[Federal Register Volume 61, Number 81 (Thursday, April 25, 1996)]
[Rules and Regulations]
[Pages 18260-18280]
From the Federal Register Online via the Government Publishing Office [www.gpo.gov]
[FR Doc No: 96-9834]
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ENVIRONMENTAL PROTECTION AGENCY
40 CFR Parts 60 and 61
[AD-FRL 5407-4]
Standards of Performance for New Stationary Sources National
Emission Standards for Hazardous Air Pollutants Addition of Method 29
to Appendix A of Part 60 and Amendments to Method 101A of Appendix B of
Part 61
AGENCY: Environmental Protection Agency (EPA).
ACTION: Final rule.
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SUMMARY: This rule adds Method 29, ``Determination of Metals Emissions
from Stationary Sources,'' to Appendix A of Part 60, and makes
amendments to Method 101A of Appendix B of Part 61. Method 29 is being
added so that it can be used to determine cadmium, lead, and mercury
emissions from municipal waste combustors (MWC) under subpart Ea of
part 60. The amendments to Method 101A of appendix B of part 61 are to
expand that method's applicability, and to revise procedures for
handling and analyzing samples collected by the sampling train.
EFFECTIVE DATE: April 25, 1996.
Incorporation by Reference. The incorporation by reference of
certain publications listed in the regulation is approved by the
Director of the Office of the Federal Register April 25, 1996.
ADDRESSES: Docket. Docket No. A-94-28, containing materials relevant to
this rulemaking, is available for public inspection and copying between
8:30 a.m. and Noon, and 1:30 and 3:30 p.m.,
[[Page 18261]]
Monday through Friday, at EPA's Air And Docket Section, Room M1500,
First Floor, Waterside Mall, Gallery 1, 401 M Street, S.W., Washington,
D.C. 20460. A reasonable fee may be charged for copying.
FOR FURTHER INFORMATION CONTACT:
William Grimley at (919) 541-1065, Source Characterization Group B (MD-
19), Emissions, Monitoring, and Analysis Division, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina 27711.
SUPPLEMENTARY INFORMATION:
I. The Rulemaking
Under Subparts Ca and Ea, the EPA promulgated guidelines and
standards to regulate mercury, cadmium, and lead emissions from MWC's
which were published in the Federal Register on December 19, 1995 (see
60 FR 65382). Method 29 is being promulgated for addition to Appendix A
of 40 CFR Part 60 and will serve as the compliance test method for
mercury, cadmium, and lead. Amendments to Method 101A of Appendix B of
Part 61 are being promulgated to provide consistency with Method 29.
These regulations were proposed on September 20, 1994 (see 59 FR
48259).
II. Public Participation
The opportunity to hold a public hearing on October 20, 1994 at 10
a.m. was present in the proposal notice, but no one wanted to make an
oral presentation. The public comment period was from September 21,
1994 to November 21, 1994.
III. Significant Comments and Changes to the Proposed Rulemaking
One comment letter was received from the proposed rulemaking. The
comments and responses are summarized in this preamble.
The first comment dealt with the analytical detection limits stated
in Method 29. The commenter believes the detection limits are
unrealistically low, and represent values achievable only under ideal
conditions. The commenter concludes by saying that the method should
state that it is the analyst's responsibility to determine the actual
detection limit achieved.
The detection limits stated in Method 29 are those listed in the
SW-846 methods manual, and EPA believes they are reasonable ones for
use in this application of SW-846 analytical methods. However, Method
29 as proposed is clear in its discussion of the application of quality
assurance procedures to document the quality of the data actually
produced, and is also clear in the description of the procedure to be
used to establish the actual detection limits achieved during the
measurement of emissions.
The second comment addressed the point that dilution is likely to
be effective in avoiding the analytical problem of spectral
interference only if the analyte is present at a much greater
concentration than the interferant. The commenter then suggests that
Method 29 be revised to say that the effective way to adjust for
spectral interference is by making background corrections or overlap
corrections.
The EPA agrees with this comment, and Section 2.5 of the Method has
been revised to permit these corrective techniques.
The third comment addressed the use of an alumina torch in the
inductively coupled argon plasma (ICAP) emission spectroscopy
procedure. The commenter believes that few ICAP users have this
capability, and that an alternative technique for dealing with hydrogen
fluoride could be suggested in the Method.
The EPA notes that the use of an alumina torch in this procedure
has been described in related methodology for several years and is
commercially available and is in use by many analysts. The alternative
procedure suggested in the comment may be suitable if the detection
limits needed in the particular emission measurement situation can be
met.
The fourth comment addressed the required purity of the nickel
nitrate used to produce the nickel nitrate matrix modifier. The
commenter suggests that commercial nickel nitrate may contain small
amounts of impurities.
The EPA is not aware of instances where commercial nickel nitrate
that would be purchased for this purpose would contain objectionable
amounts of impurities, however the Method has been revised to permit
other nickel compounds of suitable purity to be used.
The fifth and final comment made a general statement concerning the
length and complexity of the Method, with the commenter suggesting that
the EPA should attempt to streamline and simplify the Method in order
to make it less costly and easier to use.
The EPA recognizes the need to simplify methods to reduce costs,
and believes that to meet the needed quality of the data to be
generated by Method 29, that the best possible effort has been made.
IV. Administrative Requirements
A. Docket
The docket is an organized and complete file of all the information
submitted to or otherwise considered by the EPA in the development of
this final rulemaking. The principal purposes of the docket are: (1) to
allow interested parties to identify and locate documents so that they
can effectively participate in the rulemaking process, and (2) to serve
as the record in case of judicial review (except for interagency review
materials) [Section 307(d)(7)(A)].
B. Office of Management and Budget Review
1. Paperwork Reduction Act
This rule does not contain any information collection requirements
subject to the Office of Management and Budget (OMB) review under the
Paperwork Reduction Act, 44 U.S.C. 3501 et seq.
2. Executive Order 12866 Review
Under Executive Order 12866 (58 FR 51735, October 4, 1993), the EPA
must determine whether the regulatory action is ``significant'' and
therefore subject to the OMB review and the requirements of the
Executive Order. The Order defines ``significant'' regulatory action as
one that is likely to lead to a rule that may:
1. Have an annual effect on the economy of $100 million or more, or
adversely affect in a material way the economy, a sector of the
economy, productivity, competition, jobs, the environment, public
health or safety, or State, local or tribal governments or communities;
2. Create a serious inconsistency or otherwise interfere with an
action taken or planned by another agency;
3. Materially alter the budgetary impact of entitlements, grants,
users fees, or loan programs or the rights and obligations of
recipients thereof; or
4. Raise novel legal or policy issues arising out of legal
mandates, the President's priorities, or the principles set forth in
the Executive Order.
Pursuant to the terms of Executive Order 12866, the EPA does not
consider this action to be significant because it does not involve any
of the above mentioned items.
D. Unfunded Mandates Act
Section 202 of the Unfunded Mandates Reform Act of 1995 (``Unfunded
Mandates Act'') (signed into law on March 22, 1995) requires that the
Agency prepare a budgetary impact statement before promulgating a rule
that includes a Federal mandate
[[Page 18262]]
that may result in expenditure by State, local, and tribal governments,
in aggregate, or by the private sector of $100 million or more in any
one year. Section 204 requires the Agency to establish a plan for
obtaining input from and informing, educating, and advising any small
governments that may be significantly or uniquely affected by the rule.
Under section 205 of the Unfunded Mandates Act, the Agency must
identify and consider a reasonable number of regulatory alternatives
before promulgating a rule for which a budgetary impact statement must
be prepared. The agency must select from those alternatives the least
costly, most cost-effective, or least burdensome alternative that
achieves the objectives of the rule, unless the Agency explains why
this alternative is not selected or the selection of this alternative
is inconsistent with law.
Because this rule is estimated to result in the expenditure by
State, local, and tribal governments or the private sector of less than
$100 million in any one year, the Agency has not prepared a budgetary
impact statement or specifically addressed the selection of the least
costly, most cost-effective, or least burdensome alternative. Because
small governments will not be significantly or uniquely affected by
this rule, the Agency is not required to develop a plan with regard to
small governments.
E. Regulatory Flexibility Act Compliance
Pursuant to the provisions of 5 U.S.C. 601 et seq., I hereby
certify that this final rule will not have an economic impact on small
entities because no additional costs will be incurred.
List of Subjects in 40 CFR Parts 60 and 61
Environmental protection, Air pollution control, Arsenic, Asbestos,
Beryllium, Cadmium, Lead, Hazardous materials, Incorporation by
reference, Intergovernmental relations, Mercury, Municipal waste
combustors, Reporting and recordkeeping requirements, Sewage sludge
incineration.
Statutory Authority. The statutory authority for this final rule
is provided by sections 101, 111, 112, 114, 116, 129, and 301 of the
Clean Air Act, as amended; 42 U.S.C., 7401, 7411, 7412, 7414, 7416,
7429, and 7601.
Dated: January 18, 1996.
Carol M. Browner,
Administrator.
40 CFR parts 60 and 61 are amended as follows:
PART 60--[AMENDED]
1. The authority citation for part 60 continues to read as follows:
Authority: 42 U.S.C. 7401, 7411, 7412, 7414, 7416, and 7601.
2. Section 60.17 is amended by revising paragraph (a)(22) and by
adding paragraphs (i) and (j) to read as follows:
Sec. 60.17 Incorporations by reference.
* * * * *
(a) * * *
(22) ASTM D 1193-77, Standard Specification for Reagent Water,
for appendix A to part 60, Method 6, par. 3.1.1; Method 7, par.
3.2.2; Method 7C, par. 3.1.1; Method 7D, par. 3.1.1; Method 8, par.
3.1.3; Method 12, par. 4.1.3; Method 25D, par. 3.2.2.4; Method 26A,
par. 3.1.1; Method 29, pars. 4.2.2., 4.4.2., and 4.5.6.
* * * * *
(i) Test Methods for Evaluating Solid Waste, Physical/Chemical
Methods,'' EPA Publication SW-846 Third Edition (November 1986), as
amended by Updates I (July, 1992), II (September 1994), IIA (August,
1993), and IIB (January, 1995). Test Method are incorporated by
reference for appendix A to part 60, Method 29, pars. 2.2.1; 2.3.1;
2.5; 3.3.12.1; 3.3.12.2; 3.3.13; 3.3.14; 5.4.3; 6.2; 6.3; 7.2.1; 7.2.3;
and Table 29-2. The Third Edition of SW-846 and Updates I, II, IIA, and
IIB (document number 955-001-00000-1) are available from the
Superintendent of Documents, U.S. Government Printing Office,
Washington, DC 20402, (202) 512-1800. Copies may be obtained from the
Library of the U.S. Environmental Protection Agency, 401 M Street, SW.,
Washington, DC 20460.
(j) Standard Methods for the Examination of Water and Wastewater,
16th edition, 1985. Method 303F Determination of Mercury by the Cold
Vapor Technique. This document may be obtained from the American Public
Health Association, 1015 18th Street, NW., Washington, DC 20036, and is
incorporated by reference for Method 29, pars 5.4.3; 6.3; and 7.2.3 of
appendix A to part 60.
3. In part 60, by adding method 29 to appendix A to read as
follows:
Appendix A--Test Methods
* * * * *
Method 29--Determination of Metals Emissions from Stationary
Sources
1. Applicability and Principle
1.1 Applicability. This method is applicable to the
determination of antimony (Sb), arsenic (As), barium (Ba), beryllium
(Be), cadmium (Cd), chromium (Cr), cobalt (Co), copper (Cu), lead
(Pb), manganese (Mn), mercury (Hg), nickel (Ni), phosphorus (P),
selenium (Se), silver (Ag), thallium (T1), and zinc (Zn) 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.
1.1.1 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.
1.2 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, As, Tl
and Zn.
2. Range, Detection Limits, Precision, and Interferences
2.1 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.
2.2 Analytical Detection Limits. (Note: See section 2.3 for the
description of in-stack detection limits.)
2.2.1 ICAP analytical detection limits for the sample solutions
(based on Method 6010 in EPA Publication SW-846, Third Edition
(November 1986) including updates I, II, IIA, and IIB, as
incorporated by reference in Sec. 60.17(i)) 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 based on Method 6020 in EPA Publication SW-846,
Third Edition (November 1986) as incorporated by reference in
Sec. 60.17(i)) are lower generally by a factor of ten or more. Be is
lower by a factor
[[Page 18263]]
of three. The actual sample analytical detection limits are sample
dependent and may vary due to the sample matrix.
2.2.2 The analytical detection limits for analysis by direct
aspiration AAS are approximately as follow: 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).
2.2.3 The detection limit for Hg by CVAAS (on the resultant
volume of the disgestion of the aliquots taken for Hg analyses) can
be approximately 0.02 to 0.2ng/ml, depending upon the type of CVAAS
analytical instrument used.
2.2.4 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 T1 (ng/ml).
2.3 In-stack Detection Limits.
2.3.1 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 2.2 and in EPA Publication SW-846, Third
Edition (November 1986) including updates I, II, IIA and IIB, as
incorporated by reference in Sec. 60.17(i), (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 m\3\. 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.
A x B/C=D Eq. 29-1
Where:
A=Analytical detectin limit, g/ml.
B=Liquid volume of digested sample prior to aliquotting for
analysis, Ml.
C=Stack sample gas volume, dsm\3\.
D=In-stack detection limit, g/m\3\.
Table 29-1.--In-Stack Method Detection Limits (g/m \3\) for the Front-Half, the Back-Half, and the Total Sampling Train Using ICAP and AAS
--------------------------------------------------------------------------------------------------------------------------------------------------------
Front-half: Probe and
Metal filter Back-half: Impingers 1-3 Back-half: Impingers (4-6) Total train:
-------------------------------------------------------------------------------------------------------------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 ........................... 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
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a Mercury analysis only.
\1\ Detection limit when analyzed by GFAAS.
\2\ Detection limit when analyzed by CVAAS, estimated for Back-Half and Total Train. See Sections 2.2 and 5.4.3.
Note: Actual method in-stack detection limits may vary from these values, as described in Section 2.3.3.
2.3.2 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.
2.3.3 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.
2.3.3.1 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.
2.3.3.2 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.
2.3.3.3 When both of the modifications described in Sections
2.3.3.1 and 2.3.3.2 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.
2.4 Precision. The precision (relative standard deviation) for
each metal detected in a method development test performed at
[[Page 18264]]
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.
2.5 Interferences. 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 in EPA Publication SW-
846 Third Edition (November 1986) including updates I, II, IIA and
IIB, as incorporated by reference in Sec. 60.17(i) 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.
3. Apparatus
3.1 Sampling. A schematic of the sampling train is shown in
Figure 29-1. It has general similarities to the Method 5 train.
BILLING 6560-50-M
[[Page 18265]]
[GRAPHIC] [TIFF OMITTED] TR25AP96.000
BILLING 6560-50-C
[[Page 18266]]
3.1.1 Probe Nozzle (Probe Tip) and Borosilicate or Quartz Glass
Probe Liner. Same as Method 5, Sections 2.1.1 and 2.1.2, 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.
3.1.2 Pitot Tube and Differential Pressure Gauge. Same as
Method 2, Sections 2.1 and 2.2, respectively.
3.1.3 Filter Holder. Glass, same as Method 5, Section 2.1.5,
except use a Teflon filter support or other non-metallic, non-
contaminating support in place of the glass frit.
3.1.4 Filter Heating System. Same as Method 5, Section 2.1.6.
3.1.5 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 2.1.7. 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 thermometer 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.
3.1.6 Metering System, Barometer, and Gas Density Determination
Equipment. Same as Method 5, Sections 2.1.8 through 2.1.10,
respectively.
3.1.7 Teflon Tape. For capping openings and sealing
connections, if necessary, on the sampling train.
3.2. Sample Recovery. Same as Method 5, Sections 2.2.1 through
2.2.8 (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:
3.2.1 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.
3.2.2 Sample Storage Containers. Use glass bottles (see the
Precaution: in Section 4.3.2 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.
3.2.3 Graduated Cylinder. Glass or equivalent.
3.2.4 Funnel. Glass or equivalent.
3.2.5 Labels. For identifying samples.
3.2.6 Polypropylene Tweezers and/or Plastic Gloves. For
recovery of the filter from the sampling train filter holder.
3.3 Sample Preparation and Analysis.
3.3.1 Volumetric Flasks, 100-ml, 250-ml, and 100-ml. For
preparation of standards and sample dilutions.
3.3.2 Graduated Cylinders. For preparation of reagents.
3.3.3 ParrR Bombs or Microwave Pressure Relief Vessels
with Capping Station (CEM Corporation model or equivalent). For
sample digestion.
3.3.4 Beakers and Watch Glasses. 250-ml beakers, with watch
glass covers, for sample digestion.
3.3.5 Ring Stands and Clamps. For securing equipment such as
filtration apparatus.
3.3.6 Filter Funnels. For holding filter paper.
3.3.7 Disposable Pasteur Pipets and Bulbs.
3.3.8 Volumetric Pipets.
3.3.9 Analytical Balance. Accurate to within .01 mg.
3.3.10 Microwave or Conventional Oven. For heating samples at
fixed power levels or temperatures, respectively.
3.3.11 Hot Plates.
3.3.12 Atomic Absorption Spectrometer (AAS). Equipped with a
background corrector.
3.3.12.1 Graphite Furnace Attachment. With Sb, As, Cd, Co, Pb,
Se, and Tl hollow cathode lamps (HCLs) or electrodeless discharge
lamps (EDLs). Same as Methods 7041 (Sb), 7060 (As), 7131 (Cd), 7201
(Co), 7421 (Pb), 7740 (Se), and 7841 (Tl) in EPA publication SW-846
Third Edition (November 1986) including updates I, II, IIA and IIB,
as incorporated by reference in Sec. 60.17(i).
3.3.12.2 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 6020 in EPA publication SW-846 Third Edition
(November 1986) including updates I, II, IIA and IIB, as
incorporated by reference in Sec. 60.17(i). See Note No. 2: Section
5.4.3 for other acceptable approaches for analysis of Hg in which
analytical detection limits of 0.002 ng/ml were obtained.
3.3.13 Inductively Coupled Argon Plasma Spectrometer. With
either a direct or sequential reader and an alumina torch. Same as
EPA Method 6010 in EPA publication SW-846 Third Edition (November
1986) including updates I, II, IIA and IIB, as incorporated by
reference in Sec. 60.17(i).
3.3.14 Inductively Coupled Plasma-Mass Spectrometer. Same as
EPA Method 6020 in EPA publication SW-846 Third Edition (November
1986) including updates I, II, IIA and IIB, as incorporated by
reference in Sec. 60.17(i).
4. Reagents
4.1 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.
4.2 Sampling Reagents.
4.2.1 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 3.1.1 of Method 5.
4.2.2 Water. To conform to ASTM Specification D1193-77, 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.
4.2.3 Nitric Acid (HNO3). Concentrated. Baker Instra-
analyzed or equivalent.
4.2.4 Hydrochloric Acid (HCL). Concentrated. Baker Instra-
analyzed or equivalent.
4.2.5 Hydrogen Peroxide (H2O2), 30 Percent (V/V).
4.2.6 Potassium Permanganate (KMnO4).
4.2.7 Sulfuric Acid (H2SO4). Concentrated.
4.2.8 Silica Gel and Crushed Ice. Same as Method 5, Sections
3.1.2 and 3.1.4, respectively.
4.3 Pretest Preparation of Sampling Reagents.
4.3.1 HNO3/H2O2 Absorbing Solution, 5 Percent
HNO3/10 Percent H2O2. Add carefully with stirring 50
ml of concentrated HNO3 to a 1000-ml volumeric flask containing
approximately 500 ml of water, and then add 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.
4.3.2 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
[[Page 18267]]
filter paper. Also, due to the potential reaction of the potassium
permanganate with the acid, there could be pressure buildup in the
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.
4.3.3 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.
4.3.4 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.
4.4 Glassware Cleaning Reagents.
4.4.1 HNO3, Concentrated. Fisher ACS grade or equivalent.
4.4.2 Water. To conform to ASTM Specification D1193-77, Type II
(incorporated by reference--See Sec. 60.17).
4.4.3 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.
4.5 Sample Digestion and Analysis Reagents.
The metals standards, except Hg, may also be made from solid
chemicals as described in Citation 3 of the Bibliography. Refer to
Citations 1, 2, or 5 of the Bibliography for additional information
on Hg standards. The 1000 g/ml Hg stock solution standard
may be made according to Section 6.2.5 of Method 101A.
4.5.1 HCL, Concentrated.
4.5.2 Hydrofluoric Acid (HF), Concentrated.
4.5.3 HNO3, Concentrated. Baker Instra-analyzed or
equivalent.
4.5.4 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.
4.5.5 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.
4.5.6 Water. To conform to ASTM Specification D1193-77, Type II
(incorporated by reference--See Sec. 60.17).
4.5.7 Hydroxylamine Hydrochloride and Sodium Chloride Solution.
See Citation 2 of the Bibliography for preparation.
4.5.8 Stannous Chloride. See Citation 2 of the Bibliography for
preparation.
4.5.9 KMnO4, 5 Percent (W/V). See Citation 2 of the
Bibliography for preparation.
4.5.10 H2SO4, Concentrated.
4.5.11 Potassium Persulfate, 5 Percent (W/V). See Citation 2 of
the Bibliography for preparation.
4.5.12 Nickel Nitrate, Ni (NO3)2 6H2O.
4.5.13 Lanthanum Oxide, La2O3.
4.5.14 Hg Standard (AAS Grade), 1000 g/ml.
4.5.15 Pb Standard (AAS Grade), 1000 g/ml.
4.5.16 As Standard (AAS Grade), 1000 g/ml.
4.5.17 Cd Standard (AAS Grade), 1000 g/ml.
4.5.18 Cr Standard (AAS Grade), 1000 g/ml.
4.5.19 Sb Standard (AAS Grade), 1000 g/ml.
4.5.20 Ba Standard (AAS Grade), 1000 g/ml.
4.5.21 Be Standard (AAS Grade), 1000 g/ml.
4.5.22 Co Standard (AAS Grade), 1000 g/ml.
4.5.23 Cu Standard (AAS Grade), 1000 g/ml.
4.5.24 Mn Standard (AAS Grade), 1000 g/ml.
4.5.25 Ni Standard (AAS Grade), 1000 g/ml.
4.5.26 P Standard (AAS Grade), 1000 g/ml.
4.5.27 Se Standard (AAS Grade), 1000 g/ml.
4.5.28 Ag Standard (AAS Grade), 1000 g/ml.
4.5.29 Tl Standard (AAS Grade), 1000 g/ml.
4.5.30 Zn Standard (AAS Grade), 1000 g/ml.
4.5.31 Al Standard (AAS Grade), 1000 g/ml.
4.5.32 Fe Standard (AAS Grade), 1000 g/ml.
4.5.33 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 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.
4.5.34 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 and IIB, as incorporated by reference in
Sec. 60.17(i).
4.5.35 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.
4.5.36 Matrix Modifiers.
4.5.36.1 Nickel Nitrate, 1 Percent (V/V). Dissolve 4.956 g of
Ni (NO3)26H2O 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.
4.5.36.2 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.
4.5.36.3 Lanthanum. Carefully dissolve 0.5864 g of
La2O3 in 10 ml of concentrated HNO3, 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.
4.5.37 Whatman 40 and 541 Filter Papers (or equivalent). For
filtration of digested samples.
5. Procedure
5.1 Sampling. The complexity of this method is such that, to
obtain reliable results,
[[Page 18268]]
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.
5.1.1 Pretest Preparation. Follow the same general procedure
given in Method 5, Section 4.1.1, 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.
5.1.2 Preliminary Determinations. Same as Method 5, Section
4.1.2.
5.1.3 Preparation of Sampling Train.
5.1.3.1 Set up the sampling train as shown in Figure 29-1.
Follow the same general procedures given in Method 5, Section 4.1.3,
except place 100 ml of the HNO3/H2O2 solution
(Section 4.3.1. of this method) in each of the second and third
impingers as shown in Figure 29-1. Placee 100 ml of the acidic
KMnO4 absorbing solution (Section 4.3.2 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.
5.1.3.2 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.
5.1.3.3 If Hg analysis will not be performed, the fourth,
fifth, and sixth impingers as shown in Figure 29-1 are not required.
5.1.3.4 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.
5.1.4 Leak-Check Procedures. Follow the leak-check procedures
given in Method 5, Section 4.1.4.1 (Pretest Leak-Check), Section
4.1.4.2 (Leak-Checks During the Sample Run), and Section 4.1.4.3
(Post-Test Leak-Checks).
5.1.5 Sampling Train Operation. Follow the procedures given in
Method 5, Section 4.1.5. When sampling for Hg, use a procedure
analagous to that described in Section 7.1.1 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 5-2 of
Method 5.
5.1.6 Calculation of Percent Isokinetic. Same as Method 5,
Section 4.1.6.
5.2 Sample Recovery.
5.2.1 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.
5.2.2 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.
5.2.3 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.
5.2.4 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):
BILLING CODE 6560-50-M
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[GRAPHIC] [TIFF OMITTED] TR25AP96.001
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[GRAPHIC] [TIFF OMITTED] TR25AP96.002
BILLING CODE 6560-50-C
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5.2.5 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.
5.2.6 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.
5.2.6.1 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.
5.2.6.2 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 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.
5.2.6.3 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.
5.2.7 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.
(Note: The use of a total of exactly 100 ml is necessary for the
subsequent blank correction procedures.)
Perform the rinses as applicable and generally as described in
Method 12, Section 5.2.2. 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.
5.2.8 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 5.2.4.
(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.)
5.2.9 Container Nos. 5A (0.1 N HNO3), 5B (KMnO4/
H2SO4 absorbing solution), and 5C (8 N HCl rinse and
dilution).
5.2.9.1 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.
5.2.9.2 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 4.3.2. 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.
5.2.9.3 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 the HC1 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.
5.2.10 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.
5.2.11 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.
5.2.12 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.
5.2.13 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.
[[Page 18272]]
5.2.14 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.
5.2.15 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 5.2.9.2. Read the Precaution: in
Section 4.3.2. and read the Note in Section 5.2.9.2.
5.2.16 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.
5.2.17 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.
5.3 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.
5.3.1 Container No. 1 (Sample Filter).
5.3.1.1 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 4.3 of Method 5.
5.3.1.2 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 ParrR
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 ParrR 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
5.3.3.
5.3.1.3 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 5.3.1.2 and then combine the
digestate with the digested filter sample.
5.3.2 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 for 24 hours without added heat, weigh to a
constant weight according to the procedures described in Section 4.3
of Method 5, and report the results to the nearest 0.1 mg.
Redissolve the residue with 10 ml of concentrated HNO3.
BILLING CODE 6560-50-M
[[Page 18273]]
[GRAPHIC] [TIFF OMITTED] TR25AP96.003
BILLING CODE 6560-50-C
[[Page 18274]]
Quantitatively combine the resultant sample, including all liquid
and any particulate matter, with Container No. 3 before beginning
Section 5.3.3.
5.3.3 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 ParrR 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 5.3.1.2. Then combine the resultant sample
directly with the acid digested portions of the filter prepared
previously in Section 5.3.1.2. 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.
5.3.4 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 watch glass. 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 5.3.4.1 or 5.3.4.2.
5.3.4.1 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.
5.3.4.2 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 5.3.1.
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.)
5.3.5 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 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.
5.3.6 Container No. 6 (Silica Gel). Weigh the spent silica gel
(or silica gel plus impinger) to the nearest 0.5 g using a balance.
5.4 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 5.4.1 and 5.4.2, respectively. Analytical Fraction 1B is
for front-half Hg analysis as described in Section 5.4.3. 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
HNO3H2O2 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 5.4.3. 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.
5.4.1 ICAP and ICP-MS Analysis. Analyze Analytical Fractions 1A
and 2A by ICAP using Method 6010 or Method 200.7 (40 CFR part 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 7.3.1. Recommended wavelengths for
analysis are as follows:
------------------------------------------------------------------------
Wavelength
Element (nm)
------------------------------------------------------------------------
Aluminum.................................................... 308.215
Antimony.................................................... 206.833
Arsenic..................................................... 193.696
Barium...................................................... 455.403
Beryllium................................................... 313.042
Cadmium..................................................... 226.502
Chromium.................................................... 267.716
Cobalt...................................................... 228.616
Copper...................................................... 324.754
Iron........................................................ 259.940
Lead........................................................ 220.353
Manganese................................................... 257.610
Nickel...................................................... 231.604
Phosphorous................................................. 214.914
Selenium.................................................... 196.026
Silver...................................................... 328.068
Thallium.................................................... 190.864
Zinc........................................................ 213.856
------------------------------------------------------------------------
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, and IIB, as
incorporated by reference in Sec. 60.17(i).
(Note: When analyzing samples in a HF matrix, an alumina torch
should be used;
[[Page 18275]]
since all front-half samples will contain HF, use an alumina torch.)
5.4.2. 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 29-2 to determine which
techniques and procedures to apply for each target metal. Use Table
29-2, if necessary, to determine techniques for minimization of
interferences. Calibrate the instrument according to Section 6.3 and
follow the quality control procedures specified in Section 7.3.2.
Table 29-2.--Applicable Techniques, Methods and Minimization of Interference for AAS Analysis
----------------------------------------------------------------------------------------------------------------
Interferences
Metal Technique SW-846 \1\ Wavelength ---------------------------------------------
method 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 ul 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 matching or
nitrous-oxide/
acetylene flame.
Nonlinear response... 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 & scatter. Background correction
is required and
Zeeman background
correction can be
useful.
Ag............... Aspiration........... 7760 328.1 Adsorption & Scatter Background correction
AgCl insoluble. is required. Avoid
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 or Background correction
chloride. is required.
Verify that losses
are not occurring
for volatization by
spiked samples or
standard addition;
Palladium is a
suitable matrix
modifier.
Zn............... Aspiration........... 7950 213.9 High Si, Cu, & P Strontium removes Cu
Contamination. and phosphate, Great
care taken to avoid
contamination.
Sb............... Aspiration........... 7040 217.6 1000 mg/ml Pb Ni, Cu, Use secondary
or acid. wavelengths of
231.1.nm; match
sample & standards
acid concentration
or use nitrous
oxidefacetylene
flame.
Sb............... Furnace.............. 7041 217.6 High Pb.............. Secondary Wavelength
or Zeeman
correction.
As............... Furnace.............. 7060 193.7 Arsenic Spiked samples and
volatilization. add nickel nitrate
Aluminum............. solution to
digestates prior to
analysis.
Use Zeeman background
correction.
Ba............... Aspiration 7080...... 7080 553.6 Calcium.............. High hollow cathode
Barium ionization.... current and narrow
band set.
2 ml of KCl per 100
ml of sample.
Be............... Aspiration........... 7090 234.9 500 ppm Al High Mg Add 0.1% fluoride.
and Si. Use method of
standard additions.
Be............... Furnace.............. 7091 234.9 Be in optical path... Optimize parameters
to minimize effects.
Cd............... Aspiration........... 7130 228.8 Absorption and light Background correction
scattering. is required.
[[Page 18276]]
Cd............... Furnace.............. 7131 228.8 As above............. As above.
Excess Chloride...... Ammonium phosphate
Pipet tips........... used as a matrix
modifier.
Use cadmiun-free
tips.
Cr............... Aspiration........... 7190 357.9 Akali 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 known constant
effect and to
eliminate effect of
phosphate.
Cu............... Aspiration........... 7210 324.7 Absorption & scatter. Consult
manufacturer's
manual.
----------------------------------------------------------------------------------------------------------------
\1\ Refer to EPA publication SW-846 Third Edition (November 1986) including updates I, II, IIA, and IIB, as
incorporated by reference in Sec. 60.17(i).
5.4.3 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 and IIB, as
incorporated by reference in Sec. 60.17(i) or in Standard Methods
for the Examination of Water and Wastewater, 16th Edition, (1985),
Method 303F, as incorporated by reference in Sec. 60.17, or,
optionally using NOTE No. 2 in 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 in this Section). The total amount of Hg in the
aliquot shall be less than 1 g and within the range (zero
to 1000 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 in 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 to Section 5.4.3. 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 to Section 5.4.3. 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 5.4.3.: (The Leeman, Perkin Elmer,
and similar instruments described in this note add automatically the
necessary stannous chloride solution during the automated analysis
of Hg.) and
(2) Upon completion of the digestion described in paragraph (1),
of this note, analyze the sample according to the instrument
manufacturer's directions. This approach allows multiple (including
duplicate) automated analyses of a digested sample aliquot.
6. Calibration
Maintain a laboratory log of all calibrations.
6.1 Sampling Train Calibration. Calibrate the sampling train
components according to the indicated sections of Method 5: Probe
Nozzle (Section 5.1); Pitot Tube (Section 5.2); Metering System
(Section 5.3); Probe Heater (Section 5.4); Temperature Gauges
(Section 5.5); Leake-Check of the Metering System (Section 5.6); and
Barometer (Section 5.7).
6.2 Industively Coupled Argon Plasma Spectrometer Calibration.
Prepare standards as outlined in Section 4.5. 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 and IIB, as incorporated by reference in Sec. 60.17(i).
6.3 Atomic Absorption Spectrometer--Direct Aspiration AAS,
GFAAS, and CVAAS analyses. Prepare the standards as outlined in
Section 4.5 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 and IIB, as
incorporated by reference in Sec. 60.17(i) or in Standard Methods
for the Examination of Water and Wastewater, 16th Edition, (1985),
Method 303F (for Hg) as incorporated by reference in Sec. 60.17. 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.
7. Quality Control
7.1 Field Reagent Blanks, if analyzed. Perform the digestion
and analysis of the blanks in Container Nos. 7 through 12 that were
produced in Sections 5.2.11 through 5.2.17, respectively. For Hg
field reagent blanks, use a 10 ml aliquot for digestion and
analysis.
7.1.1 Digest and analyze one of the filters from Container No.
12 per Section 5.3.1, 100 ml from Container No. 7 per Section 5.3.2,
and 100 ml from Container No. 8A per Section 5.3.3. This step
produces blanks for Analytical Fractions 1A and 1B.
7.1.2 Combine 100 ml of Container No. 8A with 200 ml from
Container No. 9, and digest and analyze the resultant volume per
Section 5.3.4. This step produces blanks for Analytical Fractions 2A
and 2B.
7.1.3 Digest and analyze a 100-ml portion of Container No. 8A
to produce a blank for Analytical Fraction 3A.
7.1.4 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 5.3.5, except do not dilute the 133ml. Analyze this blank
for Hg within 48 hrs. of the filtration step, and use 400 ml as the
blank volume when calculating the blank mass value. Use the
[[Page 18277]]
actual volumes of the other analytical blanks when calculating their
mass values.
7.1.5 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 5.3.5 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.
7.1.6 Analyze the blanks for Analytical Fraction Blanks 1A and
2A per Section 5.4.1 and/or Section 5.4.2. Analyze the blanks for
Analytical Fractions 1B, 2B, 3A, 3B, and 3C per Section 5.4.3.
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.
7.2 Quality Control Samples. Analyze the following quality
control samples.
7.2.1 ICAP and ICP-MS Analysis. Follow the respective quality
control descriptions in Section 8 of Methods 6010 and 6020 of EPA
Publication SW-846 Third Edition (November 1986) including updates
I, II, IIA and IIB, 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).
7.2.2. 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.
7.2.3 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 of EPA Publication SW-846 Third Edition (November 1986)
including updates I, II, IIA and IIB, as incorporated by reference
in Sec. 60.17(i) or in Standard Methods for the Examination of Water
and Wastewater, 16th Edition, (1985), Method 303F as incorporated by
reference in Sec. 60.17.
8. Calculations
8.1 Dry Gas Volume. Using the data from this test, calculate
Vm(std), the dry gas sample volume at standard conditions as
outlined in Section 6.3 of Method 5.
8.2 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.
8.3 Stack Gas Velocity. Using the data from this test and
Equation 2-9 of Method 2, calculate the average stack gas velocity.
8.4 Metals (Except Hg) in Source Sample.
8.4.1 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:
Mfh=Ca1 Fd Vsoln,1 Eq. 29-1
where:
Mfh=Total mass of each metal (except Hg) collected in the front
half of the sampling train (Sample Fraction 1), g.
Ca1=Concentration of metal in Analytical Fraction 1A as read
from the standard curve, g/ml.
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).
Vsoln,1=Total volume of digested sample solution (Analytical
Fraction 1), ml.
8.4.1.1 If Analytical Fractions 1A and 2A are combined, use
proportional aliquots. Then make appropriate changes in Equations
29-1 through 29-3 to reflect this approach.
8.4.2 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.
Mbh=Ca2 Fa Va Eq. 29-2
where:
Mbh=Total mass of each metal (except Hg) collected in the back-
half of the sampling train (Sample Fraction 2), g.
Ca2=Concentration of metal in Analytical Fraction 2A as read
from the standard curve, (g/ml).
Fa=Aliquot factor, volume of Sample Fraction 2 divided by
volume of Sample Fraction 2A (see Section 5.3.4.)
Va=Total volume of digested sample solution (Analytical
Fraction 2A), ml (see Section 5.3.4.1 or 5.3.4.2, as applicable).
8.4.3 Total Train, Metals (except Hg). Calculate the total
amount of each of the quantified metals collected in the sampling
train as follows:
Mt=(Mfh - Mfhb) + (Mbh - Mbhb) Eq. 29-3
where:
Mt=Total mass of each metal (separately stated for each metal)
collected in the sampling train, g.
Mfhb=Blank correction value for mass of metal detected in
front-half field reagent blank, g.
Mbhb=Blank correction value for mass of metal detected in back-
half field reagent blank, g.
8.4.3.1 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 black-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.
8.5 Hg in Source Sample.
8.5.1 Analytical Fraction 1B; Front-Half Hg. Calculate the
amount of Hg collected in the front-half, Sample Fraction 1, of the
sampling train by using Equation 29-4:
[GRAPHIC] [TIFF OMITTED] TR25AP96.005
where:
Hgfh=Total mass of Hg collected in the front-half of the
sampling train (Sample Fraction 1), g.
Qfh=Quantity of Hg, g, TOTAL in the ALIQUOT of
Analytical Fraction 1B selected for digestion and analysis.
8.5.1.1 For example, if a 10 ml aliquot of Analytical Fraction
1B is taken and digested and analyzed (according to Section 5.4.3
and its NOTES Nos. 1 and 2), then calculate and use the total amount
of Hg in the 10 ml aliquot for Qfh.
Vsoln,1=Total volume of Analytical Fraction 1, ml.
Vf1B=Volume of aliquot of Analytical Fraction 1B analyzed, ml.
8.5.1.2 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 5.4.3 to bring it into the proper analytical range, and then
1 ml of that 50-ml wa digested according to Section 5.4.3 and
analyzed, Vf1B would be 0.02 ml.
8.5.2 Analytical Fractions 2B, 3A, 3B, and 3C; Back Half Hg.
8.5.2.1 Calculate the amount of Hg collected in Sample Fraction
2 by using Equation 29-5:
[GRAPHIC] [TIFF OMITTED] TR25AP96.006
where:
Hgbh2=Total mass of Hg collected in Sample Fraction 2,
g.
[[Page 18278]]
Qbh2=Quantity of Hg, g, TOTAL in the ALIQUOT of
Analytical Fraction 2B selected for digestion and analysis.
8.5.2.1.1 For example, if a 10 ml aliquot of Analytical
Fraction 2B is taken and digested and analyzed (according to Section
5.4.3 and its NOTES Nos. 1 and 2), then calculate and use the total
amount of Hg in the 10 ml aliquot for Qbh2.
V