# Guidelines Establishing Test Procedures for the Analysis of Pollutants; Chlorinated Pesticides and PCBs by Disk Extraction > Briefs, arguments, decisions, and more. URL: https://www.frixlaw.com/law-library/documents/fr%3A94-31254 ## Record - **Collection:** Federal Register - **Document type:** Uncategorized Document - **Published:** December 21, 1994 ## Text SUMMARY: This proposed amendment to 40 CFR part 136 would approve the use of an additional procedure for the determination of chlorinated pesticides and PCBs in wastewater by adding appropriate citations to Tables IC and ID and by amending the incorporation by reference section of the regulation accordingly. The proposed method differs from currently approved methods in that the proposed method incorporates a disk of octadecyl bonded silica enmeshed in a matrix of inert PFTE fibrils for extraction of the analytes. The precision and recovery for the chlorinated pesticides and PCBs using this technique are not substantially different from those obtained using the liquid-liquid extraction technique already approved. Use of approved analytical techniques is required whenever the waste constituent specified is required to be measured for: an NPDES permit application; discharge monitoring reports; state certification; and other requests from the permitting authority for quantitative or qualitative effluent data. Use of approved test procedures is also required for the expression of pollutant amounts, characteristics, or properties in effluent limitations guidelines and standards of performance and pretreatment standards, unless otherwise specifically noted or defined. DATES: Comments on this proposal will be accepted until January 20, 1995. ADDRESSES: Send comments to: James E. Longbottom, Environmental Monitoring Systems Laboratory--Cincinnati, U.S. Environmental Protection Agency, Cincinnati, OH 45268-0592. The comments should be labeled as ``Guidelines Establishing Test Procedures for the Analyses of Pollutants Under the Clean Water Act-- Chlorinated Pesticides and PCBs by Disk Extraction''. The record and all supporting information on this proposal is available to the public for inspection or copying during normal business hours at the Cincinnati Laboratory. The public should contact James E. Longbottom at (513- 569-7308) for access. An additional copy of the record and supporting information is also available to the public for inspection and copying at the EPA Public Information Reference Unit, Room 2404. For information about materials in the docket see SUPPLEMENTARY INFORMATION. FOR FURTHER INFORMATION CONTACT: Mr. James E. Longbottom, Environmental Monitoring Systems Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, Cincinnati, Ohio 45268. Telephone number: (513) 569-7308. SUPPLEMENTARY INFORMATION: Docket Materials Materials in the public docket include the following: Copy of the proposed procedure and performance data. Technical reviews of the proposed analytical techniques. Statistical reviews of the performance data. Recommendation for Nationwide Approval from the Director, Environmental Monitoring Systems Laboratory-Cincinnati. I. Authority This proposed regulation is issued under authority of sections 301, 304(h) and 501(a) of the Clean Water Act, 33 U.S.C. 1251 et seq. (the Federal Water Pollution Control Act Amendments of 1972 as amended) (the ``Act''). Section 301 of the Act prohibits the discharge of any pollutant into navigable waters unless the discharge complies with a National Pollutant Discharge Elimination System (NPDES) permit, issued under section 402. Section 304(h) of the Act requires the Administrator of the EPA to ``promulgate guidelines establishing test procedures for the analysis of pollutants that shall include the factors which must be provided in any certification pursuant to section 401 of this Act or permit application pursuant to section 402 of this Act''. Section 501(a) of the Act authorizes the Administrator to ``prescribe such regulations as are necessary to carry out his functions under this Act''. II. Regulatory Background The CWA establishes two principal bases for effluent limitations. First, existing discharges are required to meet technology-based effluent limitations. New source discharges must meet new source performance standards based on the best available demonstrated control technology. Second, where necessary, additional requirements are imposed to assure attainment and maintenance of water quality standards established by the States under section 303 of the CWA. In establishing or reviewing NPDES permit limits, EPA must ensure that permitted discharges will not cause or contribute to a violation of water quality standards, including designated water uses. For use in permit applications, discharge monitoring reports, and state certification and to ensure compliance with effluent limitations, standards of performance, and pretreatment standards, EPA has promulgated regulations providing nationally-approved testing procedures at 40 CFR part 136. Test procedures have previously been approved for 262 different parameters. Those procedures apply to the analysis of inorganic (metal, non-metal, mineral) and organic chemical, radiological, bacteriological, nutrient, demand, residue, and physical parameters. Additionally, some particular industries may discharge pollutants for which test procedures have not been proposed and approved under 40 CFR part 136. Under 40 CFR part 122.41 permit writers may impose monitoring requirements and establish test methods for pollutants for which no approved part 136 method exists. 40 CFR 122.41(j) (4). EPA may also approve additional test procedures when establishing industry-wide technology-based effluent limitations guidelines and standards as described at 40 CFR 401.13. The procedures for approval of alternate test procedures (ATPs) are described at 40 CFR 136.4 and 136.5. Under these procedures the Administrator may approve alternate test procedures for nationwide use which are developed and proposed by any person. 40 CFR 136.4 (a). Dischargers seeking to use such alternate test procedures on a limited basis (eg. for their own discharge) must apply to the State or Regional EPA permitting office in which the discharge occurs under Sec. 136.4 (d). As specified below, today's proposed rule would approve an optional nationwide alternate procedure for determination of chlorinated pesticides and PCBs in wastewater test samples. III. The Disk Extraction Test Procedure The 3 M Corporation, in accordance with the regulations published at 40 CFR 136.5, applied for nationwide approval of their ``Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk'' . 3M subsequently presented data to meet the method comparability criteria set forth in the EPA ``Protocol for Approval of Alternate Test Procedures for Inorganic and Organic Analytes in National Pollutant Discharge Elimination System Monitoring'', July 12, 1993. Extraction and concentration are preparation steps that are required prior to the determination of many organic analytes that are found in wastewater. The disk extraction procedure is proposed as an alternate to the presently approved liquid-liquid extraction procedure. A. Scope of the Procedure Method 3M 0222 is designed as an alternate test procedure for currently approved EPA Method 608. The EmporeTM disk is used in place of liquid-liquid extraction. This method is proposed as an alternate procedure for the determination of nineteen organochlorine pesticides and seven PCBs listed below: Aldrin............................. Heptachlor epoxide alpha-BHC.......................... Methoxychlor beta-BHC........................... Toxaphene Chlordane.......................... 4,4'-DDD delta-BHC.......................... 4,4'-DDE Dieldrin........................... 4,4'-DDT Endosulfan I....................... PCB-1016 Endosulfan II...................... PCB-1221 Endosulfan sulfate................. PCB-1232 Endrin............................. PCB-1242 Endrin aldehyde.................... PCB-1248 gamma-BHC.......................... PCB-1254 Heptachlor......................... PCB-1260 The parameters listed in the table can be determined by this method. EPA Method 608 is a gas chromatographic (GC) method applicable to the analysis of municipal and industrial discharges as provided under 40 CFR 136.1 for determination of the compounds listed. When the method is used to analyze unfamiliar samples for any or all of the compounds listed, compound identifications should be supported by at least one additional qualitative technique. The method describes analytical conditions for a second gas chromatographic column that can be used to confirm measurements made with the primary column. B. Summary of the Methods A measured volume of sample, approximately 1-L, is extracted using a 90 mm EmporeTM disk. The disk is eluted with acetone followed by methylene chloride. The eluant is dried by pouring through anhydrous sodium sulfate and exchanged to hexane during concentration to a volume of 10-mL or less. The eluant is separated by gas chromatography and the analytes are then measured with an electron capture detector. The method provides a Florisil column cleanup procedure and an elemental sulfur removal procedure using activated copper powder to aid in the elimination of interferences that may be encountered. C. Technical Justification for Proposed Procedure The recommendation for approval of these procedures is based on the data packages submitted by the applicant, 3M Corporation. EPA is approving the method based on the method description in EPA's Environmental Monitoring Management Council format, comparative analyses using the proposed and approved procedures, and EPA's technical and statistical reviews of each data package. 3M Corporation provided test data using both the proposed procedure and the appropriate approved procedure to extract pesticides and PCBs from 10 wastewaters. The results from the proposed alternate method were compared to the approved EPA Method by EPA statisticians and chemists, who conducted detailed reviews of the data. The recovery and precision of the submitted data for both the approved and proposed methods were also compared to the recovery and precision acceptance criteria derived for EPA Method 608 from Performance Evaluation Studies WP 18 and 23. The Agency has judged the currently approved Method 608 method to be acceptable in their evaluation of the proposed procedure. EPA's Environmental Monitoring Systems Laboratory in Cincinnati, Ohio (EMSL- Cincinnati) thoroughly reviewed and evaluated the supporting data submitted by the 3M Corporation. The reviews indicated that the analyses afforded comparable recovery and precision in the recommended concentration ranges for the listed organochlorine pesticides and PCBs. EPA is proposing approval of the EmporeTM disk procedure and is seeking public comment on the suitability of this procedure as an alternate procedure for use in the determination of the parameters listed. The administrative record is on file at EMSL-Cincinnati, 26 W. Martin Luther King Dr., Cincinnati, Ohio 45268. The record is available for public inspection. Description of the proposed procedure is also available from 3M Corporation, 3M Center Building 220-9E-10, St. Paul, MN 55144-1000. Based on EMSL-Cincinnati's review, and pursuant to 40 CFR 136.5, EPA proposes to approve the 3M Corporation's ``Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk'' method as an acceptable alternative procedure for nationwide use. Specifically, the method exhibits sufficient precision and recovery to establish (1) its acceptability under Part 136 and (2) its comparability to the approved procedure for analysis of the stated organochlorine pesticides and PCBs. As an approved alternate test procedure, this procedure is acceptable for use by any person required to test for these parameters using Method 608. Public comment is requested concerning the suitability of this method for the determination of the specified analytes in wastewater. IV. Regulatory Requirements A. Executive Order 12866 Under Executive Order 12866, EPA must judge whether a regulation is ``major'' and, therefore, requires a regulatory impact analysis. EPA has determined that this regulation is not major as it will not result in an effect on the economy of $100 million or more, a significant increase in cost or prices, or any of the effects described in the Executive Order. This proposed rule would simply specify an alternate analytical procedure which may be used by laboratories in measuring concentrations of organochlorine pesticides and PCBs using EPA Method 608 and, therefore, would have no adverse economic impacts. This action was submitted to OMB for review under the Executive Order. B. Regulatory Flexibility Act This amendment is consistent with the objectives of the Regulatory Flexibility Act (5 U.S.C. 602 et seq.) because it will not have a significant economic impact on a substantial number of small entities. The procedure included in this proposed rule would give all laboratories the flexibility to use this alternate procedure or not to use it. C. Paperwork Reduction Act This rule contains no requests for information activities and, therefore, no information collection request (ICR) was submitted to the Office of Management and Budget (OMB) for review in compliance with the Paperwork Reduction Act, (44 U.S.C. 3501 et seq.). List of Subjects in 40 CFR Part 136 Incorporation by reference, Water pollution control. Dated: December 13, 1994. Carol M. Browner, Administrator. For the reasons set out in the preamble part 136 of title 40 of the Code of Federal Regulations is proposed to be amended as follows: 1. The authority citation for part 136 continues to read as follows: Authority: Secs. 301, 304(h), 307 and 501(a), Public Law 95-217, 91 Stat. 1566, et seq. (33 U.S.C. 1251, et seq.) (the Federal Water Pollution Control Act Amendments of 1972 as amended by the Clean Water Act of 1977). 2. Section 136.3 is proposed to be amended as follows: a. In Table IC of paragraph (a) by revising entries 76. PCB-1016, 77. PCB-1221, 78. PCB-1232, 79. PCB-1242, 80. PCB-1248, 81. PCB-1254, 82. PCB-1260; and by adding footnote 8. b. In Table ID of paragraph (a) by revising entries 1. Aldrin, 8. -BHC, 9. -BHC, 10. -BHC, 11. -BHC (Lindane), 15. Chlordane, 18. 4,4'-DDD, 19. 4,4'-DDE, 20. 4,4'-DDT, 28. Dieldrin, 32. Endosulfan I, 33. Endosulfan II, 34. Endosulfan sulfate, 35. Endrin, 36. Endrin aldehyde, 40. Heptachlor, 41. Heptachlor epoxide, 46. Methoxychlor, and 69. Toxaphene; and by adding footnote 8. c. By adding paragraph (b)(34). Sec. 136.3 Identification of test procedures. (a) * * * Table IC.--List of Approved Test Procedures for Non-Pesticide Organic Compounds ---------------------------------------------------------------------------------------------------------------- EPA method No.\2\,\7\ Parameter\1\ --------------------------- Standard methods ASTM Other GC GC/MS HPLC 18th ed. ---------------------------------------------------------------------------------------------------------------- * * * * * ** 76. PCB-1016.............. 608 625 ....... 6410 B.............. ....... Note 3, p. 43; note 8. 77. PCB-1221.............. 608 625 ....... 6410 B.............. ....... Note 3, p. 43; note 8. 78. PCB-1232.............. 608 625 ....... 6410 B.............. ....... Note 3, p. 43; note 8. 79. PCB-1242.............. 608 625 ....... 6410 B.............. ....... Note 3, p. 43; note 8. 80. PCB-1248.............. 608 625 ....... .................... ....... Note 3, p. 43; note 8. 81. PCB-1254.............. 608 625 ....... 6410 B.............. ....... Note 3, p. 43; note 8. 82. PCB-1260.............. 608 625 ....... 6410 B, 6630 B...... ....... Note 3, p. 43; note 8. * * * * * * * ---------------------------------------------------------------------------------------------------------------- \1\All parameters are expressed in micrograms per liter (g/L). \2\The full text of Methods 601-613, 624, 625, 1624, and 1625, are given at appendix A, ``Test Procedures for Analysis of Organic Pollutants,'' of this part 136. The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at appendix B, ``Definition and Procedure for the Determination of the Method Detection Limit'' of this part 136. \3\``Methods for Benzidine: Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater,'' U.S. Environmental Protection Agency, September, 1978. * * * * * * * \7\Each analyst must make an initial, one-time demonstration of their ability to generate acceptable precision and accuracy with Methods 601-603, 624, 625, 1624, and 1625 (See appendix A of the part 136) in accordance with procedures each in section 8.2 of each of these Methods. Additionally, each laboratory, on and on-going bases must spike and analyze 10% (5% for Methods 624 and 625 and 100% for Methods 1624 and 1625) of all samples to monitor and evaluate laboratory data quality in accordance with sections 8.3 and 8.4 of these Methods. When the recovery of any parameter falls outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect and cannot be reported to demonstrate regulatory compliance. \8\``Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk'', 3M Corporation Revised 10/28/94. Table ID.--List of Approved Test Procedures for Pesticides\1\ ---------------------------------------------------------------------------------------------------------------- Method No. -------------------------------------------------------- Parameter g/L Standard methods Other Method EPA2,7 18th Ed. ASTM ---------------------------------------------------------------------------------------------------------------- 1. Aldrin.................. GC 608 6630 B & C....... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. GC/MS 625 6410 B........... ................. ........................... * * * * * ** 8. -BHC........... GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 8. GC/MS \5\625 6410 B........... ................. ........................... 9. -BHC........... GC 608 6630 C........... D3086-90......... Note 8. GC/MS \5\625 6410 B........... ................. ........................... 10. -BHC.......... GC 608 6030 C........... D3086-90......... Note 8. GC/MS \5\625 6410 B........... ................. ........................... 11. -BHC (Lindane) GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. GC/MS 625 6410 B........... ................. ........................... * * * * * * * 15. Chlordane.............. GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 8. GC/MS 625 6410 B........... ................. ........................... * * * * * * * 18. 4,4'-DDD............... GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. GC/MS 625 6410 B........... ................. ........................... 19. 4,4'-DDD............... GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. GC/MS 625 6410 B........... ................. ........................... 20. 4,4'-DDD............... GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. GC/MS 625 6410 B........... ................. ........................... * * * * * * * 28. Dieldrin............... GC 608 6630 B&C......... ................. Note 3, p. 7; note 4, p. 30; note 8. GC/MS 625 6410 B........... ................. ........................... * * * * * * * 32. Endosulfan I........... GC 6087 6630 B&C......... D3086-90......... Note 3, p. 7; note 8. GC/MS \5\625 6410 B........... ................. ........................... 33. Endosulfan II.......... GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 8. GC/MS \5\625 6410 B........... ................. ........................... 34. Endosulfan sulfate..... GC 608 6630 C........... ................. Note 8. GC/MS 625 6410 B........... ................. ........................... 35. Endrin................. GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. GC/MS \5\625 6410 B........... ................. ........................... 36. Endrin aldehyde........ GC 608 ................. ................. Note 8. GC/MS 625 ................. ................. ........................... * * * * * * * 40. Heptachlor............. GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. GC/MS 625 6410 B........... ................. ........................... 41. Heptachlor epoxide..... GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; Note 4, p. 30; note 6, p. S73; note 8. GC/MS 625 6410 B........... ................. ........................... * * * * * * * 46. Methoxychlor........... GC ....... 6630 B&C......... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. * * * * * * * 69. Toxaphene.............. GC 608 6630 B&C......... D3086-90......... Note 3, p. 7; note 4, p. 30; note 8. GC/MS 625 6410 B........... ................. ........................... * * * * * * * ---------------------------------------------------------------------------------------------------------------- \1\Pesticides are listed in this table by common name for the convenience of the reader. Additional pesticides may be found under Table IC, where entries are listed by chemical name. \2\The full text of Methods 608 and 625 are given at Appendix A. ``Test Procedures for Analysis of Organic Pollutants'', of this Part 136. The standardized test procedure to be used to determine the method detection limit (MDL) for these test procedures is given at Appendix B. ``Definition and Procedure for the Determination of the Method Detection Limit'', of this Part 136. \3\``Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater'', U. S. Environmental Protection Agency, September, 1978. This EPA publication includes thin-layer chromatography (TLC) methods. \4\``Methods for Analysis of Organic Substances in Water and Fluvial Sediments'', Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A3 (1987). \5\The method may be extended to include -BHC, -BHC, endosulfan I, endosulfan II, and endrin. However, when they are known to exist in the sample, Method 608 is the preferred method. \6\``Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency''. Supplement to the Fifteenth Edition of Standard Methods for the Examination of Water and Wastewater (1981). \7\Each analyst must make an initial, one-time, demonstration of their ability to generate acceptable precision and accuracy with Methods 608 and 625 (See Appendix A of this Part 136) in accordance with procedures given in section 8.2 of each of these methods. Additionally, each laboratory, on an on-going basis, must spike and analyze 10% of all samples analyzed with Method 608 or 5% of all samples analyzed with Method 625 to monitor and evaluate laboratory data quality in accordance with Sections 8.3 and 8.4 of these methods. When the recovery of any parameter falls outside the warning limits, the analytical results for that parameter in the unspiked sample are suspect and cannot be reported to demonstrate regulatory compliance. These quality control requirements also apply to the Standard Methods, ASTM Methods, and other Methods cited. \8\``Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk'', 3M Corporation, Revised 10/28/94. (b) * * * References, Sources, Costs, and Table citations: * * * * * (34) ``Organochlorine Pesticides and PCBs in Wastewater Using EmporeTM Disk'', Test Method 3M 0222, Revised 10/28/94. 3M Corporation, 3M Center Building 220-9E-10, St. Paul, MN 55144-1000. Methods available from 3M Corporation. Table IC and ID, Note 8. [FR Doc. 94-31254 Filed 12-20-94; 8:45 am] BILLING CODE 6560-50-P --- Source: Frix Law Library, https://www.frixlaw.com/law-library/documents/fr%3A94-31254. Public record. Not legal advice.