[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]



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


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.

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

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

[[Page 18269]]

[GRAPHIC] [TIFF OMITTED] TR25AP96.001



[[Page 18270]]

[GRAPHIC] [TIFF OMITTED] TR25AP96.002



BILLING CODE 6560-50-C

[[Page 18271]]

    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.

Vsoln,2=Total volume of Sample Fraction 2, ml.
Vf2B=Volume of Analytical Fraction 2B analyzed, ml.

    8.5.2.1.2  For example, if 1 ml of Analytical Fraction 2B was 
diluted to 10 ml with 0.15 percent HNO3 as described in Section 
5.4.3 to bring it into the proper analytical range, and then 5 ml of 
that 10-ml was analyzed, Vf2B would be 0.5 ml.
    8.5.2.2  Calculate each of the back-half Hg values for 
Analytical Fractions 3A, 3B, and 3C by using Equation 29-6:
[GRAPHIC] [TIFF OMITTED] TR25AP96.007

where:
Hgbh3 (A,B,C)=Total mass of Hg collected separately in Fraction 
3A, 3B, or 3C, g.
Qbh3 (A,B,C)=Quantity of Hg, g, TOTAL, separately, in 
the ALIQUOT of Analytical Fraction 3A, 3B, and 3C selected for 
digestion and analysis, (see previous notes in Sections 8.5.1 and 
8.5.2 describing the quantity ``Q'' and calculate similarly).
Vf3 (A,B,C)=Volume, separately, of Analytical Fraction 3A, 3B, 
or 3C analyzed, ml (see previous notes in Sections 8.5.1 and 8.5.2, 
describing the quantity ``V'' and calculate similarly).
Vsoln, 3 (A,B,C)=Total volume, separately, of Analytical 
Fraction 3A, 3B, or 3C, ml.

    8.5.2.3  Calculate the total amount of Hg collected in the back-
half of the sampling train by using Equation 29-7:

Hgbh=Hgbh2+Hgbh3A+Hgbh3B+Hgbh3C  Eq. 29-7

where:
Hgbh=Total mass of Hg collected in the back-half of the 
sampling train, g.

    8.5.3  Total Train Hg Catch. Calculate the total amount of Hg 
collected in the sampling train by using Equation 29-8:

Hgt=(Hgfh-Hgfhb)+(Hgbh-Hgbhb)  Eq. 29-8

where:
Hgt=Total mass of Hg collected in the sampling train, 
g.
Hgfhb=Blank correction value for mass of Hg detected in front-
half field reagent blank, g.
Hgbhb=Blank correction value for mass of Hg detected in back-
half field reagent blanks, g.

    8.5.4  If the total of the measured blank values 
(Hgfhb+Hgbhb) is in the range of 0.0 to 0.6 g, 
then use the total to correct the sample value 
(Hgfh+Hgbh); if it exceeds 0.6 g, use the greater 
of I. or II:
    I. 0.6 g.
    II. the lesser of (a) (Hgfhb+Hgbhb), or (b) 5 percent 
of the sample value (Hgfh+Hgbh).
    8.6  Individual Metal Concentrations in Stack Gas. Calculate the 
concentration of each metal in the stack gas (dry basis, adjusted to 
standard conditions) by using Equation 29-9:
[GRAPHIC] [TIFF OMITTED] TR25AP96.008

Cs=Concentration of a metal in the stack gas, mg/dscm.
K4=10-3 mg/g.
Mt=Total mass of that metal collected in the sampling train, 
g; (substitute Hgt for Mt for the Hg 
calculation).
Vm(std)=Volume of gas sample as measured by the dry gas meter, 
corrected to dry standard conditions, dscm.

    8.7  Isokinetic Variation and Acceptable Results. Same as Method 
5, Sections 6.11 and 6.12, respectively.

9. Bibliography

    1. Method 303F in Standard Methods for the Examination of Water 
Wastewater, 16th Edition, 1985. Available from the American Pubic 
Health Association, 1015 18th Street NW., Washington, DC 20036.
    2. EPA Methods 6010, 6020, 7000, 7041, 7060, 7131, 7421, 7470, 
7740, and 7841, Tesdt Methods for Evaluating Solid Waste: Physical/
Chemical Methods. SW-846, Third Edition, September 1986, with 
updates I, II, IIA and IIB. Office of Solid Waste and Emergency 
Response, U.S. Environmental Protection Agency, Washington, DC 
20460.
    3. EPA Method 200.7, Code of Federal Regulations, Title 40, Part 
136, Appendix C. July 1, 1987.
    4. EPA Methods 1 through 5, Code of Federal Regulations, Title 
40, Part 60, Appendix A. July 1, 1991.
    5. EPA Method 101A, Code of Federal Regulations, Title 40, Part 
61, Appendix B. July 1, 1991.

PART 61--[AMENDED]

    3. The authority citation for part 61 continues to read as follows:

    Authority: 42 U.S.C. 7401, 7412, 7414, 7416, and 7601.

    4. In part 61, Method 101A of appendix B, by revising the heading, 
Sections 6.1.5, 7.2.1, 7.2.3, 7.2.5, 7.3.1., 7.3.2, 7.3.3, and 9.2; and 
by adding sections 5.2.4 through 5.2.7, 6.1.7, 6.1.8, 7.2.1.1 through 
7.2.1.3, 7.2.6, 9.2.1, 9.2.2 and reference 3 of item 10 bibliograph; 
and by adding text to the end of section 6.1.6 to read as follows:

 Appendix B--Test Methods

* * * * *

Method 101A--Determination of Particulate and Gaseous Mercury Emissions 
From Stationary Sources

* * * * *
    5.2.4  Atomic Absorption Spectrophotometer or Equivalent. Any 
atomic absorption unit with an open sample presentation area in 
which to mount the optical cell is suitable. Use those instrument 
settings recommended by the particular manufacturer. Instruments 
designed specifically for the measurement of mercury using the cold-
vapor technique are commercially available and may be substituted 
for the atomic absorption spectrophotometer.
    5.2.5  Optical Cell. Alternatively, a heat lamp mounted above 
the cell or a moisture trap installed upstream of the cell may be 
used.
    5.2.6 Aeration Cell. Alternatively, aeration cells available 
with commercial cold vapor instrumentation may be used.
    5.2.7  Aeration Gas Cylinder. Nitrogen, argon, or dry, Hg-free 
air, equipped with a single-stage regulator. Alternatively, aeration 
may be provided by a peristaltic metering pump. If a commercial cold 
vapor instrument is used, follow the manufacturer's recommendations.
* * * * *
    6.1.5  Sulfuric Acid (H2SO4), 10 Percent (V/V). 
Carefully add and mix 100 ml of concentrated H2SO4 to 800 
ml of deionized distilled water. Then, by adding deionized distilled 
water, mix and bring to a final volume of 1000 ml.
    6.1.6 * * *
    Precaution: To prevent autocatalytic decomposition of the 
permanganate solution, filter the solution through Whatman 541 
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 
explosive potentials. Venting is required, but should not allow 
contamination of the solution; a No. 70-72 hole drilled in the 
container cap and Teflon liner has been used.
    6.1.7  Hydrochloric Acid (HCL). Concentrated. Trace-metals grade 
is recommended. The Hg level shall be less than 3 ng/ml.
    6.1.8  HCL, 8 N. Dilute 67 ml of concentrated HCl to 100 ml with 
water (slowly add the HCl to the water).
* * * * *
    7.2.1  Container No. 1 (Impinger, Probe, and Filter Holder) and, 
if applicable, No. 1A (HCl rinse).
    7.2.1.1  Using a graduated cylinder, measure the liquid in the 
first three

[[Page 18279]]

impingers to within 1 ml. Record the volume of liquid present (e.g., 
see Figure 5-3 of Method 5 in 40 CFR Part 60). This information is 
required to calculate the moisture content of the effluent gas. (Use 
only graduated cylinder and glass storage bottles that have been 
precleaned as in Section 7.1.2.) Place the contents of the first 
three impingers into a 1000-ml glass sample bottle labeled Container 
No. 1. See the Precaution in Section 6.1.6.

    Note No. 1 to Section 7.2.1.1: Due to the potential reaction of 
KMnO4 with acid, there could be pressure buildup in the sample 
storage bottles. These bottles shall not be filled completely and 
shall be vented to relieve excess pressure. A No. 70-72 hole drilled 
in the container cap and Teflon liner has been used successfully).
    Note No. 2 to Section 7.2.1.1: If a filter is used in the 
sampling train, remove the filter from its holder as outlined under 
``Container No. 3'' below.)

    7.2.1.2  Taking care that dust on the outside of the probe or 
other exterior surfaces does not get into the sample, quantitatively 
recover the Hg (and any condensate) from the probe nozzle, probe 
fitting, probe liner, front half of the filter holder (if 
applicable), and impingers as follows: Rinse these components with a 
total of 250 to 400 ml of fresh acidified 4 percent KMnO4 
solution carefully assuring removal of all loose particulate matter 
from the impingers; add all washings to Container No. 1. See the 
Precaution in Section 6.1.6 and see the Note No. 1 in Section 
7.2.1.1. To remove any residual brown deposits on the glassware 
following the permanganate rinse, rinse with approximately 100 ml of 
water carefully assuring removal of all loose particulate matter 
from the impingers, and add this rinse to Container No. 1. If no 
visible deposits remain after this water rinse, do not rinse with 8 
N HCl. However, if deposits do remain on the glassware after the 
water rinse, wash the impinger walls and stems with a total of only 
25 ml of 8 N HCl as follows; turn and shake the impingers so that 
the 8 N HCl contacts all inside surfaces (wash the first impinger, 
then pour the wash from the first impinger into the second impinger, 
and finally pour the wash from the second into the third). DO NOT 
PLACE THE HCl WASH INTO THE ACIDIFIED PERMANGANATE SOLUTION. Place 
the HCl wash into a separate container labeled Container No. 1A as 
follows: place 150 ml of water in an empty sample container labeled 
Container No. 1A. Pour the HCl wash carefully, with stirring, into 
Container No. 1A. Rinse the impinger walls and stem with a total of 
50 ml of water, and place this rinse into Container No. 1A.
    7.2.1.3  After all washings have been collected in the sample 
containers, prepare as described above to prevent leakage during 
shipment to the laboratory. Mark the height of the fluid level to 
determine whether leakage occurs during transport. Label the 
containers to identify their contents clearly.
    7.2.3  Container No, 3 (Filter). If a filter was used, carefully 
remove it from the filter holder, place it into a 100 ml glass 
sample container, and add 20 to 40 ml of acidified KMnO4. If it 
is necessary to fold the filter, be sure that the particulate cake 
is inside the fold. Carefully transfer to the 100 ml sample bottle 
any particulate matter and filter fibers that might adhere to the 
filter holder gasket by using a dry Nylon bristle brush and a sharp 
edged blade. See the Precaution in Section 6.1.6 and see the Note 
No. 1 in Section 7.2.1.1. Label the container to clearly identify 
its contents. Mark the height of the fluid level to determine 
whether leakage occurs during transport.
* * * * *
    7.2.5  Container No, 5 (Absorbing Solution Blank). For a blank, 
place 500 ml of acidified absorbing solution in a 1000 ml sample 
bottle. See the Precaution in Section 6.1.6 and see the Note No. 1 
in Section 7.2.1.1.
    7.2.6  Container No. 6 (HCl rinse blank). For a blank, place 200 
ml of water in a 1000-ml sample bottle, and add 25 ml of 8 N HCl 
carefully with stirring. Seal the container. Only one blank sample 
per 3 runs is required.
* * * * *
    7.3.1  Containers No. 3 and No. 4 (Filter and Filter Blank). If 
a filter is used, place the contents, including the filter, of 
Containers No. 3 and 4 in separate 250-ml beakers, and heat the 
beakers on a steam bath until most of the liquid has evaporated. Do 
not take to dryness. Add 20 ml of concentrated HNO3 to the 
beakers, cover them with a watch glass, and heat on a hot plate at 
70  deg.C for 2 hours. Remove from the hot plate. Filter the 
solution from digestion of the Container No. 3 contents through 
Whatman No. 40 filter paper, and save the filtrate for addition to 
the Container No. 1 filtrate as described in Section 7.3.2. Discard 
the filter. Filter the solution from the digestion of the Container 
No. 4 contents through Whatman No. 40 filter paper, and save the 
filtrate for addition to Container No. 5 filtrate as described in 
Section 7.3.3. Discard the filter.
    7.3.2  Container No. 1 (Impingers, Probe, and Filter Holder) 
and, if applicable, No. 1A (HCl rinse). Filter the contents of 
Container No. 1 through Whatman 40 filter paper into a 1-liter 
volumetric flask to remove the brown MnO2 precipitate. Save the 
filter for digestion of the brown MnO2 precipitate. Add the 
sample filtrate from Container No. 3 to the 1-liter volumetric 
flask, and dilute to volume with water. If the combined filtrates 
are greater than 1000 ml, determine the volume to the nearest ml and 
make the appropriate corrections for blank subtractions. Mix 
thoroughly. Mark the combined filtrates as ANALYSIS SAMPLE No. A.1. 
and analyze for Hg within 48 hr of the filtration step (Note: Do not 
confuse ANALYSIS SAMPLE No. A.1. with the contents of field Sample 
Container No. 1A which contains the 8 N HCl wash). Place the saved 
filter, which was used to remove the brown MnO2 precipitate, 
into an appropriate 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 1A through Whatman 40 paper into a 
500-ml volumetric flask. Then filter the result of the digestion of 
the brown MnO2 from Container No. 1 through Whatman 40 filter 
into the same 500-ml volumetric flask, and dilute and mix well to 
volume with water. Discard the filter. Mark this combined 500-ml 
dilute solution as ANALYSIS SAMPLE No. HCL A.2., and analyze for Hg.
    7.3.3  Container No. 5 (Absorbing Solution Blank) and No. 6 (HCl 
Rinse Blank). Prepare the contents of Container No. 5 for analysis 
by the same procedure used for Container No. 1 as described in 
Section 7.3.2. Add the filter blank filtrate from Container No. 4 to 
the 1-liter volumetric flask, and dilute to volume. Mix thoroughly. 
Mark this as ANALYSIS SAMPLE No. A.1. BLANK, and analyze for Hg 
within 48 hours of the filtration step. Digest any brown precipitate 
remaining on the filter from the filtration of Container No. 5 by 
the same procedure as described in Section 7.3.2. Filter the 
contents of Container No. 6 by the same procedure as described in 
Section 7.3.2, and combine in the 500-ml volumetric flask with the 
filtrate from the digested blank MnO2 precipitate. Mark this 
resultant 500-ml combined dilute solution as ANALYSIS SAMPLE No. HCl 
A.2 blank. (Note: When analyzing samples A.1 blank and HCl A.2 
blank, always begin with 10-ml aliquots. This applies specifically 
to blank samples.)
* * * * *
    9. * * *
    9.2  Total Mercury. For each source sample, correct the average 
maximum absorbance of the two consecutive samples whose peak heights 
agree within 3 percent of their average for the contribution of the 
blank. Then calculate the total Hg content in g in each 
sample. Correct for any dilutions made to bring the sample into the 
working range of the spectrophotometer.
[GRAPHIC] [TIFF OMITTED] TR25AP96.009


[[Page 18280]]


    where:
m(HCl) Hg=Total blank corrected g of Hg in HCl rinse 
and HCl digestate of filter sample
C(HCl) Hg=Total ng of Hg analyzed in the aliquot from the 500-
ml ANALYSIS SAMPLE No. HCl A.2.
C(HCl blk) Hg=Total ng of Hg analyzed in aliquot of the 500-ml 
ANALYSIS SAMPLE No. HCl A.2 blank.
D.F.(HCl) Hg=Dilution factor for the HCl-digested Hg-containing 
solution, ANALYSIS SAMPLE No. ``HCl A.2.'' This dilution factor 
applies only to the dilution steps, if necessary, of the 500 ml of 
the original sample volume [Vf (HCl)] of ``HCl A.2'' because 
the original volume has been factored out in the equation along with 
the sample aliquot (S). In Eq. 101A-1, the sample aliquot, S, is 
digested according to Sections 7.4, 8.1, and 8.2 and the Hg from 
this digestion is introduced directly into the aeration cell for 
analysis. A dilution factor is required only if it is necessary to 
bring the sample into the analytical instrument's calibration range. 
If no dilution is necessary, then D.F. (HCl) Hg equals 1.0.
D.F. (HCl blk)Hg=Dilution factor for the HCl-digested Hg-containing 
solution, ANALYSIS SAMPLE No. ``HCl A.2 blank.'' (Refer to sample 
No. ``HCl A.2'' dilution factor information above.)
Vf(HCl)=Solution volume of original sample, 500 ml for the HCl 
samples diluted as described in Section 7.3.
10-3=Conversion factor g/ng.
S=Aliquot volume of sample: digested according to Sections 7.4, 8.1, 
8.2 and the Hg from this digestion is introduced directly into the 
aeration cell for analysis, ml.
Sblk=Aliquot volume of blank: digested according to Sections 
7.4, 8.1, and 8.2 and the Hg from this digestion is introduced 
directly into the aeration cell for analysis, ml.

    9.2.1  The maximum allowable blank subtraction for the Hg in the 
HCl washes is the lesser of the two following values: (1) the actual 
blank measured value (ANALYSIS SAMPLE NO. HCl A.2 blank), or (2) 5% 
of the Hg content in the combined HCl rinse and digested sample 
(ANALYSIS SAMPLE No. HCl A.2).
[GRAPHIC] [TIFF OMITTED] TR25AP96.010

where:
m(fltr)Hg=Total blank corrected g of Hg in KMnO4 
filtrate and HNO3 digestion of filter sample.
C(fltr)Hg=Total ng of Hg in aliquot of KMnO4 filtrate and 
HNO3 digestion of filter analyzed (aliquot of ANALYSIS SAMPLE 
No. A.1).
C(fltr blk)Hg=Total ng of Hg analyzed in aliquot of KMnO4 
blank and HNO3 digestion of blank filter (aliquot of ANALYSIS 
SAMPLE No. A.1 blank).
Vf(fltr)=Solution volume of original sample, normally 100 ml 
for samples diluted as described in Section 7.3.
Vf(blk)=Solution volume of blank sample, 1000 ml for samples 
diluted as described in Section 7.3.
D.F.(fltr)Hg=Dilution factors, if necessary for ANALYSIS SAMPLE 
No. A.1, calculated similarly to those above for the (HC1) Hg 
samples.
D.F.(fltr blk)Hg=Dilution factors, if necessary for ANALYSIS 
SAMPLE No. A.1 blank, calculated similarly to those above for the 
(HCl blk)Hg samples.

    9.2.2  The maximum allowable blank subtraction for the HCl is 
the lesser of the two following values: (1) the actual blank 
measured value (ANALYSIS SAMPLE No. ``A.1 blank''), or (2) 5% of the 
Hg content in the filtrate (ANALYSIS SAMPLE No. ``A.1'').

mHg=m(HC1)Hg+m(fltr)Hg      Eq. 101A-3

where:
mHg=Total blank corrected Hg content in each sample, 
g.
m(HC1)Hg=Total blank corrected g of Hg in HCl rinse 
and HCl digestate of filter sample.
M(fltr)Hg=Total blank corrected g of Hg in KMnO4 
filtrate and HNO3 digestion of filter sample.
* * * * *
    10. * * *
    3. Wilshire, Frank W., J.E. Knoll, T.E. Ward, and M.R. Midgett. 
Reliability Study of the U.S. EPA's Method 101A--Determiantion of 
Particulate and Gaseous Mercury Emissions U.S. Environmental 
Protection Agency, Research Triangle Park, NC. Report No. 600/D-31/
219 AREAL 367, NTIS Acc No. PB91-23361.
* * * * *
    5. In Appendix B to part 61, Method 101A is amended by revising 
the second and last sentences of section 7.1.1 and by revising the 
last two sentences of the first paragraph of section 7.1.2 to read 
as follows:

Appendix B to Part 61--Test Methods

* * * * *

Method 101A  Determination of Particulate and Gaseous Mercury Emissions 
From Sewage Sludge Incinerators Meth. 101A

* * * * *
    7.1.1 * * * In this method, highly oxidizable matter could make 
it impossible to sample for the required minimum time.* * * In cases 
where an excess of water condensation is encountered, collect two 
runs to make one sample, or add an extra impinger in front of the 
first impinger (also containing acidified KMnO4 solution).
    7.2.1 * * * In this method, clean all the glass components (a 
hood is recommended) by rinsing with 50 percent HNO3, tap 
water, 8 N HCl, tap water, and finally deionized distilled water. 
Then place 50 ml of the acidified 4 percent KMnO4 absorbing 
solution in the first impinger and 100 ml in each of the second and 
third impingers.
* * * * *
[FR Doc. 96-9834 Filed 4-24-96; 8:45 am]
BILLING CODE 6560-50-M