-------
FOREWORD
This document presents the rationale and text for the proposed
Test Method 29 for measurement of metals emissions, and the
revisions to Method 101A for measurement of mercury. The document
is divided into two chapters. Chapter 1 is a reprint of the
proposal notice, signed by the EPA Administrator, which summarizes
the proposal. Chapter 2 is the rationale and full text of the
proposed method and method revisions. The full text of Method 29
and the Method 101A revisions should be used as the basis for
submitting public comments on the proposal.
nli,s.; Ewiwjmwtttel
L}raj)
UlJUhFfloor
-------
CHAPTER 1
-------
6560-50
U.S. ENVIRONMENTAL PROTECTION AGENCY
40 CFR Parts 60 and 61
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
[AD-FRL ]
AGENCY: U.S. Environmental .Protection Agency (EPA).
ACTION: Proposed Rule and Notice of Public Hearing.
SUMMARY: The EPA is proposing to add Method 29, "Determination
of Metals Emissions from Stationary Sources," to Appendix A of
Part 60, and to propose amendments to Method ,101A of Appendix B
of Part 61. Method 29 is being proposed 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 intended
to expand that method's applicability, and to add procedures for
handling and analyzing samples collected by the sampling train.
This notice includes a summary of the proposed method;
however, this notice does not contain the full text of the method
or method revisions. The i7ull text of the proposal is readily
available by (1) accessing the EPA's electronic bulletin board
[Technology Transfer Network (TTN)], or (2) requesting a copy
.zrcm DocKeu ;MO. rt-94-23 !_caj._L (202) 260-754SJ. The ADDRESSES ana
SUPPLEMENTARY INFORMATION sections of tnis notice can be reviewed
for instructions on accessina the TTN,
-------
As a proposed action, public comments are solicited.
Comments should address the full text of the rulemaking, which is
contained in a report entitled "Emission Test Method 29:
Determination of Metals Emissions From Stationary Sources," EPA-
454/R-94-016 (see the ADDRESSES and SUPPLEMENTARY INFORMATION
sections of this notice for information on how to obtain this
document). Whenever applicable, full supporting data and
detailed analysis should be submitted with all comments to allow
the EPA to respond to the comments. The EPA will consider all
comments and information received during the public comment
period, and will make changes in the methods, where appropriate,
prior to promulgation of the final rule. All comments should be
directed to the EPA Air and Radiation Docket and Information
Center, Docket No. A-94-28 (see ADDRESSES).
A public hearing will be held, if requested, to provide
interested persons an opportunity for oral presentation of data,
views, or arguments concerning the proposed rule.
DATES: Comments. Comments must be received on or before
(60 days after publication in the FEDERAL REGISTER) .
Public Hearing. If anyone contacts the EPA requesting to
speak at a public hearing by (21 days after
proposal), a public hearing will be held on (30
days after proposal) beginning at 10:00 a.m. Persons interested
in attending the hearing should call the contact mentioned under
ADDRESSES uO vei'iry CiiciC a. iiBdiT-Lncf wiij. £& held.
-------
Request to Speak at Hearing. Persons wishing to present
oral testimony must contact the EPA by (21 days
after proposal).
Incorporation by Reference. The incorporation by reference
of a certain publication in this method will be approved by the
Director of the Office of the Federal Register as of the date of
publication of the final rule.
ADDRESSES: Comments. Comments on the proposal should be
submitted (in duplicate if possible) to: Air and Radiation
Docket and Information Center (Mail Code 6102), ATTN:
Docket No. A-94-28, Room 1500, U.S. Environmental Protection
Agency, 401 M Street, S.W., Washington, D.C. 20460.
Background Information. The following document is
identified as suggested reading: "Emissions Test Method 29:
Determination of Metals Emissions From Stationary Sources (1994
Proposal)," EPA-454/R-94-016, April 1994. This document contains
the full text of the proposed method and method revisions, and it
can be obtained from the TTN or Docket No. A-94-28.
Public Hearing. If anyone contacts the EPA requesting a
public hearing, it will be held at the EPA's Emission Measurement
Laboratory Building, Old Page Road at 1-40, Research Triangle
Park, North Carolina. Persons interested in attending the
hearing or wishing to present oral testimony should notify Mr.
William Grimley at (919) 541-1065, Emission Measurement Branch
(MD-19), Technical Support Division, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina 27711,
-------
Docket. Docket No. A-94-28, containing materials relevant
to this rulemaking, is available for public inspection and
copying between 8:00 a.m. and 4:00 p.m., Monday through Friday,
at the EPA's Air And Radiation Docket and Information Center,
Waterside Mall, Room 1500, Central Mall, 401 M Street, S.W.,
Washington, D.C. 20460. A reasonable fee may be charged for
copying. Additionally, the docket may be accessed by calling
(202) 260-7548.
FOR FURTHER INFORMATION CONTACT: For information concerning the
methods, contact Mr. William Grimley at (919) 541-1065, Emission
Measurement Branch, Technical Support Division (MD-19), U.S.
Environmental Protection Agency, Research Triangle Park, North
Carolina 27711.
SUPPLEMENTARY INFORMATION: An electronic copy of the item listed
below is available from the EPA's TTN electronic bulletin board
system. The TTN contains 12 electronic bulletin boards, and
information related to this proposal is included in the Emissions
Measurement Technical Information Center (EMTIC) bulletin board.
The TTN is accessible 24 hours per day, 7 days per week, except
Monday from 8:00 a.m. to 12:00 a.m., when the system is updated.
The service is free, except for the cost of a phone call. Dial
(919) 541-5742 for up to 14,400 bits per second modem. Furrher
instructions for accessing the TTN can be obtained by calling the
systems operator at (919) 541-5384.
Methods 29 and 101A Item in EMTIC 51ectronic Bulletin Board
-------
1. "Emissions Test Method 29: Determination of Metals
Emissions From Stationary Sources (1994 Proposal),," EPA-454/R-
94-016, April 1994.
I. Summary of Proposed Method 29 and Method 101A Revisions
Under Subparts Ca and Ea, the EPA is proposing guidelines
and standards to regulate mercury, cadmium, and lead emissions
from MWC's. Method 29 is being proposed for addition to
Appendix A of 40 CFR Part 60 and will serve as the compliance
test method for MWC's for mercury, cadmium, and lead. Method 29
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 (Tl), and zinc (Zn)
emissions from stationary sources. Method 29 may be used to
determine particulate emissions in addition to the metals
emissions if the prescribed procedures and precautions are
followed. For both methods, 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 ara analysed for Hg by cola 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. Additionally, if desired, the tester may use
AAS for analysis of all listed metals if the resulting in-stack
method detection limits meet the goal of the testing program.
Mercury 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. Amendments to Method 101A
of Appendix B of Part 61 are being proposed to provide
consistency with Method 29.
II. Administrative Requirements
A. Public Hearing
A public hearing will be held, if requested, to discuss the
proposed rule in accordance with Section 307(d)(5) of the Clean
Air Act. Persons wishing to make oral presentations should
contact the EPA at the address given in the ADDRESSES section of
this preamble. Oral presentations will be limited to 15 minutes
each. Any member of the public may file a written statement with
the EPA before, during, or within 30 days after the hearing.
Written statements snould be addressed to the Air DocKet address
given in the ADDRESSES section of this preamble.
-------
A verbatim transcript of the hearing and written statements
will be available for public inspection and copying during normal
*
working hours at the EPA's Air Docket in Washington, D.C. (see
ADDRESSES section of this preamble).
B. 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 proposed 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)].
C. 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 sea.
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 cherefore 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:
-------
l. 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. Regulatory Flexibility Act Compliance
Pursuant to the provisions of 5 U.S.C. 601 et seq. I hereby
certify that this proposed rule, if promulgated, will not have an
economic impact on small entities because no additional costs
will be incurred.
List of Subjects in 40 CFR Part 60. Air pollution control,
Arsenic, Asbestos, Beryllium, Cadmium, Lead, Hazardous materials,
Incorporation by reference, Intergovernmental relations, Mercury,
Municipal waste combustors, Reporting and recordkeeping
requirements, and Sewage sludge incineration.
-------
Statutory Authority. The statutory authority for this
proposal 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.
Date Administrator
-------
CHAPTER 2
-------
6560-50
U.S. ENVIRONMENTAL PROTECTION AGENCY
40 CFR Parts 60 and 61
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
[AD-FRL ]
AGENCY: U.S. Environmental Protection Agency (EPA).
ACTION: Proposed Rule and Notice of Public Hearing.
SUMMARY: The EPA is proposing to add Method 29, "Determination
of Metals Emissions from Stationary Sources," to Appendix A of
Part 60, and to propose amendments to Method 101A of Appendix B
of Part 61. Method 29 is being proposed 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 intended
to expand that method's applicability, and to add procedures for
handling and analyzing samples collected by the sampling train.
As a proposed action, public comments are solicited.
Whenever applicable, full supporting data and detailed analysis
should be submitted with all comments to allow the ZPA to responc
to the comments. The EPA will consider all comments and
information received during the public comment period, and will
make changes in the methods, whcra appropriate, prior tc
promulgation of the final rule. All comments should be directed
-------
to the EPA Air and Radiation Docket and Information Center,
Docket No. A-94-28 (see ADDRESSES).
A public hearing will be held, if requested, to provide
interested persons an opportunity for oral presentation of data,
views, or arguments concerning the proposed rule.
DATES: Comments. Comments must be received on or before
(60 days after publication in the FEDERAL REGISTER).
Public Hearing. If anyone contacts the EPA requesting to
speak at a public hearing by (21 days after
proposal) , a public hearing will be held on (30
days after proposal) beginning at 10:00 a.m. Persons interested
in attending the hearing should call the contact mentioned under
ADDRESSES to verify that a hearing will be held.
Request to Speak at Hearing. Persons wishing to present
oral testimony must contact the EPA by (21 days
after proposal).
Incorporation by Reference. The incorporation by reference
of a certain publication in this method will be approved by the
Director of the Office of the Federal Register as of the date of
publication of the final rule.
ADDRESSES: Comments. Comments on the proposal should be
submitted (in duplicate if possible) to: Air and Radiation
Docket and Information Center (Mail Code 6102), ATTN:
Docket No. A-.94-28, Room 1500, U.S. Environmental Protection
Agency, 401 M Street, S.W., Washington, D.C. 2046C.
-------
Public Hearing. If anyone contacts the EPA requesting a
public hearing, it will be held at the EPA's Emission Measurement
Laboratory Building, Old Page Road at 1-40, Research Triangle
Park, North Carolina. Persons interested in attending the
hearing or wishing to present oral testimony should notify Mr.
William Grimley at (919) 541-1065, Emission Measurement Branch
(MD-19), Technical Support Division, U.S. Environmental
Protection Agency, Research Triangle Park, North Carolina 27711.
Docket. Docket No. A-94-28, containing materials relevant
to this rulemaking, is available for public inspection and
copying between 8:00 a.m. and 4:00 p.m., Monday through Friday,
at the EPA's Air And Radiation Docket and Information Center,
Waterside Mall, Room 1500, Central Mall, 401 M Street, S.W.,
Washington, D.C. 20460. A reasonable fee may be charged for
copying. Additionally, the docket may be accessed by calling
(202) 260-7548.
FOR FURTHER INFORMATION CONTACT: For information concerning the
methods, contact Mr. William Grimley at (919) 541-1065, Emission
Measurement Branch, Technical Support Division (MD-19), U.S.
Environmental Protection Agency, Research Triangle Park, North
Carolina 27711.
SUPPLEMENTARY INFORMATION:
I. THE RULEMAKING
Under Subparts Ca and Ea, the EPA is proposing guidelines
and standards to regulate mercury, cadmium, and lead emissions
from MWC's. Method 29 is being proposed 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 proposed to provide
consistency with Method 29.
II. ADMINISTRATIVE REQUIREMENTS
A. Public Hearing
A public hearing will be held, if requested, to discuss the
proposed rule in accordance with Section 307(d)(5) of the Clean
Air Act. Persons wishing to make oral presentations should
contact the EPA at the address given in the ADDRESSES section of
this preamble. Oral presentations will be limited to 15 minutes
each. Any member of the public may file a written statement with
the EPA before, during, or within 30 days after the hearing.
Written statements should be addressed to the Air Docket address
given in the ADDRESSES section of this preamble.
A verbatim transcript of the hearing and written statements
will be available for public inspection and copying during normal
working hours at the EPA's Air Docket in Washington, D.C. (see
ADDRESSES section of this preamble).
B. 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 proposed rulemaking. The principal
purposes of the docket are: (1) to allow interested parties to
identify and locare 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)].
C. 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 sea.
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. Regulatory Flexibility Act Compliance
Pursuant to the provisions of 5 U.S.C. 601 et seq. I hereby
certify that this proposed rule, if promulgated, will not have an
economic impact on small entities because no additional costs
will be incurred.
List of Subjects in 40 CFR Part 60. Air pollution control,
Arsenic, Asbestos, Beryllium, Cadmium, Lead, Hazardous materials,
Incorporation by reference, Intergovernmental relations, Mercury,
Municipal waste combustors, Reporting and recordkeeping
requirements, and Sewage sludge incineration.
Statutory Authority. The statutory authority for this
proposal 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.
Date Administrator
-------
It is proposed that 40 CFR Parts 60 and 61 be amended as
follows:
1. The authority citations for Parts 60 and 61 continue to
read as follows:
42 U.S.C. 7401, 7411, 7412, 7414, 7416, and 7601.
2. In Part 60, by adding Method 29 to Appendix A 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 (Tl), 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 bor.h 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.
Additionally, if desired, the tester may use AAS for analysis of
all listed metals if the resulting in-stack method detection
limits meet the goal of the testing program.
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 (;ug/ml) range in
the final analytical solution can be analyzed using this method.
Samples containing greater than approximately 50 Atg/ml As, Cr, or
Pb should be diluted to that level or lower for final analysis.
-------
Samples containing greater than approximately 20 jug/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 SW-846. Method 6010) are approximately as
follows: Sb (32 ng/ml) , As (53 ng/ral)', 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). 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 (based on SW-846. Method 7000 series) 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 digestion 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 Tl (1 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, (3) the normal volumes of 300 ml
(Analytical Fraction 1) for the front-half and 150 ml (Analytical
Fraction 2A) for the back-half samples, and (4) a stack gas
sample volume of 1.25 m3. The resultant in-stack method
detection limits for the above set of conditions are presented in
Table 29-1 and were calculated by using Eq. 29-1.
A X B/C = D Eq. 29-1
where:
A = Analytical detection limit, jug/ml.
B = Liquid volume of digested sample prior to
aliquotting for analysis, ml.
C = Stack sample gas volume, dsm3.
D = In-stack detection limit,
-------
METAL
Front-half:
Probe & Filter
Back-half:
Impingers 1-3
Back-half: Total Train:
Impingers (4-6)*
Antimony
Arsenic
Barium
Beryllium
Cadmium
Chromium
Cobalt
Copper
Lt=ad
Manganese
Mercury
NJ ckel
Phosphorus
Selenium
Si Iver
Thallium
Zinc
7.7
12.7
0.5
0.07
1.0
1.7
1.7
1.4
10.1
0.5
(0.
(0.
(0.
(0.
(0.
(0.
(0.
(0.
7)*
3)*
05)*
02)*
2)*
2)*
2)*
2)*
0.06**
3.6
18
18
1.7
9.6
0.5
(0.
(0.
5)*
2)*
3
6
0
0
0
0
0
0
5
0
0
1
9
9
0
4
0
.8
.4
.3
.04
.5
.8
.8
.7
.0
.2
.3**
.8
.9
.8
.3
(0.
(0.
(0.
(0.
(0.
(0.
(0.
(0.
(0.
(0.
4)*
1)*
03)*
01)*
1)*
1)*
1)*
1)*
0.2**
3)*
1)*
11.
19.
0.
0.
1.
2.
2.
2.
15.
0.
0.
5.
27
27
2.
14.
0.
5
1
8
11
5
5
5
1
1
7
(1.
(0.
(0.
(0.
(0.
(0.
(0.
(0.
56**
4
6
4
8
(0.
(0.
1)*
4)*
08)*
03)*
3)*
3)*
3)*
3)*
8)*
3)*
Mercury analysis only.
* Detection limit when analyzed by GFAAS, (_. )
*- 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.
Table 29-1. In-stack method detection limits (/ig/m3) for the front-half, the back-half,
and the total sampling train using ICAP and AAS.
11
-------
2.3.2 To ensure optimum precision/resolution in the
analyses, the target concentrations of netals 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
12
-------
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 stacJc 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 mecncd
detection limit.
-------
2.4 Precision. The precision (relative standard deviation)
for each metal detected in a method development test performed at
a sewage sludge incinerator were found to be as follows:
Sb (12.7 percent), As (13.5 percent), Ba (20.6 percent),
Cd (11.5 percent), Cr (11.2 percent), Cu (11.5 percent),
Pb (11.6 percent), P (14.6 percent), Se (15.3 percent),
Tl (12.3 percent), and Zn (11.8 percent). The precision for Ni
was 7.7 percent for another test conducted at a source simulator.
Be, Mn, and Ag were not detected in the tests. However, based on
the analytical detection limits of the ICAP for these metals,
their precisions could be similar to those for the other metals
when detected at similar levels.
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. Refer to Method 6010 of
Citation 1 of the Bibliography or the other analytical methods
used for details on potential interferences to this method. For
all GFAAS analyses, use matrix modifiers to limit interferences,
and matrix match all standards.
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.
14
-------
Thermometer
ui
Glass Filter Holder
Thermometer
Glass Probe Liner
Glass Probe Tip
Empty (Optional) | / Empty | / Silica Gel
Pitot Manometer 5% HN03/10% H202 4% KMn04/10% H2S04
Vacuum Gauge
Orifice
Dry Gas
Meter
Air-tight
Pump
Figure 29-1. Sampling train.
-------
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 desired, 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/H202 impinger) shall be identical to the
first impinger in Method 5. The third impinger (which is the
J.O
-------
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°C (2°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 tnis Method) with Teflon-
lined caps that are non-reacrive to rhe oxidizing solutions, wirh
-------
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 1000-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 0.1 ing.
3.3.10 Microwave or Conventional Oven. For heating samples
at fixed power levels or temperatures,- respectively,
3.3.11 Hot Platss.
-------
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 Bibliography Citation 1
Methods 7041 (Sb), 7060 (As), 7131 (Cd), 7201 (Co), 7421 (Pb),
7740 (Se), and 7841 (Tl).
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
1O°C above ambient, so that no condensation forms on the wall of
the quartz cell. Same as Method 7470 in Citation 2 of the
Bibliography. See Note No. 2; Section 5.4.3 for other acceptable
approaches for analysis of Hg in which analytical detection
limits of 0.02 /ug/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 Citation 1 of the Bibliography.
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.
19
-------
4.2 Sampling Reagents.
4.2.1 Sample Filters. Without organic binders. The
filters shall contain less than 1.3 /xg/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). 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.
20
-------
4.3 Pretest Preparation of Sampling Reagents.
4.3.1 HNO3/H2O2 Absorbing Solution, 5 Percent HNO3/10 Percent
H202. Add carefully with stirring 50 ml of concentrated HNO3 to a
1000-ml volumetric flask containing approximately 500 ml of
water, and then add carefully with stirring 333 ml of 30 percent
H202. Dilute to volume with water. Mix well. This reagent shall
contain less than 2 ng/ml of each target metal.
4.3.2 Acidic KMn04 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 KMn04 into 10 percent
H2S04 (V/V) and add 10 percent H2SO4 (V/V) with stirring to make a
volume of 1 liter. Prepare and store in glass bottles to prevent
degradation. This reagent shall contain less than 2 ng/ml of Hg.
Precaution! To prevent autocatalytic decomposition of the
permanganate solution, filter the solution through Whatman 541
filter paper. 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 HN03/ 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 HC1, 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 HN03/ Concentrated. Fisher ACS grade or equivalent.
4.4.2 Water. To conform to ASTM Specifications D1193-77,
Type II.
4.4.3 HNO3, 10 Percent (V/V). Add with stirring 500 ml of
concentrated HN03 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 ug/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 HN03/ 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 HN03/ 5 Percent (V/V). Add with stirring 50 ml of
concentrated HN03 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 Specifications D1193-77,
Type II.
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 KMn04, 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 (N03)2 6H20.
4.5.13 Lanthanum Oxide, La203.
4.5.14 Hg Standard (AAS Grade), 1000 /zg/ml.
4.5.15 Pb Standard (AAS Grade), 1000 jig/ml.
4.5.16 As Standard (AAS Grade), 1000 /ug/ml.
-------
4.5.17 Cd Standard (AAS Grade), 1000
4.5.18 Cr Standard (AAS Grade), 1000 /xg/ml.
4.5.19 Sb Standard (AAS Grade), 1000 jug/ml.
4.5.20 Ba Standard (AAS Grade), 1000 nq/ml.
4.5.21 Be Standard (AAS Grade), 1000 jug/ml.
4.5.22 Co Standard (AAS Grade), 1000 /xg/ml.
4.5.23 Cu Standard (AAS Grade), 1000 /zg/ml.
4.5.24 Mn Standard (AAS Grade), 1000 Mg/ral.
4.5.25 Ni Standard (AAS Grade), 1000 jug/ml.
4.5.26 P Standard (AAS Grade), 1000 jug/ml.
4.5.27 Se Standard (AAS Grade), 1000 jug/ml.
4.5.28 Ag Standard (AAS Grade), 1000 Mg/ral.
4.5.29 Tl Standard (AAS Grade), 1000 Mg/ml.
4.5.30 Zn Standard (AAS Grade), 1000 jug/ml.
4.5.31 Al Standard (AAS Grade), 1000 fj.g/ml.
4.5.32 Fe Standard (AAS Grade), 1000 /ig/ml.
4.5.33 Hg Standards and Quality Control Samples. Prepare
fresh weekly a 10 jLtg/ml intermediate Hg standard by adding 5 ml
of 1000 jiig/ml Hg stock solution 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 /ig/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 HN03, and then water. Mix well. Use at
least five separata 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 jig/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 fJLg/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 jug/ml for Al, Cr and Pb, 15 jug/ml for Fe,
and 10 jug/ml for the remaining elements. Prepare any standards
containing less than 1 ^g/mi of metal on a daily basis.
Standards containing greater than 1 ^ig/ml of metal should fae
stable for a minimum of 1 to 2 weeks.
4.5.35 GFAAS Standards. Sb, As, Ca, Co, Pb, Se, and Ti.
Prepare a 10 jig/ml standard by adding 1 ml of 1000 /ig/mi stanriarcx
-------
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 jug/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 Mg/ral standard and diluting until it is in the range
of the samples. Prepare any standards containing less than 1
;zg/ml of metal on a daily basis. Standards containing greater
than 1 /zg/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(N03)2-6H20 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 l 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 La20, in
10 ml of concentrated HN03, and dilute the solution by adding it
with stirring to approximately 50 ml of water. Dilute to 100 ml
with water, and mix well. Inject an equal amount of sample and
-------
this modifier into the graphite furnace during GFAAS analysis for
Pb.
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, both testers and analysts must be
trained and experienced with the test procedures, including
source sampling; reagent preparation and handling; sample
handling; safety equipment; 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. Place 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 The following options are available to the tester
based on the source specific sampling requirements and
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. If Hg analysis will not be performed,
the fourth, fifth, and sixth impingers as shown in Figure 29-1
are not required.
5.1.3.3 Because of possible sample contamination problems, use
Teflon tape or other non-contaminating material instead of
silicone grease to ensure leak-free sampling train connections.
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 H302 from mixing with the acidic KMn04.
28
-------
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 tne open ouria-c.
~> Q
-------
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 folowing 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):
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 ic 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
surgfaces 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.
-------
Probe Liner
and Nozzle
Rinee with
acetone
Brush liner
with nonmetallic
brush & rinse
with acetone
Check liner to cee
if particulato
removed; if not.
repeat step above
Rinse
three
times with
0.1N
HNO3
Fl
Front Half of Rltor filter Support 1 st Impinger 2nd & 3rd
Filter Housing
and Back Half (Empty at Impinger*
of Filter Housing beginning (HNO3/H2O2)
of test)
Brush with Carefully Rinse three Measure Mea
sura
nonmetallio brush remove filter times with impinger impinger
and rinse with from support 0.1N HNO3 contents contents
acetone with Teflon-
Rinse
coated tweezers
and place in
petri dish
Brush loose
participate
onto filter
Seal petri dish
with tape
three
times with
0.1N
HN03
1 AR F
Empty the Empty the
contents into contents into
container container
Rinse three Rinse three
times with times with
O.1NHNO3 0.1NHNO3
: B
H
(31* <2I (D (4)
Number in parentheses indicates container number
Figure 29-2a. Sample recovery scheme.
32
-------
4th Impinger
(Empty) & 5th
and 6th impingera
(Acidified KMnO4)
Measure
impinger
contents
Last Impinger
1
Empty the
impinger No. 4
contents into
Empty the
impingers
Nos. 5 & 6
container contents into
Rinse
with
100ml
container
\\nse three
times with
0.1N HN03 permanganate
0.1N
reagent, then
HN03 KMn04
(5A) (5B)
with water
Remove any
residue with
25ml8N
HCI solution
I
8NHCI
(5C)
Weigh for
moisture
Discard
Figure 29-2b. Sample recovery scheme.
33
-------
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 mere if needed to remove visible particulate.
Make a final rinse of the brush and filter holder. Aftar 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 I through 3, Moisture
Knockout Impinger, when used, HNO3/H202 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.
35
-------
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 HN03 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 HN03) , 5B (KMnO4/H2S04
absorbing solution), and 5C (8 N HC1 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
KMn04 solution into Container No. 5B. Using a total of exactly
36
-------
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 HC1,
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 KCI 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
3 N HC1 for rinsing both permanganate impinqers combined. Rinse
the first impinger, then pour the actual rinse used for the rirsr.
-------
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. SA (0.1 N HN03 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.
38
-------
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.
5.2.14 Container No. 9 (5 Percent HNO3/10 Percent H202
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 KMn04
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 HC1 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 HC1. 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.
40
-------
Container 3
Acid Probe Rinse
Container 2
Container 1
Container 4
Containers 5A, SB, & 5C
(Labele
d FH) (Labeled AR) (Label
ed F) (Labeled BH)
(include condensate
impinger, if used)
1
Reduce to dryness Desiccate to Aliquot taken
in a tared beaker constant weight for CVAAS
I
Determine residue
tor Hg analysis
Anal. Fraction 2B
weight in beaker Determine filter
Solubilize residue
with cone. HNO3
|
Divide int
Acidify to pH 2 sections t
with cone. HN03 each sect
-., _n.*n UC
Reduus volume to
near dryness and
digest with HF
& cono. HN03
I
Filter & dilute
to known volume
Anal. Fraction 1
T "" 1
Analyze by ICAP fur Analyze for
target metals metals by GFAAS*
Anal. Fraction 1 A Anal. Fraction 1A
and permanganate
at 95 C for 2 h
and analyze
for Hg by CVAAS
o 0.5 g
it digest
ion with
&HN03
Remove 5O to TOO ml Diaest
aliquot for Hg DermanQ
analysis by CVAAS a wgt(
Analytical Fraction 1 B
Acidify
remaining
sample to pH 2
with cone. HNO3
Anal. Fraction 2A
Reduce volume
to near dryness
and digest with
HNO3 & H202
Analyze
by ICAP for
1 5 target metals
Analyze by
GFAAS
for Metals*
with acid and
anate at 95 C in
}f bath for 2 h
Analyze aliquot for
Hg using CVAAS
Individually, three
separate digestions
and analyses:
digest with acid
and permanganate
at 95 C for 2 h
and analyze
for Hg by CVAAS
Analytical Fractions
3A, 3B, & 3C
'Analysis by A AS for metals found at less than 2 ug/ml in digestate solution,
ti do.iired. Or analyze, for each ,netal by AAS, if desired.
igure 29-3. Sample preparation and analysis scheme.
-------
For conventional heating, heat the ParrR Bombs at 140°C (285°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.
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 IB". 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 IB 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
watchglass. Reduce Sample Fraction 2A to approximately 20 ml by
heating on a hot plate at a temperature just below boiling. Then
follow either of the digestion procedures described in
Sections 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 wi
O.I ml.
44
-------
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 Mn02/ 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 Mn02 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 IA and
46
-------
IB, consist of the digested samples from the front-half of the
train. Analytical Fraction 1A is for ICAP or AAS analysis as
described in Sections 5.4.1 and 5.4.2, respectively.
Analytical Fraction IB 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 HNO3/H2O2 impingers Nos. 2
and 3. Analytical Fraction 2A is for ICAP 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 Analysis. Analyze Analytical Fractions 1A and
2A by ICAP using Method 6010 or Method 200.7 (40 CFR 136,
Appendix C). Calibrate the ICAP, and set up an analysis program
as described in Method 6010 or Method 200.7. Follow the quality
control procedures described in Section 7.3.1. Recommended
wavelengths for analysis are as follows:
-------
Element Wavelength fnm)
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.
MOTS: When analyzing samples in a HF matrix,, an alumina
torch should be used; since all front-half samples will
contain HF, use an alumina torch.
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
43
-------
Table 29-2. Applicable techniques, methods and minimization of interference iorAAS analysis.
Metal
Fe
Pb
Pb
Mn
Ni
Se
CO
Ag
Tl
Technique
Aspiration
Aspiration
Furnace
Aspiration
Aspiration
Furnace
Aspiration
Aspiration
Furnace
Aspiration
SW-846 Wavelength
Method No. (nm)
7380 248.3
7420 283.3
7421 283.3
7460 279.5
7520 232.0
7740 196.0
7760 328.1
7840 276.8
7841 276.8
7950 213.9
Interferences
Cause Minimization
Contamination
217.0 nm alternate
Poor recoveries
403.1 nm alternate
352.4 nm alternate
Fe, Co, and Cr
Nonlinear response
Volatility
Adsorption & scatter
Adsorption & scatter
AgCI insoluble
Hydrochloric acid
or chloride
High Si, Cu, & P
Contamination
Great care taken to avoid contamination
Background correction required
Matrix modifier, add 10 ul of phosphorus
acid to 1 ml of prepared sample in
sampler cup
Background correction required
Background correction required
Matrix matching or nitrous-oxide/
acetylene flame
Sample dilution or use 352.3 nm line
Spike samples and reference materials and
add nickel nitrate to minimize
volatilization
Background correction is required and
Zeeman background correction can be useful
Background correction is required
Avoid hydrochloric acid unless silver is
in solution as a chloride complex
Sample and standards monitored for
aspiration rate
Background correction is required
Hydrochloric acid should not be used
Background correction is required
Verify that losses are not occurring for
volatization by spiked samples or standard
addition; Palladium is a suitable matrix
modifier
Strontium removes Cu and phosphate
Great care taken to avoid contamination
-------
Table 29-2 cont.
Metal
Sb
Sb
As
Ba
Be
Be
Cd
Cd
Cr
Co
Or
On
Technique
Aspiration
Furnace
Furnace
Aspiration
Aspiration
Furnace
Aspiration
Furnace
Aspiration
furnace
Furnace
Aspiration
SW-846
Method No.
7040
7041
7060
7080
7090
7091
7130
7131
7190
7201
7191
7210
Wavelength
(nm)
217.6
217.6
193.7
553.6
234.9
234.9
228.8
228.8
357.9
240.7
357.9
324.7
Interferences
Cause Minimization
1000 mg/ml Pb
Ni, Cu, or acid
High Pb
°vrsenic volatilization
Aluminum
Calcium
Barium ionization
500 ppm Al
High Mg and Si
Be in optical path
Absorption and light
scattering
As above
Excess chloride
Pipet tips
Alkali metal
Excess chloride
200 mg/L Ca and P
Absorption & scatter
Use secondary wavelenthe of 231.1 nm;
natch sample & standards' acid concentra-
tion or use nitrous oxide/acetylene flame
Secondary wavelength or Zeeman correctior
Spiked samples and add nickel nitrate so-
lution to
digestates prior to analysis
Use Zeeman background correction
High hollow cathode current and narrow
band set
2 ml of KCI per 100 ml of sample
Add 0.1% fluoride
Use method of standard additions
Optimize parameters to minimize effects
Background correction is required
As above
Ammonium phosphate used as a matrix
modifier
Use cadmium-free tips
KCI ionization suppressant in samples
and standards-Consult mfgs1 literature
Use Method of Standard Additions
All calcium nitrate for a known constant
effect and to eliminate effect of phosphate
Consult manufacturer's manual
en
O
-------
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.
5.4.3 CVAAS Hg analysis. Analyze Analytical Fractions IB,
2B, 3A, 3B, and 3C separately for Hg using CVAAS following the
method outlined in EPA SW-846 Method 7470 or in Standard Methods
for Water and Wastewater Analysis. 15th Edition, Method 303F, or,
optionally using NOTE No. 2 at the end of this section. Set up
the calibration curve (zero to 1000 ng) as described in SW-846
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. Dilute the aliquot
to 100 ml with water. If no prior knowledge of the expected
amount of Hg in the sample exists, a 5 ml aliquot is suggested
for the first dilution to 100 ml (see NOTE No. 1 at end of this
Section). The total amount of Hg in the aliquot shall be less
than 1 /ig and within the range (zero to 1000 ng) of the
calibration curve. Place each 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 SW-846 Method 7470 or Method 303F. (See NOTE No. 2
at the end of this Section). If the maximum readings are of f-
-------
scale (because Hg in the aliquot exceeded the calibration range;
including the situation where only a 1-ml aliquot of the original
sample was digested), then dilute the original sample (or a
portion of it) with 0.15 percent HNO3 (1.5 ml concentrated HNO3
per liter aqueous solution) so that when a 1- to 10-ml aliquot of
the "0.15 HNO3 percent dilution of the original sample" is
digested and analyzed by the procedures described above, it will
yield an analysis within the range of the calibration curve.
NOTE No. 1; When Hg levels in the sample fractions are
below the in-stack detection limit given in Table 29-1,
select a 10 ml aliquot for digestion and analysis as
described.
NOTE No. 2; Optionally, Hg can be analyzed by using the
CVAAS analytical procedures given by some instrument
manufacturer's directions. These include calibration and
quality control procedures for the Leeman Model PS200, the
Perkin Elmer FIMS 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 Hq.); (2), Upon
completion of the digestion described in (1), analyze the
-------
sample according to the instrument manufacturer's
directions. This approach allows multiple (including
duplicate) automated analyses of a digested sample aliquot.
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); Leak-Check of the Metering System
(Section 5.6); and Barometer (Section 5.7).
6.2 Inductively 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.
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 SW-846 Method 7470 or in
Standard Methods for Water and Wastewater Method 303F (for Hg).
Run each standard curve in duplicata and use the mean values to
53
-------
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.
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 IB.
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 133 ml. Analyze this
blank for Hg within 48 hr of the filtration step, and use 400 mi
as the blank volume when calculating the blank mass value. Use
the 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 IB, 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 IB 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 Analysis. Follow the quality control shown in
Section 8 of Method 6010 in SW-846. For the purposes of a source
test that consists of three sample runs, modify those
requirements to include the following: two instrument cneck
55
-------
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 EPA SW-846 Method 7470 or in Standard
Methods for Water and Wastawater Method 303F.
-------
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:
% = C., Fd V^, Eq. 29-1
where:
Mft = Total mass of each metal (except Hg) collected
in the front half of the sampling train
(Sample Fraction 1) , jug.
Cal = Concentration of metal in Analytical
Fraction 1A as read from the standard curve,
Mg/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 Cal. 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) .
vsoin,i = Total volume of digested sample solution
(Analytical Fraction 1), ml.
NOTE: 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 = Crf Fa V, Eq. 29-2
where:
Mbh = Total mass of each metal (except Hg) collected
in the back-half of the sampling train (Sample
Fraction 2) , p.g.
Ca2 = Concentration of metal in Analytical Fraction
2A as read from the standard curve, (jug/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:
M, = (Mft - MaJ + (Mbh - MM*) Eq. 29-3
where :
Mt = Total mass of each metal (separately stated for
each metal) collected in the sampling train,
Mab = Blank correction value for mass of metal
detected in front-half field reagent blank, jug.
M^ = Blank correction value for mass of metal
detected in back-half field reagent blank, ;ng.
NOTE; If the measured blank value for the front half (m^) is in
the range 0.0 to "A" /Ltg [where "A" Mg equals the value determined
by multiplying 1.4 ng/in.2 times the actual area in in.2 of the
sample filter] , use m^ to correct the emission sample value
(1%) ; if mftb exceeds "A" jug, use the greater of I or II:
I. "A" Mg-
II. the lesser of (a) m^, or (b) 5 percent of m^.
If the measured blank value for the back-half (mbhb) is in the
range 0.0 to 1 Mg/ use mbhb to correct the emission sample value
(mbh) ; if mbhb exceeds 1 jug, use the greater of I or II:
I. 1 Mg.
II. the lesser of (a) mbhb, or (b) 5 percent of mbh.
59
-------
8.5 Hg in Source Sample.
8.5.1 Analytical Fraction IB; 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:
= r
-------
was digested according to Section 5.4.3 and
analyzed, VnB 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:
Eq. 29-5
J2B
where:
Hgbh2= Total mass of Hg collected in Sample
Fraction 2, /xg.
Qbhj = Quantity of Hg, /ig, TOTAL in the ALIQUOT of
Analytical Fraction 2B selected for digestion
and analysis . NOTE; For example, if a 10 ml
aliquot of Analytical Fraction 2B is taken and
digested and analyzed (according to
Section 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.
vTOin,2 = Total volume of Sample Fraction 2, ml.
vf2B = Volume of Analytical Fraction 2B analyzed, ml.
Note: For example, if 1 ml of Analytical
Fraction 2B was diluted to 10 ml with 0.15
percent HNO3 as described in Section 5.4.3 to
-------
bring it into the proper analytical range, and
then 5 ml of that 10-ml was analyzed, V^, 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:
O (V, Eq. 29-6
V
where:
Hgbh3(ABC) = Total mass of Hg collected separately in
Fraction 3A, 3B, or 3C, jug.
Qbh3(A,B,Q = Quantity of Hg, p.q, TOTAL, separately, in the
ALIQUOT of Analytical Fraction 3A. 3B. or 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).
V0(ABC) = 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).
Vsoln3(ABC) = Total volume, separately, of Analytical
Fraction 3A, 3B, or 3C, ml.
62
-------
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, jug.
8.5.3 Total Train Hg Catch. Calculate the total amount of
Hg collected in the sampling train by using Equation 29-8:
Hg, = (Hgft - Hgffib) + (Hgbh - Hgbhb) Eq. 29-8
where:
Hgt = Total mass of Hg collected in the sampling
train, jug.
H9fhb = Blank correction value for mass of Hg detected
in front-half field reagent blank, jug.
H9bhb = Blank correction value for mass of Hg detected
in back-half field reagent blanks, /zg.
Note: If the total of the measured blank values (Hgmb + Hgbhb) is
in the range of 0.0 to 0.6 jug, then use the total to correct the
sample value (Hg^ + Hgbh) ; if it exceeds 0.6 p.g, use the greater
of I. or II:
I. 0.6 /xg.
II. the lesser of (a) (Hgffib + Kg^,,) , or (b) 5 percent of
the sample value (Hgm + Hgbh) .
O J
-------
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:
C = K* M' Eq. 29-9
s V
v m(std)
where:
Cs = Concentration of a metal in the stack gas,
mg/dscm.
K4 = icr3 mg/jug.
Mt = Total mass of that metal collected in the
sampling train, p.g; (substitute Hgt for ^ 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, 15th Edition, 1980. Available from the
American Public Health Association, 1015 18th Street N.W.,
Washington, D.C. 20036.
64
-------
2. EPA Methods 6010, 7000, 7041, 7060, 7131, 7421, 7470,
7740, and 7841, Test Methods for Evaluating Solid Waste:
Physical/Chemical Methods. SW-846, Third Edition. September
1988. Office of Solid Waste and Emergency Response, U. S.
Environmental Protection Agency, Washington, D.C. 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.
3. In Part 61, Method 101A of Appendix B, by revising the
Title, Sections 7.2.1, 7.3.1, 7.3.2, 7.3.3, and 9.2, and by
adding Sections 5.2.4 through 5.2.7, 6.1.5 through 6.1.8, 7.2.1.1
through 7.2.1.3, 7.2.6, and Citation 3 of the Bibliography, as
follows:
Appendix B - Test Methods
*****
Method 101A - Determination of Particulate and Gaseous Mercury
Emissions from Stationary Sources
*****
5. * * *
65
-------
5.2 * * *
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. * * *
6.1 * * *
6.1.5 Sulfuric Acid (H2S04) , 10 Percent (V/V) . Carefully
add and mix 100 mi of concentrated H2S04 to 800 ml of deicnized
distilled water. Then, by adding deionized distilled water, mix
arid bring to a final volume of 1000 ml.
66
-------
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 explosion 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). Conentrated. 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. * * *
7.2 * * *
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 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 needed to calculate the moisture
content of the effluent gas. (Use only graduated cylinder and
glass storage bottles that have been preclsaned 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.l; 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; 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 KMn04 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.l 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 3 N HC1. However, if
deposits do remain on the glassware after the warer rinse, wash
-------
the impinger walls and steins with a total of only 25 ml of 8 N
HC1 as follows; turn and shake the impingers so that the 8 N HC1
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 HC1 WASH INTO THE ACIDIFIED PERMANGANATE SOLUTION.
Place the HC1 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 HC1 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. La6ei
.59
-------
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.l 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 * * *
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°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 contenrs through Whatman No. 40 filter paper,
70
-------
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 (HC1 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.I. and analyze for Hg within 48 hr of the
filtration step (NOTE; Do not confuse ANALYSIS SAMPLE No. A.I.
with the contents of field Sample Container No. 1A which contains
the 8 N HC1 wash). Place the saved filter, which was used to
remove the brown Mn02 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
Mn02, 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 Mn02
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.I.
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
Mn02 precipitate. Mark this resultant 500-ml combined dilute
solution as ANALYSIS SAMPLE No. HCl A.2 blank. (Note: When
analyzing samples A.I 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 jug in each sample. Correct for any dilutions made to bring
the sample into the working range of Che specrrophotometer.
-------
m _ r WiAing & * ?* (HC!)Hg] [C(Hdblk)Hg D 'F' (HO blf)Hg] >
m(HO)Hg ~ L = ~ = J
* ^blk
Eq. 101A-1
where:
m(Hci)Hg = Total blank corrected ^g of Hg in HC1 rinse and
HC1 digestate of filter sample
c(Hci)Hg = Total ng of Hg analyzed in the aliquot from the
500-ml ANALYSIS SAMPLE No. HC1 A.2.
c(Hcibik)Hg = Total ng of Hg analyzed in aliquot of the
500-ml ANALYSIS SAMPLE No. HC1 A.2 blank.
D'F'
-------
calibration range. If no dilution is
necessary, then D-P.^c^ equals 1.0.
DF (Habik)Hg = Dilution factor for the HCl-digested Hg-
containing solution, ANALYSIS SAMPLE No. "HC1
A.2 blank." (Refer to sample No. "HC1 A.2"
dilution factor information above.)
Vf(HCI) = Solution volume of original sample, 500 ml for
the HC1 samples diluted as described in
Section 7.3.
10"3 = Conversion factor, jug/ng.
S = Aliquot volume of sample: 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.
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.
Note: The maximum allowable blank subtraction for the Hg in the
HC1 washes is the lesser of the two following values: (1) the
actual blank measured value (ANALYSIS SAMPLE No. HC1 A.2 blank),
or (2) 5% of the Hg content in the combined HCl rinse and
digested sample (ANALYSIS SAMPLE No. HCl A.2).
74
-------
m _
mlfltr)Hg ~
D'F'
(fttr)Hg
t C
(fltr blk)Hg
D '
'
-------
value (ANALYSIS SAMPLE No. "A.I blank"), or (2) 5% of the Hg
content in the filtrate (ANALYSIS SAMPLE No. "A.l").
- 101A-3
where :
m^ = Total blank corrected Hg content in each
sample, jug.
m(HO)Hg = Total blank corrected jig of Hg in HCl rinse and
HC1 digestate of filter sample.
m(fitr)Hg = Total blank corrected ^g of Hg in KMnO4
filtrate and HN03 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 -
Determination of Particulate and Gaseous Mercury Emissions.
U.S. Environmental Protection Agency, Research Triangle Park, NC.
Report No. 600/D-31/219 AREAL 367, NTIS Ace No. PB91-233361.
*****
4. In Appendix B of Part 61, by revising the second and
last sentences, respectively, in Section 7.1.1 of Method 1Q1A to
read as follows: "In this method, highly oxidizable matter could
make it impossible to sample for the desired 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)."
5. In Appendix B of Part 61, by revising the second and
third sentences in Section 7.1.2 of Method 101A to read as
follows: "In this method, clean all the glass components (a hood
is recommended) by rinsing with 50 percent HNO3, tap water,
8 N HC1, tap water, and finally deionized distilled water. Then
place 50 ml of the acidified 4 percent KMn04 absorbing solution
in the first impinger and 100 ml in each of the second and third
impingers."
*****
-------
TECHNICAL REPORT DATA
(Pleas* read Instructions on the reverse before completing)
1. REPORT NO.
EPA-454/R-94-016
3. RECIPIENT'S ACCESSION NO.
4. TITLE AND SUBTITLE
Emissions Test Method 29:
Determination of Metals Emissions from Stationary Sources
(1994 Proposal)
5. REPORT DATE
April 1994
6. PERFORMING ORGANIZATION CODE
'. AUTHOR(S)
K.W. Grimley, Jr.
8. PERFORMING ORGANIZATION REPORT NO.
3. PERFORMING ORGANIZATION NAME AND ADDRESS
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
12. SPONSORING AGENCY NAME AND ADDRESS
U.S. Environmental Protection Agency
Research Triangle Park, NC 27711
13. TYPE OF REPORT AND PERIOD COVERED
14. SPONSORING AGENCY COOS
15. SUPPLEMENTARY NOTES
IS. ABSTRACT
This document presents the rationale and text for the proposed Test Method 29 for
measurement of metals emissions, and the revisions to Method 101A for measurement of
mercury. The document is divided into two chapters. Chapter 1 is a reprint of the
proposal notice, signed by the EPA Administrator, which summarizes the proposal.
Chapter 2 is the rationale and full text of the proposed method'and method revisions.
The full text of Method 29 and the Method 101A revisions should be used as the basis for
submitting public comments on the proposal.
17.
KEY WORDS AND DOCUMENT ANALYSIS
DESCRIPTORS
jb. !OENT!FIE=iS/OPEr\i E
Metals
Emissions from Stationary Sources
|1S. S1STH1BUTION STATEMENT
(Release unlimited
19. ScCURI TY CLASS / This
\ Unclassified
"unclassified
S?A Focm 2t2Q-l (R«». 4-77) PREVIOUS EDITION is OBSOLETE
------- |