United States Environmental Protection Agency Office of Air Quality Planning and Standards Research Triangle Park. NC 27711 EPA-454/R-94-016 April 1994 Air V EPA Emissions Test Method 29: Determination of Metals Emissions From Stationary Sources (1994 Proposal) ■ . 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. . 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 full 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 from Docket No. A-94-28 [call (202) 260-7548]. The ADDRESSES and SUPPLEMENTARY INFORMATION sections of this notice can be reviewed for instructions on accessing 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 to verify that a hearing will be held. 2 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. 3 ' 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. Further instructions for accessing the TTN can be obtained by calling the systems operator at (919) 541-5384. Methods 29 and 101A Item in EMTIC Electronic Bulletin Board 4 9 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 are analyzed for Hg by cold vapor atomic absorption spectroscopy (CVAAS) and for Sb, As, Ba, Be, Cd, Cr, Co, Cu, Pb, 5 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 should be addressed to the Air Docket address given in the ADDRESSES section of this preamble. 6 . . 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 (0MB) review under the Paperwork Reduction Act, 44 U.S.C. 3501 et seq. 2. Executive Order 12866 review Under Executive Order 12866 (58 FR 51735, October 4, 1993), the EPA must determine whether the regulatory action is "significant" and therefore subject to the OMB review and the requirements of the Executive Order. The Order defines "significant" regulatory action as one that is likely to lead to a rule that may: 1. Have an annual effect on the economy of $100 million or more, or adversely affect in a material way the economy, a sector of the economy, productivity, competition, jobs, the environment, public health or safety, or State, local or tribal governments or communities; 2. Create a serious inconsistency or otherwise interfere with an action taken or planned by another agency; 3. Materially alter the budgetary impact of entitlements, grants, users fees, or loan programs or the rights and obligations of recipients thereof; or 4. Raise novel legal or policy issues arising out of legal mandates, the President's priorities, or the principles set forth in the Executive Order. Pursuant to the terms of Executive Order 12866, the EPA does not consider this action to be significant because it does not involve any of the above mentioned items. D. 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. 8 33 Statutory Authority . The statutory authority for this proposal is provided by sections 101, 111, 112, 114, 116, and 301 of the Clean Air Act, as amended; 42 U.S.C., 7401 7412, 7414, 7416, 7429, and 7601. Date Administrator 129, 7411, 9 ' I 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 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 . *£ I ' 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. 20460. 2 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 3 • ■ ' 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 locate documents so that they can effectively participate in the rulemaking process, and (2) to serve as the 4 • - « A . 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 (0MB) review under the Paperwork Reduction Act, 44 U.S.C. 3501 et seq. 2. Executive Order 12866 review Under Executive Order 12866 (58 FR 51735, October 4, 1993), the EPA must determine whether the regulatory action is "significant" and therefore subject to the 0MB 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 5 ■ - 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 6 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 both Hg and Mn emissions. 7 • . 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 (jug/ml) range in the final analytical solution can be analyzed using this method. Samples containing greater than approximately 50 jiig/ml As, Cr, or Pb should be diluted to that level or lower for final analysis. 8 . ' Samples containing greater than approximately 20 /xg/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/ml), Ba (2 ng/ml), Be (0.3 ng/ml), Cd (4 ng/ml), Cr (7 ng/ml), Co (7 ng/ml), Cu (6 ng/ml), Pb (42 ng/ml), Mn (2 ng/ml), Ni (15 ng/ml), P (75 ng/ml), Se (75 ng/ml), Ag (7 ng/ml), T1 (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), T1 (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 9 . p (1 ng/ml), Be (0.2 ng/ml), Cd (0.1 ng/ml), Cr (1 ng/ml), Co (1 ng/ml), Pb (1 ng/ml), Se (2 ng/ml), and T1 (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 m 3 . The resultant in-stack method detection limits for the above set of conditions are presented in Table 29-1 and were calculated by using Eg. 29-1. where: A x B/C = D Eq. 29-1 A = Analytical detection limit, jug/ml. B = Liquid volume of digested sample prior to aliquotting for analysis, ml. C = Stack sample gas volume, dsm 3 . D = In-stack detection limit, jug/m 3 . 10 av sb ■ ■ Front-half: Back-half: Back-half: Total Train: Probe & Filter Impingers 1-3 Impingers (4-6) a 4-1 < w 2 * -K * * -K * * •K * * 05 0 CO CO P rH rH o o CO CO CO CO CO CO 0 05 • • Eh > rH O o o o o o O o o V-' >- V— V — " * >—' > — «* 03 d) ■K 52 m rH 4 ) 05 dJ in rH CO rH in in in rH rH in 14 ) H* CO 42 • • • 4 H p rH oo o o rH CM CM CM in o o in r- CM o rH rH rH rH CM CM rH ’ 05 g * * CM * * — — -K * co «h ^ ^ O O rH H ■K * h o o o o o o * -K rH i—l O O * CO o -K * co^rooincocot^ocNfoco cp co co • ••••••••••• • • • co^ooooooinooHCPCPO^o * * 05 05 0 ■K * ■K * ■K * * ■K ►s. 03 03 d) in CM ^ C C 52 0 05 CO o O CM CM CM CM in CM ^2 a) d) 05 42 • • S 42 42 P C o o o O O O O O o o CM i P g m p g g d) ( 1 ) P 52 0 •H g P Q) >i o p P p d) 0 0 •H g • p •H P p 52 P rH 42 •H p •H |S d) W 2 g c P rH •H g rH 1 g O 05 £ 2 i T 5 CP 0 44 C /5 d) > rH 0 p in P P 03 P 42 CU 05 52 P 0 o rH rH 05 52 52 p (0 0 05 42 0 0 d> 05 d) -H 42 d) •H 42 •H * < < CQ CQ U O O U p 2 2 2 cu c /5 c /5 tS 3 « -K * o5 22 I 44 O 05 CQ 5-1 0 4-1 03 0 4-> (0 g •H p I w 0) c/5 c/5 3 3 IP > o o >1 >1 42 42 03 03 d) 0) • N N CO >i >i • r —I r —I fO 05 • c in in 05 c/5 0 ) o p 4- 1 >i 5 - ( 05 > >i 05 g m p •H g •H c o •H p o 0 ) -p 0) • 03 co • 44 co O • 05 CM p 01 I c O C2 *H •H p 05 42 I 44 O 05 42 0 ) 42 P 4-1 rH 05 42 I P C O p 4 h d) 42 P p o 4H tr> a. C /5 p •H g •H c/5 03 £2 05 52 O •H p o dJ p d) 03 03 O 42 P d) g 44 O 05 P 01 I c I (T\ CM dJ rH 42 05 E-* and the total sampling train using ICAP 2.3.2 To ensure optimum precision/resolution in the analyses, the target concentrations of metals in the analytical solutions should be at least ten times their respective analytical detection limits. Under certain conditions, and with greater care in the analytical procedure, these concentrations can be as low as approximately three times the respective analytical detection limits without seriously impairing the precision of the analyses. On at least one sample run in the source test, and for each metal analyzed, perform either repetitive analyses, Method of Standard Additions, serial dilution, or matrix spike addition, etc., to document the quality of the data. 2.3.3 Actual in-stack method detection limits are based on actual source sampling parameters and analytical results as described above. If required, the method in-stack detection limits can be improved over those shown in Table 29-1 for a specific test by either increasing the sampled stack gas volume, reducing the total volume of the digested samples, improving the analytical detection limits, or any combination of the three. For extremely low levels of Hg only , the aliquot size selected for digestion and analysis can be increased to as much as 10 ml, thus improving the in-stack detection limit by a factor of ten compared to a 1 ml aliquot size. 2.3.3.1 A nominal one hour sampling run will collect a stack gas sampling volume of about 1.25 m 3 . If the sampling time is increased to four hours and 5 m 3 are collected, the in-stack 12 ■ 3 method detection limits would be improved by a factor of four compared to the values shown in Table 29-1. 2.3.3.2 The in-stack detection limits assume that all of the sample is digested and the final liquid volumes for analysis are the normal values of 300 ml for Analytical Fraction 1, and 150 ml for Analytical Fraction 2A. If the volume of Analytical Fraction 1 is reduced from 300 to 30 ml, the in-stack detection limits for that fraction of the sample would be improved by a factor of ten. If the volume of Analytical Fraction 2A is reduced from 150 to 25 ml, the in-stack detection limits for that fraction of the sample would be improved by a factor of six. Matrix effect checks are necessary on sample analyses and typically are of much greater significance for samples that have been concentrated to less than the normal original sample volume. Reduction of Analytical Fractions 1 and 2A to volumes of less than 30 and 25 ml, respectively, could interfere with the redissolving of the residue and could increase interference by other compounds to an intolerable level. 2.3.3.3 When both of the modifications described in Sections 2.3.3.1 and 2.3.3.2 are used simultaneously on one sample, the resultant improvements are multiplicative. For example, an increase in stack gas volume by a factor of four and a reduction in the total liquid sample digested volume of both Analytical Fractions 1 and 2A by a factor of six would result in an improvement by a factor of twenty-four of the in-stack method detection limit. 13 ' ■ 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), T1 (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 * ■ Glass Filter Holder Thermometer f \ o co CM X o- • O O’ CN O CM I vP o CO O - X £ l o L_ Q CD 15 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 HN0 3 /H 2 0 2 impinger) shall be identical to the first impinger in Method 5. The third impinger (which is the 16 I second HN0 3 /H 2 0 2 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 KMn0 4 ) 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 this Method) with Teflon- lined caps that are non-reactive to the oxidizing solutions, with 17 . capacities of 1000- and 500-ml, for storage of acidified KMn0 4 - 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 Parr R 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 mg. 3.3.10 Microwave or Conventional Oven. For heating samples at fixed power levels or temperatures, respectively. 3.3.11 Hot Plates. . 3.3.12 Atomic Absorption Spectrometer (AAS). Equipped with a background corrector. 3.3.12.1 Graphite Furnace Attachment. With Sb, As, Cd, Co, Pb, Se, and T1 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 10°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 /Lig/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. 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 (S0 2 ) or sulfur trioxide (S0 3 ) 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 (HN0 3 ) . Concentrated. Baker Instra- analyzed or equivalent. 4.2.4 Hydrochloric Acid (HCL). Concentrated. Baker Instra-analyzed or equivalent. 4.2.5 Hydrogen Peroxide (H 2 0 2 ) , 30 Percent (V/V) . 4.2.6 Potassium Permanganate (KMn0 4 ) . 4.2.7 Sulfuric Acid (H 2 S0 4 ) . Concentrated. 4.2.8 Silica Gel and Crushed Ice. Same as Method 5, Sections 3.1.2 and 3.1.4, respectively. 20 I . I 4.3 Pretest Preparation of Sampling Reagents. 4.3.1 HN0 3 /H 2 0 2 Absorbing Solution, 5 Percent HNO 3 /10 Percent H 2 0 2 . Add carefully with stirring 50 ml of concentrated HN0 3 to a 1000-ml volumetric flask containing approximately 500 ml of water, and then add carefully with stirring 333 ml of 30 percent H 2 0 2 . Dilute to volume with water. Mix well. This reagent shall contain less than 2 ng/ml of each target metal. 4.3.2 Acidic KMn0 4 Absorbing Solution, 4 Percent KMn0 4 (W/V), 10 Percent H 2 S0 4 (V/V). Prepare fresh daily. Mix carefully, with stirring, 100 ml of concentrated H 2 S0 4 into approximately 800 ml of water, and add water with stirring to make a volume of 1 liter: this solution is 10 percent H 2 S0 4 (V/V) . Dissolve, with stirring, 40 g of KMn0 4 into 10 percent H 2 S0 4 (V/V) and add 10 percent H 2 S0 4 (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. 21 ■ 4.3.3 HN0 3 , 0.1 N. Add with stirring 6.3 ml of concentrated HN0 3 (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 HC1 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 HN0 3 , Concentrated. Fisher ACS grade or equivalent. 4.4.2 Water. To conform to ASTM Specifications D1193-77, Type II. 4.4.3 HN0 3 , 10 Percent (V/V). Add with stirring 500 ml of concentrated HN0 3 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 fig/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. 22 . I E ; 4.5.3 HN0 3 , Concentrated. Baker Instra-analyzed or equivalent. 4.5.4 HN0 3 , 50 Percent (V/V) . Add with stirring 125 ml of concentrated HN0 3 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 HN0 3 , 5 Percent (V/V). Add with stirring 50 ml of concentrated HN0 3 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 KMn0 4 , 5 Percent (W/V). See Citation 2 of the Bibliography for preparation. 4.5.10 H 2 S0 4 , Concentrated. 4.5.11 Potassium Persulfate, 5 Percent (W/V). See Citation 2 of the Bibliography for preparation. 4.5.12 Nickel Nitrate, Ni (N0 3 ) 2 6H 2 0 . 4.5.13 Lanthanum Oxide, La 2 0 3 . 4.5.14 Hg Standard (AAS Grade), 1000 /zg/ml. 4.5.15 Pb Standard (AAS Grade), 1000 /xg/ml. 4.5.16 As Standard (AAS Grade), 1000 /ig/ml. 23 ■ 4.5.17 Cd Standard (AAS Grade), 1000 /xg/ml. 4.5.18 Cr Standard (AAS Grade), 1000 /xg/ml. 4.5.19 Sb Standard (AAS Grade), 1000 /xg/ml. 4.5.20 Ba Standard (AAS Grade), 1000 /xg/ml. 4.5.21 Be Standard (AAS Grade), 1000 /xg/ml. 4.5.22 Co Standard (AAS Grade), 1000 /xg/ml. 4.5.23 Cu Standard (AAS Grade), 1000 /xg/ml. 4.5.24 Mn Standard (AAS Grade), 1000 /xg/ml. 4.5.25 Ni Standard (AAS Grade), 1000 /xg/ml. 4.5.26 P Standard (AAS Grade), 1000 /xg/ml. 4.5.27 Se Standard (AAS Grade), 1000 /xg/ml. 4.5.28 Ag Standard (AAS Grade), 1000 /xg/ml. 4.5.29 T1 Standard (AAS Grade), 1000 /xg/ml. 4.5.30 Zn Standard (AAS Grade), 1000 /xg/ml. 4.5.31 A1 Standard (AAS Grade), 1000 /xg/ml. 4.5.32 Fe Standard (AAS Grade), 1000 /xg/ml. 4.5.33 Hg Standards and Quality Control Samples. Prepare fresh weekly a 10 /xg/ml intermediate Hg standard by adding 5 ml of 1000 /xg/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 HN0 3 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 /xg/ml intermediate standard to a 250- ml volumetric flask, and dilute to 250 ml with 5 ml of 4 percent KMn0 4/ 5 ml of 15 percent HN0 3 , and then water. Mix well. Use at least five separate aliquots of the working Hg standard solution 24 - ■ 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 /Lig/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 As, Be, Cd, Mn, Pb, Se, Zn Ba, Co, Cu, Fe Al, Cr, Ni Ag, P, Sb, T1 I II III IV Prepare these standards by combining and diluting the appropriate volumes of the 1000 jtig/ml solutions with 5 percent HN0 3 . 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 /ig/ml for Al, Cr and Pb, 15 /xg/ml for Fe, and 10 jLig/ml for the remaining elements. Prepare any standards containing less than 1 jLtg/ml of metal on a daily basis. Standards containing greater than 1 /xg/ml of metal should be stable for a minimum of 1 to 2 weeks. 4.5.35 GFAAS Standards. Sb, As, Cd, Co, Pb, Se, and Tl. Prepare a 10 jug/ml standard by adding 1 ml of 1000 fiq/ml standard 25 . to a 100-ml volumetric flask. Dilute with stirring to 100 ml with 10 percent HN0 3 . 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 guality control samples by making a separate 10 /ig/ml standard and diluting until it is in the range of the samples. Prepare any standards containing less than 1 /xg/ml of metal on a daily basis. Standards containing greater than 1 /ig/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 (N0 3 ) 2 • 6H 2 0 in approximately 50 ml of water in a 100-ml volumetric flask. Dilute to 100 ml with water. 4.5.36.2 Nickel Nitrate, 0.1 Percent (V/V). Dilute 10 ml of 1 percent nickel nitrate solution to 100 ml with water. Inject an egual 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 La 2 0 3 in 10 ml of concentrated HN0 3 , 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 egual amount of sample and 26 . 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 eguipment; 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. 27 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 HN0 3 /H 2 0 2 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 KMn0 4 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 KMn0 4 from contacting any glassware that contains sample material to be analyzed for Mn. Prevent acidic H 2 0 2 from mixing with the acidic KMn0 4 . 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 the open outlet. 29 . 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 it is 30 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. 31 Probe Liner and Nozzle Rinse with acetone Brush liner with nonmetallic brush & rinse with acetone Check liner to see if particulate removed; if not, repeat step above Front Half of Filter Housing Brush with nonmetallic brush and rinse with acetone Filter Carefully remove fitter from support with Teflon- coated tweezers and place in petri dish Brush loose particulate onto fitter Seal petri dish with tape Flinse three times with 0.1 N HN03 Rinse three times with 0.1N HN03 Filter Support and Back Half of Fitter Housing Rinse three times with 0.1 N HN03 1 st Imping or (Empty at beginning of test) I Measure impinger contents Empty the contents into container Rinse three times with 0.1 N HN03 FH AR F BH (31* (2) (1) ,4) * Number in parentheses indicates container number Figure 29-2a. Sample recovery scheme. 2nd & 3rd Imping ers (HN03/H202) Measure impinger contents Empty the contents into container Rinse three times with 0.1 N HN03 32 I Empty the impinger No. ^ contents into container Rinse with 100 ml 0.1 N HN03 0.1N HN03 (5A) 4th Impinger (Empty) & 5th and 6th impingers (Acidified KMn04) Measure impinger contents Empty the Discard impingers Nos. 5 & 6 contents into container Last Impinger Weigh for moisture Rinse three times with permanganate reagent, then with water Remove any residue with 25 ml 8N HCI solution KMn04 8N HCI (5B) (5C) 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 more if needed to remove visible particulate. Make a final rinse of the brush and filter holder. After all ■ t 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 HN0 3 , and place the wash into a sample storage container. NOTE : The use of a total of exactly 100 ml is necessary for the subsequent blank correction procedures. Perform the rinses as applicable and generally as described in Method 12, Section 5.2.2. Record the volume of the rinses. Mark the height of the fluid level on the outside of the storage container and use this mark to determine if leakage occurs during transport. Seal the container, and clearly label the contents. Finally, rinse the nozzle, probe liner, and front-half of the filter holder with water followed by acetone, and discard these rinses. 5.2.8 Container No. 4 (Impingers 1 through 3, Moisture Knockout Impinger, when used, HN0 3 /H 2 0 2 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 HN0 3 using the procedure as applicable in Method 12, Section 5.2.4. NOTE : The use of exactly 100 ml of 0.1 N HN0 3 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 HN0 3 ) , 5B (KMn0 4 /H 2 S0 4 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 HN0 3 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 KMn0 4 solution into Container No. 5B. Using a total of exactly ■ » 100 ml of fresh acidified KMn0 4 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 KMn0 4 with acid, pressure buildup can occur in the sample storage bottles. Do not fill these bottles completely and take precautions to relieve excess pressure. A No. 70-72 hole drilled in the container cap and Teflon liner has been used successfully. 5.2.9.3 If no visible deposits remain after the water rinse, no further rinse is necessary. However, if deposits remain on the impinger surfaces, wash them with 25 ml of 8 N HCl, and place the wash in a separate sample container labeled No. 5C containing 200 ml of water. First, place 200 ml of water in the container. Then wash the impinger walls and stem with the HCl by turning the impinger on its side and rotating it so that the HCl contacts all inside surfaces. Use a total of only 25 ml of 8 N HCl for rinsing both permanganate impingers combined . Rinse the first impinger, then pour the actual rinse used for the first 37 » impinger into the second impinger for its rinse. Finally, pour the 25 ml of 8 N HC1 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 liguids to transfer the silica gel since weight gained in the silica gel impinger is used for moisture calculations. Alternatively, if a balance is available in the field, record the weight of the spent silica gel (or silica gel plus impinger) to the nearest 0.5 g. 5.2.11 Container No. 7 (Acetone Blank). If particulate emissions are to be determined, at least once during each field test, place a 100-ml portion of the acetone used in the sample recovery process into a container labeled No. 7. Seal the container. 5.2.12 Container No. 8A (0.1 N HN0 3 Blank). At least once during each field test, place 300 ml of the 0.1 N HN0 3 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 HNO 3 /10 Percent H 2 0 2 Blank). At least once during each field test, place 200 ml of the 5 Percent HN0 3 /10 Percent H 2 0 2 solution used as the nitric acid impinger reagent into a container labeled No. 9. Seal the container. 5.2.15 Container No. 10 (Acidified KMn0 4 Blank). At least once during each field test, place 100 ml of the acidified KMn0 4 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 liguid in each of the containers and determine if any sample was lost during shipment. If a noticeable amount of leakage has occurred, 39 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 Parr R Bombs. Add 6 ml of concentrated HN0 3 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 o IT) 08 00 Lf) < in in k— 0 c 5 4—> c o u k— 0 c ‘co c o O 0 c c o o CN k_ 0 c ’ CO c o U CO 0 c '0 c o O 0 GD C 'o. E CN o CN I CO O I CO “O _0 0 -Q 0 0 _q o "O 0 a- -s 0 c o 4-> 0 o < 0 n o ^3 O "O 0 0 -Q 0 < 0 4-> 0 CO c 0 ■O c o o 0 "O _3 O c c 0 '■*-> 3 O CO 0 4-* 0 4-* CO 0 cp "O c • TJ __ 0 E t— CO O 0 3 "O CN c 0 CO -C < < CO CO > 0 A 4-» “0 0 4— 1 0 T5 c £ 3 _c O 0 0 co © 0 k_ 4-> 0 0 H— £ 0 Nl k_ 0 > 0 tn < C 0 < k_ O > _q • "O 22 0 '35 k_ _> CO 0 03 c ■O < Itl 4 / Figure 29-3. Sample preparation and analysis scheme. For conventional heating, heat the Parr R 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 HN0 3 . Quantitatively combine the resultant sample, including all liquid and any particulate matter, with Container No. 3 before beginning Section 5.3.3. 42 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 HN0 3 to pH 2. Use water to rinse the sample into a beaker, and cover the beaker with a ribbed watch glass. Reduce the sample volume to approximately 20 ml by heating on a hot plate at a temperature just below boiling. Digest the sample in microwave vessels or Parr R Bombs by quantitatively transferring the sample to the vessel or bomb, carefully adding the 6 ml of concentrated HN0 3 , 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 M . 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 43 % ‘"-035 initmm*0 "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 HN0 3 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 HN0 3/ and heat for 30 minutes on a hot plate to just below boiling. Add 10 ml of 3 percent H 2 0 2 and heat for 10 more minutes. Add 50 ml of hot water, and heat the sample for an additional 20 minutes. Cool, filter the sample, and dilute to 150 ml (or the appropriate volume for the expected metals concentrations) with water. This dilution produces Analytical Fraction 2A. Measure and record the volume to within 0.1 ml. 44 5.3.4.2 Microwave Digestion Procedure. Add 10 ml of i 50 percent HN0 3 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 H 2 0 2 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 Mn0 2 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 45 filter for digestion of the brown Mn0 2 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 Mn0 2 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 Mn0 2 , add 25 ml of 8 N HC1 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 Mn0 2 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 HC1 solution as Analytical Fraction 3C. 5.3.6 Container No. 6 (Silica Gel). Weigh the spent silica gel (or silica gel plus impinger) to the nearest 0.5 g using a balance. 5.4 Sample Analysis. For each sampling train sample run, seven individual analytical samples are generated ; two for all desired metals except Hg, and five for Hg. A schematic identifying each sample container and the prescribed analytical preparation and analysis scheme is shown in Figure 29-3. The first two analytical samples, labeled Analytical Fractions 1A and 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 HN0 3 /H 2 0 2 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 H 2 S0 4 /KMn0 4 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 Cnm) 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. NOTE : When analyzing samples in a HF matrix, an alumina torch should be used; since all front-half samples will contain HF, use an alumina torch. 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 48 Table 29-2. Applicable techniques, methods and minimization of interference for AAS analysis. c o ’4-4 0 N E c 0 0 o c 0 4— 0 44— k_ 0 c o 4-4 0 c E 0 4-4 c o o ■g o > 0 o ■ 4 -> c 0 -X 0 4-4 0 0 o 4-J 0 0 (5 -O 0 ‘5 cr 0 c o 4-4 o 0 k_ v_ o u TJ c 3 O O) .X O 0 CQ 0 3 CL 0 O _c Q. -o c 0 0 0 3 TJ TJ 0 k_ 0 _0 CL E 0 0 "O 0 k_ 0 CL 0 g o TJ O E X 4— 1 CD E t o o <5 ^ Q. £ E CJ 0 0 0 TJ 0 '5 cr 0 v— c o ■ 4-1 o 0 V. k_ o o TJ c 3 O k_ O) -X O 0 CQ 0 TJ -O 2 X 3 cr 0 o ■ 0 3 O c £ .2 c ■*-> ° o fc CO o C u z ■a c 3 O 0 E o £ 0 E 0 c co x -X c a - >. 0 CQ 0 0 0 _0 -o 0 0 L. O 0 c JC 4 — L. TJ 44 — c 0 0 c 0 > O M— 0 0 OJ E c 4 -> 0 E TJ 0 v_ 0 0 c TJ 0 0 0 X 0 TJ 0 k_ TJ 0 4 _ O 0 TJ 0 L. L. 3 ro 0 o c 0 l— 0 3 0 '5 0 CL O 'O -LJ '5 O csi in 00 N E 'c O' 0 k. 0 +-> 0 0 t— cr 0 4 — 0 0 c D E 0 0 4-1 'c 0 E cr 0 4 _ 0 0 c TJ cr 0 4 _ 0 O O 4 -> O 0 0 44 — E c 0 c ■g 0 0 c O c c 0 0 o y—f 0 0 L_ TJ 0 O 0 0 3 k_ tj o 4— 1 ' 4-1 0 ■O c ' 4 -j 0 0 0 _o r“ 4 _ 0 ■ 4-1 O 0 ' 4-4 0 0 O c 0 0 0 0 4 _ _L_ TJ 0 *o 0 0 0 4-4 0 L_ O W C 4 _ 0 c o 0 0 4 — 0 OJ O z 0 0 4 -> 0 4 — O 0 0 k_ 0 0 0 0 4-4 * — t _ 0 O 0 0 0 4 -> O 0 O _3 CL C 5 "o 0 TJ 0 0 TJ 0 TJ 0 TJ Z 0 E 0 0 0 m □ ^ S o O N k 0 JC c C O O L- TJ >- JZ c 0 ' 4-1 C 0 0 c 0 ' 4 —< C D O 4 _ L— O JZ O C u 0 k_ 4 —< 0 -C 4-4 CL 0 •p — CJ) 0 OJ TJ D Q_ 0 OJ O OJ > E -X rz -X TJ -2 o E 0 JX O O O 0 E 4 _ ‘Z -X 0 TJ 0 H— k_ 0 CL TJ C D 0 CD 0 > 0 0 0 > 0 0 CO CO 0 : > CQ N CQ < c CO 0 CQ X CQ > 0 1 * 0 *- ■ 4-1 *■* 0 0 o E 0 0 — CD O 2 E '5 0 w w 0 f I 0 .2 .a = C o Q- '+-• •- CO c N O 0 +-> 0 .c CL 0 o -C Q. TJ C 0 3 u 0 0 > O E 0 ».1 0 "a o -o 2 > 0 E c o c o 4-4 0 c E 0 -i-j c o o ■g 'o > 0 o ■ 4-1 c 0 .X 0 4-4 0 4— 0 o ■ 4-1 0 0 CO CD 0 0 3 0 o c o 4-4 0 c E 0 ■*-< c o cj 0 0 0 0 0 4-4 4-4 4-4 4-4 4-4 0 0 0 0 0 c 0 C c c 0 4— 4 — k_ 0 0 0 0 CD 0 Q_ 4-> TI 4—> 4-1 CJ 0 03 0 0 > 0 0 TJ 0 c E c O O E c E c c 0 4 _ 0 > 4 -> 0 ’ 4-4 0 0 CL 0 4_ O 00 csi 0 CJ c z •k4 0 0 0 CM O CL 0 LO 00 0 LL 0 z O > TJ < 0 -l-l ■*-1 0 a 0 o 3 c o _0 -Q _g o 0 a c 0 U TJ CO < < o 0 o £ -g u TJ O X O CL o 3 3 U co JZ gj X c o ■ 4-1 0 c E 0 c o U OJ c _ 2 ? E 0 00 TJ §1 c n 0 00 00 00 If) O 0 T- 00 00 06 00 00 CT) csi CD 00 CD CO , 3 - 00 00 r^ 00 OJ CM CM CM CM CM CM 00 CM CM a> oo CM o o 00 CM 00 p* CM O 0 O 0 r— O CM CD , cf ID ID pv pv 00 00 CD r-* p^ P^ P" 0 c c C ZJ 0 0 O g - ’4-4 4-4 0 '4-4 c 0 0 u 0 JZ 0 0 h- k_ 'Z 0 < ‘Z 0 < 0 c 0 LL u. 'Z 0 < c o 4-4 0 k_ '5. 0 < 0 0 0 c c c C 0 O O 4-4 0 V-» CD L. 0 0 0 ’ 4-4 0 k_ 'Z Q. c 'Z 0 C/) < k_ 0 < 3 LL < 0 • 4-1 0 0 JC JC CL CL 0 CO OJ < c N 49 Table 29-2 cont. ~cr o '+-< o CD i_ i_ O o c CD £ CD CD N CD C _0 CD > CD CD ■o C o o CD CO c o +-' CD N £ 'c co CD O c CD L— CD 4— u_ CD ■*-> C i CD ■ - -F Q) £ c c c o r- c • O Q) O c O CD "to -c -a •*-< i_ C CD CD "O is ><*5 o V. CD •- •go. C £ F £ < CD O CD Id ■a X o c o I o to CD +- 1 CD CD -X a "O tz CD tz c CD to 0 o. £ CD to TZ CD C o a- F CO -2 c o ■t—I o CD „ o CO o I? | s o 2 ~ o O _g Cl C CD £ _ .0 w N « CD O) (/) tz D to CD CD C TZ c CD ■t— 1 c CO CD +-> CD £ CD i— CD Q. CD N (D tz ■a < Z) O QQ ■a CD '5 O’ CD i_ CO c O Vj o CD i— >_ O o ■a c Z O l_ 05 JX o CD CD £ CD CO CD ■a CD to D CD -t-* CD JZ a. CO O JZ CL £ Z 'c O co CD ZJ _ ■»—> Q_ ^3 £ © CD CD > o JZ CD CO < < £ z> £ o CO a. CD CD £ Z £ *a CD o CD CO CD CO c TO CO CO CD <0 s: ,1 0)« E *g - 0 - £ § % o U CD t— D ■*-> O CD 4— D C CD £ CD CO z CD O to JZ TD V-* CD _N c o CO JZ +-> 0 Q. TZ c 0 T3 1 -a c 0 +-> 0 O CO CL £ O) O 0 U- o JZ +-> 0 o > £ Z5 £ D 0 N ’c o < £ TZ C 0 05 "0 O "■*-< 1 CL 0 c _o +-1 1 05 _c 0 > k. O JZ o CO Q. 0 ■t-j 0 F c: •c o 0 CJ _i 05 o3 c o £ Z3 Q. o _C £ CL Q. o Q. L— CD O J2 CO co V-» <0 <0 £ CL o o o CJ JZ 05 I c 0 to < £ Z3 < O 0 O c u. 0 CD o o ID JZ 05 I _c 0 CO o CO JZ < -*- 1 0 o CO 0 CO < 0 a X LU ■t- 1 0 CL Q_ 0 < 0 CJ o o CM o co JZ < 05 C - £ si CD § CD CN CD CN 00 CJ) CD CO ID LD CD CO CN CD CD 00 CO CN CN CN 00 00 CN CN CD IN CD C) LD ID CN CO CN co co o T— o CD o CN rs CD CN r- O r- 00 "TO 5 ° CO 0 o o T— o CD O o o T _ o N O 00 o CD o CD O co T— 1 ^ 1 n. r** co 0 o O' c JZ o 0 c o 0 "o. CO < 0 o 0 c 0 o 0 c L_ o LL c c C C o o o o +-> 0 ’■)— 11 0 0 o 0 0 o 0 l— 0 0 ’o. ‘CL c i_ 'cl c l_ 'a. CO CO D CO D CO < < LL < LL < 0 0 S § I i i£ u. c o ’+-< 0 "5. CO < 0 0 JZ CO _Q CO CO < 0 CD 0 CD 0 "O CD CJ ~o CJ CJ o *- CJ CJ o o 50 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 fig 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 off- 51 ■ 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 HN0 3 (1.5 ml concentrated HN0 3 per liter aqueous solution) so that when a 1- to 10-ml aliquot of the "0.15 HN0 3 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 Hg.) ; (2), Upon completion of the digestion described in (1), analyze the 52 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 duplicate 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 ml as the blank volume when calculating the blank mass value. Use the actual volumes of the other analytical blanks when calculating their mass values. 54 ■ 7.1.5 Digest the filter that was used to remove any brown Mn0 2 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 check 55 k i$ 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 Wastewater Method 303F. 56 8 . Calculations 8.1 Dry Gas Volume. Using the data from this test, calculate V m(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 V w(std) and the moisture content B ws 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 al F d V sohU Eq. 2 9-1 where: Mft = Total mass of each metal (except Hg) collected in the front half of the sampling train (Sample Fraction 1) , /ig. C al = Concentration of metal in Analytical Fraction 1A as read from the standard curve, Hq/ml . F d = Dilution factor (F d = the inverse of the fractional portion of the concentrated sample 57 in the solution actually used in the instrument to produce the reading C al . For example, if a 2 ml aliquot of Analytical Fraction 1A is diluted to 10 ml to place it in the calibration range, F d = 5) . V soin,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. M bh = C a2 F a V a Eq. 29-2 where: M bh = Total mass of each metal (except Hg) collected in the back-half of the sampling train (Sample Fraction 2) , /xg. C a2 = Concentration of metal in Analytical Fraction 2A as read from the standard curve, (/xg/ml) . F a = Aliquot factor, volume of Sample Fraction 2 divided by volume of Sample Fraction 2A (see Section 5.3.4. ) V a = Total volume of digested sample solution (Analytical Fraction 2A), ml (see Section 5.3.4.1 or 5.3.4.2, as applicable). 58 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 - MflJ + (M bh - M bhb ) Eg. 29-3 where: Mt = Total mass of each metal (separately stated for each metal) collected in the sampling train, Mg - M ftb = Blank correction value for mass of metal detected in front-half field reagent blank, /xg. Myjb = Blank correction value for mass of metal detected in back-half field reagent blank, /xg. NOTE : If the measured blank value for the front half (m^) is in the range 0.0 to "A" /xg [where "A" /xg equals the value determined by multiplying 1.4 /xg/in. 2 times the actual area in in. 2 of the sample filter], use m^ to correct the emission sample value (]%) ; if m^ exceeds "A" /xg, use the greater of I or II: I. "A" /xg. II. the lesser of (a) m^, or (b) 5 percent of m^. If the measured blank value for the back-half (m bhb ) is in the range 0.0 to 1 /xg, use m bhb to correct the emission sample value (m bh ) ; if m bhb exceeds 1 /xg, use the greater of I or II: I. 1 /xg. II. the lesser of (a) m bhb , or (b) 5 percent of m bh . 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 Eguation 29-4: ffg* = Eq. 29-4 V flB where: Hg^ = Total mass of Hg collected in the front- half of the sampling train (Sample Fraction 1) , iig . Qn, = Quantity of Hg, \ig, TOTAL in the ALIQUOT of Analytical Fraction IB selected for digestion and analysis . NOTE : For example, if a 10 ml aliquot of Analytical Fraction IB 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 Q^. V soin,i = Total volume of Analytical Fraction 1, ml. V nB = Volume of aliquot of Analytical Fraction IB analyzed, ml. Note : For example, if a 1 ml aliquot of Analytical Fraction IB was diluted to 50 ml with 0.15 percent HN0 3 as described in Section 5.4.3 to bring it into the proper analytical range, and then 1 ml of that 50-ml 60 was digested according to Section 5.4.3 and analyzed, V nB 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: Hg bh2 = ~ (V soln2 ) Eq. 2 9-5 V J2B where: Hg bh 2 = Total mass of Hg collected in Sample Fraction 2, ng. ^ Qbh 2 = Quantity of Hg, fig, 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 Q bh2 . V soin ,2 = Total volume of Sample Fraction 2, ml. Vf 2 B = 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 HN0 3 as described in Section 5.4.3 to I 61 •: bring it into the proper analytical range, and then 5 ml of that 10-ml was analyzed, V^g 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: bh3(A,B,C) Qbh3(A,B,C) (v tt ' v soln,3(A,B,C,) V J3(A.B,Q Eq. 29-6 where: Hg bh 3 (A,B,Q = Total mass of Hg collected separately in Fraction 3A, 3B, or 3C, n g. Qbh 3 (A,B,Q = Quantity of Hg, jixg, 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). v o ( a , b,q = 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). V S oin, 3 (A,B,o = T °tal 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: = Hg bh2 + Hg bh3A + Hg bh3B + Hg bh3c Eq. 2 9-7 where: Hg bh = Total mass of Hg collected in the back-half of the sampling train, /ig. 8.5.3 Total Train Hg Catch. Calculate the total amount of Hg collected in the sampling train by using Equation 29-8: Hg t = (Hgfc - HgnJ + (Hg bh - Hg bhb ) Eq. 29-8 where: Hg t = Total mass of Hg collected in the sampling train, /ig. Hg^ = Blank correction value for mass of Hg detected in front-half field reagent blank, /ig. Hg^ = Blank correction value for mass of Hg detected in back-half field reagent blanks, /ig. Note : If the total of the measured blank values (Hg^ + Hg bhb ) is in the range of 0.0 to 0.6 /ig, then use the total to correct the sample value (Hg^ + Hg bh ) ; if it exceeds 0.6 /ig, use the greater of I. or II: I. 0.6 /ig. II. the lesser of (a) (Hg^ + Hg^) , or (b) 5 percent of the sample value (Hg^ + Hg bh ) . 63 ' 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: K. M, C = _ i Eq. 29-9 V m(sld) where: C s = Concentration of a metal in the stack gas, mg/dscm. K 4 = 10' 3 mg/jixg. M< = Total mass of that metal collected in the sampling train, iiq; (substitute Hg t for Mj for the Hg calculation). V m(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 ■ EPA Methods 6010, 7000, 7041, 7060, 7131, 7421, 7470, 2 . 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 (H 2 S0 4 ) , 10 Percent (V/V) . Carefully add and mix 100 ml of concentrated H 2 S0 4 to 800 ml of deionized distilled water. Then, by adding deionized distilled water, mix and 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 HC1 to 100 ml with water (slowly add the HC1 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 precleaned as in Section 7.1.2.) Place the contents of the first three impingers 67 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 KMn0 4 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 KMn0 4 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 8 N HC1. However, if deposits do remain on the glassware after the water rinse, wash 68 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 HCl contacts all inside surfaces (wash the first impinger, then pour the wash from the first impinger into the second impinger, and finally pour the wash from the second into the third). DO NOT PLACE THE HCl WASH INTO THE ACIDIFIED PERMANGANATE SOLUTION. Place the HCl wash into a separate container labeled Container No. 1A as follows: place 150 ml of water in an empty sample container labeled Container No. 1A. Pour the HCl wash carefully, with stirring, into Container No. 1A. Rinse the impinger walls and stem with a total of 50 ml of water, and place this rinse into Container No. 1A. 7.2.1.3 After all washings have been collected in the sample containers, prepare as described above to prevent leakage during shipment to the laboratory. Mark the height of the fluid level to determine whether leakage occurs during transport. Label the containers to identify their contents clearly. 7.2.3 Container No, 3 (Filter). If a filter was used, carefully remove it from the filter holder, place it into a 100 ml glass sample container, and add 20 to 40 ml of acidified KMn0 4 . 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.l in Section 7.2.1.1. Label 69 the container to clearly identify its contents. Mark the height of the fluid level to determine whether leakage occurs during transport. * * * * * 7.2.5 Container No, 5 (Absorbing Solution Blank). For a blank, place 500 ml of acidified absorbing solution in a 1000 ml sample bottle. See the Precaution in Section 6.1.6 and see the NOTE No.1 in Section 7.2.1.1. 7.2.6 Container No. 6 (HC1 rinse blank). For a blank, place 200 ml of water in a 1000-ml sample bottle, and add 25 ml of 8 N HC1 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 HN0 3 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 contents 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 Mn0 2 precipitate. Save the filter for digestion of the brown Mn0 2 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.l. and analyze for Hg within 48 hr of the filtration step ( NOTE : Do not confuse ANALYSIS SAMPLE No. A.l. 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 Mn0 2 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 Mn0 2 , add 25 ml of 8 N HC1 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 Mn0 2 from Container No. 1 through Whatman 40 filter into the same 500- ml volumetric flask, and dilute and mix well to volume with 71 ' water. Discard the filter. Mark this combined 500-ml dilute solution as ANALYSIS SAMPLE No. HC1 A.2., and analyze for Hg. 7.3.3 Container No. 5 (Absorbing Solution Blank) and No. 6 (HC1 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.l. 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 Mn0 2 precipitate. Mark this resultant 500-ml combined dilute solution as ANALYSIS SAMPLE No. HC1 A.2 blank. (Note: When analyzing samples A.l blank and HC1 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 /xg in each sample. Correct for any dilutions made to bring the sample into the working range of the spectrophotometer. 72 m (HCDHg = [ [C, (HCDHg D.F. (HCl)Hg ] [C (.HO blk)Hg D.F. 0 HCI blk)Hg ] 'blk ] Vj[HO) ( ^ 0 3 ) Eq. 101A-1 where: m (Hci)H g = Total blank corrected /iq 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(hci t>ik)Hg = Total ng of Hg analyzed in aliquot of the 500-ml ANALYSIS SAMPLE No. HC1 A.2 blank. D.F.(HCDH g = Dilution factor for the HCl-digested Hg-containing solution, ANALYSIS SAMPLE No. "HC1 A.2." This dilution factor applies only to the dilution steps, if necessary, of the 500 ml of the original sample volume [V f(HC1) ] of "HCI A.2" because the original volume has been factored out in the equation along with the sample aliquot (S). In Eq. 101A-1, the sample aliquot, S, is digested according to Sections 7.4, 8.1, and 8.2 and the Hg from this digestion is introduced directly into the aeration cell for analysis. A dilution factor is required only if it is necessary to bring the sample into the analytical instrument's 73 calibration range. If no dilution is necessary, then D.F. (HC1)Hg equals 1.0. D • F • (hci bik)H g = Dilution factor for the HCl-digested Hg- containing solution, ANALYSIS SAMPLE No. "HCI A.2 blank." (Refer to sample No. "HCI A.2" dilution factor information above.) Vf(Hci) = Solution volume of original sample, 500 ml for the HCI samples diluted as described in Section 7.3. 10' 3 = Conversion factor, jLtg/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. S blk = 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 HCI washes is the lesser of the two following values: (1) the actual blank measured value (ANALYSIS SAMPLE No. HCI A.2 blank), or (2) 5% of the Hg content in the combined HCI rinse and digested sample (ANALYSIS SAMPLE No. HCI A.2). 74 m ’ TECHNICAL REPORT DATA (Pleas'' read Instructions on the reverse before completing) 1. REPORT NO. 2. 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 7. AUTHORIS) K.W. Grimley, Jr. 8. PERFORMING ORGANIZATION REPORT NO. 9. PERFORMING ORGANIZATION NAME ANO AOORESS U.S. Environmental Protection Agency Research Triangle Park, NC 27711 10. PROGRAM ELEMENT NO. 11. CONTRACT/GRANT NO. 12. SPONSORING AGENCY NAME AND AOORESS U.S. Environmental Protection Agency Research Triangle Park, NC 27711 13. TYPE OF REPORT AND PERIOD COVERED 14. SPONSORING AGENCY CODE 15. supplementary notes 16. 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 a. DESCRIPTORS —---— b.IDENTIFIERS/OPEN ENDED TERMS c. COSati Field/Group Metals Emissions from Stationary Sources 13. DISTRIBUTION STATEMENT Release unlimited f _ 19. SECURITY CLASS (This Report) Unclassified 21. NC. OF PAGES 77 20. SECURITY CLASS (This page) Unclassified 22. PRICE EPA Form 2220-1 (R«V. 4-77) PREVIOUS EDITION IS OBSOLETE A