Even though it is possible to have gas temperatures reach
600 deg.F within two to three minutes after a fire is started, if the
fire is allowed to die down immediately it may go out or the combustor
may stop working. Once the combustor starts working, heat generated in
it by burning the smoke will keep it working.''
Example Text for item C:
REFUELING:
``During the refueling and rekindling of a cool fire, or a fire that
has burned down to the charcoal phase, operate the stove at a medium to
high firing rate for about 10 minutes to ensure that the catalyst
reaches approximately 600 deg.F.''

3.3.6 Catalyst Monitoring

Owner's manuals shall include:
A. Recommendation to visually inspect combustor at least three times
during the heating season,
B. Discussion on expected combustor temperatures for monitor-
equipped units, and
C. Suggested monitoring and inspection techniques.
Example Text covering A, B, and C:
``It is important to periodically monitor the operation of the
catalytic combustor to ensure that it is functioning properly and to
determine when it needs to be replaced. A non-functioning combustor will
result in a loss of heating efficiency, and an increase in creosote and
emissions. Following is a list of items that should be checked on a
periodic basis.
Combustors should be visually inspected at least three
times during the heating season to determine if physical degradation has
occurred. Actual removal of the combustor is not recommended unless more
detailed inspection is warranted because of decreased performance. If
any of these conditions exist, refer to Catalyst Troubleshooting section
of this owner's manual.
This catalytic heater is equipped with a temperature probe
to monitor catalyst operation. Properly functioning combustors typically
maintain temperatures in excess of 500 deg.F, and often reach
temperatures in excess of 1,000 deg.F. If catalyst temperatures are not
in

[[Page 670]]

excess of 500 deg.F, refer to Catalyst Troubleshooting section of this
owner's manual.
You can get an indication of whether the catalyst is
working by comparing the amount of smoke leaving the chimney when the
smoke is going through the combustor and catalyst light-off has been
achieved, to the amount of smoke leaving the chimney when the smoke is
not routed through the combustor (bypass mode).
Step 1--Light stove in accordance with instructions in 3.3.5.
Step 2--With smoke routed through the catalyst, go outside and
observe the emissions leaving the chimney.
Step 3--Engage the bypass mechanism and again observe the emissions
leaving the chimney.
Significantly more smoke should be seen when the exhaust is not
routed through the combustor (bypass mode). Be careful not to confuse
smoke with steam from wet wood.''

3.3.7 Catalyst Troubleshooting

The owner's manual should provide clear descriptions of symptoms and
remedies to common combustor problems. It is recommended that
photographs of catalyst peeling, plugging, thermal cracking, mechanical
cracking, and masking be included in the manual to aid the consumer in
identifying problems and to provide direction for corrective action.

3.3.8 Catalyst Replacement

The owner's manual should provide clear step-by-step instructions on
how to remove and replace the catalytic combustor. The section should
include diagrams and/or photographs.

3.3.9 Wood Heater Operation and Maintenance

Owner's manual shall include:
A. Recommendations about building and maintaining a fire,
B. Instruction on proper use of air controls,
C. Ash removal and disposal,
D. Instruction on gasket replacement, and
E. Warning against overfiring.
No example text is supplied for A, B, and D since these items are
model specific. Manufacturers should provide detailed instructions on
building and maintaining a fire including selection of fuel pieces, fuel
quantity, and stacking arrangement. Manufacturers should also provide
instruction on proper air settings (both primary and secondary) for
attaining minimum and maximum heat outputs and any special instructions
for operating thermostatic controls. Step-by-step instructions on
inspection and replacement of gaskets should also be included.
Manufacturers should provide diagrams and/or photographs to assist the
consumer. Gasket type and size should be specified.
Example Text for item C:
``Whenever ashes get 3 to 4 inches deep in your firebox or ash pan,
and when the fire has burned down and cooled, remove excess ashes. Leave
an ash bed approximately 1 inch deep on the firebox bottom to help
maintain a hot charcoal bed.''
``Ashes should be placed in a metal container with a tight-fitting
lid. The closed container of ashes should be placed on a noncombustible
floor or on the ground, away from all combustible materials, pending
final disposal. The ashes should be retained in the closed container
until all cinders have thoroughly cooled.''
Example Text covering item E:
``DO NOT OVERFIRE THIS HEATER''
``Attempts to achieve heat output rates that exceed heater design
specifications can result in permanent damage to the heater and to the
catalytic combustor if so equipped.''

3.3.10 Wood Heater Installation: Achieving Proper Draft

Owner's manual shall include:
A. Importance of proper draft,
B. Conditions indicating inadequate draft, and
C. Conditions indicating excessive draft.
Example Text for Item A:
``Draft is the force which moves air from the appliance up through
the chimney. The amount of draft in your chimney depends on the length
of the chimney, local geography, nearby obstructions, and other factors.
Too much draft may cause excessive temperatures in the appliance and may
damage the catalytic combustor. Inadequate draft may cause backpuffing
into the room and `plugging' of the chimney or the catalyst.''
Example text for Item B:
``Inadequate draft will cause the appliance to leak smoke into the
room through appliance and chimney connector joints.''
Example text Item C:
``An uncontrollable burn or a glowing red stove part or chimney
connector indicates excessive draft.''

[[Page 671]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.297

[[Page 672]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.298

[[Page 673]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.299

[[Page 674]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.300

[[Page 675]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.301

[[Page 676]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.302

[[Page 677]]

[GRAPHIC] [TIFF OMITTED] TC01JN92.303

[53 FR 5913, Feb. 26, 1988]

[[Page 679]]

FINDING AIDS

--------------------------------------------------------------------

A list of CFR titles, subtitles, chapters, subchapters and parts and
an alphabetical list of agencies publishing in the CFR are included in
the CFR Index and Finding Aids volume to the Code of Federal Regulations
which is published separately and revised annually.

Material Approved for Incorporation by Reference
Table of CFR Titles and Chapters
Alphabetical List of Agencies Appearing in the CFR
List of CFR Sections Affected

[[Page 681]]

Material Approved for Incorporation by Reference

(Revised as of July 1, 2001)

The Director of the Federal Register has approved under 5 U.S.C.
552(a) and 1 CFR Part 51 the incorporation by reference of the following
publications. This list contains only those incorporations by reference
effective as of the revision date of this volume. Incorporations by
reference found within a regulation are effective upon the effective
date of that regulation. For more information on incorporation by
reference, see the preliminary pages of this volume.

40 CFR (PART 60 APPENDICES):

ENVIRONMENTAL PROTECTION AGENCY
40 CFR

American Public Health Association, American Water Works Association,
and Water Pollution Control Federation

1015 Fifteenth Street NW., Washington, DC 20005;
Telephone: (202) 777-APHA
Standard Methods for the Examination of Water and Appendix A to Part
Wastewater, 16th ed. (1985), Method 308 F. 60, Method 29, pars.
4.2.2, 4.4.2, and
4.5.6

American Society for Testing and Materials

100 Barr Harbor Drive, West Conshohocken, PA
19428-2959; Telephone: (610) 832-9585, FAX
(610): 832-9555
ASTM D129-64, 78, 95, Standard Test Method for Appendix A to Part
Sulfur in Petroleum Products (General Bomb 60, Method 19,
Method). Section 12.5.2.2.3
ASTM D240-76, 92 Standard Test Method for Heat of Appendix A to Part
Combustion of Liquid Hydrocarbon Fuels by Bomb 60, Method 19,
Calorimeter. Section 12.5.2.2.3
ASTM D270-65 (Reapproved 1975), Standard Method of Appendix A to Part
Sampling Petroleum and Petroleum Products. 60, Method 19

[[Page 682]]

ASTM D1193-77, 91, Standard Specification for Appendix A to Part
Reagent Water. 60, Method 5, Section
7.1.3; Method 5E,
Section 7.2.1, Method
5F, Method 7.2.1;
Method 6, Section
7.1.1; Method 7,
Section 7.1.1; Method
7C, Section 7.1.1;
Method 7D, Section
7.1.1; Method 10A,
Section 7.1.1; Method
11, Section 7.1.3;
Method 12, Section
7.1.3; Method 13A,
Section 7.1.2; Method
26, Section 7.1.2;
Method 26A, Section
7.1.2; Method 29,
Section 7.2.2;
Appendix B of Part
61; Method 101,
Section 7.1.1; Method
101A, Section 7.1.1;
Method 104, Section
7.1; Method 108,
Section 7.1.3; Method
108A, Section 7.1.1;
Method 108B, Section
7.1.1; Method 108C,
Section 7.1.1; Method
111, Section 7.3;
Appendix A of Part
63; Method 306,
Sections 7.1.1 and
7.4.2.
ASTM D1475-60, 80, 90, Standard Test Method for Appendix A to Part
Density of Paint, Varnish Lacquer, and Related 60, Method 24,
Products. Section 6.1, and
Method 24A, Sections
6.5 and 7.1

[[Page 683]]

ASTM D1552-83, Standard Test Method for Sulfur in Appendix A to Part
Petroleum Products (High-Temperature Method). 60, Method 19,
Section 12.5.2.2.3
ASTM D1608-77, Standard Test Method for Oxides of Method 7, par. 3.2.2
Nitrogen in Gaseous Combustion Products (Phenol-
Disulfonic Acid Procedures).
ASTM D1826-77, Standard Test Method for Calorific Appendix A: Method
Value of Gases in Natural Gas Range by 19, Section 12.3.2.4
Continuous Recording Calorimeter.
ASTM D2013-72, 86, Standard Method of Preparing Appendix A to Part
Coal Samples for Analysis. 60; Method 19,
Section 12.5.2.1.3
ASTM D2015-77, (Reapproved 1978), 96, Standard Appendix A to Part
Test Method for Gross Calorific Value of Solid 60, Method 19,
Fuel by the Adiabatic Bomb Calorimeter. Section 12.5.2.1.3
ASTM D2016-74 (Reapproved 1983), Standard Text Appendix A to Part
Methods for Moisture Content of Wood. 60, Method 28
ASTM D2234-76, 96, 97a, 97b, 98, Standard Methods Appendix A to Part
for Collection of a Gross Sample of Coal. 60, Method 19,
Section 12.5.2.1.1
ASTM D2369-81, 87, 90, 92, 93, 95, Standard Test Appendix A to Part
Method for Volatile Content of Coatings. 60, Method 24,
Section 6.2
ASTM D2986-71 (Reapproved 1978), 95a, Standard Appendix A to Part
Method for Evaluation of Air, Assay Media by the 60, Method 5, Section
Monodisperse DOP (Dioctyl Phthalate) Smoke Test. 7.1.1; Method 12,
Section 7.1.1; Method
13A, Section 7.1.1.2
ASTM D 2986-95A, Standard Practice for Evaluation Appendix A to Part
of Air Assay Media by the Monodisperse DOP 60, Method 315, par.
(Dioctyl Phthalate) Smoke Test. 7.1.1
ASTM D3173-73, 87, Standard Test Method for Appendix A to Part
Moisture in the Analysis Sample of Coal and 60, Method 19,
Coke. Section 12.5.2.1.3
ASTM D3176-74, 89, Standard Method for Ultimate Appendix A to Part
Analysis of Coal and Coke. 60, Method 19,
12.3.2.3
ASTM D3177-75, 89, Standard Test Method for Total Appendix A to Part
Sulfur in the Analysis Sample of Coal and Coke. 60, Method 19,
section 12.5.2.1.3
ASTM D3286-85, 96, Standard Test Method for Gross Appendix A to Part
Calorific Value of Coal and Coke by the 60, Method 19,
Isothermal-Jacket Bomb calorimeter. Section 12.5.2.1.3
ASTM D3431-80, Standard Test Method for Trace Appendix A to Part
Nitrogen in Liquid Petroleum Hydrocarbons 60, Method 19
(Microcoulometric Method).
ASTM D3792-79, 91, Standard Test Method for Water Appendix A to Part
Content of Water-Reducible Paints by Direct 60, Method 24,
Injection Into a Gas Chromatograph. Section 6.3
ASTM D4017-81, 90, 96a, Standard Test Method for Appendix A to Part
Water in Paints and Paint Materials by the Karl 60, Method 24,
Fischer Titration Method. Section 6.4
ASTM D4057-81, Standard Practive for Manual Appendix A to Part
Sampling of Petroleum and Petroleum Products. 60, Method 19

[[Page 684]]

ASTM D4239-85, 94, 97, Standard Test Methods for Appendix A to Part
Sulfur in the Analysis Sample of Coal and Coke 60, Method 19,
Using High Temperature Tube Furnace Combustion Section 12.5.2.1.3
Methods.
ASTM D4442-84, 92, Standard Test Methods for Appendix A to Part
Direct Moisture Content Measurement of Wood and 60, Method 28,
Wood-base Materials. Section 16.1.1
ASTM D4457-85, (Reapproved 1991), Test Method for Appendix A to Part
Determination of Dichloromethane and 1,1,1- 60, Method 24,
Trichloroethane in Paints and Coatings by Direct Section 6.5
Injection into a Gas Chromatograph.
ASTM D 6216-98, Standard Practice for Opacity Appendix B to Part
Monitor Manufacturers To Certify Conformance 60, Specification 1,
with Design and Performance Specifications. Section 8.2

U.S. Environmental Protection Agency

401 M Street, SW., Washington, DC 20460
Test Methods for Evaluating Solid Waste, Physical/ Appendix A to Part
Chemical Methods, EPA Publication SW-846 Third 60, Method 29, pars.
Edition (November, 1986), as amended by Updates 2.2.1, 2.3.1, 2.5,
I (July 1992), II (September 1994), IIA (August 3.3.12.1, 3.3.12.2,
1993) and IIB (January 1995). 3.3.13, 3.3.14,
5.4.3, 6.2, 6.3,
7.2.1, 7.2.3, and
Table 29-2

[[Page 685]]

Table of CFR Titles and Chapters

(Revised as of July 1, 2001)

Title 1--General Provisions

I Administrative Committee of the Federal Register
(Parts 1--49)
II Office of the Federal Register (Parts 50--299)
IV Miscellaneous Agencies (Parts 400--500)

Title 2--[Reserved]

Title 3--The President

I Executive Office of the President (Parts 100--199)

Title 4--Accounts

I General Accounting Office (Parts 1--99)

Title 5--Administrative Personnel

I Office of Personnel Management (Parts 1--1199)
II Merit Systems Protection Board (Parts 1200--1299)
III Office of Management and Budget (Parts 1300--1399)
V The International Organizations Employees Loyalty
Board (Parts 1500--1599)
VI Federal Retirement Thrift Investment Board (Parts
1600--1699)
VII Advisory Commission on Intergovernmental Relations
(Parts 1700--1799)
VIII Office of Special Counsel (Parts 1800--1899)
IX Appalachian Regional Commission (Parts 1900--1999)
XI Armed Forces Retirement Home (Part 2100)
XIV Federal Labor Relations Authority, General Counsel of
the Federal Labor Relations Authority and Federal
Service Impasses Panel (Parts 2400--2499)
XV Office of Administration, Executive Office of the
President (Parts 2500--2599)
XVI Office of Government Ethics (Parts 2600--2699)
XXI Department of the Treasury (Parts 3100--3199)
XXII Federal Deposit Insurance Corporation (Part 3201)
XXIII Department of Energy (Part 3301)
XXIV Federal Energy Regulatory Commission (Part 3401)

[[Page 686]]

XXV Department of the Interior (Part 3501)
XXVI Department of Defense (Part 3601)
XXVIII Department of Justice (Part 3801)
XXIX Federal Communications Commission (Parts 3900--3999)
XXX Farm Credit System Insurance Corporation (Parts 4000--
4099)
XXXI Farm Credit Administration (Parts 4100--4199)
XXXIII Overseas Private Investment Corporation (Part 4301)
XXXV Office of Personnel Management (Part 4501)
XL Interstate Commerce Commission (Part 5001)
XLI Commodity Futures Trading Commission (Part 5101)
XLII Department of Labor (Part 5201)
XLIII National Science Foundation (Part 5301)
XLV Department of Health and Human Services (Part 5501)
XLVI Postal Rate Commission (Part 5601)
XLVII Federal Trade Commission (Part 5701)
XLVIII Nuclear Regulatory Commission (Part 5801)
L Department of Transportation (Part 6001)
LII Export-Import Bank of the United States (Part 6201)
LIII Department of Education (Parts 6300--6399)
LIV Environmental Protection Agency (Part 6401)
LVII General Services Administration (Part 6701)
LVIII Board of Governors of the Federal Reserve System (Part
6801)
LIX National Aeronautics and Space Administration (Part
6901)
LX United States Postal Service (Part 7001)
LXI National Labor Relations Board (Part 7101)
LXII Equal Employment Opportunity Commission (Part 7201)
LXIII Inter-American Foundation (Part 7301)
LXV Department of Housing and Urban Development (Part
7501)
LXVI National Archives and Records Administration (Part
7601)
LXIX Tennessee Valley Authority (Part 7901)
LXXI Consumer Product Safety Commission (Part 8101)
LXXIII Department of Agriculture (Part 8301)
LXXIV Federal Mine Safety and Health Review Commission (Part
8401)
LXXVI Federal Retirement Thrift Investment Board (Part 8601)
LXXVII Office of Management and Budget (Part 8701)

Title 6--[Reserved]

Title 7--Agriculture

Subtitle A--Office of the Secretary of Agriculture
(Parts 0--26)
Subtitle B--Regulations of the Department of
Agriculture

[[Page 687]]

I Agricultural Marketing Service (Standards,
Inspections, Marketing Practices), Department of
Agriculture (Parts 27--209)
II Food and Nutrition Service, Department of Agriculture
(Parts 210--299)
III Animal and Plant Health Inspection Service, Department
of Agriculture (Parts 300--399)
IV Federal Crop Insurance Corporation, Department of
Agriculture (Parts 400--499)
V Agricultural Research Service, Department of
Agriculture (Parts 500--599)
VI Natural Resources Conservation Service, Department of
Agriculture (Parts 600--699)
VII Farm Service Agency, Department of Agriculture (Parts
700--799)
VIII Grain Inspection, Packers and Stockyards
Administration (Federal Grain Inspection Service),
Department of Agriculture (Parts 800--899)
IX Agricultural Marketing Service (Marketing Agreements
and Orders; Fruits, Vegetables, Nuts), Department
of Agriculture (Parts 900--999)
X Agricultural Marketing Service (Marketing Agreements
and Orders; Milk), Department of Agriculture
(Parts 1000--1199)
XI Agricultural Marketing Service (Marketing Agreements
and Orders; Miscellaneous Commodities), Department
of Agriculture (Parts 1200--1299)
XIII Northeast Dairy Compact Commission (Parts 1300--1399)
XIV Commodity Credit Corporation, Department of
Agriculture (Parts 1400--1499)
XV Foreign Agricultural Service, Department of
Agriculture (Parts 1500--1599)
XVI Rural Telephone Bank, Department of Agriculture (Parts
1600--1699)
XVII Rural Utilities Service, Department of Agriculture
(Parts 1700--1799)
XVIII Rural Housing Service, Rural Business-Cooperative
Service, Rural Utilities Service, and Farm Service
Agency, Department of Agriculture (Parts 1800--
2099)
XXVI Office of Inspector General, Department of Agriculture
(Parts 2600--2699)
XXVII Office of Information Resources Management, Department
of Agriculture (Parts 2700--2799)
XXVIII Office of Operations, Department of Agriculture (Parts
2800--2899)
XXIX Office of Energy, Department of Agriculture (Parts
2900--2999)
XXX Office of the Chief Financial Officer, Department of
Agriculture (Parts 3000--3099)
XXXI Office of Environmental Quality, Department of
Agriculture (Parts 3100--3199)
XXXII Office of Procurement and Property Management,
Department of Agriculture (Parts 3200--3299)

[[Page 688]]

XXXIII Office of Transportation, Department of Agriculture
(Parts 3300--3399)
XXXIV Cooperative State Research, Education, and Extension
Service, Department of Agriculture (Parts 3400--
3499)
XXXV Rural Housing Service, Department of Agriculture
(Parts 3500--3599)
XXXVI National Agricultural Statistics Service, Department
of Agriculture (Parts 3600--3699)
XXXVII Economic Research Service, Department of Agriculture
(Parts 3700--3799)
XXXVIII World Agricultural Outlook Board, Department of
Agriculture (Parts 3800--3899)
XLI [Reserved]
XLII Rural Business-Cooperative Service and Rural Utilities
Service, Department of Agriculture (Parts 4200--
4299)

Title 8--Aliens and Nationality

I Immigration and Naturalization Service, Department of
Justice (Parts 1--599)

Title 9--Animals and Animal Products

I Animal and Plant Health Inspection Service, Department
of Agriculture (Parts 1--199)
II Grain Inspection, Packers and Stockyards
Administration (Packers and Stockyards Programs),
Department of Agriculture (Parts 200--299)
III Food Safety and Inspection Service, Department of
Agriculture (Parts 300--599)

Title 10--Energy

I Nuclear Regulatory Commission (Parts 0--199)
II Department of Energy (Parts 200--699)
III Department of Energy (Parts 700--999)
X Department of Energy (General Provisions) (Parts
1000--1099)
XVII Defense Nuclear Facilities Safety Board (Parts 1700--
1799)
XVIII Northeast Interstate Low-Level Radioactive Waste
Commission (Part 1800)

Title 11--Federal Elections

I Federal Election Commission (Parts 1--9099)

Title 12--Banks and Banking

I Comptroller of the Currency, Department of the
Treasury (Parts 1--199)

[[Page 689]]

II Federal Reserve System (Parts 200--299)
III Federal Deposit Insurance Corporation (Parts 300--399)
IV Export-Import Bank of the United States (Parts 400--
499)
V Office of Thrift Supervision, Department of the
Treasury (Parts 500--599)
VI Farm Credit Administration (Parts 600--699)
VII National Credit Union Administration (Parts 700--799)
VIII Federal Financing Bank (Parts 800--899)
IX Federal Housing Finance Board (Parts 900--999)
XI Federal Financial Institutions Examination Council
(Parts 1100--1199)
XIV Farm Credit System Insurance Corporation (Parts 1400--
1499)
XV Department of the Treasury (Parts 1500--1599)
XVII Office of Federal Housing Enterprise Oversight,
Department of Housing and Urban Development (Parts
1700--1799)
XVIII Community Development Financial Institutions Fund,
Department of the Treasury (Parts 1800--1899)

Title 13--Business Credit and Assistance

I Small Business Administration (Parts 1--199)
III Economic Development Administration, Department of
Commerce (Parts 300--399)
IV Emergency Steel Guarantee Loan Board (Parts 400--499)
V Emergency Oil and Gas Guaranteed Loan Board (Parts
500--599)

Title 14--Aeronautics and Space

I Federal Aviation Administration, Department of
Transportation (Parts 1--199)
II Office of the Secretary, Department of Transportation
(Aviation Proceedings) (Parts 200--399)
III Commercial Space Transportation, Federal Aviation
Administration, Department of Transportation
(Parts 400--499)
V National Aeronautics and Space Administration (Parts
1200--1299)

Title 15--Commerce and Foreign Trade

Subtitle A--Office of the Secretary of Commerce (Parts
0--29)
Subtitle B--Regulations Relating to Commerce and
Foreign Trade
I Bureau of the Census, Department of Commerce (Parts
30--199)
II National Institute of Standards and Technology,
Department of Commerce (Parts 200--299)
III International Trade Administration, Department of
Commerce (Parts 300--399)

[[Page 690]]

IV Foreign-Trade Zones Board, Department of Commerce
(Parts 400--499)
VII Bureau of Export Administration, Department of
Commerce (Parts 700--799)
VIII Bureau of Economic Analysis, Department of Commerce
(Parts 800--899)
IX National Oceanic and Atmospheric Administration,
Department of Commerce (Parts 900--999)
XI Technology Administration, Department of Commerce
(Parts 1100--1199)
XIII East-West Foreign Trade Board (Parts 1300--1399)
XIV Minority Business Development Agency (Parts 1400--
1499)
Subtitle C--Regulations Relating to Foreign Trade
Agreements
XX Office of the United States Trade Representative
(Parts 2000--2099)
Subtitle D--Regulations Relating to Telecommunications
and Information
XXIII National Telecommunications and Information
Administration, Department of Commerce (Parts
2300--2399)

Title 16--Commercial Practices

I Federal Trade Commission (Parts 0--999)
II Consumer Product Safety Commission (Parts 1000--1799)

Title 17--Commodity and Securities Exchanges

I Commodity Futures Trading Commission (Parts 1--199)
II Securities and Exchange Commission (Parts 200--399)
IV Department of the Treasury (Parts 400--499)

Title 18--Conservation of Power and Water Resources

I Federal Energy Regulatory Commission, Department of
Energy (Parts 1--399)
III Delaware River Basin Commission (Parts 400--499)
VI Water Resources Council (Parts 700--799)
VIII Susquehanna River Basin Commission (Parts 800--899)
XIII Tennessee Valley Authority (Parts 1300--1399)

Title 19--Customs Duties

I United States Customs Service, Department of the
Treasury (Parts 1--199)
II United States International Trade Commission (Parts
200--299)
III International Trade Administration, Department of
Commerce (Parts 300--399)

[[Page 691]]

Title 20--Employees' Benefits

I Office of Workers' Compensation Programs, Department
of Labor (Parts 1--199)
II Railroad Retirement Board (Parts 200--399)
III Social Security Administration (Parts 400--499)
IV Employees' Compensation Appeals Board, Department of
Labor (Parts 500--599)
V Employment and Training Administration, Department of
Labor (Parts 600--699)
VI Employment Standards Administration, Department of
Labor (Parts 700--799)
VII Benefits Review Board, Department of Labor (Parts
800--899)
VIII Joint Board for the Enrollment of Actuaries (Parts
900--999)
IX Office of the Assistant Secretary for Veterans'
Employment and Training, Department of Labor
(Parts 1000--1099)

Title 21--Food and Drugs

I Food and Drug Administration, Department of Health and
Human Services (Parts 1--1299)
II Drug Enforcement Administration, Department of Justice
(Parts 1300--1399)
III Office of National Drug Control Policy (Parts 1400--
1499)

Title 22--Foreign Relations

I Department of State (Parts 1--199)
II Agency for International Development (Parts 200--299)
III Peace Corps (Parts 300--399)
IV International Joint Commission, United States and
Canada (Parts 400--499)
V Broadcasting Board of Governors (Parts 500--599)
VII Overseas Private Investment Corporation (Parts 700--
799)
IX Foreign Service Grievance Board Regulations (Parts
900--999)
X Inter-American Foundation (Parts 1000--1099)
XI International Boundary and Water Commission, United
States and Mexico, United States Section (Parts
1100--1199)
XII United States International Development Cooperation
Agency (Parts 1200--1299)
XIII Board for International Broadcasting (Parts 1300--
1399)
XIV Foreign Service Labor Relations Board; Federal Labor
Relations Authority; General Counsel of the
Federal Labor Relations Authority; and the Foreign
Service Impasse Disputes Panel (Parts 1400--1499)
XV African Development Foundation (Parts 1500--1599)
XVI Japan-United States Friendship Commission (Parts
1600--1699)
XVII United States Institute of Peace (Parts 1700--1799)

[[Page 692]]

Title 23--Highways

I Federal Highway Administration, Department of
Transportation (Parts 1--999)
II National Highway Traffic Safety Administration and
Federal Highway Administration, Department of
Transportation (Parts 1200--1299)
III National Highway Traffic Safety Administration,
Department of Transportation (Parts 1300--1399)

Title 24--Housing and Urban Development

Subtitle A--Office of the Secretary, Department of
Housing and Urban Development (Parts 0--99)
Subtitle B--Regulations Relating to Housing and Urban
Development
I Office of Assistant Secretary for Equal Opportunity,
Department of Housing and Urban Development (Parts
100--199)
II Office of Assistant Secretary for Housing-Federal
Housing Commissioner, Department of Housing and
Urban Development (Parts 200--299)
III Government National Mortgage Association, Department
of Housing and Urban Development (Parts 300--399)
IV Office of Housing and Office of Multifamily Housing
Assistance Restructuring, Department of Housing
and Urban Development (Parts 400--499)
V Office of Assistant Secretary for Community Planning
and Development, Department of Housing and Urban
Development (Parts 500--599)
VI Office of Assistant Secretary for Community Planning
and Development, Department of Housing and Urban
Development (Parts 600--699) [Reserved]
VII Office of the Secretary, Department of Housing and
Urban Development (Housing Assistance Programs and
Public and Indian Housing Programs) (Parts 700--
799)
VIII Office of the Assistant Secretary for Housing--Federal
Housing Commissioner, Department of Housing and
Urban Development (Section 8 Housing Assistance
Programs, Section 202 Direct Loan Program, Section
202 Supportive Housing for the Elderly Program and
Section 811 Supportive Housing for Persons With
Disabilities Program) (Parts 800--899)
IX Office of Assistant Secretary for Public and Indian
Housing, Department of Housing and Urban
Development (Parts 900--999)
X Office of Assistant Secretary for Housing--Federal
Housing Commissioner, Department of Housing and
Urban Development (Interstate Land Sales
Registration Program) (Parts 1700--1799)
XII Office of Inspector General, Department of Housing and
Urban Development (Parts 2000--2099)
XX Office of Assistant Secretary for Housing--Federal
Housing Commissioner, Department of Housing and
Urban Development (Parts 3200--3899)
XXV Neighborhood Reinvestment Corporation (Parts 4100--
4199)

[[Page 693]]

Title 25--Indians

I Bureau of Indian Affairs, Department of the Interior
(Parts 1--299)
II Indian Arts and Crafts Board, Department of the
Interior (Parts 300--399)
III National Indian Gaming Commission, Department of the
Interior (Parts 500--599)
IV Office of Navajo and Hopi Indian Relocation (Parts
700--799)
V Bureau of Indian Affairs, Department of the Interior,
and Indian Health Service, Department of Health
and Human Services (Part 900)
VI Office of the Assistant Secretary-Indian Affairs,
Department of the Interior (Parts 1000--1199)
VII Office of the Special Trustee for American Indians,
Department of the Interior (Part 1200)

Title 26--Internal Revenue

I Internal Revenue Service, Department of the Treasury
(Parts 1--799)

Title 27--Alcohol, Tobacco Products and Firearms

I Bureau of Alcohol, Tobacco and Firearms, Department of
the Treasury (Parts 1--299)

Title 28--Judicial Administration

I Department of Justice (Parts 0--199)
III Federal Prison Industries, Inc., Department of Justice
(Parts 300--399)
V Bureau of Prisons, Department of Justice (Parts 500--
599)
VI Offices of Independent Counsel, Department of Justice
(Parts 600--699)
VII Office of Independent Counsel (Parts 700--799)
VIII Court Services and Offender Supervision Agency for the
District of Columbia (Parts 800--899)
IX National Crime Prevention and Privacy Compact Council
(Parts 900--999)

Title 29--Labor

Subtitle A--Office of the Secretary of Labor (Parts
0--99)
Subtitle B--Regulations Relating to Labor
I National Labor Relations Board (Parts 100--199)
II Office of Labor-Management Standards, Department of
Labor (Parts 200--299)
III National Railroad Adjustment Board (Parts 300--399)
IV Office of Labor-Management Standards, Department of
Labor (Parts 400--499)

[[Page 694]]

V Wage and Hour Division, Department of Labor (Parts
500--899)
IX Construction Industry Collective Bargaining Commission
(Parts 900--999)
X National Mediation Board (Parts 1200--1299)
XII Federal Mediation and Conciliation Service (Parts
1400--1499)
XIV Equal Employment Opportunity Commission (Parts 1600--
1699)
XVII Occupational Safety and Health Administration,
Department of Labor (Parts 1900--1999)
XX Occupational Safety and Health Review Commission
(Parts 2200--2499)
XXV Pension and Welfare Benefits Administration,
Department of Labor (Parts 2500--2599)
XXVII Federal Mine Safety and Health Review Commission
(Parts 2700--2799)
XL Pension Benefit Guaranty Corporation (Parts 4000--
4999)

Title 30--Mineral Resources

I Mine Safety and Health Administration, Department of
Labor (Parts 1--199)
II Minerals Management Service, Department of the
Interior (Parts 200--299)
III Board of Surface Mining and Reclamation Appeals,
Department of the Interior (Parts 300--399)
IV Geological Survey, Department of the Interior (Parts
400--499)
VI Bureau of Mines, Department of the Interior (Parts
600--699)
VII Office of Surface Mining Reclamation and Enforcement,
Department of the Interior (Parts 700--999)

Title 31--Money and Finance: Treasury

Subtitle A--Office of the Secretary of the Treasury
(Parts 0--50)
Subtitle B--Regulations Relating to Money and Finance
I Monetary Offices, Department of the Treasury (Parts
51--199)
II Fiscal Service, Department of the Treasury (Parts
200--399)
IV Secret Service, Department of the Treasury (Parts
400--499)
V Office of Foreign Assets Control, Department of the
Treasury (Parts 500--599)
VI Bureau of Engraving and Printing, Department of the
Treasury (Parts 600--699)
VII Federal Law Enforcement Training Center, Department of
the Treasury (Parts 700--799)
VIII Office of International Investment, Department of the
Treasury (Parts 800--899)
IX Federal Claims Collection Standards (Department of the
Treasury--Department of Justice) (Parts 900--999)

[[Page 695]]

Title 32--National Defense

Subtitle A--Department of Defense
I Office of the Secretary of Defense (Parts 1--399)
V Department of the Army (Parts 400--699)
VI Department of the Navy (Parts 700--799)
VII Department of the Air Force (Parts 800--1099)
Subtitle B--Other Regulations Relating to National
Defense
XII Defense Logistics Agency (Parts 1200--1299)
XVI Selective Service System (Parts 1600--1699)
XVIII National Counterintelligence Center (Parts 1800--1899)
XIX Central Intelligence Agency (Parts 1900--1999)
XX Information Security Oversight Office, National
Archives and Records Administration (Parts 2000--
2099)
XXI National Security Council (Parts 2100--2199)
XXIV Office of Science and Technology Policy (Parts 2400--
2499)
XXVII Office for Micronesian Status Negotiations (Parts
2700--2799)
XXVIII Office of the Vice President of the United States
(Parts 2800--2899)

Title 33--Navigation and Navigable Waters

I Coast Guard, Department of Transportation (Parts 1--
199)
II Corps of Engineers, Department of the Army (Parts
200--399)
IV Saint Lawrence Seaway Development Corporation,
Department of Transportation (Parts 400--499)

Title 34--Education

Subtitle A--Office of the Secretary, Department of
Education (Parts 1--99)
Subtitle B--Regulations of the Offices of the
Department of Education
I Office for Civil Rights, Department of Education
(Parts 100--199)
II Office of Elementary and Secondary Education,
Department of Education (Parts 200--299)
III Office of Special Education and Rehabilitative
Services, Department of Education (Parts 300--399)
IV Office of Vocational and Adult Education, Department
of Education (Parts 400--499)
V Office of Bilingual Education and Minority Languages
Affairs, Department of Education (Parts 500--599)
VI Office of Postsecondary Education, Department of
Education (Parts 600--699)
VII Office of Educational Research and Improvement,
Department of Education (Parts 700--799)
XI National Institute for Literacy (Parts 1100--1199)
Subtitle C--Regulations Relating to Education
XII National Council on Disability (Parts 1200--1299)

[[Page 696]]

Title 35--Panama Canal

I Panama Canal Regulations (Parts 1--299)

Title 36--Parks, Forests, and Public Property

I National Park Service, Department of the Interior
(Parts 1--199)
II Forest Service, Department of Agriculture (Parts 200--
299)
III Corps of Engineers, Department of the Army (Parts
300--399)
IV American Battle Monuments Commission (Parts 400--499)
V Smithsonian Institution (Parts 500--599)
VII Library of Congress (Parts 700--799)
VIII Advisory Council on Historic Preservation (Parts 800--
899)
IX Pennsylvania Avenue Development Corporation (Parts
900--999)
X Presidio Trust (Parts 1000--1099)
XI Architectural and Transportation Barriers Compliance
Board (Parts 1100--1199)
XII National Archives and Records Administration (Parts
1200--1299)
XV Oklahoma City National Memorial Trust (Part 1501)
XVI Morris K. Udall Scholarship and Excellence in National
Environmental Policy Foundation (Parts 1600--1699)

Title 37--Patents, Trademarks, and Copyrights

I United States Patent and Trademark Office, Department
of Commerce (Parts 1--199)
II Copyright Office, Library of Congress (Parts 200--299)
IV Assistant Secretary for Technology Policy, Department
of Commerce (Parts 400--499)
V Under Secretary for Technology, Department of Commerce
(Parts 500--599)

Title 38--Pensions, Bonuses, and Veterans' Relief

I Department of Veterans Affairs (Parts 0--99)

Title 39--Postal Service

I United States Postal Service (Parts 1--999)
III Postal Rate Commission (Parts 3000--3099)

Title 40--Protection of Environment

I Environmental Protection Agency (Parts 1--799)
IV Environmental Protection Agency and Department of
Justice (Parts 1400--1499)
V Council on Environmental Quality (Parts 1500--1599)
VI Chemical Safety and Hazard Investigation Board (Parts
1600--1699)

[[Page 697]]

VII Environmental Protection Agency and Department of
Defense; Uniform National Discharge Standards for
Vessels of the Armed Forces (Parts 1700--1799)

Title 41--Public Contracts and Property Management

Subtitle B--Other Provisions Relating to Public
Contracts
50 Public Contracts, Department of Labor (Parts 50-1--50-
999)
51 Committee for Purchase From People Who Are Blind or
Severely Disabled (Parts 51-1--51-99)
60 Office of Federal Contract Compliance Programs, Equal
Employment Opportunity, Department of Labor (Parts
60-1--60-999)
61 Office of the Assistant Secretary for Veterans
Employment and Training, Department of Labor
(Parts 61-1--61-999)
Subtitle C--Federal Property Management Regulations
System
101 Federal Property Management Regulations (Parts 101-1--
101-99)
102 Federal Management Regulation (Parts 102-1--102-299)
105 General Services Administration (Parts 105-1--105-999)
109 Department of Energy Property Management Regulations
(Parts 109-1--109-99)
114 Department of the Interior (Parts 114-1--114-99)
115 Environmental Protection Agency (Parts 115-1--115-99)
128 Department of Justice (Parts 128-1--128-99)
Subtitle D--Other Provisions Relating to Property
Management [Reserved]
Subtitle E--Federal Information Resources Management
Regulations System
201 Federal Information Resources Management Regulation
(Parts 201-1--201-99) [Reserved]
Subtitle F--Federal Travel Regulation System
300 General (Parts 300-1--300-99)
301 Temporary Duty (TDY) Travel Allowances (Parts 301-1--
301-99)
302 Relocation Allowances (Parts 302-1--302-99)
303 Payment of Expenses Connected with the Death of
Certain Employees (Part 303-70)
304 Payment from a Non-Federal Source for Travel Expenses
(Parts 304-1--304-99)

Title 42--Public Health

I Public Health Service, Department of Health and Human
Services (Parts 1--199)
IV Health Care Financing Administration, Department of
Health and Human Services (Parts 400--499)
V Office of Inspector General-Health Care, Department of
Health and Human Services (Parts 1000--1999)

[[Page 698]]

Title 43--Public Lands: Interior

Subtitle A--Office of the Secretary of the Interior
(Parts 1--199)
Subtitle B--Regulations Relating to Public Lands
I Bureau of Reclamation, Department of the Interior
(Parts 200--499)
II Bureau of Land Management, Department of the Interior
(Parts 1000--9999)
III Utah Reclamation Mitigation and Conservation
Commission (Parts 10000--10005)

Title 44--Emergency Management and Assistance

I Federal Emergency Management Agency (Parts 0--399)
IV Department of Commerce and Department of
Transportation (Parts 400--499)

Title 45--Public Welfare

Subtitle A--Department of Health and Human Services
(Parts 1--199)
Subtitle B--Regulations Relating to Public Welfare
II Office of Family Assistance (Assistance Programs),
Administration for Children and Families,
Department of Health and Human Services (Parts
200--299)
III Office of Child Support Enforcement (Child Support
Enforcement Program), Administration for Children
and Families, Department of Health and Human
Services (Parts 300--399)
IV Office of Refugee Resettlement, Administration for
Children and Families Department of Health and
Human Services (Parts 400--499)
V Foreign Claims Settlement Commission of the United
States, Department of Justice (Parts 500--599)
VI National Science Foundation (Parts 600--699)
VII Commission on Civil Rights (Parts 700--799)
VIII Office of Personnel Management (Parts 800--899)
X Office of Community Services, Administration for
Children and Families, Department of Health and
Human Services (Parts 1000--1099)
XI National Foundation on the Arts and the Humanities
(Parts 1100--1199)
XII Corporation for National and Community Service (Parts
1200--1299)
XIII Office of Human Development Services, Department of
Health and Human Services (Parts 1300--1399)
XVI Legal Services Corporation (Parts 1600--1699)
XVII National Commission on Libraries and Information
Science (Parts 1700--1799)
XVIII Harry S. Truman Scholarship Foundation (Parts 1800--
1899)
XXI Commission on Fine Arts (Parts 2100--2199)

[[Page 699]]

XXIII Arctic Research Commission (Part 2301)
XXIV James Madison Memorial Fellowship Foundation (Parts
2400--2499)
XXV Corporation for National and Community Service (Parts
2500--2599)

Title 46--Shipping

I Coast Guard, Department of Transportation (Parts 1--
199)
II Maritime Administration, Department of Transportation
(Parts 200--399)
III Coast Guard (Great Lakes Pilotage), Department of
Transportation (Parts 400--499)
IV Federal Maritime Commission (Parts 500--599)

Title 47--Telecommunication

I Federal Communications Commission (Parts 0--199)
II Office of Science and Technology Policy and National
Security Council (Parts 200--299)
III National Telecommunications and Information
Administration, Department of Commerce (Parts
300--399)

Title 48--Federal Acquisition Regulations System

1 Federal Acquisition Regulation (Parts 1--99)
2 Department of Defense (Parts 200--299)
3 Department of Health and Human Services (Parts 300--
399)
4 Department of Agriculture (Parts 400--499)
5 General Services Administration (Parts 500--599)
6 Department of State (Parts 600--699)
7 United States Agency for International Development
(Parts 700--799)
8 Department of Veterans Affairs (Parts 800--899)
9 Department of Energy (Parts 900--999)
10 Department of the Treasury (Parts 1000--1099)
12 Department of Transportation (Parts 1200--1299)
13 Department of Commerce (Parts 1300--1399)
14 Department of the Interior (Parts 1400--1499)
15 Environmental Protection Agency (Parts 1500--1599)
16 Office of Personnel Management Federal Employees
Health Benefits Acquisition Regulation (Parts
1600--1699)
17 Office of Personnel Management (Parts 1700--1799)
18 National Aeronautics and Space Administration (Parts
1800--1899)
19 Broadcasting Board of Governors (Parts 1900--1999)
20 Nuclear Regulatory Commission (Parts 2000--2099)

[[Page 700]]

21 Office of Personnel Management, Federal Employees
Group Life Insurance Federal Acquisition
Regulation (Parts 2100--2199)
23 Social Security Administration (Parts 2300--2399)
24 Department of Housing and Urban Development (Parts
2400--2499)
25 National Science Foundation (Parts 2500--2599)
28 Department of Justice (Parts 2800--2899)
29 Department of Labor (Parts 2900--2999)
34 Department of Education Acquisition Regulation (Parts
3400--3499)
35 Panama Canal Commission (Parts 3500--3599)
44 Federal Emergency Management Agency (Parts 4400--4499)
51 Department of the Army Acquisition Regulations (Parts
5100--5199)
52 Department of the Navy Acquisition Regulations (Parts
5200--5299)
53 Department of the Air Force Federal Acquisition
Regulation Supplement (Parts 5300--5399)
54 Defense Logistics Agency, Department of Defense (Part
5452)
57 African Development Foundation (Parts 5700--5799)
61 General Services Administration Board of Contract
Appeals (Parts 6100--6199)
63 Department of Transportation Board of Contract Appeals
(Parts 6300--6399)
99 Cost Accounting Standards Board, Office of Federal
Procurement Policy, Office of Management and
Budget (Parts 9900--9999)

Title 49--Transportation

Subtitle A--Office of the Secretary of Transportation
(Parts 1--99)
Subtitle B--Other Regulations Relating to
Transportation
I Research and Special Programs Administration,
Department of Transportation (Parts 100--199)
II Federal Railroad Administration, Department of
Transportation (Parts 200--299)
III Federal Motor Carrier Safety Administration,
Department of Transportation (Parts 300--399)
IV Coast Guard, Department of Transportation (Parts 400--
499)
V National Highway Traffic Safety Administration,
Department of Transportation (Parts 500--599)
VI Federal Transit Administration, Department of
Transportation (Parts 600--699)
VII National Railroad Passenger Corporation (AMTRAK)
(Parts 700--799)
VIII National Transportation Safety Board (Parts 800--999)
X Surface Transportation Board, Department of
Transportation (Parts 1000--1399)

[[Page 701]]

XI Bureau of Transportation Statistics, Department of
Transportation (Parts 1400--1499)

Title 50--Wildlife and Fisheries

I United States Fish and Wildlife Service, Department of
the Interior (Parts 1--199)
II National Marine Fisheries Service, National Oceanic
and Atmospheric Administration, Department of
Commerce (Parts 200--299)
III International Fishing and Related Activities (Parts
300--399)
IV Joint Regulations (United States Fish and Wildlife
Service, Department of the Interior and National
Marine Fisheries Service, National Oceanic and
Atmospheric Administration, Department of
Commerce); Endangered Species Committee
Regulations (Parts 400--499)
V Marine Mammal Commission (Parts 500--599)
VI Fishery Conservation and Management, National Oceanic
and Atmospheric Administration, Department of
Commerce (Parts 600--699)

CFR Index and Finding Aids

Subject/Agency Index
List of Agency Prepared Indexes
Parallel Tables of Statutory Authorities and Rules
List of CFR Titles, Chapters, Subchapters, and Parts
Alphabetical List of Agencies Appearing in the CFR

[[Page 703]]

Alphabetical List of Agencies Appearing in the CFR

(Revised as of July 1, 2001)

CFR Title, Subtitle or
Agency Chapter

Administrative Committee of the Federal Register 1, I
Advanced Research Projects Agency 32, I
Advisory Commission on Intergovernmental 5, VII
Relations
Advisory Council on Historic Preservation 36, VIII
African Development Foundation 22, XV
Federal Acquisition Regulation 48, 57
Agency for International Development, United 22, II
States
Federal Acquisition Regulation 48, 7
Agricultural Marketing Service 7, I, IX, X, XI
Agricultural Research Service 7, V
Agriculture Department 5, LXXIII
Agricultural Marketing Service 7, I, IX, X, XI
Agricultural Research Service 7, V
Animal and Plant Health Inspection Service 7, III; 9, I
Chief Financial Officer, Office of 7, XXX
Commodity Credit Corporation 7, XIV
Cooperative State Research, Education, and 7, XXXIV
Extension Service
Economic Research Service 7, XXXVII
Energy, Office of 7, XXIX
Environmental Quality, Office of 7, XXXI
Farm Service Agency 7, VII, XVIII
Federal Acquisition Regulation 48, 4
Federal Crop Insurance Corporation 7, IV
Food and Nutrition Service 7, II
Food Safety and Inspection Service 9, III
Foreign Agricultural Service 7, XV
Forest Service 36, II
Grain Inspection, Packers and Stockyards 7, VIII; 9, II
Administration
Information Resources Management, Office of 7, XXVII
Inspector General, Office of 7, XXVI
National Agricultural Library 7, XLI
National Agricultural Statistics Service 7, XXXVI
Natural Resources Conservation Service 7, VI
Operations, Office of 7, XXVIII
Procurement and Property Management, Office of 7, XXXII
Rural Business-Cooperative Service 7, XVIII, XLII
Rural Development Administration 7, XLII
Rural Housing Service 7, XVIII, XXXV
Rural Telephone Bank 7, XVI
Rural Utilities Service 7, XVII, XVIII, XLII
Secretary of Agriculture, Office of 7, Subtitle A
Transportation, Office of 7, XXXIII
World Agricultural Outlook Board 7, XXXVIII
Air Force Department 32, VII
Federal Acquisition Regulation Supplement 48, 53
Alcohol, Tobacco and Firearms, Bureau of 27, I
AMTRAK 49, VII
American Battle Monuments Commission 36, IV
American Indians, Office of the Special Trustee 25, VII
Animal and Plant Health Inspection Service 7, III; 9, I
Appalachian Regional Commission 5, IX
Architectural and Transportation Barriers 36, XI
Compliance Board
[[Page 704]]

Arctic Research Commission 45, XXIII
Armed Forces Retirement Home 5, XI
Army Department 32, V
Engineers, Corps of 33, II; 36, III
Federal Acquisition Regulation 48, 51
Benefits Review Board 20, VII
Bilingual Education and Minority Languages 34, V
Affairs, Office of
Blind or Severely Disabled, Committee for 41, 51
Purchase From People Who Are
Board for International Broadcasting 22, XIII
Broadcasting Board of Governors 22, V
Federal Acquisition Regulation 48, 19
Census Bureau 15, I
Central Intelligence Agency 32, XIX
Chief Financial Officer, Office of 7, XXX
Child Support Enforcement, Office of 45, III
Children and Families, Administration for 45, II, III, IV, X
Civil Rights, Commission on 45, VII
Civil Rights, Office for 34, I
Coast Guard 33, I; 46, I; 49, IV
Coast Guard (Great Lakes Pilotage) 46, III
Commerce Department 44, IV
Census Bureau 15, I
Economic Affairs, Under Secretary 37, V
Economic Analysis, Bureau of 15, VIII
Economic Development Administration 13, III
Emergency Management and Assistance 44, IV
Export Administration, Bureau of 15, VII
Federal Acquisition Regulation 48, 13
Fishery Conservation and Management 50, VI
Foreign-Trade Zones Board 15, IV
International Trade Administration 15, III; 19, III
National Institute of Standards and Technology 15, II
National Marine Fisheries Service 50, II, IV, VI
National Oceanic and Atmospheric 15, IX; 50, II, III, IV,
Administration VI
National Telecommunications and Information 15, XXIII; 47, III
Administration
National Weather Service 15, IX
Patent and Trademark Office, United States 37, I
Productivity, Technology and Innovation, 37, IV
Assistant Secretary for
Secretary of Commerce, Office of 15, Subtitle A
Technology, Under Secretary for 37, V
Technology Administration 15, XI
Technology Policy, Assistant Secretary for 37, IV
Commercial Space Transportation 14, III
Commodity Credit Corporation 7, XIV
Commodity Futures Trading Commission 5, XLI; 17, I
Community Planning and Development, Office of 24, V, VI
Assistant Secretary for
Community Services, Office of 45, X
Comptroller of the Currency 12, I
Construction Industry Collective Bargaining 29, IX
Commission
Consumer Product Safety Commission 5, LXXI; 16, II
Cooperative State Research, Education, and 7, XXXIV
Extension Service
Copyright Office 37, II
Corporation for National and Community Service 45, XII, XXV
Cost Accounting Standards Board 48, 99
Council on Environmental Quality 40, V
Court Services and Offender Supervision Agency 28, VIII
for the District of Columbia
Customs Service, United States 19, I
Defense Contract Audit Agency 32, I
Defense Department 5, XXVI; 32, Subtitle A;
40, VII
Advanced Research Projects Agency 32, I

[[Page 705]]

Air Force Department 32, VII
Army Department 32, V; 33, II; 36, III,
48, 51
Defense Intelligence Agency 32, I
Defense Logistics Agency 32, I, XII; 48, 54
Engineers, Corps of 33, II; 36, III
Federal Acquisition Regulation 48, 2
National Imagery and Mapping Agency 32, I
Navy Department 32, VI; 48, 52
Secretary of Defense, Office of 32, I
Defense Contract Audit Agency 32, I
Defense Intelligence Agency 32, I
Defense Logistics Agency 32, XII; 48, 54
Defense Nuclear Facilities Safety Board 10, XVII
Delaware River Basin Commission 18, III
District of Columbia, Court Services and 28, VIII
Offender Supervision Agency for the
Drug Enforcement Administration 21, II
East-West Foreign Trade Board 15, XIII
Economic Affairs, Under Secretary 37, V
Economic Analysis, Bureau of 15, VIII
Economic Development Administration 13, III
Economic Research Service 7, XXXVII
Education, Department of 5, LIII
Bilingual Education and Minority Languages 34, V
Affairs, Office of
Civil Rights, Office for 34, I
Educational Research and Improvement, Office 34, VII
of
Elementary and Secondary Education, Office of 34, II
Federal Acquisition Regulation 48, 34
Postsecondary Education, Office of 34, VI
Secretary of Education, Office of 34, Subtitle A
Special Education and Rehabilitative Services, 34, III
Office of
Vocational and Adult Education, Office of 34, IV
Educational Research and Improvement, Office of 34, VII
Elementary and Secondary Education, Office of 34, II
Emergency Oil and Gas Guaranteed Loan Board 13, V
Emergency Steel Guarantee Loan Board 13, IV
Employees' Compensation Appeals Board 20, IV
Employees Loyalty Board 5, V
Employment and Training Administration 20, V
Employment Standards Administration 20, VI
Endangered Species Committee 50, IV
Energy, Department of 5, XXIII; 10, II, III, X
Federal Acquisition Regulation 48, 9
Federal Energy Regulatory Commission 5, XXIV; 18, I
Property Management Regulations 41, 109
Energy, Office of 7, XXIX
Engineers, Corps of 33, II; 36, III
Engraving and Printing, Bureau of 31, VI
Environmental Protection Agency 5, LIV; 40, I, IV, VII
Federal Acquisition Regulation 48, 15
Property Management Regulations 41, 115
Environmental Quality, Office of 7, XXXI
Equal Employment Opportunity Commission 5, LXII; 29, XIV
Equal Opportunity, Office of Assistant Secretary 24, I
for
Executive Office of the President 3, I
Administration, Office of 5, XV
Environmental Quality, Council on 40, V
Management and Budget, Office of 25, III, LXXVII; 48, 99
National Drug Control Policy, Office of 21, III
National Security Council 32, XXI; 47, 2
Presidential Documents 3
Science and Technology Policy, Office of 32, XXIV; 47, II
Trade Representative, Office of the United 15, XX
States
Export Administration, Bureau of 15, VII
Export-Import Bank of the United States 5, LII; 12, IV

[[Page 706]]

Family Assistance, Office of 45, II
Farm Credit Administration 5, XXXI; 12, VI
Farm Credit System Insurance Corporation 5, XXX; 12, XIV
Farm Service Agency 7, VII, XVIII
Federal Acquisition Regulation 48, 1
Federal Aviation Administration 14, I
Commercial Space Transportation 14, III
Federal Claims Collection Standards 31, IX
Federal Communications Commission 5, XXIX; 47, I
Federal Contract Compliance Programs, Office of 41, 60
Federal Crop Insurance Corporation 7, IV
Federal Deposit Insurance Corporation 5, XXII; 12, III
Federal Election Commission 11, I
Federal Emergency Management Agency 44, I
Federal Acquisition Regulation 48, 44
Federal Employees Group Life Insurance Federal 48, 21
Acquisition Regulation
Federal Employees Health Benefits Acquisition 48, 16
Regulation
Federal Energy Regulatory Commission 5, XXIV; 18, I
Federal Financial Institutions Examination 12, XI
Council
Federal Financing Bank 12, VIII
Federal Highway Administration 23, I, II
Federal Home Loan Mortgage Corporation 1, IV
Federal Housing Enterprise Oversight Office 12, XVII
Federal Housing Finance Board 12, IX
Federal Labor Relations Authority, and General 5, XIV; 22, XIV
Counsel of the Federal Labor Relations
Authority
Federal Law Enforcement Training Center 31, VII
Federal Management Regulation 41, 102
Federal Maritime Commission 46, IV
Federal Mediation and Conciliation Service 29, XII
Federal Mine Safety and Health Review Commission 5, LXXIV; 29, XXVII
Federal Motor Carrier Safety Administration 49, III
Federal Prison Industries, Inc. 28, III
Federal Procurement Policy Office 48, 99
Federal Property Management Regulations 41, 101
Federal Railroad Administration 49, II
Federal Register, Administrative Committee of 1, I
Federal Register, Office of 1, II
Federal Reserve System 12, II
Board of Governors 5, LVIII
Federal Retirement Thrift Investment Board 5, VI, LXXVI
Federal Service Impasses Panel 5, XIV
Federal Trade Commission 5, XLVII; 16, I
Federal Transit Administration 49, VI
Federal Travel Regulation System 41, Subtitle F
Fine Arts, Commission on 45, XXI
Fiscal Service 31, II
Fish and Wildlife Service, United States 50, I, IV
Fishery Conservation and Management 50, VI
Food and Drug Administration 21, I
Food and Nutrition Service 7, II
Food Safety and Inspection Service 9, III
Foreign Agricultural Service 7, XV
Foreign Assets Control, Office of 31, V
Foreign Claims Settlement Commission of the 45, V
United States
Foreign Service Grievance Board 22, IX
Foreign Service Impasse Disputes Panel 22, XIV
Foreign Service Labor Relations Board 22, XIV
Foreign-Trade Zones Board 15, IV
Forest Service 36, II
General Accounting Office 4, I
General Services Administration 5, LVII; 41, 105
Contract Appeals, Board of 48, 61
Federal Acquisition Regulation 48, 5
Federal Management Regulation 41, 102
Federal Property Management Regulations 41, 101

[[Page 707]]

Federal Travel Regulation System 41, Subtitle F
General 41, 300
Payment From a Non-Federal Source for Travel 41, 304
Expenses
Payment of Expenses Connected With the Death 41, 303
of Certain Employees
Relocation Allowances 41, 302
Temporary Duty (TDY) Travel Allowances 41, 301
Geological Survey 30, IV
Government Ethics, Office of 5, XVI
Government National Mortgage Association 24, III
Grain Inspection, Packers and Stockyards 7, VIII; 9, II
Administration
Harry S. Truman Scholarship Foundation 45, XVIII
Health and Human Services, Department of 5, XLV; 45, Subtitle A
Child Support Enforcement, Office of 45, III
Children and Families, Administration for 45, II, III, IV, X
Community Services, Office of 45, X
Family Assistance, Office of 45, II
Federal Acquisition Regulation 48, 3
Food and Drug Administration 21, I
Health Care Financing Administration 42, IV
Human Development Services, Office of 45, XIII
Indian Health Service 25, V
Inspector General (Health Care), Office of 42, V
Public Health Service 42, I
Refugee Resettlement, Office of 45, IV
Health Care Financing Administration 42, IV
Housing and Urban Development, Department of 5, LXV; 24, Subtitle B
Community Planning and Development, Office of 24, V, VI
Assistant Secretary for
Equal Opportunity, Office of Assistant 24, I
Secretary for
Federal Acquisition Regulation 48, 24
Federal Housing Enterprise Oversight, Office 12, XVII
of
Government National Mortgage Association 24, III
Housing--Federal Housing Commissioner, Office 24, II, VIII, X, XX
of Assistant Secretary for
Housing, Office of, and Multifamily Housing 24, IV
Assistance Restructuring, Office of
Inspector General, Office of 24, XII
Public and Indian Housing, Office of Assistant 24, IX
Secretary for
Secretary, Office of 24, Subtitle A, VII
Housing--Federal Housing Commissioner, Office of 24, II, VIII, X, XX
Assistant Secretary for
Housing, Office of, and Multifamily Housing 24, IV
Assistance Restructuring, Office of
Human Development Services, Office of 45, XIII
Immigration and Naturalization Service 8, I
Independent Counsel, Office of 28, VII
Indian Affairs, Bureau of 25, I, V
Indian Affairs, Office of the Assistant 25, VI
Secretary
Indian Arts and Crafts Board 25, II
Indian Health Service 25, V
Information Resources Management, Office of 7, XXVII
Information Security Oversight Office, National 32, XX
Archives and Records Administration
Inspector General
Agriculture Department 7, XXVI
Health and Human Services Department 42, V
Housing and Urban Development Department 24, XII
Institute of Peace, United States 22, XVII
Inter-American Foundation 5, LXIII; 22, X
Intergovernmental Relations, Advisory Commission 5, VII
on
Interior Department
American Indians, Office of the Special 25, VII
Trustee
Endangered Species Committee 50, IV
Federal Acquisition Regulation 48, 14
Federal Property Management Regulations System 41, 114
Fish and Wildlife Service, United States 50, I, IV

[[Page 708]]

Geological Survey 30, IV
Indian Affairs, Bureau of 25, I, V
Indian Affairs, Office of the Assistant 25, VI
Secretary
Indian Arts and Crafts Board 25, II
Land Management, Bureau of 43, II
Minerals Management Service 30, II
Mines, Bureau of 30, VI
National Indian Gaming Commission 25, III
National Park Service 36, I
Reclamation, Bureau of 43, I
Secretary of the Interior, Office of 43, Subtitle A
Surface Mining and Reclamation Appeals, Board 30, III
of
Surface Mining Reclamation and Enforcement, 30, VII
Office of
Internal Revenue Service 26, I
International Boundary and Water Commission, 22, XI
United States and Mexico, United States
Section
International Development, United States Agency 22, II
for
Federal Acquisition Regulation 48, 7
International Development Cooperation Agency, 22, XII
United States
International Fishing and Related Activities 50, III
International Investment, Office of 31, VIII
International Joint Commission, United States 22, IV
and Canada
International Organizations Employees Loyalty 5, V
Board
International Trade Administration 15, III; 19, III
International Trade Commission, United States 19, II
Interstate Commerce Commission 5, XL
James Madison Memorial Fellowship Foundation 45, XXIV
Japan-United States Friendship Commission 22, XVI
Joint Board for the Enrollment of Actuaries 20, VIII
Justice Department 5, XXVIII; 28, I; 40, IV
Drug Enforcement Administration 21, II
Federal Acquisition Regulation 48, 28
Federal Claims Collection Standards 31, IX
Federal Prison Industries, Inc. 28, III
Foreign Claims Settlement Commission of the 45, V
United States
Immigration and Naturalization Service 8, I
Offices of Independent Counsel 28, VI
Prisons, Bureau of 28, V
Property Management Regulations 41, 128
Labor Department 5, XLII
Benefits Review Board 20, VII
Employees' Compensation Appeals Board 20, IV
Employment and Training Administration 20, V
Employment Standards Administration 20, VI
Federal Acquisition Regulation 48, 29
Federal Contract Compliance Programs, Office 41, 60
of
Federal Procurement Regulations System 41, 50
Labor-Management Standards, Office of 29, II, IV
Mine Safety and Health Administration 30, I
Occupational Safety and Health Administration 29, XVII
Pension and Welfare Benefits Administration 29, XXV
Public Contracts 41, 50
Secretary of Labor, Office of 29, Subtitle A
Veterans' Employment and Training, Office of 41, 61; 20, IX
the Assistant Secretary for
Wage and Hour Division 29, V
Workers' Compensation Programs, Office of 20, I
Labor-Management Standards, Office of 29, II, IV
Land Management, Bureau of 43, II
Legal Services Corporation 45, XVI
Library of Congress 36, VII
Copyright Office 37, II
Management and Budget, Office of 5, III, LXXVII; 48, 99
Marine Mammal Commission 50, V
Maritime Administration 46, II

[[Page 709]]

Merit Systems Protection Board 5, II
Micronesian Status Negotiations, Office for 32, XXVII
Mine Safety and Health Administration 30, I
Minerals Management Service 30, II
Mines, Bureau of 30, VI
Minority Business Development Agency 15, XIV
Miscellaneous Agencies 1, IV
Monetary Offices 31, I
Morris K. Udall Scholarship and Excellence in 36, XVI
National Environmental Policy Foundation
National Aeronautics and Space Administration 5, LIX; 14, V
Federal Acquisition Regulation 48, 18
National Agricultural Library 7, XLI
National Agricultural Statistics Service 7, XXXVI
National and Community Service, Corporation for 45, XII, XXV
National Archives and Records Administration 5, LXVI; 36, XII
Information Security Oversight Office 32, XX
National Bureau of Standards 15, II
National Capital Planning Commission 1, IV
National Commission for Employment Policy 1, IV
National Commission on Libraries and Information 45, XVII
Science
National Council on Disability 34, XII
National Counterintelligence Center 32, XVIII
National Credit Union Administration 12, VII
National Crime Prevention and Privacy Compact 28, IX
Council
National Drug Control Policy, Office of 21, III
National Foundation on the Arts and the 45, XI
Humanities
National Highway Traffic Safety Administration 23, II, III; 49, V
National Imagery and Mapping Agency 32, I
National Indian Gaming Commission 25, III
National Institute for Literacy 34, XI
National Institute of Standards and Technology 15, II
National Labor Relations Board 5, LXI; 29, I
National Marine Fisheries Service 50, II, IV, VI
National Mediation Board 29, X
National Oceanic and Atmospheric Administration 15, IX; 50, II, III, IV,
VI
National Park Service 36, I
National Railroad Adjustment Board 29, III
National Railroad Passenger Corporation (AMTRAK) 49, VII
National Science Foundation 5, XLIII; 45, VI
Federal Acquisition Regulation 48, 25
National Security Council 32, XXI
National Security Council and Office of Science 47, II
and Technology Policy
National Telecommunications and Information 15, XXIII; 47, III
Administration
National Transportation Safety Board 49, VIII
National Weather Service 15, IX
Natural Resources Conservation Service 7, VI
Navajo and Hopi Indian Relocation, Office of 25, IV
Navy Department 32, VI
Federal Acquisition Regulation 48, 52
Neighborhood Reinvestment Corporation 24, XXV
Northeast Dairy Compact Commission 7, XIII
Northeast Interstate Low-Level Radioactive Waste 10, XVIII
Commission
Nuclear Regulatory Commission 5, XLVIII; 10, I
Federal Acquisition Regulation 48, 20
Occupational Safety and Health Administration 29, XVII
Occupational Safety and Health Review Commission 29, XX
Offices of Independent Counsel 28, VI
Oklahoma City National Memorial Trust 36, XV
Operations Office 7, XXVIII
Overseas Private Investment Corporation 5, XXXIII; 22, VII
Panama Canal Commission 48, 35
Panama Canal Regulations 35, I
Patent and Trademark Office, United States 37, I

[[Page 710]]

Payment From a Non-Federal Source for Travel 41, 304
Expenses
Payment of Expenses Connected With the Death of 41, 303
Certain Employees
Peace Corps 22, III
Pennsylvania Avenue Development Corporation 36, IX
Pension and Welfare Benefits Administration 29, XXV
Pension Benefit Guaranty Corporation 29, XL
Personnel Management, Office of 5, I, XXXV; 45, VIII
Federal Acquisition Regulation 48, 17
Federal Employees Group Life Insurance Federal 48, 21
Acquisition Regulation
Federal Employees Health Benefits Acquisition 48, 16
Regulation
Postal Rate Commission 5, XLVI; 39, III
Postal Service, United States 5, LX; 39, I
Postsecondary Education, Office of 34, VI
President's Commission on White House 1, IV
Fellowships
Presidential Documents 3
Presidio Trust 36, X
Prisons, Bureau of 28, V
Procurement and Property Management, Office of 7, XXXII
Productivity, Technology and Innovation, 37, IV
Assistant Secretary
Public Contracts, Department of Labor 41, 50
Public and Indian Housing, Office of Assistant 24, IX
Secretary for
Public Health Service 42, I
Railroad Retirement Board 20, II
Reclamation, Bureau of 43, I
Refugee Resettlement, Office of 45, IV
Regional Action Planning Commissions 13, V
Relocation Allowances 41, 302
Research and Special Programs Administration 49, I
Rural Business-Cooperative Service 7, XVIII, XLII
Rural Development Administration 7, XLII
Rural Housing Service 7, XVIII, XXXV
Rural Telephone Bank 7, XVI
Rural Utilities Service 7, XVII, XVIII, XLII
Saint Lawrence Seaway Development Corporation 33, IV
Science and Technology Policy, Office of 32, XXIV
Science and Technology Policy, Office of, and 47, II
National Security Council
Secret Service 31, IV
Securities and Exchange Commission 17, II
Selective Service System 32, XVI
Small Business Administration 13, I
Smithsonian Institution 36, V
Social Security Administration 20, III; 48, 23
Soldiers' and Airmen's Home, United States 5, XI
Special Counsel, Office of 5, VIII
Special Education and Rehabilitative Services, 34, III
Office of
State Department 22, I
Federal Acquisition Regulation 48, 6
Surface Mining and Reclamation Appeals, Board of 30, III
Surface Mining Reclamation and Enforcement, 30, VII
Office of
Surface Transportation Board 49, X
Susquehanna River Basin Commission 18, VIII
Technology Administration 15, XI
Technology Policy, Assistant Secretary for 37, IV
Technology, Under Secretary for 37, V
Tennessee Valley Authority 5, LXIX; 18, XIII
Thrift Supervision Office, Department of the 12, V
Treasury
Trade Representative, United States, Office of 15, XX
Transportation, Department of 5, L
Coast Guard 33, I; 46, I; 49, IV
Coast Guard (Great Lakes Pilotage) 46, III
Commercial Space Transportation 14, III
Contract Appeals, Board of 48, 63
Emergency Management and Assistance 44, IV

[[Page 711]]

Federal Acquisition Regulation 48, 12
Federal Aviation Administration 14, I
Federal Highway Administration 23, I, II
Federal Motor Carrier Safety Administration 49, III
Federal Railroad Administration 49, II
Federal Transit Administration 49, VI
Maritime Administration 46, II
National Highway Traffic Safety Administration 23, II, III; 49, V
Research and Special Programs Administration 49, I
Saint Lawrence Seaway Development Corporation 33, IV
Secretary of Transportation, Office of 14, II; 49, Subtitle A
Surface Transportation Board 49, X
Transportation Statistics Bureau 49, XI
Transportation, Office of 7, XXXIII
Transportation Statistics Brureau 49, XI
Travel Allowances, Temporary Duty (TDY) 41, 301
Treasury Department 5, XXI; 12, XV; 17, IV;
31, IX
Alcohol, Tobacco and Firearms, Bureau of 27, I
Community Development Financial Institutions 12, XVIII
Fund
Comptroller of the Currency 12, I
Customs Service, United States 19, I
Engraving and Printing, Bureau of 31, VI
Federal Acquisition Regulation 48, 10
Federal Law Enforcement Training Center 31, VII
Fiscal Service 31, II
Foreign Assets Control, Office of 31, V
Internal Revenue Service 26, I
International Investment, Office of 31, VIII
Monetary Offices 31, I
Secret Service 31, IV
Secretary of the Treasury, Office of 31, Subtitle A
Thrift Supervision, Office of 12, V
Truman, Harry S. Scholarship Foundation 45, XVIII
United States and Canada, International Joint 22, IV
Commission
United States and Mexico, International Boundary 22, XI
and Water Commission, United States Section
Utah Reclamation Mitigation and Conservation 43, III
Commission
Veterans Affairs Department 38, I
Federal Acquisition Regulation 48, 8
Veterans' Employment and Training, Office of the 41, 61; 20, IX
Assistant Secretary for
Vice President of the United States, Office of 32, XXVIII
Vocational and Adult Education, Office of 34, IV
Wage and Hour Division 29, V
Water Resources Council 18, VI
Workers' Compensation Programs, Office of 20, I
World Agricultural Outlook Board 7, XXXVIII

[[Page 713]]

List of CFR Sections Affected

All changes in this volume of the Code of Federal Regulations which were
made by documents published in the Federal Register since January 1,
1986, are enumerated in the following list. Entries indicate the nature
of the changes effected. Page numbers refer to Federal Register pages.
The user should consult the entries for chapters and parts as well as
sections for revisions.
For the period before January 1, 1986, see the ``List of CFR Sections
Affected, 1949-1963, 1964-1972, and 1973-1985'' published in seven
separate volumes.

1986

40 CFR
51 FR
Page
Chapter I
60 Appendix A amended......................................20288, 21166
Appendix A corrected...........................................29104
Appendix A amended......................................32455, 42842
Appendix B amended.............................................21766

1987

40 CFR
52 FR
Page
Chapter I
60 Appendix A amended....5106, 9658, 20392, 34639, 36410, 36415, 41425,
47853
Appendix A corrected...............10852, 19797, 22888, 33316, 42061
Appendixes A and B amended.....................................30675
Appendix B amended.............................................34650
Appendix B corrected...........................................17556
Appendix F added...............................................21007
Appendix F corrected...........................................27612
Appendix G added...............................................28955

1988

40 CFR
53 FR
Page
Chapter I
60 Appendix A corrected...........................................2914,
11591, 12498, 14889
Appendix A amended.............................................4142,
5884, 29682
Appendixes A and B amended.....................................41333
Appendix A corrected...........................................41649
Appendix B amended..............................................7515
Appendix I added................................................5913

1989

40 CFR
54 FR
Page
Chapter I
60 Appendix A amended...............................12622, 46235, 46238
Appendix A corrected...........................................51550

1990

40 CFR
55 FR
Page
Chapter I
60 Appendix A amended.............................................5212,
5616, 21753, 25604
Appendix A amended.......................................47472-47474
Appendix A corrected...........................................48208
Appendix B amended.............................................18876
Appendix B amended......................................40178, 47474

1991

40 CFR
56 FR
Page
Chapter I
60 Appendix B amended..............................................5526
Appendix F amended..............................................5527
Appendix A amended........................................5760, 5774

1992

40 CFR
57 FR
Page
Chapter I
60 Appendix A corrected...........................................24550
Appendix A amended.............................................30656

[[Page 714]]

1993

40 CFR
58 FR
Page
Chapter I
60 Appendix G amended; eff. 7-16-93...............................28785

1994

40 CFR
59 FR
Page
Chapter I
60 Appendix G amended..............................................8135
Appendix A amended............................................19308,
19309, 19311, 19319, 62924
Appendix B amended.............................................64593

1995

40 CFR
60 FR
Page
Chapter I
60 Appendix A amended.............................................47096
Regulation at 59 FR 62924 eff. date delayed to 6-6-96..........56952

1996

40 CFR
61 FR
Page
Chapter I
60 Appendix A amended.......................................9929, 18262

1997

40 CFR
62 FR
Page
Chapter I
60 Appendix A amended.............................................52399

1998

40 CFR
63 FR
Page
Chapter I
60 Appendix A Regulation at 61 FR 18262 eff. date corrected to
2-9-98......................................................6493

1999

40 CFR
64 FR
Page
Chapter I
60 Appendix A corrected....................................37196, 38241
Appendix A amended.............................................53027
Appendix B amended.............................................53032

2000

40 CFR
65 FR
Page
Chapter I
60 Appendix A amended......................................42297, 61779
Appendix B amended...............................48920, 62130, 62144

2001

(Regulations published from January 1, 2001, through July 1, 2001)

40 CFR
65 FR
Page
60 Regulation at 65 FR 48920, eff. date delayed....................9034