[Federal Register Volume 77, Number 146 (Monday, July 30, 2012)]
[Rules and Regulations]
[Pages 44488-44494]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 2012-18513]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Part 60
[EPA-HQ-OAR-2010-0115; FRL-9701-9]
RIN 2060-AQ23
Method 16C for the Determination of Total Reduced Sulfur
Emissions From Stationary Sources
AGENCY: Environmental Protection Agency (EPA).
ACTION: Final rule.
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SUMMARY: This action promulgates Method 16C for measuring total reduced
sulfur (TRS) emissions from stationary sources. Method 16C offers the
advantages of real-time data collection and uses procedures that are
already in use for measuring other pollutants. Method 16C will be a
testing option that is used at the discretion of the tester.
DATES: This final rule is effective on July 30, 2012.
ADDRESSES: The EPA has established a docket for this action under
Docket ID No. EPA-HQ-OAR-2010-0115. All documents in the docket are
listed in the http://www.regulations.gov index. Although listed in the
index, some information is not publicly available, e.g., confidential
business information (CBI) or other information whose disclosure is
restricted by statute. Certain other material, such as copyrighted
material, is not placed on the Internet and will be publicly available
only in hard copy form. Publicly available docket materials are
[[Page 44489]]
available either electronically at www.regulations.gov or in hard copy
at the Air Docket, EPA/DC, EPA West, Room 3334, 1301 Constitution
Avenue NW., Washington, DC. The Docket Facility and the Public Reading
Room are open from 8:30 a.m. to 4:30 p.m., Monday through Friday,
excluding legal holidays. The telephone number for the Public Reading
Room is (202) 566-1744, and the telephone number for the Air Docket is
(202) 566-1742.
FOR FURTHER INFORMATION CONTACT: Mr. Foston Curtis, Office of Air
Quality Planning and Standards, Air Quality Assessment Division,
Measurement Technology Group (E143-02), U.S. Environmental Protection
Agency, Research Triangle Park, North Carolina 27711; telephone number:
(919) 541-1063; fax number: (919) 541-0516; email address:
[email protected].
SUPPLEMENTARY INFORMATION:
Table of Contents
I. General Information
A. Does this action apply to me?
B. Where can I obtain a copy of this action?
C. Judicial Review
II. Background
III. Summary of Method 16C
IV. Public Comments on Proposed Method 16C
V. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review and
Executive Order 13563: Improving Regulation and Regulatory Review
B. Paperwork Reduction Act
C. Regulatory Flexibility Act
D. Unfunded Mandates Reform Act
E. Executive Order 13132: Federalism
F. Executive Order 13175: Consultation and Coordination With
Indian Tribal Governments
G. Executive Order 13045: Protection of Children From
Environmental Health Risks and Safety Risks
H. Executive Order 13211: Actions Concerning Regulations That
Significantly Affect Energy Supply, Distribution, or Use
I. National Technology Transfer and Advancement Act
J. Executive Order 12898: Federal Actions To Address
Environmental Justice in Minority Populations and Low- Income
Populations
K. Congressional Review Act
I. General Information
A. Does this action apply to me?
Method 16C applies to TRS measurement from kraft pulp mills subject
to Subpart BB of the New Source Performance Standards (NSPS). The
methods required under Subpart BB for TRS are sometimes used under the
petroleum refineries NSPS (Subpart J). Method 16C may also be
applicable to sources regulated by state and local regulations that
adopt the Subpart BB testing requirements.
Regulated Entities. Categories and entities potentially affected
include the following:
------------------------------------------------------------------------
NAICS Examples of regulated
Category \a\ entities
------------------------------------------------------------------------
Industry........................ 322110 Kraft Pulp Mills.
Industry........................ 324110 Petroleum Refineries.
------------------------------------------------------------------------
\a\ North American Industry Classification System.
This table is not intended to be exhaustive, but rather to provide
a guide for readers regarding entities likely to be affected by this
action. This table lists examples of the types of entities the EPA is
now aware could potentially be affected by this final action. Other
types of entities not listed could also be affected. If you have any
questions regarding the applicability of this action to a particular
entity, consult the person listed in the preceding FOR FURTHER
INFORMATION CONTACT section.
B. Where can I obtain a copy of this action?
In addition to being available in the docket, an electronic copy of
this rule will also be available on the Worldwide Web (www) through the
Technology Transfer Network (TTN). Following the Administrator's
signature, a copy of the final rule will be placed on the TTN's policy
and guidance page for newly proposed or promulgated rules at http://www.epa.gov/ttn/oarpg. The TTN provides information and technology
exchange in various areas of air pollution control.
C. Judicial Review
Under section 307(b)(1) of the Clean Air Act (CAA), judicial review
of this final rule is available by filing a petition for review in the
U.S. Court of Appeals for the District of Columbia Circuit by September
28, 2012. Under section 307(d)(7)(B) of the CAA, only an objection to
this final rule that was raised with reasonable specificity during the
period for public comment can be raised during judicial review.
Moreover, under section 307(b)(2) of the CAA, the requirements
established by this action may not be challenged separately in any
civil or criminal proceedings brought by EPA to enforce these
requirements.
II. Background
Method 16C was proposed in the Federal Register on September 2,
2010, with a public comment period that ended November 1, 2010. Two
comment letters were received from the public.
III. Summary of Method 16C
Method 16C uses the sampling procedures of Method 16A and the
analytical procedures of Method 6C to measure TRS. Total reduced sulfur
is defined as hydrogen sulfide, methyl mercaptan, dimethyl sulfide, and
dimethyl disulfide. As in Method 16A, the sample is collected from the
source through a heated probe and immediately conditioned in a citrate
buffer scrubber. The conditioned sample is oxidized in a tube furnace
to convert TRS to sulfur dioxide (SO2). The oxidized sample
is then analyzed for SO2 using a real-time SO2
analyzer as in Method 6C.
This method may be used as an alternative to Methods 16, 16A, and
16B for determining TRS. Its use has been allowed on a case-by-case
basis and, based on our experience, it is a good alternative. Method
16C offers advantages over currently required methods by supplying
real-time data in the field using analyzers and procedures that are
currently used for other pollutants. Performance checks contained in
the method ensure that bias and calibration precision are periodically
checked and maintained.
This rule will not require the use of Method 16C but will allow it
as an alternative method at the discretion of the user. This method
does not impact testing stringency; data are collected under the same
conditions and time intervals as the current methods.
IV. Public Comments on Proposed Method 16C
Two public comment letters were received on the proposed rule. The
comments pointed out contradictions in different sections of the method
for the analyzer calibration error test and the system bias check. In
one instance, the analyzer calibration acceptance criterion was listed
as 5 percent and in another place it was listed as 2 percent. The rule
was corrected to state that 5 percent is the correct criterion for this
test. For the system bias check, unclear language was amended to
specifically state that the pre-test bias check is mandatory, not
optional. An additional comment led to the dropping of the sample
correction for moisture since it is not needed for most analyzers. The
public comments are addressed in the Summary of Comments and Responses
Document that has been added to the docket.
[[Page 44490]]
V. Statutory and Executive Order Reviews
A. Executive Order 12866: Regulatory Planning and Review and Executive
Order 13563: Improving Regulation and Regulatory Review
This action is not a ``significant regulatory action'' under the
terms of Executive Order 12866 (58 FR 51735, October 4, 1993) and is,
therefore, not subject to review under Executive Orders 12866 and 13563
(76 FR 3821, January 21, 2011).
B. Paperwork Reduction Act
This action does not impose an information collection burden under
the provisions of the Paperwork Reduction Act, 44 U.S.C. 3501 et seq.
Burden is defined at 5 CFR 1320.3(b). This final rule does not add
information collection requirements beyond those currently required
under the applicable regulations. This final rule adds an alternative
test method that may be used at the discretion of the source.
C. Regulatory Flexibility Act
The Regulatory Flexibility Act (RFA) generally requires an agency
to prepare a regulatory flexibility analysis of any rule subject to
notice and comment rulemaking requirements under the Administrative
Procedure Act or any other statute unless the agency certifies that the
rule will not have a significant economic impact on a substantial
number of small entities. Small entities include small businesses,
small organizations, and small governmental jurisdictions.
For purposes of assessing the impacts of this rule on small
entities, small entity is defined as: (1) A small business as defined
by the Small Business Administration's (SBA) regulations at 13 CFR
121.201; (2) a small governmental jurisdiction that is a government of
a city, county, town, school district or special district with a
population of less than 50,000; and (3) a small organization that is
any not-for-profit enterprise which is independently owned and operated
and is not dominant in its field.
After considering the economic impacts of this final rule on small
entities, I certify that this action will not have a significant
economic impact on a substantial number of small entities. This final
rule will not impose any requirements on small entities because Method
16C is not a required test method but may be used at the discretion of
the source. Any small entity choosing to use Method 16C would likely do
so because it is less burdensome or more advantageous than the other
methods allowed.
D. Unfunded Mandates Reform Act
This action contains no federal mandates under the provisions of
Title II of the Unfunded Mandates Reform Act of 1995 (UMRA), 2 U.S.C.
1531-1538 for State, local, or tribal governments or the private
sector. This action imposes no enforceable duty on any State, local or
tribal governments or the private sector. Therefore, this action is not
subject to the requirements of sections 202 or 205 of the UMRA. This
action is also not subject to the requirements of section 203 of UMRA
because it contains no regulatory requirements that might significantly
or uniquely affect small governments. Any small entity choosing to use
Method 16C would likely do so because it is less burdensome or more
advantageous than the other methods allowed.
E. Executive Order 13132: Federalism
This action does not have federalism implications. It will not have
substantial direct effects on the states, on the relationship between
the national government and the states, or on the distribution of power
and responsibilities among the various levels of government, as
specified in Executive Order 13132. This final rule adds Method 16C for
use as a new alternative method. Thus, Executive Order 13132 does not
apply to this action.
F. Executive Order 13175: Consultation and Coordination With Indian
Tribal Governments
This action does not have tribal implications, as specified in
Executive Order 13175 (65 FR 67249, November 9, 2000). This final rule
provides an additional testing option for measuring pollutants to what
is currently mandated. It does not add any new requirements and does
not affect pollutant emissions or air quality. Thus, Executive Order
13175 does not apply to this action.
G. Executive Order 13045: Protection of Children From Environmental
Health Risks and Safety Risks
The EPA interprets EO 13045 (62 FR 19885, April 23, 1997) as
applying only to those regulatory actions that concern health or safety
risks, such that the analysis required under section 5-501 of the EO
has the potential to influence the regulation. This action is not
subject to EO 13045 because it does not establish an environmental
standard intended to mitigate health or safety risks.
H. Executive Order 13211: Actions Concerning Regulations That
Significantly Affect Energy Supply, Distribution, or Use
This rule is not subject to Executive Order 13211 (66 FR 28355 (May
22, 2001)), because it is not a significant regulatory action under
Executive Order 12866.
I. National Technology Transfer and Advancement Act
Section 12(d) of the National Technology Transfer and Advancement
Act of 1995 (``NTTAA''), Public Law 104-113, 12(d)(15 U.S.C. 272 note)
directs the EPA to use voluntary consensus standards in its regulatory
activities unless to do so would be inconsistent with applicable law or
otherwise impractical. Voluntary consensus standards are technical
standards (e.g., materials specifications, test methods, sampling
procedures, and business practices) that are developed or adopted by
voluntary consensus standards bodies. The NTTAA directs the EPA to
provide Congress, through OMB, explanations when the Agency decides not
to use available and applicable voluntary consensus standards.
This action does not involve technical standards. Therefore, the
EPA did not consider the use of any voluntary consensus standards.
J. Executive Order 12898: Federal Actions To Address Environmental
Justice in Minority Populations and Low-Income Populations
Executive Order (EO) 12898 (59 FR 7629 (Feb. 16, 1994)) establishes
federal executive policy on environmental justice. Its main provision
directs federal agencies, to the greatest extent practicable and
permitted by law, to make environmental justice part of their mission
by identifying and addressing, as appropriate, disproportionately high
and adverse human health or environmental effects of their programs,
policies, and activities on minority populations and low-income
populations in the United States.
The EPA has determined that this final rule will not have
disproportionately high and adverse human health or environmental
effects on minority or low-income populations because it does not
affect the level of protection provided to human health or the
environment. This final rule does not relax the control measures on
sources regulated by the rule and, therefore, will not cause emissions
increases from these sources.
[[Page 44491]]
K. Congressional Review Act
The Congressional Review Act, 5 U.S.C. 801 et seq., as added by the
Small Business Regulatory Enforcement Fairness Act of 1996, generally
provides that before a rule may take effect, the agency promulgating
the rule must submit a rule report, which includes a copy of the rule,
to each House of the Congress and to the Comptroller General of the
United States. The EPA will submit a report containing this rule and
other required information to the U.S. Senate, the U.S. House of
Representatives, and the Comptroller General of the United States prior
to publication of the rule in the Federal Register. A major rule cannot
take effect until 60 days after it is published in the Federal
Register. This action is not a ``major rule'' as defined by 5 U.S.C.
804(2). This rule will be effective on July 30, 2012.
List of Subjects in 40 CFR Part 60
Administrative practice and procedures, Air pollution control,
Intergovernmental relations, Reporting and recordkeeping requirements.
Dated: July 23, 2012.
Lisa P. Jackson,
Administrator.
For the reasons set out in the preamble, Title 40, Chapter I of the
Code of Federal Regulations is amended as follows:
PART 60--STANDARDS OF PERFORMANCE FOR NEW STATIONARY SOURCES
0
1. The authority citation for part 60 continues to read as follows:
Authority: 42 U.S.C. 7401-7601.
0
2. Amend Appendix A-6 to Part 60 by adding ``Method 16C'' in
alphanumeric order to read as follows:
Appendix A-6 to Part 60--Test Methods 16 Through 18
* * * * *
Method 16C--Determination of Total Reduced Sulfur Emissions From
Stationary Sources
1.0 Scope and Application
What is Method 16C?
Method 16C is a procedure for measuring total reduced sulfur
(TRS) in stationary source emissions using a continuous instrumental
analyzer. Quality assurance and quality control requirements are
included to assure that you, the tester, collect data of known
quality. You must document your adherence to these specific
requirements for equipment, supplies, sample collection and
analysis, calculations, and data analysis. This method does not
completely describe all equipment, supplies, and sampling and
analytical procedures you will need but refers to other methods for
some of the details. Therefore, to obtain reliable results, you
should also have a thorough knowledge of these additional test
methods which are found in appendix A to this part:
(a) Method 6C--Determination of Sulfur Dioxide Emissions from
Stationary Sources (Instrumental Analyzer Procedure)
(b) Method 7E--Determination of Nitrogen Oxides Emissions from
Stationary Sources (Instrumental Analyzer Procedure)
(c) Method 16A--Determination of Total Reduced Sulfur Emissions
from Stationary Sources (Impinger Technique)
1.1 Analytes. What does Method 16C determine?
------------------------------------------------------------------------
Analyte CAS No.
------------------------------------------------------------------------
Total reduced sulfur 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.
1.3 Data Quality Objectives. Adherence to the requirements
described in Method 16C will enhance the quality of the data
obtained.
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 determined as SO2 by an
instrumental analyzer. This method is a combination of the sampling
procedures of Method 16A and the analytical procedures of Method 6C
(referenced in Method 7E), with minor modifications to facilitate
their use together.
3.0 Definitions
Analyzer calibration error, Calibration curve, Calibration gas,
Low-level gas, Mid-level gas, High-level gas, Calibration drift,
Calibration span, Data recorder, Direct calibration mode, Gas
analyzer, Interference check, Measurement system, Response time,
Run, System calibration mode, System performance check, and Test are
the same as used in Methods 16A and 6C.
4.0 Interferences
4.1 Reduced sulfur compounds other than those defined as TRS, if
present, may be measured by this method. Compounds like carbonyl
sulfide, which is partially oxidized to SO2 and may be
present in a lime kiln exit stack, would be a positive interferent.
Interferences may vary among instruments, and instrument-specific
interferences must be evaluated through the interference check.
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.
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 to establish appropriate safety and
health practices before performing this test method.
5.2 Hydrogen Sulfide. Hydrogen sulfide is a flammable, poisonous
gas with the odor of rotten eggs. Hydrogen sulfide is extremely
hazardous and can cause collapse, coma, and death within a few
seconds of one or two inhalations at sufficient concentrations. Low
concentrations irritate the mucous membranes and may cause nausea,
dizziness, and headache after exposure. It is the responsibility of
the user of this test method to establish appropriate safety and
health practices.
6.0 Equipment and Supplies
What do I need for the measurement system?
The measurement system is similar to those applicable components
in Methods 16A and 6C. Modifications to the apparatus are accepted
provided the performance criteria in Section 13.0 are met.
6.1 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
must 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 must 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) must be attached to the inlet
of the probe, and a 2.54 cm (1 in.) piece of Teflon tubing must 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 of Method 16A.
6.2 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.
6.3 Particulate Filter. 50-mm Teflon filter holder and a 1- to
2-[mu]m porosity, Teflon filter (may be available through Savillex
Corporation, 5325 Highway 101, Minnetonka, Minnesota 55343, or other
suppliers of filters). 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
[[Page 44492]]
be sufficient when testing a lime kiln under sub-freezing ambient
conditions.
6.4 SO2 Scrubber. Three 300-ml Teflon segmented
impingers connected in series with flexible, thick-walled, Teflon
tubing. (Impinger parts and tubing may be available through Savillex
or other suppliers.) 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.).
6.5 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. Alternative combustion tubes
are acceptable provided they are shown to combust TRS at
concentrations encountered during tests.
6.6 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.
6.7 Sampling Pump. A leak-free pump is required to pull the
sample gas through the system at a flow rate sufficient to minimize
the response time of the measurement system and must be constructed
of material that is non-reactive to the gas it contacts. For
dilution-type measurement systems, an eductor pump may be used to
create a vacuum that draws the sample through a critical orifice at
a constant rate.
6.8 Calibration Gas Manifold. The calibration gas manifold must
allow the introduction of calibration gases either directly to the
gas analyzer in direct calibration mode or into the measurement
system, at the probe, in system calibration mode, or both, depending
upon the type of system used. In system calibration mode, the system
must be able to flood the sampling probe and vent excess gas.
Alternatively, calibration gases may be introduced at the
calibration valve following the probe. Maintain a constant pressure
in the gas manifold. For in-stack dilution-type systems, a gas
dilution subsystem is required to transport large volumes of
purified air to the sample probe, and a probe controller is needed
to maintain the proper dilution ratio.
6.9 Sample Gas Manifold. The sample gas manifold diverts a
portion of the sample to the analyzer, delivering the remainder to
the by-pass discharge vent. The manifold should also be able to
introduce calibration gases directly to the analyzer. The manifold
must be made of material that is non-reactive to SO2 and
be configured to safely discharge the bypass gas.
6.10 SO2 Analyzer. You must use an instrument that
uses an ultraviolet, non-dispersive infrared, fluorescence, or other
detection principle to continuously measure SO2 in the
gas stream provided it meets the performance specifications in
Section 13.0.
6.11 Data Recording. A strip chart recorder, computerized data
acquisition system, digital recorder, or data logger for recording
measurement data must 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. When such specifications
are not available, the best available grade must be used.
7.1 Water. Deionized distilled water must 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.
7.2 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.
7.3 Calibration Gas. Refer to Section 7.1 of Method 7E (as
applicable) for the calibration gas requirements. Example
calibration gas mixtures are listed below.
(a) SO2 in nitrogen (N2).
(b) SO2 in air.
(c) SO2 and carbon dioxide (CO2) in
N2.
(d) SO2 and oxygen (O2) in N2.
(e) SO2/CO2/O2 gas mixture in
N2.
(f) CO2/NOX gas mixture in N2.
(g) CO2/SO2/NOX gas mixture in
N2.
For fluorescence-based analyzers, the O2 and
CO2 concentrations of the calibration gases as introduced
to the analyzer must be within 1.0 percent (absolute) O2
and 1.0 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). This requirement does not apply to ambient-level
fluorescence analyzers that are used in conjunction with sample
dilution systems. Alternatively, H2S in O2 or
air may be used to calibrate the analyzer through the tube furnace.
7.4 System Performance Check Gas. You must use H2S
(100 ppmv or less) stored in aluminum cylinders with the
concentration certified by the manufacturer. Hydrogen sulfide in
nitrogen is more stable than H2S in air, but air may be
used as the balance gas. Note: Alternatively, H2S
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
the appropriate dilution gas flow rate, an H2S
concentration can be generated in the range of the stack gas or
within 20 percent of the emission standard.
7.5 Interference Check. Examples of test gases for the
interference check are listed in Table 7E-3 of Method 7E.
8.0 Sample Collection, Preservation, Storage, and Transport
8.1 Pre-sampling Tests. Before measuring emissions, perform the
following procedures:
(a) Calibration gas verification,
(b) Calibration error test,
(c) System performance check,
(d) Verification that the interference check has been satisfied.
8.1.1 Calibration Gas Verification. Obtain a certificate from
the gas manufacturer documenting the quality of the gas. Confirm
that the manufacturer certification is complete and current. Ensure
that your calibration gas certifications have not expired. This
documentation should be available on-site for inspection. To the
extent practicable, select a high-level gas concentration that will
result in the measured emissions being between 20 and 100 percent of
the calibration span.
8.1.2 Analyzer Calibration Error Test. After you have assembled,
prepared, and calibrated your sampling system and analyzer, you must
conduct a 3-point analyzer calibration error test before the first
run and again after any failed system performance check or failed
drift test to ensure the calibration is acceptable. Introduce the
low-, mid-, and high-level calibration gases sequentially to the
analyzer in direct calibration mode. For each calibration gas,
calculate the analyzer calibration error using Equation 16C-1 in
Section 12.2. The calibration error for the low-, mid-, and high-
level gases must not exceed 5.0 percent or 0.5 ppmv. If the
calibration error specification is not met, take corrective action
and repeat the test until an acceptable 3-point calibration is
achieved.
8.1.3 System Performance Check. A system performance check is
done (1) to validate the sampling train components and procedure
(prior to testing), and (2) to validate a test run (after a run).
You must conduct a performance check in the field prior to testing,
and after each 3-hour run or after three 1-hour runs. A performance
check consists of sampling and analyzing a known concentration of
H2S (system performance check gas) and comparing the
analyzed concentration to the known concentration. To conduct the
system performance check, mix the system performance check gas
(Section 7.4) and ambient air, that has been conditioned to remove
moisture and sulfur-containing gases, in a dilution system such as
that shown in Figure 16A-3 of Method 16A. Alternatively, ultra-high
purity (UHP) grade air may be used. Adjust the gas 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 ft3/hr). Use Equation 16A-3 from Method
16A to calculate the concentration of system performance check gas
generated. Calibrate the flow rate from both gas sources with a soap
bubble flow meter so that the diluted concentration of
H2S can be accurately calculated. Alternatively, mass
flow controllers with documented calibrations may be used if UHP
grade air is being used. Sample duration should be sufficiently long
to ensure a stable response from the analyzer.
[[Page 44493]]
Analyze in the same manner as the emission samples. Collect the
sample through the probe of the sampling train using a manifold or
other suitable device that will ensure extraction of a
representative sample. The TRS sample concentration measured between
system performance checks is corrected by the average of the pre-
and post-system performance checks.
8.1.4 Interference Check. Same as in Method 7E, Section 8.2.7.
8.2 Measurement System Preparation.
8.2.1 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. Prepare the oxidation furnace and
maintain at 800 100[deg]C (1472
180[deg]F).
8.2.2 Citrate Scrubber Conditioning Procedure. Condition the
citrate buffer scrubbing solution by pulling stack gas through the
Teflon impingers as described in Section 8.4.1.
8.3 Pretest Procedures. After the complete measurement system
has been set up at the site and deemed to be operational, the
following procedures must be completed before sampling is initiated.
8.3.1 Leak-Check. Appropriate leak-check procedures must be
employed to verify the integrity of all components, sample lines,
and connections. 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.
8.3.2 Initial System Performance Check. A system performance
check using the test gas (Section 7.4) is performed prior to testing
to validate the sampling train components and procedure.
8.4 Sample Collection and Analysis.
8.4.1 After performing the required pretest procedures described
in Section 8.1, insert the sampling probe into the test port
ensuring that no dilution air enters the stack through the port.
Condition the sampling system and citrate buffer solution for a
minimum of 15 minutes before beginning analysis. Begin sampling and
analysis. A source test consists of three test runs. A test run
shall consist of a single sample collected over a 3-hour period or
three separate 1-hour samples collected over a period not to exceed
six hours.
8.5 Post-Run Evaluations.
8.5.1 System Performance Check. Perform a post-run system
performance check before replacing the citrate buffer solution and
particulate filter and before the probe is cleaned. The check
results must not exceed the 100 20 percent limit set
forth in Section 13.2. If this limit is exceeded, the intervening
run is considered invalid. 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.
8.5.2 Calibration Drift. After a run or series of runs, not to
exceed a 24-hour period after initial calibration, perform a
calibration drift test using a calibration gas (preferably the level
that best approximates the sample concentration) in direct
calibration mode. This drift must not differ from the initial
calibration error percent by more than 3.0 percent or 0.5 ppm. If
the drift exceeds this limit, the intervening run or runs are
considered valid, but a new analyzer calibration error test must be
performed and passed before continuing sampling.
9.0 Quality Control
------------------------------------------------------------------------
Quality control
Section measure Effect
------------------------------------------------------------------------
8.1.2......................... Analyzer Establishes initial
calibration error calibration
test. accuracy within
5.0%.
8.1.3, 8.5.1.................. System performance Ensures accuracy of
check. sampling/
analytical
procedure to 100
20%.
8.5.2......................... Calibration drift Ensures calibration
test. drift is within
3.0%.
8.1.4......................... Interference check. Checks for
analytical
interferences.
8.3........................... Sampling equipment Ensures accurate
leak-check. measurement of
sample gas flow
rate, sample
volume.
------------------------------------------------------------------------
10.0 Calibration
10.1 Calibrate the system using the gases described in Section
7.3. Perform the initial 3-point calibration error test as described
in Section 8.1.2 before you start the test. The specification in
Section 13 must be met. Conduct an initial system performance test
described in Section 8.1.3 as well before the test to validate the
sampling components and procedures before sampling. After the test
commences, a system performance check is required after each run.
You must include a copy of the manufacturer's certification of the
calibration gases used in the testing as part of the test report.
This certification must include the 13 documentation requirements in
the EPA Traceability Protocol for Assay and Certification of Gaseous
Calibration Standards, September 1997, as amended August 25, 1999.
11.0 Analytical Procedure
Because sample collection and analysis are performed together
(see Section 8.0), additional discussion of the analytical procedure
is not necessary.
12.0 Calculations and Data Analysis
12.1 Nomenclature.
ACE = Analyzer calibration error, percent of calibration span.
CD = Calibration drift, percent.
CDir = Measured concentration of a calibration gas (low,
mid, or high) when introduced in direct calibration mode, ppmv.
CH2S = Concentration of the system performance check gas,
ppmv H2S.
CM = Average of initial and final system calibration bias
check responses for the upscale calibration gas, ppmv.
CMA = Actual concentration of the upscale calibration
gas, ppmv.
CO = Average of the initial and final system calibration
bias check responses from the low-level (or zero) calibration gas,
ppmv.
COA = Actual concentration of the low-level calibration
gas, ppmv.
CS = Measured concentration of the system performance gas
when introduced in system calibration mode, ppmv H2S.
CV = Manufacturer certified concentration of a
calibration gas (low, mid, or high), ppmv SO2.
CSO2 = Unadjusted sample SO2 concentration,
ppmv.
CTRS = Total reduced sulfur concentration corrected for
system performance, ppmv.
DF = Dilution system (if used) dilution factor, dimensionless.
SP = System performance, percent.
12.2 Analyzer Calibration Error. Use Equation 16C-1 to calculate
the analyzer calibration error for the low-, mid-, and high-level
calibration gases.
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[[Page 44494]]
12.3 System Performance Check. Use Equation 16C-2 to calculate the
system performance.
[GRAPHIC] [TIFF OMITTED] TR30JY12.176
12.4 Calibration Drift. Use Equation 16C-3 to calculate the
calibration drift at a single concentration level after a run or series
of runs (not to exceed a 24-hr period) from initial calibration.
Compare the single-level calibration gas error (ACEn) to the
original error obtained for that gas in the initial analyzer
calibration error test (ACEi).
[GRAPHIC] [TIFF OMITTED] TR30JY12.177
12.5 TRS Concentration as SO2. For each sample or test
run, calculate the arithmetic average of SO2 concentration
values (e.g., 1-minute averages). Then calculate the sample TRS
concentration by adjusting the average value of CSO2 for
system performance using Equation 16C-4a if you use a non-zero gas as
your low-level calibration gas, or Equation 16C-4b if you use a zero
gas as your low-level calibration gas.
[GRAPHIC] [TIFF OMITTED] TR30JY12.178
13.0 Method Performance
13.1 Analyzer Calibration Error. At each calibration gas level
(low, mid, and high), the calibration error must either not exceed 5.0
percent of the calibration gas concentration or
[verbarlm]CDir-Cv[verbarlm] must be <=0.5 ppmv.
13.2 System Performance. Each system performance check must not
deviate from the system performance gas concentration by more than 20
percent. Alternatively, the results are acceptable if
[verbarlm]Cs-CH2S[verbarlm] is <=0.5 ppmv.
13.3 Calibration Drift. The calibration drift at the end of any run
or series of runs within a 24-hour period must not differ by more than
3.0 percent from the original ACE at the test concentration level or
[verbarlm]ACEi-ACEn[verbarlm] must not exceed 0.5 ppmv.
13.4 Interference Check. For the analyzer, the total interference
response (i.e., the sum of the interference responses of all tested
gaseous components) must not be greater than 2.5 percent of the
calibration span. Any interference is also acceptable if the sum of the
responses does not exceed 0.5 ppmv for a calibration span of 5 to 10
ppmv, or 0.2 ppmv for a calibration span <5 ppmv.
14.0 Pollution Prevention [Reserved]
15.0 Waste Management [Reserved]
16.0 References
1. The references are the same as in Section 16.0 of Method 16,
Section 17.0 of Method 16A, and Section 17.0 of Method 6C.
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.
17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved]
* * * * *
[FR Doc. 2012-18513 Filed 7-27-12; 8:45 am]
BILLING CODE 6560-50-P