CODE OF FEDERAL REGULATIONS
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The Code of Federal Regulations is a codification of the general and permanent rules published in the Federal Register by the Executive departments and agencies of the Federal Government. The Code is divided into 50 titles which represent broad areas subject to Federal regulation. Each title is divided into chapters which usually bear the name of the issuing agency. Each chapter is further subdivided into parts covering specific regulatory areas.
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Title 40—
Chapter I—Environmental Protection Agency appears in all twenty-nine volumes. An alphabetical Listing of Pesticide Chemicals Index appears in parts 150-189. Regulations issued by the Council on Environmental Quality appear in the volume containing part 790 to End. The OMB control numbers for title 40 appear in § 9.1 of this chapter.
(This book contains parts 136 to 149)
Nomenclature changes to chapter I appear at 65 FR 47324, 47325, Aug. 2, 2000; 66 FR 34375, 34376, June 28, 2001.
Secs. 301, 304(h), 307 and 501(a), Pub. L. 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).
The procedures prescribed herein shall, except as noted in § 136.5, be used to perform the measurements indicated whenever the waste constituent specified is required to be measured for:
(a) An application submitted to the Administrator, or to a State having an approved NPDES program for a permit under section 402 of the Clean Water Act of 1977, as amended (CWA), and/or to reports required to be submitted under NPDES permits or other requests for quantitative or qualitative effluent data under parts 122 to 125 of title 40, and,
(b) Reports required to be submitted by discharges under the NPDES established by parts 124 and 125 of this chapter, and,
(c) Certifications issued by States pursuant to section 401 of the CWA, as amended.
As used in this part, the term:
(a)
(b)
(c)
(d)
(e)
(f)
(a) Parameters or pollutants, for which methods are approved, are listed together with test procedure descriptions and references in Tables IA, IB, IC, ID, IE, and IF. The full text of the referenced test procedures are incorporated by reference into Tables IA, IB, IC, ID, IE, and IF. The incorporation by reference of these documents, as specified in paragraph (b) of this section, was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the documents may be obtained from the sources listed in paragraph (b) of
(b) The full texts of the methods from the following references which are cited in Tables IA, IB, IC, ID, IE,and IF are incorporated by reference into this regulation and may be obtained from the sources identified. All costs cited are subject to change and must be verified from the indicated sources. The full texts of all the test procedures cited are available for inspection at the National Exposure Research Laboratory, Office of Research and Development, U.S. Environmental Protection Agency, 26 West Martin Luther King Dr., Cincinnati, OH 45268 and the Office of the Federal Register, 800 North Capitol Street, NW., Suite 700, Washington, DC.
(1) The full texts of Methods 601-613, 624, 625, 1613, 1624, and 1625 are printed in appendix A of this part 136. The full text for determining the method detection limit when using the test procedures is given in appendix B of this part 136. The full text of Method 200.7 is printed in appendix C of this part 136. Cited in: Table IB, Note 5; Table IC, Note 2; and Table ID, Note 2.
(2) USEPA. 1978. Microbiological Methods for Monitoring the Environment, Water, and Wastes. Environmental Monitoring and Support Laboratory, U.S. Environmental Protection Agency, Cincinnati, Ohio. EPA/600/8-78/017. Available from: National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161, Publ. No. PB-290329/AS. Cost: $36.95. Table IA, Note 3.
(3) “Methods for Chemical Analysis of Water and Wastes,” U.S. Environmental Protection Agency, EPA-600/4-79-020, March 1979, or “Methods for Chemical Analysis of Water and Wastes,” U.S. Environmental Protection Agency, EPA-600/4-79-020, Revised March 1983. Available from: ORD Publications, CERI, U.S. Environmental
(4) “Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol and Pesticides in Water and Wastewater,” U.S. Environmental Protection Agency, 1978. Available from: ORD Publications, CERI, U.S. Environmental Protection Agency, Cincinnati, Ohio 45268, Table IC, Note 3; Table D, Note 3.
(5) “Prescribed Procedures for Measurement of Radioactivity in Drinking Water,” U.S. Environmental Protection Agency, EPA-600/4-80-032, 1980. Available from: ORD Publications, CERI, U.S. Environmental Protection Agency, Cincinnati, Ohio 45268, Table IE, Note 1.
(6) American Public Health Association. 1992, 1995, and 1998. Standard Methods for the Examination of Water and Wastewater. 18th, 19th, and 20th Edition (respectively). Available from: Amer. Publ. Hlth. Assoc., 1015 15th Street, NW., Washington, DC 20005. Table IA, Note 4. Tables IB, IC, ID, IE.
(7) Ibid, 15th Edition, 1980. Table IB, Note 30; Table ID.
(8) Ibid, 14th Edition, 1975. Table IB, Notes 17 and 27.
(9) “Selected Analytical Methods Approved and Cited by the United States Environmental Protection Agency,” Supplement to the 15th Edition of Standard Methods for the Examination of Water and Wastewater, 1981. Available from: American Public Health Association, 1015 Fifteenth Street NW., Washington, DC 20036. Cost available from publisher. Table IB, Note 10; Table IC, Note 6; Table ID, Note 6.
(10) Annual Book of ASTM Standards, Water, and Environmental Technology, Section 11, Volumes 11.01 and 11.02, 1994, 1996, and 1999. Available from: ASTM International, 100 Barr Harbor Drive, P.O. Box C-700, West Conshohocken, PA 19428-2959. Tables IB, IC, ID, and IE.
(11) USGS. 1989. U.S. Geological Survey Techniques of Water-Resources Investigations, Book 5, Laboratory Analysis, Chapter A4, Methods for Collection and Analysis of Aquatic Biological and Microbiological Samples, U.S. Geological Survey, U.S. Department of the Interior, Reston, Virginia. Available from: USGS Books and Open-File Reports Section, Federal Center, Box 25425, Denver, Colorado 80225. Cost: $18.00. Table IA, Note 5.
(12) “Methods for Determination of Inorganic Substances in Water and Fluvial Sediments,” by M.J. Fishman and Linda C. Friedman, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5 Chapter A1 (1989). Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Cost: $108.75 (subject to change). Table IB, Note 2.
(13) “Methods for Determination of Inorganic Substances in Water and Fluvial Sediments,” N.W. Skougstad and others, editors. Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A1 (1979). Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Cost: $10.00 (subject to change), Table IB, Note 8.
(14) “Methods for the Determination of Organic Substances in Water and Fluvial Sediments,” Wershaw, R.L., et al, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A3 (1987). Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Cost: $0.90 (subject to change). Table IB, Note 24; Table ID, Note 4.
(15) “Water Temperature—Influential Factors, Field Measurement and Data Presentation,” by H.H. Stevens, Jr., J. Ficke, and G.F. Smoot, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 1, Chapter D1, 1975. Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Cost: $1.60 (subject to change). Table IB, Note 32.
(16) “Selected Methods of the U.S. Geological Survey of Analysis of Wastewaters,” by M.J. Fishman and Eugene Brown; U.S. Geological Survey Open File Report 76-77 (1976). Available from: U.S. Geological Survey, Branch of Distribution, 1200 South Eads Street, Arlington, VA 22202. Cost: $13.50 (subject to change). Table IE, Note 2.
(17) “Official Methods of Analysis of the Association of Official Analytical Chemicals”, Methods manual, 15th Edition (1990). Price: $240.00. Available
(18) “American National Standard on Photographic Processing Effluents,” April 2, 1975. Available from: American National Standards Institute, 1430 Broadway, New York, New York 10018. Table IB, Note 9.
(19) “An Investigation of Improved Procedures for Measurement of Mill Effluent and Receiving Water Color,” NCASI Technical Bulletin No. 253, December 1971. Available from: National Council of the Paper Industry for Air and Stream Improvements, Inc., 260 Madison Avenue, New York, NY 10016. Cost available from publisher. Table IB, Note 18.
(20) Ammonia, Automated Electrode Method, Industrial Method Number 379-75WE, dated February 19, 1976. Technicon Auto Analyzer II. Method and price available from Technicon Industrial Systems, Tarrytown, New York 10591. Table IB, Note 7.
(21) Chemical Oxygen Demand, Method 8000, Hach Handbook of Water Analysis, 1979. Method price available from Hach Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table IB, Note 14.
(22) OIC Chemical Oxygen Demand Method, 1978. Method and price available from Oceanography International Corporation, 512 West Loop, P.O. Box 2980, College Station, Texas 77840. Table IB, Note 13.
(23) ORION Research Instruction Manual, Residual Chlorine Electrode Model 97-70, 1977. Method and price available from ORION Research Incorporation, 840 Memorial Drive, Cambridge, Massachusetts 02138. Table IB, Note 16.
(24) Bicinchoninate Method for Copper. Method 8506, Hach Handbook of Water Analysis, 1979, Method and price available from Hach Chemical Company, P.O. Box 300, Loveland, Colorado 80537. Table IB, Note 19.
(25) Hydrogen Ion (pH) Automated Electrode Method, Industrial Method Number 378-75WA. October 1976. Bran & Luebbe (Technicon) Auto Analyzer II. Method and price available from Bran & Luebbe Analyzing Technologies, Inc. Elmsford, N.Y. 10523. Table IB, Note 21.
(26) 1,10-Phenanthroline Method using FerroVer Iron Reagent for Water, Hach Method 8008, 1980. Method and price available from Hach Chemical Company, P.O. Box 389 Loveland, Colorado 80537. Table IB, Note 22.
(27) Periodate Oxidation Method for Manganese, Method 8034, Hach Handbook for Water Analysis, 1979. Method and price available from Hach Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table IB, Note 23.
(28) Nitrogen, Nitrite—Low Range, Diazotization Method for Water and Wastewater, Hach Method 8507, 1979. Method and price available from Hach Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table IB, Note 25.
(29) Zincon Method for Zinc, Method 8009. Hach Handbook for Water Analysis, 1979. Method and price available from Hach Chemical Company, P.O. Box 389, Loveland, Colorado 80537. Table IB, Note 33.
(30) “Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography,” by R.F. Addison and R.G. Ackman, Journal of Chromatography, Volume 47, No. 3, pp. 421-426, 1970. Available in most public libraries. Back volumes of the Journal of Chromatography are available from Elsevier/North-Holland, Inc., Journal Information Centre, 52 Vanderbilt Avenue, New York, NY 10164. Cost available from publisher. Table IB, Note 28.
(31) “Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes”, Method AES 0029, 1986-Revised 1991, Fison Instruments, Inc., 32 Commerce Center, Cherry Hill Drive, Danvers, MA 01923. Table B, Note 34.
(32) “Closed Vessel Microwave Digestion of Wastewater Samples for Determination of Metals, CEM Corporation, P.O. Box 200, Matthews, North Carolina 28106-0200, April 16, 1992. Available from the CEM Corporation. Table IB, Note 36.
(33) “Organochlorine Pesticides and PCBs in Wastewater Using Empore
(34) USEPA. October 2002. Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms. Fifth Edition. U.S. Environmental Protection Agency, Office of Water, Washington, D.C. EPA 821-R-02-012. Available from: National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161, Publ. No. PB2002-108488. Table IA, Note 7.
(35) “Nitrogen, Total Kjeldahl, Method PAI-DK01 (Block Digestion, Steam Distillation, Titrimetric Detection)”, revised 12/22/94. Available from Perstorp Analytical Corporation, 9445 SW Ridder Rd., Suite 310, P.O. Box 648, Wilsonville, OK 97070. Table IB, Note 39.
(36) “Nitrogen, Total Kjeldahl, Method PAI-DK02 (Block Digestion, Steam Distillation, Colorimetric Detection)”, revised 12/22/94. Available from Perstorp Analytical Corporation, 9445 SW Ridder Rd., Suite 310, P.O. Box 648, Wilsonville, OK 97070. Table IB, Note 40.
(37) “Nitrogen, Total Kjeldahl, Method PAI-DK03 (Block Digestion, Automated FIA Gas Diffusion)”, revised 12/22/94. Available from Perstorp Analytical Corporation, 9445 SW Ridder Rd., Suite 310, P.O. Box 648, Wilsonville, OK 97070. Table IB, Note 41.
(38) USEPA. October 2002. Short-Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms. Fourth Edition. U.S. Environmental Protection Agency, Office of Water, Washington, D.C. EPA 821-R-02-013. Available from: National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161, Publ. No. PB2002-108489. Table IA, Note 8.
(39) USEPA. October 2002. Short-Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms. Third Edition. U.S. Environmental Protection Agency, Office of Water, Washington, D.C. EPA 821-R-02-014. Available from: National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161, Publ. No. PB2002-108490. Table IA, Note 9.
(40) EPA Methods 1666, 1667, and 1671 listed in the table above are published in the compendium titled Analytical Methods for the Determination of Pollutants in Pharmaceutical Manufacturing Industry Wastewaters (EPA 821-B-98-016). EPA Methods 502.2 and 524.2 have been incorporated by reference into 40 CFR 141.24 and are in Methods for the Determination of Organic Compounds in Drinking Water, EPA-600/4-88-039, December 1988, Revised, July 1991, and Methods for the Determination of Organic Compounds in Drinking Water-Supplement II, EPA-600/R-92-129, August 1992, respectively. These EPA test method compendia are available from the National Technical Information Service, NTIS PB91-231480 and PB92-207703, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, Virginia 22161. The toll-free number is 800-553-6847. ASTM test methods D3371, D3695, and D4763 are available from the American Society for Testing and Materials, 100 Barr Harbor Drive, West Conshohocken, PA 19428-2959.
(41) USEPA. 2002. Method 1631, Revision E, “Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry.” September 2002. Office of Water, U.S. Environmental Protection Agency (EPA-821-R-02-019). Available from: National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161. Publication No. PB2002-108220. Cost: $25.50 (subject to change).
(42) [Reserved]
(43) Method OIA-1677, Available Cyanide by Flow Injection, Ligand Exchange, and Amperometry. August 1999. ALPKEM, OI Analytical, Box 648, Wilsonville, Oregon 97070 (EPA-821-R-99-013). Available from: National Technical Information Service, 5285 Port Royal Road, Springfield, Virginia 22161. Publication No. PB99-132011. Cost: $22.50. Table IB, Note 44.
(44) “Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory Determination of Ammonium Plus Organic Nitrogen by a Kjeldahl Digestion Method and an Automated Photometric Finish that Includes Digest Cleanup by Gas Diffusion”, Open File Report (OFR) 00-170. Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Table IB, Note 45.
(45) “Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Chromium in Water by Graphite Furnace Atomic Absorption Spectrophotometry”, Open File Report (OFR) 93-449. Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Table IB, Note 46.
(46) “Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Molybdenum in Water by Graphite Furnace Atomic Absorption Spectrophotometry”, Open File Report (OFR) 97-198. Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Table IB, Note 47.
(47) “Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Total Phosphorus by Kjeldahl Digestion Method and an Automated Colorimetric Finish That Includes Dialysis” Open File Report (OFR) 92-146. Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Table IB, Note 48.
(48) “Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Arsenic and Selenium in Water and Sediment by Graphite Furnace—Atomic Absorption Spectrometry” Open File Report (OFR) 98-639. Table IB, Note 49.
(49) “Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Elements in Whole-Water Digests Using Inductively Coupled Plasma-Optical Emission Spectrometry and Inductively Coupled Plasma-Mass Spectrometry” , Open File Report (OFR) 98-165. Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Table IB, Note 50.
(50) “Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Triazine and Other Nitrogen-containing Compounds by Gas Chromatography with Nitrogen Phosphorus Detectors” U.S.Geological Survey Open File Report 94-37. Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Table ID, Note 9.
(51) “Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments”, Open File Report (OFR) 93-125. Available from: U.S. Geological Survey, Denver Federal Center, Box 25425, Denver, CO 80225. Table IB, Note 51; Table IC, Note 9.
(c) Under certain circumstances the Regional Administrator or the Director in the Region or State where the discharge will occur may determine for a particular discharge that additional parameters or pollutants must be reported. Under such circumstances, additional test procedures for analysis of pollutants may be specified by the Regional Administrator, or the Director upon the recommendation of the Director of the Environmental Monitoring Systems Laboratory—Cincinnati.
(d) Under certain circumstances, the Administrator may approve, upon recommendation by the Director, Environmental Monitoring Systems Laboratory—Cincinnati, additional alternate test procedures for nationwide use.
(e) Sample preservation procedures, container materials, and maximum allowable holding times for parameters cited in Tables IA, IB, IC, ID, and IE are prescribed in Table II. Any person may apply for a variance from the prescribed preservation techniques, container materials, and maximum holding times applicable to samples taken from a specific discharge. Applications for variances may be made by letters to the Regional Administrator in the Region in which the discharge will occur. Sufficient data should be provided to assure such variance does not adversely affect the integrity of the sample. Such data will be forwarded, by the Regional Administrator, to the Director of the Environmental Monitoring Systems Laboratory—Cincinnati, Ohio for technical review and recommendations for action on the variance application. Upon receipt of the recommendations from the Director of the Environmental Monitoring
(a) Any person may apply to the Regional Administrator in the Region where the discharge occurs for approval of an alternative test procedure.
(b) When the discharge for which an alternative test procedure is proposed occurs within a State having a permit program approved pursuant to section 402 of the Act, the applicant shall submit his application to the Regional Administrator through the Director of the State agency having responsibility for issuance of NPDES permits within such State.
(c) Unless and until printed application forms are made available, an application for an alternate test procedure may be made by letter in triplicate. Any application for an alternate test procedure under this paragraph (c) shall:
(1) Provide the name and address of the responsible person or firm making the discharge (if not the applicant) and the applicable ID number of the existing or pending permit, issuing agency, and type of permit for which the alternate test procedure is requested, and the discharge serial number.
(2) Identify the pollutant or parameter for which approval of an alternate testing procedure is being requested.
(3) Provide justification for using testing procedures other than those specified in Table I.
(4) Provide a detailed description of the proposed alternate test procedure, together with references to published studies of the applicability of the alternate test procedure to the effluents in question.
(d) An application for approval of an alternate test procedure for nationwide use may be made by letter in triplicate to the Director, Analytical Methods Staff, Office of Science and Technology (4303), Office of Water, U.S. Environmental Protection Agency, 1200 Pennsylvania Ave., NW., Washington, DC 20460. Any application for an alternate test procedure under this paragraph (d) shall:
(1) Provide the name and address of the responsible person or firm making the application.
(2) Identify the pollutant(s) or parameter(s) for which nationwide approval of an alternate testing procedure is being requested.
(3) Provide a detailed description of the proposed alternate procedure, together with references to published or other studies confirming the general applicability of the alternate test procedure to the pollutant(s) or para-meter(s) in waste water discharges from representative and specified industrial or other categories.
(4) Provide comparability data for the performance of the proposed alternate test procedure compared to the performance of the approved test procedures.
(a) The Regional Administrator of the region in which the discharge will occur has final responsibility for approval of any alternate test procedure proposed by the responsible person or firm making the discharge.
(b) Within thirty days of receipt of an application, the Director will forward such application proposed by the responsible person or firm making the discharge, together with his recommendations, to the Regional Administrator. Where the Director recommends rejection of the application for scientific and technical reasons which he provides, the Regional Administrator shall deny the application, and shall forward a copy of the rejected application and his decision to the Director of the State Permit Program and to the Director of the Analytical Methods Staff, Washington, DC.
(c) Before approving any application for an alternate test procedure proposed by the responsible person or firm making the discharge, the Regional Administrator shall forward a copy of the application to the Director of the Analytical Methods Staff, Washington, DC.
(d) Within ninety days of receipt by the Regional Administrator of an application for an alternate test procedure, proposed by the responsible person or firm making the discharge, the Regional Administrator shall notify the applicant and the appropriate State agency of approval or rejection, or shall specify the additional information which is required to determine whether to approve the proposed test procedure. Prior to the expiration of such ninety day period, a recommendation providing the scientific and other technical basis for acceptance or rejection will be forwarded to the Regional Administrator by the Director of the Analytical Methods Staff, Washington, DC. A copy of all approval and rejection notifications will be forwarded to the Director, Analytical Methods Staff, Washington, DC, for the purposes of national coordination.
(e)
(2) Within ninety days of the receipt of a complete package, the Analytical Methods Staff shall perform any analysis necessary to determine whether the alternate method satisfies the applicable requirements of this part, and the Director of the Analytical Methods Staff shall recommend to the Administrator that he/she approve or reject the application and shall also notify the applicant of such recommendation.
(3) As expeditiously as practicable, an alternate method determined by the Administrator to satisfy the applicable requirements of this part shall be proposed by EPA for incorporation in subsection 136.3 of 40 CFR part 136. EPA shall make available for review all the factual bases for its proposal, including any performance data submitted by the applicant and any available EPA analysis of those data.
(4) Following a period of public comment, EPA shall, as expeditiously as practicable, publish in the
1.1This method covers the determination of 29 purgeable halocarbons.
The following parameters may be determined by this method:
1.2This is a purge and trap gas chro-ma-tographic (GC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compounds above, compound identifications should be supported by at least one additional qualitative technique. This method describes analytical conditions for a second gas chromatographic column that can be used to confirm measurements made with the primary column. Method 624 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for most of the parameters listed above.
1.3The method detection limit (MDL, defined in Section 12.1)
1.4Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.5This method is restricted to use by or under the supervision of analysts experienced in the operation of a purge and trap system and a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1An inert gas is bubbled through a 5-mL water sample contained in a specially-designed purging chamber at ambient temperature. The halocarbons are efficiently transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbent trap where the halocarbons are trapped. After purging is completed, the trap is heated and backflushed with the inert gas to desorb the halocarbons onto a gas chromatographic column. The gas chromatograph is temperature programmed to separate the halocarbons which are then detected with a halide-specific detector.
2.2The method provides an optional gas chromatographic column that may be helpful in resolving the compounds of interest from interferences that may occur.
3.1Impurities in the purge gas and organic compounds outgassing from the plumbing ahead of the trap account for the majority of contamination problems. The analytical system must be demonstrated to be free from contamination under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3. The use of non-Teflon plastic tubing, non-Teflon thread sealants, or flow controllers with rubber components in the purge and trap system should be avoided.
3.2Samples can be contaminated by diffusion of volatile organics (particularly fluorocarbons and methylene chloride) through the septum seal ilto the sample during shipment and storage. A field reagent blank prepared from reagent water and carried through the sampling and handling protocol can serve as a check on such contamination.
3.3Contamination by carry-over can occur whenever high level and low level samples are sequentially analyzed. To reduce carry-over, the purging device and sample syringe must be rinsed with reagent water between sample analyses. Whenever an unusually concentrated sample is encountered, it should be followed by an analysis of reagent water to check for cross contamination. For samples containing large amounts of water-soluble materials, suspended solids, high boiling compounds or high organohalide levels, it may be necessary to wash out the purging device with a detergent solution, rinse it with distilled water, and then dry it in a 105°C oven between analyses. The trap and other parts of the system are also subject to contamination; therefore, frequent bakeout and purging of the entire system may be required.
4.1The toxicity or carcinogenicity of each -reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of
4.2The following parameters covered by this method have been tentatively classified as known or suspected, human or mammalian carcinogens: carbon tetrachloride, chloroform, 1,4-dichlorobenzene, and vinyl chloride. Primary standards of these toxic compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles high concentrations of these toxic compounds.
5.1Sampling equipment, for discrete sampling.
5.1.1Vial—25-mL capacity or larger, equipped with a screw cap with a hole in the center (Pierce #13075 or equivalent). Detergent wash, rinse with tap and distilled water, and dry at 105 °C before use.
5.1.2Septum—Teflon-faced silicone (Pierce #12722 or equivalent). Detergent wash, rinse with tap and distilled water, and dry at 105 °C for 1 h before use.
5.2Purge and trap system—The purge and trap system consists of three separate pieces of equipment: a purging device, trap, and desorber. Several complete systems are now commercially available.
5.2.1The purging device must be designed to accept 5-mL samples with a water column at least 3 cm deep. The gaseous head space between the water column and the trap must have a total volume of less than 15 mL. The purge gas must pass through the water column as finely divided bubbles with a diameter of less than 3 mm at the origin. The purge gas must be introduced no more than 5 mm from the base of the water column. The purging device illustrated in Figure 1 meets these design criteria.
5.2.2The trap must be at least 25 cm long and have an inside diameter of at least 0.105 in. The trap must be packed to contain the following minimum lengths of adsorbents: 1.0 cm of methyl silicone coated packing (Section 6.3.3), 7.7 cm of 2,6-diphenylene oxide polymer (Section 6.3.2), 7.7 cm of silica gel (Section 6.3.4), 7.7 cm of coconut charcoal (Section 6.3.1). If it is not necessary to analyze for dichlorodifluoromethane, the charcoal can be eliminated, and the polymer section lengthened to 15 cm. The minimum specifications for the trap are illustrated in Figure 2.
5.2.3The desorber must be capable of rapidly heating the trap to 180 °C. The polymer section of the trap should not be heated higher than 180 °C and the remaining sections should not exceed 200 °C. The desorber illustrated in Figure 2 meets these design criteria.
5.2.4The purge and trap system may be assembled as a separate unit or be coupled to a gas chromatograph as illustrated in Figures 3 and 4.
5.3Gas chromatograph—An analytical system complete with a temperature programmable gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.3.1Column 1—8 ft long × 0.1 in. ID stainless steel or glass, packed with 1% SP-1000 on Carbopack B (60/80 mesh) or equivalent. This column was used to develop the method performance statements in Section 12. Guidelines for the use of alternate column packings are provided in Section 10.1.
5.3.2Column 2—6 ft long × 0.1 in. ID stainless steel or glass, packed with chemically bonded n-octane on Porasil-C (100/120 mesh) or equivalent.
5.3.3Detector—Electrolytic conductivity or microcoulometric detector. These types of detectors have proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1). The electrolytic conductivity detector was used to develop the method performance statements in Section 12. Guidelines for the use of alternate detectors are provided in Section 10.1.
5.4Syringes—5-mL glass hypodermic with Luerlok tip (two each), if applicable to the purging device.
5.5Micro syringes—25-μL, 0.006 in. ID needle.
5.6Syringe valve—2-way, with Luer ends (three each).
5.7Syringe—5-mL, gas-tight with shut-off valve.
5.8Bottle—15-mL, screw-cap, with Teflon cap liner.
5.9Balance—Analytical, capable of accurately weighing 0.0001 g.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.1.1Reagent water can be generated by passing tap water through a carbon filter bed containing about 1 lb of activated carbon (Filtrasorb-300, Calgon Corp., or equivalent).
6.1.2A water purification system (Millipore Super-Q or equivalent) may be used to generate reagent water.
6.1.3Reagent water may also be prepared by boiling water for 15 min. Subsequently, while maintaining the temperature at 90
6.2Sodium thiosulfate—(ACS) Granular.
6.3Trap Materials:
6.3.1Coconut charcoal—6/10 mesh sieved to 26 mesh, Barnabey Cheney, CA-580-26 lot # M-2649 or equivalent.
6.3.22,6-Diphenylene oxide polymer—Tenax, (60/80 mesh), chromatographic grade or equivalent.
6.3.3Methyl silicone packing—3% OV-1 on Chromosorb-W (60/80 mesh) or equivalent.
6.3.4Silica gel—35/60 mesh, Davison, grade-15 or equivalent.
6.4Methanol—Pesticide quality or equivalent.
6.5Stock standard solutions—Stock standard solutions may be prepared from pure standard materials or purchased as certified solutions. Prepare stock standard solutions in methanol using assayed liquids or gases as appropriate. Because of the toxicity of some of the organohalides, primary dilutions of these materials should be prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be used when the analyst handles high concentrations of such materials.
6.5.1Place about 9.8 mL of methanol into a 10-mL ground glass stoppered volumetric flask. Allow the flask to stand, unstoppered, for about 10 min or until all alcohol wetted surfaces have dried. Weigh the flask to the learest 0.1 mg.
6.5.2Add the assayed reference material:
6.5.2.1Liquid—Using a 100 μL syringe, immediately add two or more drops of assayed reference material to the flask, then reweigh. Be sure that the drops fall directly into the alcohol without contacting the neck of the flask.
6.5.2.2Gases—To prepare standards for any of the six halocarbons that boil below 30 ° C (bromomethane, chloroethane, chloro-methane, dichlorodifluoromethane, -trichlorofluoromethane, vinyl chloride), -fill a 5-mL valved gas-tight syringe with the reference standard to the 5.0-mL mark. Lower the needle to 5 mm above the methanol meniscus. Slowly introduce the reference standard above the surface of the liquid (the heavy gas will rapidly dissolve into the methanol).
6.5.3Reweigh, dilute to volume, stopper, then mix by inverting the flask several times. Calculate the concentration in μg/μL from the net gain in weight. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the malufacturer or by an independent source.
6.5.4Transfer the stock standard solution into a Teflon-sealed screw-cap bottle. Store, with minimal headspace, at −10 to −20 °C and protect from light.
6.5.5Prepare fresh standards weekly for the six gases and 2-chloroethylvinyl ether. All other standards must be replaced after one month, or sooner if comparison with check standards indicates a problem.
6.6Secondary dilution standards—Using stock standard solutions, prepare secondary dilution standards in methanol that contain the compounds of interest, either singly or mixed together. The secondary dilution standards should be prepared at concentrations such that the aqueous calibration standards prepared in Section 7.3.1 or 7.4.1 will bracket the working range of the analytical system. Secondary dilution standards should be stored with minimal headspace and should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.7Quality control check sample concentrate—See Section 8.2.1.
7.1Assemble a purge and trap system that meets the specifications in Section 5.2. Condition the trap overnight at 180 °C by backflushing with an inert gas flow of at least 20 mL/min. Condition the trap for 10 min once daily prior to use.
7.2Connect the purge and trap system to a gas chromatograph. The gas chromatograph must be operated using temperature and flow rate conditions equivalent to those given in Table 1. Calibrate the purge and trap-gas chromatographic system using either the external standard technique (Section 7.3) or the internal standard technique (Section 7.4).
7.3External standard calibration procedure:
7.3.1Prepare calibration standards at a miminum of three concentration levels for each parameter by carefully adding 20.0 μL of one or more secondary dilution standards to 100, 500, or 1000 μL of reagent water. A 25-μL syringe with a 0.006 in. ID needle should be used for this operation. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector. These aqueous standards can be stored up to 24 h, if held in sealed vials with zero headspace as described in Section 9.2. If not so stored, they must be discarded after 1 h.
7.3.2Analyze each calibration standard according to Section 10, and tabulate peak height or area responses versus the concentration in the standard. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of
7.4Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples. The compounds recommended for use as surrogate spikes in Section 8.7 have been used successfully as internal standards, because of their generally unique retention times.
7.4.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest as described in Section 7.3.1.
7.4.2Prepare a spiking solution containing each of the internal standards using the procedures described in Sections 6.5 and 6.6. It is recommended that the secondary dilution standard be prepared at a concentration of 15 μg/mL of each internal standard compound. The addition of 10 μL of this standard to 5.0 mL of sample or calibration standard would be equivalent to 30 μg/L.
7.4.3Analyze each calibration standard according to Section 10, adding 10 μL of internal standard spiking solution directly to the syringe (Section 10.4). Tabulate peak height or area responses against concentration for each compound and internal standard, and calculate response factors (RF) for each compound using Equation 1.
7.5The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of a QC check sample.
7.5.1Prepare the QC check sample as described in Section 8.2.2.
7.5.2Analyze the QC check sample according to Section 10.
7.5.3For each parameter, compare the response (Q) with the corresponding calibration acceptance criteria found in Table 2. If the responses for all parameters of interest fall within the designated ranges, analysis of actual samples can begin. If any individual Q falls outside the range, proceed according to Section 7.5.4.
The large number of parameters in Table 2 present a substantial probability that one or more will not meet the calibration acceptance criteria when all parameters are analyzed.
7.5.4Repeat the test only for those parameters that failed to meet the calibration acceptance criteria. If the response for a parameter does not fall within the range in this second test, a new calibration curve, calibration factor, or RF must be prepared for that parameter according to Section 7.3 or 7.4.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Section 10.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Each day, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system are under control.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 10 μg/mL in methanol. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Prepare a QC check sample to contain 20 μg/L of each parameter by adding 200 μL of QC check sample concentrate to 100 mL of reagent water.
8.2.3Analyze four 5-mL aliquots of the well-mixed QC check sample according to Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
The large number of parameters in Table 2 present a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.
8.2.6When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.
8.2.6.1Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.3.
8.2.6.2Beginning with Section 8.2.3, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compounds of interest beginning with Section 8.2.3.
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 20 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.2Analyze one 5-mL sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second 5-mL sample aliquot with 10 μL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory. If the entire list of parameters in Table 2 must be measured in the sample in Section 8.3, the probability that the analysis of a QC check standard will be required is high. In this case the QC check standard should be routinely analyzed with the spiked sample.
8.4.1Prepare the QC check standard by adding 10 μL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 5 mL of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as gas chromatography with a dissimilar column, specific element detector, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
8.7The analyst should monitor both the performance of the analytical system and the effectiveness of the method in deal-ing with each sample matrix by spiking -each sample, standard, and reagent -water blank with surrogate halocarbons. -A combination of bromochloromethane, -2-bromo-1-chloropropane, and 1,4-dichlorobu-tane is recommended to encompass the range of the temperature program used in this method. From stock standard solutions prepared as in Section 6.5, add a volume to give 750 μg of each surrogate to 45 mL of reagent water contained in a 50-mL volumetric flask, mix and dilute to volume for a concentration of 15 ng/μL. Add 10 μL of this surrogate spiking solution directly into the 5-mL syringe with every sample and reference standard analyzed. Prepare a fresh surrogate spiking solution on a weekly basis. If the internal standard calibration procedure is being used, the surrogate compounds may be added directly to the internal standard spiking solution (Section 7.4.2).
9.1All samples must be iced or refrigerated from the time of collection until analysis. If the sample contains free or combined chlorine, add sodium thiosulfate preservative (10 mg/40 mL is sufficient for up to 5 ppm Cl
9.2Grab samples must be collected in glass containers having a total volume of at least 25 mL. Fill the sample bottle just to overflowing in such a manner that no air bubbles pass through the sample as the bottle is being filled. Seal the bottle so that no air bubbles are entrapped in it. If preservative has been added, shake vigorously for 1 min. Maintain the hermetic seal on the sample bottle until time of analysis.
9.3All samples must be analyzed within 14 days of collection.
10.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are estimated retention times and MDL that can be achieved under these conditions. An example of the separations achieved by Column 1 is shown in Figure 5. Other packed columns,
10.2Calibrate the system daily as described in Section 7.
10.3Adjust the purge gas (nitrogen or helium) flow rate to 40 mL/min. Attach the trap inlet to the purging device, and set the purge and trap system to purge (Figure 3). Open the syringe valve located on the purging device sample introduction needle.
10.4Allow the sample to come to ambient temperature prior to introducing it to the syringe. Remove the plunger from a 5-mL syringe and attach a closed syringe valve. Open the sample bottle (or standard) and carefully pour the sample into the syringe barrel to just short of overflowing. Replace the syringe plunger and compress the sample. Open the syringe valve and vent any residual air while adjusting the sample volume to 5.0 mL. Since this process of taking an aliquot destroys the validity of the sample for future analysis, the analyst should fill a second syringe at this time to protect against possible loss of data. Add 10.0 μL of the surrogate spiking solution (Section 8.7) and 10.0 μL of the internal standard spiking solution (Section 7.4.2), if applicable, through the valve bore, then close the valve.
10.5Attach the syringe-syringe valve assembly to the syringe valve on the purging device. Open the syringe valves and inject the sample into the purging chamber.
10.6Close both valves and purge the sample for 11.0±0.1 min at ambient temperature.
10.7After the 11-min purge time, attach the trap to the chromatograph, adjust the purge and trap system to the desorb mode (Figure 4), and begin to temperature program the gas chromatograph. Introduce the trapped materials to the GC column by rapidly heating the trap to 180 °C while backflushing the trap with an inert gas between 20 and 60 mL/min for 4 min. If rapid heating of the trap cannot be achieved, the GC column must be used as a secondary trap by cooling it to -30 °C (subambient temperature, if poor peak geometry or random retention time problems persist) instead of the initial program temperature of 45 °C
10.8While the trap is being desorbed into the gas chromatograph, empty the purging chamber using the sample introduction syringe. Wash the chamber with two 5-mL flushes of reagent water.
10.9After desorbing the sample for 4 min, recondition the trap by returning the purge and trap system to the purge mode. Wait 15 s then close the syringe valve on the purging device to begin gas flow through the trap. The trap temperature should be maintained at -180 °C After approximately 7 min, turn off the trap heater and open the syringe valve to stop the gas flow through the trap. When the trap is cool, the next sample can be analyzed.
10.10Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
10.11If the response for a peak exceeds the working range of the system, prepare a dilution of the sample with reagent water from the aliquot in the second syringe and reanalyze.
11.1Determine the concentration of individual compounds in the sample.
11.1.1If the external standard calibration procedure is used, calculate the concentration of the parameter being measured from the peak response using the calibration curve or calibration factor determined in Section 7.3.2.
11.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.4.3 and Equation 2.
11.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
12.1 The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and re-ported with 99% confidence that the value is -above zero.
12.2This method is recommended for use in the concentration range from the MDL to
12.3This method was tested by 20 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations over the range 8.0 to 500 μg/L.
1. 40 CFR part 136, appendix B.
2. Bellar, T.A., and Lichtenberg, J.J. “Determining Volatile Organics at Microgram-per-Litre-Levels by Gas Chromatography,”
3. Bellar, T.A., and Lichtenberg, J.J. “Semi-Automated Headspace Analysis of Drinking Waters and Industrial Waters for Purgeable Volatile Organic Compounds,” Proceedings from Symposium on Measurement of Organic Pollutants in Water and Wastewater, American Society for Testing and Materials, STP 686, C.E. Van Hall, editor, 1978.
4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA 600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
9. “EPA Method Study 24, Method 601—Purgeable Halocarbons by the Purge and Trap Method,” EPA 600/4-84-064, National Technical Information Service, PB84-212448, Springfield, Virginia 22161, July 1984.
10. “Method Validation Data for EPA Method 601,” Memorandum from B. Potter, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, November 10, 1983.
11. Bellar, T. A., Unpublished data, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, 1981.
1.1This method covers the determination of various purgeable aromatics. The following parameters may be determined by this method:
1.2This is a purge and trap gas chromatographic (GC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compounds above, compound identifications should be supported by at least one additional qualitative technique. This method describes analytical conditions for a second gas chromatographic column that can be used to confirm measurements made with the primary column. Method 624 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for all of the parameters listed above.
1.3The method detection limit (MDL, defined in Section 12.1)
1.4Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.5This method is restricted to use by or under the supervision of analysts experienced in the operation of a purge and trap system and a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1An inert gas is bubbled through a 5-mL water sample contained in a specially-designed purging chamber at ambient temperature. The aromatics are efficiently transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbent trap where the aromatics are trapped. After purging is completed, the trap is heated and backflushed with the inert gas to desorb the aromatics onto a gas chromatographic column. The gas chromatograph is temperature programmed to separate the aromatics which are then detected with a photoionization detector.
2.2The method provides an optional gas chromatographic column that may be helpful in resolving the compounds of interest from interferences that may occur.
3.1Impurities in the purge gas and organic compounds outgassing from the plumbing ahead of the trap account for the majority of contamination problems. The analytical system must be demonstrated to be free from contamination under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3. The use of non-Teflon plastic tubing, non-Teflon thread sealants, or flow controllers with rubber components in the purge and trap system should be avoided.
3.2Samples can be contaminated by diffusion of volatile organics through the septum seal into the sample during shipment and storage. A field reagent blank prepared from reagent water and carried through the sampling and handling protocol can serve as a check on such contamination.
3.3Contamination by carry-over can occur whenever high level and low level samples are sequentially analyzed. To reduce carry-over, the purging device and sample syringe must be rinsed with reagent water between sample analyses. Whenever an unusually concentrated sample is encountered, it should be followed by an analysis of reagent water to check for cross contamination. For samples containing large amounts of water-soluble materials, suspended solids, high boiling compounds or high aromatic levels, it may be necessary to wash the purging device with a detergent solution, rinse it with distilled water, and then dry it in an oven at 105 °C between analyses. The trap and other parts of the system are also subject to contamination; therefore, frequent bakeout and purging of the entire system may be required.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety
4.2The following parameters covered by this method have been tentatively classified as known or suspected, human or mam-malian carcinogens: benzene and 1,4--dichlorobenzene. Primary standards of -these toxic compounds should be prepared -in a hood. A NIOSH/MESA approved -toxic gas respirator should be worn -when the analyst handles high con-centrations of these toxic compounds.
5.1Sampling equipment, for discrete sampling.
5.1.1Vial]25-mL capacity or larger, equipped with a screw cap with a hole in the center (Pierce #13075 or equivalent). Detergent wash, rinse with tap and distilled water, and dry at 105 °C before use.
5.1.2Septum—Teflon-faced silicone (Pierce -#12722 or equivalent). Deter-gent wash, rinse with tap and distilled -water, and dry at 105 °C for 1 h before use.
5.2Purge and trap system—The purge and trap system consists of three separate pieces of equipment: A purging device, trap, and desorber. Several complete systems are now commercially available.
5.2.1The purging device must be designed to accept 5-mL samples with a water column at least 3 cm deep. The gaseous head space between the water column and the trap must have a total volume of less than 15 mL. The purge gas must pass through the water column as finely divided bubbles with a diameter of less than 3 mm at the origin. The purge gas must be introduced no more than 5 mm from the base of the water column. The purging device illustrated in Figure 1 meets these design criteria.
5.2.2The trap must be at least 25 cm long and have an inside diameter of at least 0.105 in.
5.2.2.1The trap is packed with 1 cm of methyl silicone coated packing (Section 6.4.2) and 23 cm of 2,6-diphenylene oxide polymer (Section 6.4.1) as shown in Figure 2. This trap was used to develop the method performance statements in Section 12.
5.2.2.2Alternatively, either of the two traps described in Method 601 may be used, although water vapor will preclude the measurement of low concentrations of benzene.
5.2.3The desorber must be capable of rapidly heating the trap to 180 °C. The polymer section of the trap should not be heated higher than 180 °C and the remaining sections should not exceed 200 °C. The desorber illustrated in Figure 2 meets these design criteria.
5.2.4The purge and trap system may be assembled as a separate unit or be coupled to a gas chromatograph as illustrated in Figures 3, 4, and 5.
5.3Gas chromatograph—An analytical system complete with a temperature programmable gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.3.1Column 1—6 ft long × 0.082 in. ID stainless steel or glass, packed with 5% SP-1200 and 1.75% Bentone-34 on Supelcoport (100/120 mesh) or equivalent. This column was used to develop the method performance statements in Section 12. Guidelines for the use of alternate column packings are provided in Section 10.1.
5.3.2Column 2—8 ft long × 0.1 in ID stainless steel or glass, packed with 5% 1,2,3-Tris(2-cyanoethoxy)propane on Chromosorb W-AW (60/80 mesh) or equivalent.
5.3.3Detector—Photoionization detector (h-Nu Systems, Inc. Model PI-51-02 or equivalent). This type of detector has been proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1), and was used to develop the method performance statements in Section 12. Guidelines for the use of alternate detectors are provided in Section 10.1.
5.4Syringes—5-mL glass hypodermic with Luerlok tip (two each), if applicable to the purging device.
5.5Micro syringes—25-μL, 0.006 in. ID needle.
5.6Syringe valve—2-way, with Luer ends (three each).
5.7Bottle—15-mL, screw-cap, with Teflon cap liner.
5.8Balance—Analytical, capable of accurately weighing 0.0001 g.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.1.1Reagent water can be generated by passing tap water through a carbon filter bed containing about 1 lb of activated carbon (Filtrasorb-300, Calgon Corp., or equivalent).
6.1.2A water purification system (Millipore Super-Q or equivalent) may be used to generate reagent water.
6.1.3Reagent water may also be prepared by boiling water for 15 min. Subsequently, while maintaining the temperature at 90 °C, bubble a contaminant-free inert gas through the water for 1 h. While still hot, transfer the water to a narrow mouth screw-cap bottle and seal with a Teflon-lined septum and cap.
6.2Sodium thiosulfate—(ACS) Granular.
6.3Hydrochloric acid (1+1)—Add 50 mL of concentrated HCl (ACS) to 50 mL of reagent water.
6.4Trap Materials:
6.4.12,6-Diphenylene oxide polymer—Tenax, -(60/80 mesh), chromatographic grade or equiv-alent.
6.4.2Methyl silicone packing—3% OV-1 on Chromosorb-W (60/80 mesh) or equivalent.
6.5Methanol—Pesticide quality or equivalent.
6.6Stock standard solutions—Stock stand-ard solutions may be prepared from pure -standard materials or purchased as certified -solutions. Prepare stock standard solutions in -methanol using assayed liquids. Because -of the toxicity of benzene and 1,4-dichloro-benzene, primary dilutions of these mate-rials should be prepared in a hood. A -NIOSH/MESA approved toxic gas respirator should be used when the analyst handles high concentrations of such materials.
6.6.1Place about 9.8 mL of methanol into a 10-mL ground glass stoppered volumetric flask. Allow the flask to stand, unstoppered, for about 10 min or until all alcohol wetted surfaces have dried. Weigh the flask to the nearest 0.1 mg.
6.6.2Using a 100-μL syringe, immediately add two or more drops of assayed reference material to the flask, then reweigh. Be sure that the drops fall directly into the alcohol without contacting the neck of the flask.
6.6.3Reweigh, dilute to volume, stopper, then mix by inverting the flask several times. Calculate the concentration in μg/μL from the net gain in weight. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.6.4Transfer the stock standard solution into a Teflon-sealed screw-cap bottle. Store at 4 °C and protect from light.
6.6.5All standards must be replaced after one month, or sooner if comparison with check standards indicates a problem.
6.7Secondary dilution standards—Using stock standard solutions, prepare secondary dilution standards in methanol that contain the compounds of interest, either singly or mixed together. The secondary dilution standards should be prepared at concentrations such that the aqueous calibration standards prepared in Section 7.3.1 or 7.4.1 will bracket the working range of the analytical system. Secondary solution standards must be stored with zero headspace and should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.8Quality control check sample concentrate—See Section 8.2.1.
7.1Assemble a purge and trap system that meets the specifications in Section 5.2. Condition the trap overnight at 180 °C by backflushing with an inert gas flow of at least 20 mL/min. Condition the trap for 10 min once daily prior to use.
7.2Connect the purge and trap system to a gas chromatograph. The gas chromatograph must be operated using temperature and flow rate conditions equivalent to those given in Table 1. Calibrate the purge and trap-gas chromatographic system using either the external standard technique (Section 7.3) or the internal standard technique (Section 7.4).
7.3External standard calibration procedure:
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter by carefully adding 20.0 μL of one or more secondary dilution standards to 100, 500, or 1000 mL of reagent water. A 25-μL syringe with a 0.006 in. ID needle should be used for this operation. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector. These aqueous standards must be prepared fresh daily.
7.3.2Analyze each calibration standard according to Section 10, and tabulate peak height or area responses versus the concentration in the standard. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to concentration (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.4Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples. The compound, α,α,α,-trifluorotoluene, recommended as a surrogate spiking compound in Section 8.7 has been used successfully as an internal standard.
7.4.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest as described in Section 7.3.1.
7.4.2Prepare a spiking solution containing each of the internal standards using the procedures described in Sections 6.6 and 6.7. It is recommended that the secondary dilution standard be prepared at a concentration of 15 μg/mL of each internal standard compound. The addition of 10 μl of this
7.4.3Analyze each calibration standard according to Section 10, adding 10 μL of internal standard spiking solution directly to the syringe (Section 10.4). Tabulate peak height or area responses against concentration for each compound and internal standard, and calculate response factors (RF) for each compound using Equation 1.
7.5The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of a QC check sample.
7.5.1Prepare the QC check sample as described in Section 8.2.2.
7.5.2Analyze the QC check sample according to Section 10.
7.5.3For each parameter, compare the response (Q) with the corresponding calibration acceptance criteria found in Table 2. If the responses for all parameters of interest fall within the designated ranges, analysis of actual samples can begin. If any individual Q falls outside the range, a new calibration curve, calibration factor, or RF must be prepared for that parameter according to Section 7.3 or 7.4.
8.1 Each laboratory that uses this method is required to operate a formal quality control program. The mimimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Section 10.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Each day, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system are under control.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 10 μg/mL in methanol. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Prepare a QC check sample to contain 20 μg/L of each parameter by adding 200 μL of QC check sample concentrate to 100 mL of reagant water.
8.2.3Analyze four 5-mL aliquots of the well-mixed QC check sample according to Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
The large number of parameters in Table 2 present a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.
8.2.6When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.
8.2.6.1Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.3.
8.2.6.2Beginning with Section 8.2.3, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compounds of interest beginning with Section 8.2.3.
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 20 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.2Analyze one 5-mL sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second 5-mL sample aliquot with 10 μL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory.
8.4.1Prepare the QC check standard by adding 10 μL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 5 mL of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as gas chromatography with a dissimilar column, specific element detector, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
8.7The analyst should monitor both the performance of the analytical system and the effectiveness of the method in dealing with each sample matrix by spiking each sample, standard, and reagent water blank with surrogate compounds (e.g.
9.1The samples must be iced or refrigerated from the time of collection until analysis. If the sample contains free or combined chlorine, add sodium thiosulfate preservative (10 mg/40 mL is sufficient for up to 5 ppm Cl
9.2Collect about 500 mL of sample in a clean container. Adjust the pH of the sample to about 2 by adding 1+1 HCl while stirring. Fill the sample bottle in such a manner that no air bubbles pass through the sample as the bottle is being filled. Seal the bottle so that no air bubbles are entrapped in it. Maintain the hermetic seal on the sample bottle until time of analysis.
9.3All samples must be analyzed within 14 days of collection.
10.1Table 1 summarizes the recommended operating conditions for the gas chrom-atograph. Included in this table -are estimated retention times and MDL -that can be achieved under these conditions. An ex-ample of the separations achieved by Column 1 is shown in Figure 6. Other packed columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met.
10.2Calibrate the system daily as described in Section 7.
10.3Adjust the purge gas (nitrogen or helium) flow rate to 40 mL/min. Attach the trap inlet to the purging device, and set the purge and trap system to purge (Figure 3). Open the syringe valve located on the purging device sample introduction needle.
10.4Allow the sample to come to ambient temperature prior to introducing it to the syringe. Remove the plunger from a 5-mL syringe and attach a closed syringe valve. Open the sample bottle (or standard) and carefully pour the sample into the syringe barrel to just short of overflowing. Replace the syringe plunger and compress the sample. Open the syringe valve and vent any residual air while adjusting the sample volume to 5.0 mL. Since this process of taking an aliquot destroys the validity of the sample for future analysis, the analyst should fill a second syringe at this time to protect against possible loss of data. Add 10.0 μL of the surrogate spiking solution (Section 8.7) and 10.0 μL of the internal standard spiking solution (Section 7.4.2), if applicable, through the valve bore, then close the valve.
10.5Attach the syringe-syringe valve assembly to the syringe valve on the purging device. Open the syringe valves and inject the sample into the purging chamber.
10.6Close both valves and purge the sample for 12.0±0.1 min at ambient temperature.
10.7After the 12-min purge time, disconnect the purging device from the trap. Dry the trap by maintaining a flow of 40 mL/min of dry purge gas through it for 6 min (Figure 4). If the purging device has no provision for bypassing the purger for this step, a dry purger should be inserted into the device to minimize moisture in the gas. Attach the trap to the chromatograph, adjust the purge and trap system to the desorb mode (Figure 5), and begin to temperature program the gas chromatograph. Introduce the trapped materials to the GC column by rapidly heating the trap to 180 °C while backflushing the trap with an inert gas between 20 and 60 mL/min for 4 min. If rapid heating of the trap cannot be achieved, the GC column must be used as
10.8While the trap is being desorbed into the gas chromatograph column, empty the purging chamber using the sample introduction syringe. Wash the chamber with two 5-mL flushes of reagent water.
10.9After desorbing the sample for 4 min, recondition the trap by returning the purge and trap system to the purge mode. Wait 15 s, then close the syringe valve on the purging device to begin gas flow through the trap. The trap temperature should be maintained at 180 °C. After approximately 7 min, turn off the trap heater and open the syringe valve to stop the gas flow through the trap. When the trap is cool, the next sample can be analyzed.
10.10Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. -The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
10.11If the response for a peak exceeds the working range of the system, prepare a dilution of the sample with reagent water from the aliquot in the second syringe and reanalyze.
11.1Determine the concentration of individual compounds in the sample.
11.1.1If the external standard calibration procedure is used, calculate the concentration of the parameter being measured from the peak response using the calibration curve or calibration factor determined in Section 7.3.2.
11.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.4.3 and Equation 2.
Equation 2
11.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
12.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
12.2This method has been demonstrated to be applicable for the concentration range from the MDL to 100 × MDL.
12.3This method was tested by 20 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations over the range 2.1 to 550 μg/L.
1. 40 CFR part 136, appendix B.
2. Lichtenberg, J.J. “Determining Volatile Organics at Microgram-per-Litre-Levels by Gas Chromatography,” Journal American Water Works Association,
3. Bellar, T.A., and Lichtenberg, J.J. “Semi-Automated Headspace Analysis of Drinking Waters and Industrial Waters for Purgeable Volatile Organic Compounds,” Proceedings of Symposium on Measurement of Organic Pollutants in Water and Wastewater. American Society for Testing and Materials, STP 686, C.E. Van Hall, editor, 1978.
4. “Carcinogens—Working with Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health. Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8.“Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Office of Research and Development, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268. March 1979.
9. “EPA Method Study 25, Method 602, Purgeable Aromatics,” EPA 600/4-84-042, National Technical Information Service, PB84-196682, Springfield, Virginia 22161, May 1984.
1.1This method covers the determination of acrolein and acrylonitrile. The following parameters may be determined by this method:
1.2This is a purge and trap gas chromatographic (GC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for either or both of the compounds above, compound identifications should be supported by at least one additional qualitative technique. This method describes analytical conditions for a second gas chromatographic column that can be used to confirm measurements made with the primary column. Method 624 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for the parameters listed above, if used with the purge and trap conditions described in this method.
1.3The method detection limit (MDL, defined in Section 12.1)
1.4Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.5This method is restricted to use by or under the supervision of analysts experienced in the operation of a purge and trap system and a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1An inert gas is bubbled through a 5-mL water sample contained in a heated purging chamber. Acrolein and acrylonitrile are transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbent trap where the analytes are trapped. After the purge is completed, the trap is heated and backflushed with the inert gas to desorb the compound onto a gas chromatographic column. The gas chromatograph is temperature programmed to separate the analytes which are then detected with a flame ionization detector.
2.2The method provides an optional gas chromatographic column that may be helpful in resolving the compounds of interest from the interferences that may occur.
3.1Impurities in the purge gas and organic compound outgassing from the plumbing of the trap account for the majority of contamination problems. The analytical system must be demonstrated to be free from contamination under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3. The use of non-Teflon plastic tubing, non-Teflon thread sealants, or flow controllers with rubber components in the purge and trap system should be avoided.
3.2Samples can be contaminated by diffusion of volatile organics through the septum seal into the sample during shipment and storage. A field reagent blank prepared from reagent water and carried through the sampling and handling protocol can serve as a check on such contamination.
3.3Contamination by carry-over can occur whenever high level and low level samples are sequentially analyzed. To reduce carry-over, the purging device and sample syringe must be rinsed between samples with reagent water. Whenever an unusually concentrated sample is encountered, it should be followed by an analysis of reagent water to check for cross contamination. For samples containing large amounts of water-soluble materials, suspended solids, high boiling compounds or high analyte levels, it may be necessary to wash the purging device with a detergent solution, rinse it with distilled water, and then dry it in an oven at 105 °C between analyses. The trap and other parts of the system are also subject to contamination, therefore, frequent bakeout and purging of the entire system may be required.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this view point, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
5.1Sampling equipment, for discrete sampling.
5.1.1Vial—25-mL capacity or larger, equipped with a screw cap with a hole in the center (Pierce #13075 or equivalent). Detergent wash, rinse with tap and distilled water, and dry at 105 °C before use.
5.1.2Septum—Teflon-faced silicone (Pierce #12722 or equivalent). Detergent wash, rinse with tap and distilled water and dry at 105 °C for 1 h before use.
5.2Purge and trap system—The purge and trap system consists of three separate pieces of equipment: a purging device, trap, and desorber. Several complete systems are now commercially available.
5.2.1The purging device must be designed to accept 5-mL, samples with a water column at least 3 cm deep. The gaseous head space between the water column and the trap must have a total volume of less than 15 mL. The purge gas must pass through the water column as finely divided bubbles with a diameter of less than 3 mm at the origin. The purge gas must be introduced no more than 5 mm from the base of the water column. The purging device must be capable of being heated to 85 °C within 3.0 min after transfer of the sample to the purging device and being held at 85 ±2 °C during the purge cycle. The entire water column in the purging device must be heated. Design of this modification to the standard purging device is optional, however, use of a water bath is suggested.
5.2.1.1Heating mantle—To be used to heat water bath.
5.2.1.2Temperature controller—Equipped with thermocouple/sensor to accurately control water bath temperature to ±2 °C. The purging device illustrated in Figure 1 meets these design criteria.
5.2.2The trap must be at least 25 cm long and have an inside diameter of at least 0.105 in. The trap must be packed to contain 1.0 cm of methyl silicone coated packing (Section 6.5.2) and 23 cm of 2,6-diphenylene oxide polymer (Section 6.5.1). The minimum specifications for the trap are illustrated in Figure 2.
5.2.3The desorber must be capable of rapidly heating the trap to 180 °C, The desorber illustrated in Figure 2 meets these design criteria.
5.2.4The purge and trap system may be assembled as a separate unit as illustrated in Figure 3 or be coupled to a gas chromatograph.
5.3pH paper—Narrow pH range, about 3.5 to 5.5 (Fisher Scientific Short Range Alkacid No. 2, #14-837-2 or equivalent).
5.4Gas chromatograph—An analytical system complete with a temperature programmable gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.4.1Column 1—10 ft long × 2 mm ID glass or stainless steel, packed with Porapak-QS (80/100 mesh) or equivalent. This column was used to develop the method performance statements in Section 12. Guidelines for the use of alternate column packings are provided in Section 10.1.
5.4.2Column 2—6 ft long × 0.1 in. ID glass or stainless steel, packed with Chromosorb 101 (60/80 mesh) or equivalent.
5.4.3Detector—Flame ionization detector. This type of detector has proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1), and was used to develop the method performance statements in Section 12. Guidelines for the use of alternate detectors are provided in Section 10.1.
5.5Syringes—5-mL, glass hypodermic with Luerlok tip (two each).
5.6Micro syringes—25-μL, 0.006 in. ID needle.
5.7Syringe valve—2-way, with Luer ends (three each).
5.8Bottle—15-mL, screw-cap, with Teflon cap liner.
5.9Balance—Analytical, capable of accurately weighing 0.0001 g.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.1.1Reagent water can be generated by passing tap water through a carbon filter bed containing about 1 lb of activated carbon (Filtrasorb-300, Calgon Corp., or equivalent).
6.1.2A water purification system (Millipore Super-Q or equivalent) may be used to generate reagent water.
6.1.3Regent water may also be prepared by boiling water for 15 min. Subsequently, while maintaining the temperature at 90 °C, bubble a contaminant-free inert gas through the water for 1 h. While still hot, transfer the water to a narrow mouth screw-cap bottle and seal with a Teflon-lined septum and cap.
6.2Sodium thiosulfate—(ACS) Granular.
6.3Sodium hydroxide solution (10 N)—Dissolve 40 g of NaOH (ACS) in reagent water and dilute to 100 mL.
6.4Hydrochloric acid (1+1)—Slowly, add 50 mL of concentrated HCl (ACS) to 50 mL of reagent water.
6.5Trap Materials:
6.5.12,6-Diphenylene oxide polymer—Tenax (60/80 mesh), chromatographic grade or equivalent.
6.5.2Methyl silicone packing—3% OV-1 on Chromosorb-W (60/80 mesh) or equivalent.
6.6Stock standard solutions—Stock standard solutions may be prepared from pure standard materials or purchased as certified solutions. Prepare stock standard solutions in reagent water using assayed liquids. Since acrolein and acrylonitrile are lachrymators, primary dilutions of these compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be used when the analyst handles high concentrations of such materials.
6.6.1Place about 9.8 mL of reagent water into a 10-mL ground glass stoppered volumetric flask. For acrolein standards the reagent water must be adjusted to pH 4 to 5. Weight the flask to the nearest 0.1 mg.
6.6.2Using a 100-μL syringe, immediately add two or more drops of assayed reference material to the flask, then reweigh. Be sure that the drops fall directly into the water without contacting the neck of the flask.
6.6.3Reweigh, dilute to volume, stopper, then mix by inverting the flask several times. Calculate the concentration in μg/μL from the net gain in weight. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock staldard. Optionally, stock standard solutions may be prepared using the pure standard material by volumetrically measuring the appropriate amounts and determining the weight of the material using the density of the material. Commercially prepared stock standards may be used at any concentration if they are certified by the manufactaurer or by an independent source.
6.6.4Transfer the stock standard solution into a Teflon-sealed screw-cap bottle. Store at 4 °C and protect from light.
6.6.5Prepare fresh standards daily.
6.7Secondary dilution standards—Using stock standard solutions, prepare secondary dilution standards in reagent water that contain the compounds of interest, either singly or mixed together. The secondary dilution standards should be prepared at concentrations such that the aqueous calibration standards prepared in Section 7.3.1 or 7.4.1 will bracket the working range of the analytical system. Secondary dilution standards should be prepared daily and stored at 4 °C.
6.8Quality control check sample concentrate—See Section 8.2.1.
7.1Assemble a purge and trap system that meets the specifications in Section 5.2. Condition the trap overnight at 180 °C by backflushing with an inert gas flow of at least 20 mL/min. Condition the trap for 10 min once daily prior to use.
7.2Connect the purge and trap system to a gas chromatograph. The gas chromatograph must be operated using temperature and flow rate conditions equivalent to those given in Table 1. Calibrate the purge and trap-gas chromatographic system using either the external standard technique (Section 7.3) or the internal standard technique (Section 7.4).
7.3External standard calibration procedure:
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter by carefully adding 20.0 μL of one or more secondary dilution standards to 100, 500, or 1000 mL of reagent water. A 25-μL syringe with a 0.006 in. ID needle should be used for this operation. One of the external standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector. These standards must be prepared fresh daily.
7.3.2Analyze each calibration standard according to Section 10, and tabulate peak height or area responses versus the concentration of the standard. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to concentration (calibration factor) is a constant over the working range (< 10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.4Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples.
7.4.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest as described in Section 7.3.1.
7.4.2Prepare a spiking solution containing each of the internal standards using the procedures described in Sections 6.6 and 6.7. It is recommended that the secondary dilution standard be prepared at a concentration of 15 μg/mL of each internal standard compound. The addition of 10 μL of this standard to 5.0 mL of sample or calibration standard would be equivalent to 30 μg/L.
7.4.3Analyze each calibration standard according to Section 10, adding 10 μL of internal standard spiking solution directly to the syringe (Section 10.4). Tabulate peak height or area responses against concentration for each compound and internal standard, and calculate response factors (RF) for each compound using Equation 1.
7.5The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of a QC check sample.
7.5.1Prepare the QC check sample as described in Section 8.2.2.
7.5.2Analyze the QC check sample according to Section 10.
7.5.3For each parameter, compare the response (Q) with the corresponding calibration acceptance criteria found in Table 2. If the responses for all parameters of interest fall within the designated ranges, analysis of actual samples can begin. If any individual Q falls outside the range, a new calibration curve, calibration factor, or RF must be prepared for that parameter according to Section 7.3 or 7.4.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Section 10.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Each day, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system are under control.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 25 μg/mL in reagent water. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Prepare a QC check sample to contain 50 μg/L of each parameter by adding 200 μL of QC check sample concentrate to 100 mL of reagent water.
8.2.3Analyze four 5-mL aliquots of the well-mixed QC check sample according to Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 50
8.3.2Analyze one 5-mL sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second 5-mL sample aliquot with 10
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 3. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory.
8.4.1Prepare the QC check standard by adding 10
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as gas chromatography with a dissimilar column or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1All samples must be iced or refrigerated from the time of collection until analysis. If the sample contains free or combined chlorine, add sodium thiosulfate preservative (10 mg/40 mL is sufficient for up to 5 ppm Cl
9.2If acrolein is to be analyzed, collect about 500 mL of sample in a clean glass container. Adjust the pH of the sample to 4 to 5 using acid or base, measuring with narrow
9.3Grab samples must be collected in glass containers having a total volume of at least 25 mL. Fill the sample bottle just to overflowing in such a manner that no air bubbles pass through the sample as the bottle is being filled. Seal the bottle so that no air bubbles are entrapped in it. If preservative has been added, shake vigorously for 1 min. Maintain the hermetic seal on the sample bottle until time of analysis.
9.4All samples must be analyzed within 14 days of collection.
10.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are estimated retention times and MDL that can be achieved under these conditions. An example of the separations achieved by Column 1 is shown in Figure 5. Other packed columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met.
10.2Calibrate the system daily as described in Section 7.
10.3Adjust the purge gas (nitrogen or helium) flow rate to 20 mL-min. Attach the trap inlet to the purging device, and set the purge and trap system to purge (Figure 3). Open the syringe valve located on the purging device sample introduction needle.
10.4Remove the plunger from a 5-mL syringe and attach a closed syringe valve. Open the sample bottle (or standard) and carefully pour the sample into the syringe barrel to just short of overflowing. Replace the syringe plunger and compress the sample. Open the syringe valve and vent any residual air while adjusting the sample volume to 5.0 mL. Since this process of taking an aliquot destroys the validity of the sample for future analysis, the analyst should fill a second syringe at this time to protect against possible loss of data. Add 10.0 μL of the internal standard spiking solution (Section 7.4.2), if applicable, through the valve bore then close the valve.
10.5Attach the syringe-syringe valve assembly to the syringe valve on the purging device. Open the syringe valves and inject the sample into the purging chamber.
10.6Close both valves and purge the sample for 15.0 ± 0.1 min while heating at 85 ± 2 °C.
10.7After the 15-min purge time, attach the trap to the chromatograph, adjust the purge and trap system to the desorb mode (Figure 4), and begin to temperature program the gas chromatograph. Introduce the trapped materials to the GC column by rapidly heating the trap to 180 °C while backflushing the trap with an inert gas between 20 and 60 mL/min for 1.5 min.
10.8While the trap is being desorbed into the gas chromatograph, empty the purging chamber using the sample introduction syringe. Wash the chamber with two 5-mL flushes of reagent water.
10.9After desorbing the sample for 1.5 min, recondition the trap by returning the purge and trap system to the purge mode. Wait 15 s then close the syringe valve on the purging device to begin gas flow through the trap. The trap temperature should be maintained at 210 °C. After approximately 7 min, turn off the trap heater and open the syringe valve to stop the gas flow through the trap. When the trap is cool, the next sample can be analyzed.
10.10Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
11.1Determine the concentration of individual compounds in the sample.
11.1.1If the external standard calibration procedure is used, calculate the concentration of the parameter being measured from the peak response using the calibration curve or calibration factor determined in Section 7.3.2.
11.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.4.3 and Equation 2.
11.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
12.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above
12.2This method is recommended for the concentration range from the MDL to 1,000×MDL. Direct aqueous injection techniques should be used to measure concentration levels above 1,000×MDL.
12.3In a single laboratory (Battelle-Columbus), the average recoveries and standard deviations presented in Table 2 were obtained.
1. 40 CFR part 136, appendix B.
2. Bellar, T.A., and Lichtenberg, J.J. “Determining Volatile Organics at Microgram-per-Litre-Levels by Gas Chromatography,”
3. “Evaluate Test Procedures for Acrolein and Acrylonitrile,” Special letter report for EPA Project 4719-A, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, 27 June 1979.
4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
9. “Evaluation of Method 603 (Modified),” EPA-600/4-84-ABC, National Technical Information Service, PB84-, Springfield, Virginia 22161, Nov. 1984.
1.1 This method covers the determination of phenol and certain substituted phenols. The following parameters may be determined by this method:
1.2This is a flame ionization detector gas chromatographic (FIDGC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compounds above, compound identifications should be supported by at least one additional qualitative technique. This method describes analytical conditions for derivatization, cleanup, and electron capture detector gas chromatography (ECDGC) that can be used to confirm measurements made by FIDGC. Method 625 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for all of the parameters listed above, using the extract produced by this method.
1.3 The method detection limit (MDL, defined in Section 14.1)
1.4Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.5This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is acidified and extracted with methylene chloride using a separatory funnel. The methylene chloride extract is dried and exchanged to 2-propanol during concentration to a volume of 10 mL or less. The extract is separated by gas chromatography and the phenols are then measured with an FID.
2.2A preliminary sample wash under basic conditions can be employed for samples having high general organic and organic base interferences.
2.3The method also provides for a derivatization and column chromatography cleanup procedure to aid in the elimination of interferences.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in gas chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are coextracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. The derivatization cleanup procedure in Section 12 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Tables 1 and 2.
3.3The basic sample wash (Section 10.2) may cause significantly reduced recovery of phenol and 2,4-dimethylphenol. The analyst must recognize that results obtained under these conditions are minimum concentrations.
4.1The toxicity or carcinogenicity of each reagent used in this mothod has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
4.2Special care should be taken in handling pentafluorobenzyl bromide, which is a lachrymator, and 18-crown-6-ether, which is highly toxic.
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnel—2-L, with Teflon stopcock.
5.2.2Drying column—Chromatographic column, 400 mm long × 19 mm ID, with coarse frit filter disc.
5.2.3Chromatographic column—100 mm long × 10 mm ID, with Teflon stopcock.
5.2.4Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.5Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.6Snyder column, Kuderna-Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.7Snyder column, Kuderna-Danish—Two-ball micro (Kontes K-569001-0219 or equivalent).
5.2.8Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.9Reaction flask—15 to 25-mL round bottom flask, with standard tapered joint, fitted with a water-cooled condenser and U-shaped drying tube containing granular calcium chloride.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2°C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighting 0.0001 g.
5.6Gas chromatograph—An analytical system complete with a temperature programmable gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.6.1Column for underivatized phenols—1.8 m long × 2 mm ID glass, packed with 1% SP-1240DA on Supelcoport (80/100 mesh) or equivalent. This column was used to develop the method performance statements in Section 14. Guidelines for the use of alternate column packings are provided in Section 11.1.
5.6.2Column for derivatized phenols—1.8 m long × 2 mm ID glass, packed with 5% OV-17 on Chromosorb W-AW-DMCS (80/100 mesh) or equivalent. This column has proven effective in the analysis of wastewaters for derivatization products of the parameters listed in the scope (Section 1.1), and was used to develop the method performance statements in Section 14. Guidelines for the use of alternate column packings are provided in Section 11.1.
5.6.3Detectors—Flame ionization and electron capture detectors. The FID is used when determining the parent phenols. The ECD is used when determining the derivatized phenols. Guidelines for the use of alternatve detectors are provided in Section 11.1.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Sodium hydroxide solution (10 N)—Dissolve 40 g of NaOH (ACS) in reagent water and dilute to 100 mL.
6.3Sodium hydroxide solution (1 N)—Dissolve 4 g of NaOH (ACS) in reagent water and dilute to 100 mL.
6.4Sodium sulfate—(ACS) Granular, anhydrous. Purify by heating at 400°C for 4 h in a shallow tray.
6.5Sodium thiosulfate—(ACS) Granular.
6.6Sulfuric acid (1+1)—Slowly, add 50 mL of H
6.7Sulfuric acid (1 N)—Slowly, add 58 mL of H
6.8Potassium carbonate—(ACS) Powdered.
6.9Pentafluorobenzyl bromide (α-Bromopentafluorotoluene)—97% minimum purity.
This chemical is a lachrymator. (See Section 4.2.)
6.1018-crown-6-ether (1,4,7,10,13,16-Hexaoxacyclooctadecane)—98% minimum purity.
This chemical is highly toxic.
6.11Derivatization reagent—Add 1 mL of pentafluorobenzyl bromide and 1 g of 18-crown-6-ether to a 50-mL volumetric flask and dilute to volume with 2-propanol. Prepare fresh weekly. This operation should be carried out in a hood. Store at 4 °C and protect from light.
6.12Acetone, hexane, methanol, methylene chloride, 2-propanol, toluene—Pesticide quality or equivalent.
6.13Silica gel—100/200 mesh, Davison, grade-923 or equivalent. Activate at 130 °C overnight and store in a desiccator.
6.14Stock standard solutions (1.00 μg/μL)—Stock standard solutions may be prepared from pure standard materials or purchased as certified solutions.
6.14.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in 2-propanol
6.14.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4 °C and protect from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.14.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.15Quality control check sample concentrate—See Section 8.2.1.
7.1To calibrate the FIDGC for the anaylsis of underivatized phenols, establish gas chromatographic operating conditions equivalent to those given in Table 1. The gas chromatographic system can be calibrated using the external standard technique (Section 7.2) or the internal standard technique (Section 7.3).
7.2External standard calibration procedure for FIDGC:
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with 2-propanol. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using injections of 2 to 5 μl, analyze each calibration standard according to Section 11 and tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure for FIDGC—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples.
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with 2-propanol. One of the standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 11 and tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
If the RF value over the working range is a constant (<10% RSD), the RF can be assumed to be invariant and the average RF can be used for calculations. Alternatively, the results can be used to plot a calibration curve of response ratios, A
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, a new calibration curve must be prepared for that compound.
7.5To calibrate the ECDGC for the analysis of phenol derivatives, establish gas chromatographic operating conditions equivalent to those given in Table 2.
7.5.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with 2-propanol. One of the external standards should be at a concentration near, but above, the MDL (Table 2) and the other concentrations should correspond to the expected
7.5.2Each time samples are to be derivatized, simultaneously treat a 1-mL aliquot of each calibration standard as described in Section 12.
7.5.3After derivatization, analyze 2 to 5 μL of each column eluate collected according to the method beginning in Section 12.8 and tabulate peak height or area responses against the calculated equivalent mass of underivatized phenol injected. The results can be used to prepare a calibration curve for each compound.
7.6Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.6 and 11.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 100 μg/mL in 2-propanol. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at a concentration of 100 μg/L by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
The large number of parameters in Talbe 3 present a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.
8.2.6When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.
8.2.6.1Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2Beginning with Section 8.2.2, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compounds of interest beginning with Section 8.2.2.
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 100 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any, or, if none, (2) the larger of either 5 times higher than the expected background concentration or 100 μg/L.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 3. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6.It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All samples must be iced or refrigerated at 4 °C from the time of collection until extraction. Fill the sample bottles and, if residual chlorine is present, add 80 mg of sodium thiosulfate per liter of sample and mix well. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine.
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Mark the water meniscus on the side of sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel.
10.2For samples high in organic content, the analyst may solvent wash the sample at basic pH as prescribed in Sections 10.2.1 and 10.2.2 to remove potential method interferences. Prolonged or exhaustive contact with solvent during the wash may result in low recovery of some of the phenols, notably phenol and 2,4-dimethylphenol. For relatively clean samples, the wash should be omitted and the extraction, beginning with Section 10.3, should be followed.
10.2.1Adjust the pH of the sample to 12.0 or greater with sodium hydroxide solution.
10.2.2Add 60 mL of methylene chloride to the sample by shaking the funnel for 1 min with periodic venting to release excess pressure. Discard the solvent layer. The wash can be repeated up to two additional times if significant color is being removed.
10.3Adjust the sample to a pH of 1 to 2 with sulfuric acid.
10.4Add 60 mL of methylene chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min. with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
10.5Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner.
10.6Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.7Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.8Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
10.9Increase the temperature of the hot water bath to 95 to 100 °C. Remove the Synder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of 2-propanol. A 5-mL syringe is recommended for this operation. Attach a two-ball micro-Snyder column to the concentrator tube and prewet the column by adding about 0.5 mL of 2-propanol to the top. Place the micro-K-D apparatus on the water bath so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete
10.10Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with a minimum amount of 2-propanol. Adjust the extract volume to 1.0 mL. Stopper the concentrator tube and store refrigerated at 4 °C if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial. If the sample extract requires no further cleanup, proceed with FIDGC analysis (Section 11). If the sample requires further cleanup, proceed to Section 12.
10.11Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. An example of the separations achieved by this column is shown in Figure 1. Other packed or capillary (open-tubular) columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met.
11.2Calibrate the system daily as described in Section 7.
11.3If the internal standard calibration procedure is used, the internal standard must be added to the sample extract and mixed thoroughly immediately before injection into the gas chromatograph.
11.4Inject 2 to 5 μL of the sample extract or standard into the gas chromatograph using the solvent-flush technique.
11.5Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound may be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
11.6If the response for a peak exceeds the working range of the system, dilute the extract and reanalyze.
11.7If the measurement of the peak response is prevented by the presence of interferences, an alternative gas chromatographic procedure is required. Section 12 describes a derivatization and column chromatographic procedure which has been tested and found to be a practical means of analyzing phenols in complex extracts.
12.1Pipet a 1.0-mL aliquot of the 2-propanol solution of standard or sample extract into a glass reaction vial. Add 1.0 mL of derivatizing reagent (Section 6.11). This amount of reagent is sufficient to derivatize a solution whose total phenolic content does not exceed 0.3 mg/mL.
12.2Add about 3 mg of potassium carbonate to the solution and shake gently.
12.3Cap the mixture and heat it for 4 h at 80 °C in a hot water bath.
12.4Remove the solution from the hot water bath and allow it to cool.
12.5Add 10 mL of hexane to the reaction flask and shake vigorously for 1 min. Add 3.0 mL of distilled, deionized water to the reaction flask and shake for 2 min. Decant a portion of the organic layer into a concentrator tube and cap with a glass stopper.
12.6Place 4.0 g of silica gel into a chromatographic column. Tap the column to settle the silica gel and add about 2 g of anhydrous sodium sulfate to the top.
12.7Preelute the column with 6 mL of hexane. Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, pipet onto the column 2.0 mL of the hexane solution (Section 12.5) that contains the derivatized sample or standard. Elute the column with 10.0 mL of hexane and discard the eluate. Elute the column, in order, with: 10.0 mL of 15% toluene in hexane (Fraction 1); 10.0 mL of 40% toluene in hexane (Fraction 2); 10.0 mL of 75% toluene in hexane (Fraction 3); and 10.0 mL of 15% 2-propanol in toluene (Fraction 4). All elution mixtures are prepared on a volume: volume basis. Elution patterns for the phenolic derivatives are shown in Table 2. Fractions may be combined as desired, depending upon the specific phenols of interest or level of interferences.
12.8Analyze the fractions by ECDGC. Table 2 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. An example of the separations
12.9Calibrate the system daily with a minimum of three aliquots of calibration standards, containing each of the phenols of interest that are derivatized according to Section 7.5.
12.10Inject 2 to 5 μL of the column fractions into the gas chromatograph using the solvent-flush technique. Smaller (1.0 μL) volumes can be injected if automatic devices are employed. Record the volume injected to the nearest 0.05 μL, and the resulting peak size in area or peak height units. If the peak response exceeds the linear range of the system, dilute the extract and reanalyze.
13.1Determine the concentration of individual compounds in the sample analyzed by FIDGC (without derivatization) as indicated below.
13.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
13.2Determine the concentration of individual compounds in the sample analyzed by derivatization and ECDGC according to Equation 4.
13.3Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method was tested by 20 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked as six concentrations over the range 12 to 450 μg/L.
1. 40 CFR part 136, appendix B.
2. “Determination of Phenols in Industrial and Municipal Wastewaters,” EPA 600/4-84-ABC, National Technical Information Service, PBXYZ, Springfield, Virginia 22161, November 1984.
3. Kawahara, F. K. “Microdetermination of Derivatives of Phenols and Mercaptans by
4. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
5. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
6. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
7. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
8. Provost, L. P., and Elder, R. S. “Interpretation of Percent Recovery Data,”
9. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
10. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methmds for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
11. Burke, J. A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
12. “Development of Detection Limits, EPA Method 604, Phenols,” Special letter report for EPA Contract 68-03-2625, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
13. “EPA Method Study 14 Method 604-Phenols,” EPA 600/4-84-044, National Technical Information Service, PB84-196211, Springfield, Virginia 22161, May 1984.
1.1This method covers the determination of certain benzidines. The following parameters can be determined by this method:
1.2This is a high performance liquid chromatography (HPLC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for the compounds above, identifications should be supported by at least one additional qualitative technique. This method describes electrochemical conditions at a second potential which can be used to confirm measurements made with this method. Method 625 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for the parameters listed above, using the extract produced by this method.
1.3The method detection limit (MDL, defined in Section 14.1)
1.4Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.5This method is restricted to use by or under the supervision of analysts experienced in the use of HPLC instrumentation and in the interpretation of liquid chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is extracted with chloroform using liquid-liquid extractions in a separatory funnel. The chloroform extract is extracted with acid. The acid extract is then neutralized and extracted with chloroform. The final chloroform extract is exchanged to methanol while being concentrated using a rotary evaporator. The extract is mixed with buffer and separated by HPLC. The benzidine compounds are measured with an electrochemical detector.
2.2The acid back-extraction acts as a general purpose cleanup to aid in the elimination of interferences.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality -being sampled. The cleanup procedures -that are inherent in the extraction step are -used to overcome many of these interfer-ences, but unique samples may require addi-tional cleanup approaches to achieve -the MDL listed in Table 1.
3.3Some dye plant effluents contain -large amounts of components with re-tention times closed to benzidine. In -these cases, it has been found useful to reduce the electrode potential in order to eliminate interferences and still detect benzidine. (See Section 12.7.)
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health harzard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
4.2The following parameters covered by this method have been tentatively classified as known or suspected, human or mammalian carcinogens: benzidine and 3,3′-dichlorobenzidine. Primary standards of these toxic compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles high concentrations of these toxic compounds.
4.3Exposure to chloroform should be minimized by performing all extractions and extract concentrations in a hood or other well-ventiliated area.
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4°C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flow meter is required to collect flow proportional composites.
5.2Glassware (All specifications are suggested):
5.2.1Separatory funnels—2000, 1000, and 250-mL, with Teflon stopcock.
5.2.2Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.3Rotary evaporator.
5.2.4Flasks—Round bottom, 100-mL, with 24/40 joints.
5.2.5Centrifuge tubes—Conical, graduated, with Teflon-lined screw caps.
5.2.6Pipettes—Pasteur, with bulbs.
5.3Balance—Analytical, capable of accurately weighing 0.0001 g.
5.4High performance liquid chromatograph (HPLC)—An analytical system complete with column supplies, high pressure syringes, detector, and compatible recorder. A data system is recommended for measuring peak areas and retention times.
5.4.1Solvent delivery system—With pulse damper, Altex 110A or equivalent.
5.4.2Injection valve (optional)—Waters U6K or equivalent.
5.4.3Electrochemical detector—Bioanalyti-cal Systems LC-2A with glassy carbon -electrode, or equivalent. This detector has -proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1), and was used to develop the method performance statements in Section 14. Guidelines for the use of alternate detectors are provided in Section 12.1.
5.4.4Electrode polishing kit—Princeton Applied Research Model 9320 or equivalent.
5.4.5Column—Lichrosorb RP-2, 5 micron particle diameter, in a 25 cm × 4.6 mm ID stainless steel column. This column was used to develop the method performance statements in Section 14. Guidelines for the use of alternate column packings are provided in Section 12.1.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Sodium hydroxide solution (5 N)—Dissolve 20 g of NaOH (ACS) in reagent water and dilute to 100 mL.
6.3Sodium hydroxide solution (1 M)—Dissolve 40 g of NaOH (ACS) in reagent water and dilute to 1 L.
6.4Sodium thiosulfate—(ACS) Granular.
6.5Sodium tribasic phosphate (0.4 M)—Dissolve 160 g of trisodium phosphate decahydrate (ACS) in reagent water and dilute to 1 L.
6.6Sulfuric acid (1+1)—Slowly, add 50 mL of H
6.7Sulfuric acid (1 M)—Slowly, add 58 mL of H
6.8Acetate buffer (0.1 M, pH 4.7)—Dissolve 5.8 mL of glacial acetic acid (ACS) and 13.6 g of sodium acetate trihydrate (ACS) in reagent water which has been purified by filtration through a RO-4 Millipore System or equivalent and dilute to 1 L.
6.9Acetonitrile, chloroform (preserved with 1% ethanol), methanol—Pesticide quality or equivalent.
6.10Mobile phase—Place equal volumes of filtered acetonitrile (Millipore type FH filter or equivalent) and filtered acetate buffer (Millipore type GS filter or equivalent) in a narrow-mouth, glass container and mix thoroughly. Prepare fresh weekly. Degas daily by sonicating under vacuum, by heating an stirring, or by purging with helium.
6.11Stock standard solutions (1.00 μg/μL)—Stock standard solutions may be prepared from pure standard materials or purchased as certified solutions.
6.11.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in methanol and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.11.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4 °C and protect from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.11.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.12Quality control check sample concentrate—See Section 8.2.1.
7.1Establish chromatographic operating conditions equivalent to those given in Table 1. The HPLC system can be calibrated using the external standard technique (Section 7.2) or the internal standard technique (Section 7.3).
7.2External standard calibration procedure:
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with mobile phase. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using syringe injections of 5 to 25 μL or a constant volume injection loop, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples.
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with mobile phase. One of the standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using syringe injections of 5 to 25 μL or a constant volume injection loop, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
If the RF value over the working range is a constant (<10% RSD), the RF can be assumed to be invariant and the average RF can be used for calculations. Alternatively, the results can be used to plot a calibration curve of response ratios, A
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, a new calibration curve must be prepared for that compound. If serious loss of response occurs, polish the electrode and recalibrate.
7.5Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.9, 11.1, and 12.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing benzidine and/or 3,3′-dichlorobenzidine at a concentration of 50 μg/mL each in methanol. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at a concentration of 50 μg/L by adding 1.00 mL of QC check sample concentrate to each of four 1-L-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 50 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none (2) the larger of either 5 times higher than the expected background concentration or 50 μg/L.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Sections 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as HPLC with a dissimilar column, gas chromatography, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All samples must be iced or refrigerated at 4°C and stored in the dark from the time of collection until extraction. Both benzidine and 3,3′-dichlorobenzidine are easily oxidized. Fill the sample bottles and, if residual chlorine is present, add 80 mg of sodium thiosulfate per liter of sample and mix well. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine.
9.3If 1,2-diphenylhydrazine is likely to be present, adjust the pH of the sample to 4.0± 0.2 to prevent rearrangement to benzidine.
9.4All samples must be extracted within 7 days of collection. Extracts may be held up to 7 days before analysis, if stored under an inert (oxidant free) atmosphere.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel. Check the pH of the sample with wide-range pH paper and adjust to within the range of 6.5 to 7.5 with sodium hydroxide solution or sulfuric acid.
10.2Add 100 mL of chloroform to the sample bottle, seal, and shake 30 s to rinse the inner surface. (Caution: Handle chloroform in a well ventilated area.) Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass
10.3Add a 50-mL volume of chloroform to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the separatory funnel. Perform a third extraction in the same manner.
10.4Separate and discard any aqueous layer remaining in the 250-mL separatory funnel after combining the organic extracts. Add 25 mL of 1 M sulfuric acid and extract the sample by shaking the funnel for 2 min. Transfer the aqueous layer to a 250-mL beaker. Extract with two additional 25-mL portions of 1 M sulfuric acid and combine the acid extracts in the beaker.
10.5Place a stirbar in the 250-mL beaker and stir the acid extract while carefully adding 5 mL of 0.4 M sodium tribasic phosphate. While monitoring with a pH meter, neutralize the extract to a pH between 6 and 7 by dropwise addition of 5 N sodium hydroxide solution while stirring the solution vigorously. Approximately 25 to 30 mL of 5 N sodium hydroxide solution will be required and it should be added over at least a 2-min period. Do not allow the sample pH to exceed 8.
10.6Transfer the neutralized extract into a 250-mL separatory funnel. Add 30 mL of chloroform and shake the funnel for 2 min. Allow the phases to separate, and transfer the organic layer to a second 250-mL separatory funnel.
10.7Extract the aqueous layer with two additional 20-mL aliquots of chloroform as before. Combine the extracts in the 250-mL separatory funnel.
10.8Add 20 mL of reagent water to the combined organic layers and shake for 30 s.
10.9Transfer the organic extract into a 100-mL round bottom flask. Add 20 mL of methanol and concentrate to 5 mL with a rotary evaporator at reduced pressure and 35 °C. An aspirator is recommended for use as the source of vacuum. Chill the receiver with ice. This operation requires approximately 10 min. Other concentration techniques may be used if the requirements of Section 8.2 are met.
10.10Using a 9-in. Pasteur pipette, transfer the extract to a 15-mL, conical, screw-cap centrifuge tube. Rinse the flask, including the entire side wall, with 2-mL portions of methanol and combine with the original extract.
10.11Carefully concentrate the extract to 0.5 mL using a gentle stream of nitrogen while heating in a 30 °C water bath. Dilute to 2 mL with methanol, reconcentrate to 1 mL, and dilute to 5 mL with acetate buffer. Mix the extract thoroughly. Cap the centrifuge tube and store refrigerated and protected from light if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial. If the sample extract requires no further cleanup, proceed with HPLC analysis (Section 12). If the sample requires further cleanup, proceed to Section 11.
10.12Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1,000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use of a cleanup procedure, the analyst first must demonstrate that the requirements of Section 8.2 can be met using the method as revised to incorporate the cleanup procedure.
12.1Table 1 summarizes the recommended operating conditions for the HPLC. Included in this table are retention times, capacity factors, and MDL that can be achieved under these conditions. An example of the separations achieved by this HPLC column is shown in Figure 1. Other HPLC columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met. When the HPLC is idle, it is advisable to maintain a 0.1 mL/min flow through the column to prolong column life.
12.2Calibrate the system daily as described in Section 7.
12.3If the internal standard calibration procedure is being used, the internal standard must be added to the sample extract and mixed thoroughly immediately before injection into the instrument.
12.4Inject 5 to 25 μL of the sample extract or standard into the HPLC. If constant volume injection loops are not used, record the volume injected to the nearest 0.05 μL, and the resulting peak size in area or peak height units.
12.5Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
12.6If the response for a peak exceeds the working range of the system, dilute the extract with mobile phase and reanalyze.
12.7If the measurement of the peak response for benzidine is prevented by the presence of interferences, reduce the electrode
13.1Determine the concentration of individual compounds in the sample.
13.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
13.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method has been tested for linearity of spike recovery from reagent water and has been demonstrated to be applicable over the concentration range from 7×MDL to 3000×MDL.
14.3This method was tested by 17 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations over the range 1.0 to 70 μg/L.
1. 40 CFR part 136, appendix B.
2. “Determination of Benzidines in Industrial and Muncipal Wastewaters,” EPA 600/4-82-022, National Technical Information Service, PB82-196320, Springfield, Virginia 22161, April 1982.
3. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
9. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
10. “EPA Method Study 15, Method 605 (Benzidines),” EPA 600/4-84-062, National Technical Information Service, PB84-211176, Springfield, Virginia 22161, June 1984.
11. “EPA Method Validation Study 15, Method 605 (Benzidines),” Report for EPA Contract 68-03-2624 (In preparation).
1.1This method covers the determination of certain phthalate esters. The following parameters can be determined by this method:
1.2This is a gas chromatographic (GC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compounds above, compound identifications should be supported by at least one additional qualitative technique. This method describes analytical conditions for a second gas chromatographic column that can be used to confirm measurements made with the primary column. Method 625 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for all of the parameters listed above, using the extract produced by this method.
1.3The method detection limit (MDL, defined in Section 14.1)
1.4The sample extraction and concentration steps in this method are essentially the same as in Methods 608, 609, 611, and 612. Thus, a single sample may be extracted to measure the parameters included in the scope of each of these methods. When cleanup is required, the concentration levels must be high enough to permit selecting aliquots, as necessary, to apply appropriate cleanup procedures. The analyst is allowed the latitude, under Section 12, to select chromatographic conditions appropriate for the simultaneous measurement of combinations of these parameters.
1.5Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.6This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is extracted with methylene chloride using a separatory funnel. The methylene chloride extract is dried and exchanged to hexane during concentration to a volume of 10 mL or less. The extract is separated by gas chromatography and the phthalate esters are then measured with an electron capture detector.
2.2Analysis for phthalates is especially complicated by their ubiquitous occurrence in the environment. The method provides Florisil and alumina column cleanup procedures to aid in the elimination of interferences that may be encountered.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in gas chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Phthalate esters are contaminants in many products commonly found in the laboratory. It is particularly important to avoid the use of plastics because phthalates are commonly used as plasticizers and are easily extracted from plastic materials. Serious phthalate contamination can result at any time, if consistent quality control is not practiced. Great care must be experienced to prevent such contamination. Exhaustive cleanup of reagents and glassware may be required to eliminate background phthalate contamination.
3.3Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. The cleanup procedures in Section 11 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Table 1.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flow meter is required to collect flow proportional composites.
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only).
5.2.1Separatory funnel—2-L, with Teflon stopcock.
5.2.2Drying column—Chromatographic column, approximately 400 mm long × 19 mm ID, with coarse frit filter disc.
5.2.3Chromatographic column—300 mm long × 10 mm ID, with Teflon stopcock and coarse frit filter disc at bottom (Kontes K-420540-0213 or equivalent).
5.2.4Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.5Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.6Snyder column, Kuderna-Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.7Snyder column, Kuderna-Danish—Two-ball micro (Kontes K-569001-0219 or equivalent).
5.2.8Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2 °C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighing 0.0001 g.
5.6Gas chromatograph—An analytical system complete with gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.6.1Column 1—1.8 m long × 4 mm ID glass, packed with 1.5% SP-2250/1.95% SP-2401 Supelcoport (100/120 mesh) or equivalent. This column was used to develop the method performance statemelts in Section 14. Guidelines for the use of alternate column packings are provided in Section 12.1.
5.6.2Column 2—1.8 m long × 4 mm ID glass, packed with 3% OV-1 on Supelcoport (100/120 mesh) or equivalent.
5.6.3Detector—Electron capture detector. This detector has proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1), and was used to develop the method performance statements in Section 14. Guidelines for the use of alternate detectors are provided in Section 12.1.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Acetone, hexane, isooctane, methylene chloride, methanol—Pesticide quality or equivalent.
6.3Ethyl ether—nanograde, redistilled in glass if necessary.
6.3.1Ethyl ether must be shown to be free of peroxides before it is used as indicated by
6.3.2Procedures recommended for removal of peroxides are provided with the test strips. After cleanup, 20 mL of ethyl alcohol preservative must be added to each liter of ether.
6.4Sodium sulfate—(ACS) Granular, anhydrous. Several levels of purification may be required in order to reduce background phthalate levels to an acceptable level: 1) Heat 4 h at 400 °C in a shallow tray, 2) Heat 16 h at 450 to 500 °C in a shallow tray, 3) Soxhlet extract with methylene chloride for 48 h.
6.5Florisil—PR grade (60/100 mesh). Purchase activated at 1250 °F and store in the dark in glass containers with ground glass stoppers or foil-lined screw caps. To prepare for use, place 100 g of Florisil into a 500-mL beaker and heat for approximately 16 h at 40 °C. After heating transfer to a 500-mL reagent bottle. Tightly seal and cool to room temperature. When cool add 3 mL of reagent water. Mix thoroughly by shaking or rolling for 10 min and let it stand for at least 2 h. Keep the bottle sealed tightly.
6.6Alumina—Neutral activity Super I, W200 series (ICN Life Sciences Group, No. 404583). To prepare for use, place 100 g of alumina into a 500-mL beaker and heat for approximately 16 h at 400 °C. After heating transfer to a 500-mL reagent bottle. Tightly seal and cool to room temperature. When cool add 3 mL of reagent water. Mix thoroughly by shaking or rolling for 10 min and let it stand for at least 2 h. Keep the bottle sealed tightly.
6.7Stock standard solutions (1.00 μg/μL)—Stock standard solutions can be prepared from pure standard materials or purchased as certified solutions.
6.7.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in isooctane and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.7.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4 °C and protect from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.7.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.8Quality control check sample concentrate—See Section 8.2.1.
7.1Establish gas chromatograph operating conditions equivalent to those given in Table 1. The gas chromatographic system can be calibrated using the external standard technique (Section 7.2) or the internal standard technique (Section 7.3).
7.2External standard calibration procedure:
7.2.1Prepared calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with isooctane. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples.
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flash. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with isooctane. One of the standards should be at a concentraton near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
If the RF value over the working range is a constant (<10% RSD), the RF can be assumed to be invariant and the average RF can be used for calculations. Alternatively, the results can be used to plot a calibration curve of response ratios, A
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, a new calibration curve must be prepared for that compound.
7.5Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.4, 11.1, and 12.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality contrml (QC) check sample concentrate is required containing each parameter of interest at the following concentrations in acetone: butyl benzyl phthalate, 10 μg/mL; bis(2-ethylhexyl) phthalate, 50 μg/mL; di-n-octyl phthalate, 50 μg/mL; any other phthlate, 25 μg/mL. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agancy, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at the test concentrations shown in Table 2 by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at the test concentration in Section 8.2.2 or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none (2) the larger of either 5 times higher than the expected background concentration or the test concentration in Section 8.2.2.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as gas chromatography with a dissimilar column, specific element detector, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All samples must be iced or refrigerated at 4 °C from the time of collection until extraction.
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel.
10.2Add 60 mL of methylene chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min. with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phrase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner.
10.4Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentrator devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.5Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.6Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
10.7Increase the temperature of the hot water bath to about 80 °C. Momentarily remove the Snyder column, add 50 mL of hexane and a new boiling chip, and reattach the Snyder column. Concentrate the extract as in Section 10.6, except use hexane to prewet the column. The elapsed time of concentration should be 5 to 10 min.
10.8Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL syringe is recommended for this operation. Adjust the extract volume to 10 mL. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial. If the sample extract requires no further cleanup, proceed with gas chromatographic analysis (Section 12). If the sample requires further cleanup, proceed to Section 11.
10.9Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use
11.2If the entire extract is to be cleaned up by one of the following procedures, it must be concentrated to 2.0 mL. To the concentrator tube in Section 10.8, add a clean boiling chip and attach a two-ball micro-Snyder column. Prewet the column by adding about 0.5 mL of hexane to the top. Place the micro-K-D apparatus on a hot water bath (80 °C) so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood. When the apparent volume of liquid reaches about 0.5 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min. Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with 0.2 mL of hexane. Adjust the final volume to 2.0 mL and proceed with one of the following cleanup procedures.
11.3Florisil column cleanup for phthalate esters:
11.3.1Place 10 g of Florisil into a chromatographic column. Tap the column to settle the Florisil and add 1 cm of anhydrous sodium sulfate to the top.
11.3.2Preelute the column with 40 mL of hexane. The rate for all elutions should be about 2 mL/min. Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the 2-mL sample extract onto the column using an additional 2 mL of hexane to complete the transfer. Just prior to exposure of the sodium sulfate layer to the air, add 40 mL of hexane and continue the elution of the column. Discard this hexane eluate.
11.3.3Next, elute the column with 100 mL of 20% ethyl ether in hexane (V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator tube. Concentrate the collected fraction as in Section 10.6. No solvent exchange is necessary. Adjust the volume of the cleaned up extract to 10 mL in the concentrator tube and analyze by gas chromatography (Section 12).
11.4Alumina column cleanup for phthalate esters:
11.4.1Place 10 g of alumina into a chromatographic column. Tap the column to settle the alumina and add 1 cm of anhydrous sodium sulfate to the top.
11.4.2Preelute the column with 40 mL of hexane. The rate for all elutions should be about 2 mL/min. Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the 2-mL sample extract onto the column using an additional 2 mL of hexane to complete the transfer. Just prior to exposure of the sodium sulfate layer to the air, add 35 mL of hexane and continue the elution of the column. Discard this hexane eluate.
11.4.3Next, elute the column with 140 mL of 20% ethyl ether in hexane (V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator type. Concentrate the collected fraction as in Section 10.6. No solvent exchange is necessary. Adjust the volume of the cleaned up extract to 10 mL in the concentrator tube and analyze by gas chromatography (Section 12).
12.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. Examples of the separations achieved by Column 1 are shown in Figures 1 and 2. Other packed or capillary (open-tubular) columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met.
12.2Calibrate the system daily as described in Section 7.
12.3If the internal standard calibration procedure is being used, the internal staldard must be added to the sample extract and mixed thoroughly immediately before injection into the gas chromatograph.
12.4Inject 2 to 5 μL of the sample extract or standard into the gas-chromatograph using the solvent-flush technique.
12.5Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
12.6If the response for a peak exceeds the working range of the system, dilute the extract and reanalyze.
12.7If the measurement of the peak response is prevented by the presence of interferences, further cleanup is required.
13.1Determine the concentration of individual compounds in the sample.
13.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
13.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method has been tested for linearity of spike recovery from reagent water and has been demonstrated to be applicable over the concentration range from 5 × MDL to 1000 × MDL with the following exceptions: dimethyl and diethyl phthalate recoveries at 1000 × MDL were low (70%); bis-2-ethylhexyl and di-n-octyl phthalate recoveries at 5 × MDL were low (60%).
14.3This method was tested by 16 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations over the range 0.7 to 106 μg/L.
1. 40 CFR part 136, appendix B.
2. “Determination of Phthalates in Industrial and Muncipal Wastewaters,” EPA 600/4-81-063, National Technical Information Service, PB81-232167, Springfield, Virginia 22161, July 1981.
3. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
4. Giam, C.S., Chan, H.S., and Nef, G.S. “Sensitive Method for Determination of Phthalate Ester Plasticizers in Open-Ocean Biota Samples,”
5. Giam, C.S., and Chan, H.S. “Control of Blanks in the Analysis of Phthalates in Air and Ocean Biota Samples,” U.S. National Bureau of Standards, Special Publication 442, pp. 701-708, 1976.
6. “Carcinogens—Working with Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
7. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
8. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
9. Provost L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
10. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
11. Burke, J.A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
12. “Method Detection Limit and Analytical Curve Studies, EPA Methods 606, 607, and 608,” Special letter report for EPA Contract 68-03-2606, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, June 1980.
13. “EPA Method Study 16 Method 606 (Phthalate Esters),” EPA 600/4-84-056, National Technical Information Service, PB84-211275, Springfield, Virginia 22161, June 1984.
1.1This method covers the determination of certain nitrosamines. The following parameters can be determined by this method:
1.2This is a gas chromatographic (GC) method applicable to the determination of the parameters listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compmunds above, compound identifications should be supported by at least one additional qualitative technique. This method describes analytical conditimns for a second gas chromatographic column that can be used to confirm measurements made with the primary column. Method 625 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for N-nitrosodi-n-propylamine. In order to confirm the presence of N-nitrosodiphenylamine, the cleanup procedure specified in Section 11.3 or 11.4 must be used. In order to confirm the presence of N-nitrosodimethylamine by GC/MS, Column 1 of this method must be substituted for the column recommended in Method 625. Confirmation of these parameters using GC-high resolution mass spectrometry or a Thermal Energy Analyzer is also recommended.
1.3The method detection limit (MDL, defined in Section 14.1)
1.4Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.5This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is extracted with methylene chloride using a separatory funnel. The methylene chloride extract is washed with dilute hydrochloric acid to remove free amines, dried, and concentrated to a volume of 10 mL or less. After the extract has been exchanged to methanol, it is separated by gas chromatography and the parameters are then measured with a nitrogen-phosphorus detector.
2.2The method provides Florisil and alumina column cleanup procedures to separate diphenylamine from the nitrosamines and to aid in the elimination of interferences that may be encountered.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in gas chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. The cleanup procedures in Section 11 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Table 1.
3.3N-Nitrosodiphenylamine is reported
3.4The sensitive and selective Thermal Energy Analyzer and the reductive Hall detector may be used in place of the nitrogen-phosphorus detector when interferences are encountered. The Thermal Energy Analyzer offers the highest selectivity of the non-MS detectors.
4.1The toxicity or carcinogenicity of each -reagent used in this method has not been -precisely defined; however, each chemical -compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
4.2These nitrosamines are known carcinogens
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flowmeter is required to collect flow proportional composites.
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnels—2-L and 250-mL, with Teflon stopcock.
5.2.2Drying column—Chromatographic -column, approximately 400 mm long × 19 mm -ID, with coarse frit filter disc.
5.2.3Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.4Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.5Snyder column, Kuderna-Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.6Snyder column, Kuderna-Danish—Two-ball micro (Kontes K-569001-0219 or equivalent).
5.2.7Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.8Chromatographic column—Approximately 400 mm long × 22 mm ID, with Teflon stopcock and coarse frit filter disc at bottom (Kontes K-420540-0234 or equivalent), for use in Florisil column cleanup procedure.
5.2.9Chromatographic column—Approximately 300 mm long × 10 mm ID, with Teflon stopcock and coarse frit filter disc at bottom (Kontes K-420540-0213 or equivalent), for use in alumina column cleanup procedure.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2 °C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighing 0.0001 g.
5.6Gas chromatograph—An analytical system complete with gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.6.1Column 1—1.8 m long × 4 mm ID glass, packed with 10% Carbowax 20 M/2% KOH on Chromosorb W-AW (80/100 mesh) or equivalent. This column was used to develop the method performance statements in Section 14. Guidelines for the use of alternate column packings are provided in Section 12.2.
5.6.2Column 2—1.8 m long × 4 mm ID glass, packed with 10% SP-2250 on Supel- coport (100/120 mesh) or equivalent.
5.6.3Detector—Nitrogen-phosphorus, reductive Hall, or Thermal Energy Analyzer detector.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Sodium hydroxide solution (10 N)—Dissolve 40 g of NaOH (ACS) in reagent water and dilute to 100 ml.
6.3Sodium thiosulfate—(ACS) Granular.
6.4Sulfuric acid (1+1)—Slowly, add 50 mL of H
6.5Sodium sulfate—(ACS) Granular, anhydrous. Purify by heating at 400 °C for 4 h in a shallow tray.
6.6Hydrochloric acid (1+9)—Add one volume of concentrated HCl (ACS) to nine volumes of reagent water.
6.7Acetone, methanol, methylene chloride, pentane—Pesticide quality or equivalent.
6.8Ethyl ether—Nanograde, redistilled in glass if necessary.
6.8.1Ethyl ether must be shown to be free of peroxides before it is used as indicated by EM Laboratories Quant test strips. (Available from Scientific Products Co., Cat No. P1126-8, and other suppliers.)
6.8.2Procedures recommended for removal of peroxides are provided with the test strips. After cleanup, 20 mL of ethyl alcohol preservative must be added to each liter of ether.
6.9Florisil—PR grade (60/100 mesh). Purchase activated at 1250 °F and store in the dark in glass containers with ground glass stoppers or foil-lined screw caps. Before use, activate each batch at least 16 h at 130 °C in a foil-covered glass container and allow to cool.
6.10Alumina—Basic activity Super I, W200 series (ICN Life Sciences Group, No. 404571, or equivalent). To prepare for use, place 100 g of alumina into a 500-mL reagent bottle and add 2 mL of reagent water. Mix the alumina preparation thoroughly by shaking or rolling for 10 min and let it stand for at least 2 h. The preparation should be homogeneous before use. Keep the bottle sealed tightly to ensure proper activity.
6.11Stock standard solutions (1.00 μg/μL)—Stock standard solutions can be prepared from pure standard materials or purchased as certified solutions.
6.11.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in methanol and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.11.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4 °C and protect from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.11.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.12Quality control check sample concentrate—See Section 8.2.1.
7.1Establish gas chromatographic operating conditions equivalent to those given in Table 1. The gas chromatographic system can be calibrated using the external standard technique (Section 7.2) or the internal standard technique (Section 7.3).
7.2External standard calibration procedure:
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with methanol. One of the external standards should be at a concentraton near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples.
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with methanol. One of the standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
If the RF value over the working range is a constant (<10% RSD), the RF can be assumed to be invariant and the average RF can be used for calculations. Alternatively, the results can be used to plot a calibration curve of response ratios, A
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, a new calibration curve must be prepared for that compound.
7.5Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.4, 11.1, and 12.2) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 20 μg/mL in methanol. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at a concentration of 20 μg/L by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 20 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none (2) the larger of either 5 times higher than the expected background concentration or 20 μg/L.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were caluclated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices
9.1Grab samples must be collected in glass -containers. Conven-tional sampling practices
9.2All samples must be iced or refrigerated at 4 °C from the time of collection until extraction. Fill the sample bottles and, if residual chlorine is present, add 80 mg of sodium thiosulfate per liter of sample and mix well. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine.
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
9.4Nitrosamines are known to be light sen-sitive.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel. Check the pH of the sample with wide-range pH paper and adjust to within the range of 5 to 9 with sodium hydroxide solution or sulfuric acid.
10.2Add 60 mL of methylene chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner.
10.4Assemble a Kuderna-Danish (K-D) con-centrator by attaching a 10-mL concentra-tor tube to a 500-mL evaporative flask. Other -concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.5Add 10 mL of hydrochloric acid to the combined extracts and shake for 2 min. Allow the layers to separate. Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.6Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65°C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
10.7Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of methylene chloride. A 5-mL syringe is recommended for this operation. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial. If N-nitro-sodi-phe-nylamine is to be measured by gas chromatography, the analyst must first use a cleanup column to eliminate diphenylamine interference (Section 11). If N-nitrosodiphenylamine is of no interest, the analyst may proceed directly with gas chromatographic analysis (Section 12).
10.8Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-
11.1Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use of a cleanup procedure, the analyst may use either procedure below or any other appropriate procedure. However, the analyst first must demonstrate that the requirements of Section 8.2 can be met using the method as revised to incorporate the cleanup procedure. Diphenylamine, if present in the original sample extract, must be separated from the nitrosamines if N-nitrosodiphenylamine is to be determined by this method.
11.2If the entire extract is to be cleaned up by one of the following procedures, it must be concentrated to 2.0 mL. To the concentrator tube in Section 10.7, add a clean boiling chip and attach a two-ball micro-Snyder column. Prewet the column by adding about 0.5 mL of methylene chloride to the top. Place the micr-K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood. When the apparent volume of liquid reaches about 0.5 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min. Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with 0.2 mL of methylene chloride. Adjust the final volume to 2.0 mL and proceed with one of the following cleanup procedures.
11.3Florisil column cleanup for nitro-samines:
11.3.1Place 22 g of activated Florisil into a 22-mm ID chromatographic column. Tap the column to settle the Florisil and add about 5 mm of anhydrous sodium sulfate to the top.
11.3.2Preelute the column with 40 mL of ethyl ether/pentane (15+85)(V/V). Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the 2-mL sample extract onto the column using an additional 2 mL of pentane to complete the transfer.
11.3.3Elute the column with 90 mL of ethyl ether/pentane (15+85)(V/V) and discard the eluate. This fraction will contain the diphenylamine, if it is present in the extract.
11.3.4Next, elute the column with 100 mL of acetone/ethyl ether (5+95)(V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator tube. This fraction will contain all of the nitrosamines listed in the scope of the method.
11.3.5Add 15 mL of methanol to the collected fraction and concentrate as in Section 10.6, except use pentane to prewet the column and set the water bath at 70 to 75 °C. When the apparatus is cool, remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of pentane. Analyze by gas chromatography (Section 12).
11.4Alumina column cleanup for nitro-samines:
11.4.1Place 12 g of the alumina preparation (Section 6.10) into a 10-mm ID chromatographic column. Tap the column to settle the alumina and add 1 to 2 cm of anhydrous sodium sulfate to the top.
11.4.2Preelute the column with 10 mL of ethyl ether/pentane (3+7)(V/V). Discard the eluate (about 2 mL) and just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the 2 mL sample extract onto the column using an additional 2 mL of pentane to complete the transfer.
11.4.3Just prior to exposure of the sodium sulfate layer to the air, add 70 mL of ethyl ether/pentane (3+7)(V/V). Discard the first 10 mL of eluate. Collect the remainder of the eluate in a 500-mL K-D flask equipped with a 10 mL concentrator tube. This fraction contains N-nitrosodiphenylamine and probably a small amount of N-nitrosodi-n-propylamine.
11.4.4Next, elute the column with 60 mL of ethyl ether/pentane (1+1)(V/V), collecting the eluate in a second K-D flask equipped with a 10-mL concentrator tube. Add 15 mL of methanol to the K-D flask. This fraction will contain N-nitrosodimethylamine, most of the N-nitrosodi-n-propylamine and any diphenylamine that is present.
11.4.5Concentrate both fractions as in Section 10.6, except use pentane to prewet the column. When the apparatus is cool, remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of pentane. Analyze the fractions by gas chromatography (Section 12).
12.1N-nitrosodiphenylamine completely reacts to form diphenylamine at the normal operating temperatures of a GC injection port (200 to 250 °C). Thus, N-nitro-sodi-phenylamine is chromatographed and detected as di-phe-nyla-mine. Accurate determination depends on removal of di-phe-nyla-mine that may be present in the original extract prior to GC analysis (See Section 11).
12.2Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. Examples of the separations achieved by Column 1 are shown in
12.3Calibrate the system daily as described in Section 7.
12.4If the extract has not been subjected to one of the cleanup procedures in Section 11, it is necessary to exchange the solvent from methylene chloride to methanol before the thermionic detector can be used. To a 1 to 10-mL volume of methylene chloride extract in a concentrator tube, add 2 mL of methanol and a clean boiling chip. Attach a two-ball micro-Snyder column to the concentrator tube. Prewet the column by adding about 0.5 mL of methylene chloride to the top. Place the micro-K-D apparatus on a boiling (100 °C) water bath so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood. When the apparent volume of liquid reaches about 0.5 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min. Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with 0.2 mL of methanol. Adjust the final volume to 2.0 mL.
12.5If the internal standard calibration procedure is being used, the internal standard must be added to the sample extract and mixed thoroughly immediately before injection into the gas chromatograph.
12.6Inject 2 to 5 μL of the sample extract or standard into the gas chromatograph using the solvent-flush technique.
12.7Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
12.8If the response for a peak exceeds the working range of the system, dilute the extract and reanalyze.
12.9If the measurement of the peak response is prevented by the presence of interferences, further cleanup is required.
13.1Determine the concentration of individual compounds in the sample.
13.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
13.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method has been tested for linearity of spike recovery from reagent water and has been demonstrated to be applicable over the concentration range from 4 × MDL to 1000 × MDL.
14.3This method was tested by 17 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations
1. Fine, D.H., Lieb, D., and Rufeh, R. “Principle of Operation of the Thermal Energy Analyzer for the Trace Analysis of Volatile and Non-volatile N-nitroso Compounds,”
2. Fine, D.H., Hoffman, F., Rounbehler, D.P., and Belcher, N.M. “Analysis of N-nitroso Compounds by Combined High Performance Liquid Chromatography and Thermal Energy Analysis,” Walker, E.A., Bogovski, P. and Griciute, L., Editors, N-nitroso Compounds—Analysis and Formation, Lyon, International Agency for Research on Cancer (IARC Scientific Publications No. 14), pp. 43-50 (1976).
3. 40 CFR part 136, appendix B.
4. “Determination of Nitrosamines in Industrial and Municipal Wastewaters,” EPA 600/4-82-016, National Technical Information Service, PB82-199621, Springfield, Virginia 22161, April 1982.
5. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
6. Buglass, A.J., Challis, B.C., and Osborn, M.R. “Transnitrosation and Decomposition of Nitrosamines,” Bogovski, P. and Walker, E.A., Editors, N-nitroso Compounds in the Environment, Lyon, International Agency for Research on Cancer (IARC Scientific Publication No. 9), pp. 94-100 (1974).
7. Burgess, E.M., and Lavanish, J.M. “Photochemical Decomposition of N-nitrosamines,”
8. Druckrey, H., Preussmann, R., Ivankovic, S., and Schmahl, D. “Organotrope Carcinogene Wirkungen bei 65 Verschiedenen N-NitrosoVerbindungen an BD-Ratten,”
9. Fiddler, W. “The Occurrence and Determination of N-nitroso Compounds,”
10. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
11. “OSHA Safety and Health Standards, General Industry,” (29 CFR Part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
12. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
13. Lijinsky, W. “How Nitrosamines Cause Cancer,”
14. Mirvish, S.S. “N-Nitroso compounds: Their Chemical and in vivo Formation and Possible Importance as Environmental Carcinogens,”
15. “Reconnaissance of Environmental Levels of Nitrosamines in the Central United States,” EPA-330/1-77-001, National Enforcement Investigations Center, U.S. Environmental Protection Agency (1977).
16. “Atmospheric Nitrosamine Assessment Report,” Office of Air Quality Planning and Standards, U.S. Environmental Protection Agency, Research Triangle Park, North Carolina (1976).
17. “Scientific and Technical Assessment Report on Nitrosamines,” EPA-660/6-7-001, Office of Research and Development, U.S. Environmental Protection Agency (1976).
18. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
19. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
20. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
21. Burke, J. A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
22. “Method Detection Limit and Analytical Curve Studies EPA Methods 606, 607, and 608,” Special letter report for EPA Contract 68-03-2606, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, June 1980.
23. “EPA Method Study 17 Method 607—Nitrosamines,” EPA 600/4-84-051, National Technical Information Service, PB84-207646, Springfield, Virginia 22161, June 1984.
1.1This method covers the determination of certain organochlorine pesticides and PCBs. The following parameters can be determined by this method:
1.2This is a gas chromatographic (GC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compounds above, compound identifications should be supported by at least one additional qualitative technique. This method describes analytical conditions for a second gas chromatographic column that can be used to confirm measurements made with the primary column. Method 625 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for all of the parameters listed above, using the extract produced by this method.
1.3The method detection limit (MDL, defined in Section 14.1)
1.4The sample extraction and concentration steps in this method are essentially the same as in Methods 606, 609, 611, and 612. Thus, a single sample may be extracted to measure the parameters included in the scope of each of these methods. When cleanup is required, the concentration levels must be high enough to permit selecting aliquots, as necessary, to apply appropriate cleanup procedures. The analyst is allowed the latitude, under Section 12, to select chromatographic conditions appropriate for the simultaneous measurement of combinations of these parameters.
1.5Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.6This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is extracted with methylene chloride using a separatory funnel. The methylene chloride extract is dried and exchanged to hexane during concentration to a volume of 10 mL or less. The extract is separated by gas chromatography and the parameters are then measured with an electron capture detector.
2.2The method provides a Florisil column cleanup procedure and an elemental sulfur removal procedure to aid in the elimination of interferences that may be encountered.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in gas chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Interferences by phthalate esters can pose a major problem in pesticide analysis when using the electron capture detector. These compounds generally appear in the chromatogram as large late eluting peaks, especially in the 15 and 50% fractions from Florisil. Common flexible plastics contain varying amounts of phthalates. These phthalates are easily extracted or leached from such materials during laboratory operations. Cross contamination of clean glassware routinely occurs when plastics are handled during extraction steps, especially when solvent-wetted surfaces are handled. Interferences from phthalates can best be minimized by avoiding the use of plastics in the laboratory. Exhaustive cleanup of reagents and glassware may be required to eliminate background phthalate contamination.
3.3Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. The cleanup procedures in Section 11 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Table 1.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
4.2The following parameters covered by this method have been tentatively classified as known or suspected, human or mammalian carcinogens: 4,4′-DDT, 4,4′-DDD, the BHCs, and the PCBs. Primary standards of these toxic compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles high concentrations of these toxic compounds.
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during composting. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flow meter is required to collect flow proportional composites.
5.2.Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnel—2-L, with Teflon stopcock.
5.2.2Drying column—Chromatographic column, approximately 400 mm long × 19 mm ID, with coarse frit filter disc.
5.2.3Chromatographic column—400 mm long × 22 mm ID, with Teflon stopcock and coarse frit filter disc (Kontes K-42054 or equivalent).
5.2.4Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.5Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.6Snyder column, Kuderna/Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.7Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2 °C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighing 0.0001 g.
5.6Gas chromatograph—An analytical system complete with gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-
5.6.1Column 1—1.8 m long × 4 mm ID glass, packed with 1.5% SP-2250/1.95% SP-2401 on Supelcoport (100/120 mesh) or equivalent. This column was used to develop the method performance statements in Section 14. Guidelines for the use of alternate column packings are provided in Section 12.1.
5.6.2Column 2—1.8 m long × 4 mm ID glass, packed with 3% OV-1 on Supelcoport (100/120 mesh) or equivalent.
5.6.3Detector—Electron capture detector. This detector has proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1), and was used to develop the method performance statements in Section 14. Guidelines for the use of alternate detectors are provided in Section 12.1.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Sodium hydroxide solution (10 N)—Dissolve 40 g of NaOH (ACS) in reagent water and dilute to 100 mL.
6.3Sodium thiosulfate—(ACS) Granular.
6.4Sulfuric acid (1+1)—Slowly, add 50 mL to H
6.5Acetone, hexane, isooctane, methylene chloride—Pesticide quality or equivalent.
6.6Ethyl ether—Nanograde, redistilled in glass if necessary.
6.6.1Ethyl ether must be shown to be free of peroxides before it is used as indicated by EM Laboratories Quant test strips. (Available from Scientific Products Co., Cat. No. P1126-8, and other suppliers.)
6.6.2Procedures recommended for removal of peroxides are provided with the test strips. After cleanup, 20 mL of ethyl alcohol preservative must be added to each liter of ether.
6.7Sodium sulfate—(ACS) Granular, anhydrous. Purify by heating at 400 °C for 4 h in a shallow tray.
6.8Florisil—PR grade (60/100 mesh). Purchase activated at 1250 °F and store in the dark in glass containers with ground glass stoppers or foil-lined screw caps. Before use, activate each batch at least 16 h at 130 °C in a foil-covered glass container and allow to cool.
6.9Mercury—Triple distilled.
6.10Copper powder—Activated.
6.11Stock standard solutions (1.00 μg/μL)—Stock standard solutions can be prepared from pure standard materials or purchased as certified solutions.
6.11.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in isooctane and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.11.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4 °C and protect from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.11.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.12Quality control check sample concentrate—See Section 8.2.1.
7.1Establish gas chromatographic operating conditions equivalent to those given in Table 1. The gas chromatographic system can be calibrated using the external standard technique (Section 7.2) or the internal standard technique (Section 7.3).
7.2External standard calibration procedure:
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with isooctane. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with isooctane. One of the standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
If the RF value over the working range is a constant (<10% RSD), the RF can be assumed to be invariant and the average RF can be used for calculations. Alternatively, the results can be used to plot a calibration curve of response ratios, A
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, the test must be repeated using a fresh calibration standard. Alternatively, a new calibration curve must be prepared for that compound.
7.5The cleanup procedure in Section 11 utilizes Florisil column chromatography. Florisil from different batches or sources may vary in adsorptive capacity. To standardize the amount of Florisil which is used, the use of lauric acid value
7.6Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.4, 11.1, and 12.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each single-component parameter of interest at the following concentrations in acetone: 4,4′-DDD, 10 μg/mL; 4,4′-DDT, 10 μg/mL; endosulfan II, 10 μg/mL; endosulfan sulfate, 10 μg/mL; endrin, 10 μg/mL; any other single-component pesticide, 2 μg/mL. If this method is only to be used to analyze for PCBs, chlordane, or toxaphene, the QC check sample concentrate should contain the most representative multicomponent parameter at a concentration of 50 μg/mL in acetone. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at the test concentrations shown in Table 3 by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
The large number of parameters in Table 3 present a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.
8.2.6When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.
8.2.6.1Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2Beginning with Section 8.2.2, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compmunds of interest beginning with Section 8.2.2.
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at the test concentration in Section 8.2.2 or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none (2) the larger of either 5 times higher than the expected background concentration or the test concentration in Section 8.2.2.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 3. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory. If the entire list of parameters in Table 3 must be measured in the sample in Section 8.3, the probability that the analysis of a QC check standard will be required is high. In this case the QC check standard should be routinely analyzed with the spike sample.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standards to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as gas chromatography with a dissimilar column, specific element detector, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All samples must be iced or refrigerated at 4 °C from the time of collection until extraction. If the samples will not be extracted within 72 h of collection, the sample should be adjusted to a pH range of 5.0 to 9.0 with sodium hydroxide solution or sulfuric acid. Record the volume of acid or base used. If aldrin is to be determined, add sodium thiosulfate when residual chlorine is present. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine.
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel.
10.2Add 60 mL of methylene chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min. with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optium technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner.
10.4Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.5Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.6Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
10.7Increase the temperature of the hot water bath to about 80 °C. Momeltarily remove the Snyder column, add 50 mL of hexane and a new boiling chip, and reattach the Snyder column. Concentrate the extract as in Section 10.6, except use hexane to prewet the column. The elapsed time of concentration should be 5 to 10 min.
10.8Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL syringe is recommended for this operation. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial. If the sample extract requires no further cleanup, proceed with gas chroma-tographic analysis (Section 12). If the sample -requires further cleanup, proceed to Sec-tion 11.
10.9Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use of a cleanup procedure, the analyst may use either procedure below or any other appropriate procedure. However, the analyst first must demonstrate that the requirements of Section 8.2 can be met using the method as revised to incorporate the cleanup procedure. The Florisil column allows for a select fractionation of the compounds and will eliminate polar interferences. Elemental sulfur, which interferes with the electron capture gas chromatography of certain pesticides, can be removed by the technique described in Section 11.3.
11.2Florisil column cleanup:
11.2.1Place a weight of Florisil (nominally 20 g) predetermined by calibration (Section 7.5), into a chromatographic column. Tap the column to settle the Florisil and add 1 to 2 cm of anhydrous sodium sulfate to the top.
11.2.2Add 60 mL of hexane to wet and rinse the sodium sulfate and Florisil. Just prior to exposure of the sodium sulfate layer to the air, stop the elution of the hexane by closing the stopcock on the chromatographic column. Discard the eluate.
11.2.3Adjust the sample extract volume to 10 mL with hexane and transfer it from the K-D concentrator tube onto the column. Rinse the tube twice with 1 to 2 mL of hexane, adding each rinse to the column.
11.2.4Place a 500-mL K-D flask and clean concentrator tube under the chroma-tographic column. Drain the column into -the flask until the sodium sulfate layer -is nearly exposed. Elute the column with 200 mL of 6% ethyl ether in hexane (V/V) (Fraction 1) at a rate of about 5 mL/min. Remove the K-D flask and set it aside for later concentration. Elute the column again, using 200 mL of 15% ethyl ether in hexane (V/V) (Fraction 2), into a second K-D flask. Perform the third elution using 200 mL of 50% ethyl ether in hexane (V/V) (Fraction 3). The elution patterns for the pesticides and PCBs are shown in Table 2.
11.2.5Concentrate the fractions as in Section 10.6, except use hexane to prewet the column and set the water bath at about 85 °C. When the apparatus is cool, remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with hexane. Adjust the volume of each fraction to 10 mL with hexane and analyze by gas chromatography (Section 12).
11.3Elemental sulfur will usually elute entirely in Fraction 1 of the Florisil column cleanup. To remove sulfur interference from this fraction or the original extract, pipet 1.00 mL of the concentrated extract into a clean concentrator tube or Teflon-sealed vial. Add one to three drops of mercury and
12.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. Examples of the separations achieved by Column 1 are shown in Figures 1 to 10. Other packed or capillary (open-tubular) columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met.
12.2Calibrate the system daily as described in Section 7.
12.3If the internal standard calibration procedure is being used, the internal standard must be added to the sample extract and mixed thoroughly immediately before injection into the gas chromatograph.
12.4Inject 2 to 5 μL of the sample extract or standard into the gas chromatograph using the solvent-flush technique.
12.5Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
12.6If the response for a peak exceeds the working range of the system, dilute the extract and reanalyze.
12.7If the measurement of the peak response is prevented by the presence of interferences, further cleanup is required.
13.1Determine the concentration of individual compounds in the sample.
13.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
13.2When it is apparent that two or more PCB (Aroclor) mixtures are present, the Webb and McCall procedure
13.3For multicomponent mixtures (chlordane, toxaphene, and PCBs) match retention times of peaks in the standards with peaks in the sample. Quantitate every identifiable peak unless interference with individual peaks persist after cleanup. Add peak height or peak area of each identified peak in the chromatogram. Calculate as total response in the sample versus total response in the standard.
13.4Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method has been tested for linearity of spike recovery from reagent water and has been demonstrated to be applicable over the concentration range from 4×MDL to 1000×MDL with the following exceptions: Chlordane recovery at 4×MDL was low (60%);
14.3This method was tested by 20 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations.
1. 40 CFR part 136, appendix B.
2. “Determination of Pesticides and PCBs in Industrial and Municipal Wastewaters,” EPA 600/4-82-023, National Technical Information Service, PB82-214222, Springfield, Virginia 22161, April 1982.
3. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
4. Giam, C.S., Chan, H.S., and Nef, G.S., “Sensitive Method for Determination of Phthalate Ester Plasticizers in Open-Ocean Biota Samples,”
5. Giam, C.S., Chan, H.S. “Control of Blanks in the Analysis of Phthalates in Air and Ocean Biota Samples,” U.S. National Bureau of Standards, Special Publication 442, pp. 701-708, 1976.
6. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
7. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
8. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
9. Mills, P.A. “Variation of Florisil Activity: Simple Method for Measuring Absorbent Capacity and Its Use in Standardizing Florisil Columns,”
10. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
11. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
12. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
13. Goerlitz, D.F., and Law, L.M.
14. “Manual of Analytical Methods for the Analysis of Pesticides in Human and Environmental Samples,” EPA-600/8-80-038, U.S. Environmental Protection Agency, Health Effects Research Laboratory, Research Triangle Park, North Carolina.
15. Burke, J.A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
16. Webb, R.G., and McCall, A.C. “Quantitative PCB Standards for Election Capture Gas Chromatography,”
17. “Method Detection Limit and Analytical Curve Studies, EPA Methods 606, 607, and 608,” Special letter report for EPA Contract 68-03-2606, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, June 1980.
18. “EPA Method Study 18 Method 608—Organochlorine Pesticides and PCBs,” EPA 600/4-84-061, National Technical Information Service, PB84-211358, Springfield, Virginia 22161, June 1984.
1.1This method covers the determination of certain nitroaromatics and isophorone. The following parameters may be determined by this method:
1.2This is a gas chromatographic (GC) method applicable to the determination of
1.3The method detection limit (MDL, defined in Section 14.1)
1.4The sample extraction and concentration steps in this method are essentially the same as in Methods 606, 608, 611, and 612. Thus, a single sample may be extracted to measure the parameters included in the scope of each of these methods. When cleanup is required, the concentration levels must be high enough to permit selecting aliquots, as necessary, to apply appropriate cleanup procedures. The analyst is allowed the latitude, under Section 12, to select chromatographic conditions appropriate for the simultaneous measurement of combinations of these parameters.
1.5Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.6This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is extracted with methylene chloride using a separatory funnel. The methylene chloride extract is dried and exchanged to hexane during concentration to a volume of 10 mL or less. Isophorone and nitrobenzene are measured by flame ionization detector gas chromatography (FIDGC). The dinitrotoluenes are measured by electron capture detector gas chromatography (ECDGC).
2.2The method provides a Florisil column cleanup procedure to aid in the elimination of interferences that may be encountered.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baseliles in gas chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. The cleanup procedure in Section 11 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Table 1.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flow meter is required to collect flow proportional composites.
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnel—2-L, with Teflon stopcock.
5.2.2Drying column—Chromatographic column, approximately 400 mm long × 19 mm ID, with coarse frit filter disc.
5.2.3Chromatographic column—100 mm long × 10 mm ID, with Teflon stopcock.
5.2.4Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.5Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.6Snyder column, Kuderna-Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.7Snyder column, Kuderna-Danish—Two-ball micro (Kontes K-569001-0219 or equivalent).
5.2.8Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2 °C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighing 0.0001 g.
5.6Gas chromatograph—An analytical system complete with gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.6.1Column 1—1.2 m long × 2 or 4 mm ID glass, packed with 1.95% QF-1/1.5% OV-17 on Gas-Chrom Q (80/100 mesh) or equivalent. This column was used to develop the method performance statements given in Section 14. Guidelines for the use of alternate column packings are provided in Section 12.1.
5.6.2Column 2—3.0 m long × 2 or 4 mm ID glass, packed with 3% OV-101 on Gas-Chrom Q (80/100 mesh) or equivalent.
5.6.3Detectors—Flame ionization and electron capture detectors. The flame ionization detector (FID) is used when determining isophorone and nitrobenzene. The electron capture detector (ECD) is used when determining the dinitrotoluenes. Both detectors have proven effective in the analysis of wastewaters and were used in develop the method performance statements in Section 14. Guidelines for the use to alternate detectors are provided in Section 12.1.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Sodium hydroxide solution (10 N)—Dissolve 40 g of NaOH (ACS) in reagent water and dilute to 100 mL.
6.3Sulfuric acid (1+1)—Slowly, add 50 mL of H
6.4Acetone, hexane, methanol, methylene chloride—Pesticide quality or equivalent.
6.5Sodium sulfate—(ACS) Granular, anhydrous. Purify by heating at 400 °C for 4 h in a shallow tray.
6.6Florisil—PR grade (60/100 mesh). Purchase activated at 1250 °F and store in dark in glass containers with ground glass stoppers or foil-lined screw caps. Before use, activate each batch at least 16 h at 200 °C in a foil-covered glass container and allow to cool.
6.7Stock standard solutions (1.00 μg/μL)—Stock standard solutions can be prepared from pure standard materials or purchased as certified solutions.
6.7.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in hexane and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.7.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles.
6.7.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.8Quality control check sample concentrate—See Section 8.2.1.
7.1Establish gas chromatographic operating conditions equivalent to those given in Table 1. The gas chromatographic system can be calibrated using the external standard technique (Section 7.2) or the internal standard technique (Section 7.3).
7.2External standard calibration procedure:
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with hexane. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD) linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples.
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flash. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with hexane. One of the standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
Equation 1.
If the RF value over the working range is a constant (<10% RSD), the RF can be assumed to be invariant and the average RF can be used for calculations. Alternatively, the results can be used to plot a calibration curve of response ratios, A
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, a new calibration curve must be prepared for that compound.
7.5Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.4, 11.1, and 12.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1,5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest in acetone at a concentration of 20 μg/mL for each dinitrotoluene and 100 μg/mL for isophorone and nitrobenzene. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at the test concentrations shown in Table 2 by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at the test concentration in Section 8.2.2 or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determile background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none (2) the larger of either 5 times higher than the expected background concentration or the test concentration in Section 8.2.2.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100 (A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were calculated to include an allowance for error in measurement
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4.If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as gas chromatography with a dissimilar column, specific element detector, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All samples must be iced or refrigerated at 4 °C from the time of collection until extraction.
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel. Check the pH of the sample with wide-range pH paper and adjust to within the range of 5 to 9 with sodium hydroxide solution or sulfuric acid.
10.2Add 60 mL of methylene chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min. with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration
10.3Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner.
10.4Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.5Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.6Sections 10.7 and 10.8 describe a procedure for exchanging the methylene chloride solvent to hexane while concentrating the extract volume to 1.0 mL. When it is not necessary to achieve the MDL in Table 2, the solvent exchange may be made by the addition of 50 mL of hexane and concentration to 10 mL as described in Method 606, Sections 10.7 and 10.8.
10.7Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
10.8Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of methylene chloride. A 5-mL syringe is recommended for this operation. Add 1 to 2 mL of hexane and a clean boiling chip to the concentrator tube and attach a two-ball micro-Snyder column. Prewet the column by adding about 0.5 mL of hexane to the top. Place the micro-K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood. When the apparent volume of liquid reaches 0.5 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
10.9Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with a minimum amount of hexane. Adjust the extract volume to 1.0 mL. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial. If the sample extract requires no further cleanup, proceed with gas chromatographic analysis (Section 12). If the sample requires further cleanup, proceed to Section 11.
10.10Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use of a cleanup procedure, the analyst may use the procedure below or any other appropriate procedure. However, the analyst first must demonstrate that the requirements of Section 8.2 can be met using the method as revised to incorporate the cleanup procedure.
11.2Florisil column cleanup:
11.2.1Prepare a slurry of 10 g of acti-vated Florisil in methylene chloride/-hexane (1+9)(V/V) and place the Florisil -into a chromatographic column. Tap the column to settle the Florisil and add 1 cm of anhydrous sodium sulfate to the top. Adjust the elution rate to about 2 mL/min.
11.2.2Just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the sample extract onto the column using an additional 2 mL of hexane to complete the transfer. Just prior to exposure of the sodium sulfate layer to the air, add 30 mL of methylene chloride/hexane (1 + 9)(V/V) and continue the elution of the column. Discard the eluate.
11.2.3Next, elute the column with 30 mL of acetone/methylene chloride (1 + 9)(V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator tube. Concentrate the collected fraction as in Sections 10.6, 10.7, 10.8, and 10.9 including the solvent exchange to 1 mL of hexane. This fraction should contain the nitroaromatics and isophorone. Analyze by gas chromatography (Section 12).
12.1Isophorone and nitrobenzene are analyzed by injection of a portion of the extract into an FIDGC. The dinitrotoluenes are analyzed by a separate injection into an ECDGC.
12.2Calibrate the system daily as described in Section 7.
12.3If the internal standard calibration procedure is being used, the internal standard must be added to the same extract and mixed thoroughly immediately before injection into the gas chromatograph.
12.4Inject 2 to 5 μL of the sample extract or standard into the gas chromatograph using the solvent-flush technique.
12.5Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
12.6If the response for a peak exceeds the working range of the system, dilute the extract and reanalyze.
12.7If the measurement of the peak response is prevented by the presence of interferences, further cleanup is required.
13.1Determine the concentration of individual compounds in the sample.
13.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
13.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method has been tested for linearity of spike recovery from reagent water and has been demonstrated to be applicable over the concentration range from 7×MDL to 1000×MDL.
14.3This method was tested by 18 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations over the range 1.0 to 515 μg/L.
1. 40 CFR part 136, appendix B.
2. “Determination of Nitroaromatic Compounds and Isophorone in Industrial and Municipal Wastewaters,” EPA 600/ 4-82-024, National Technical Information Service, PB82-208398, Springfield, Virginia 22161, May 1982.
3. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
9. Burke, J.A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
10. “Determination of Method Detection Limit and Analytical Curve for EPA Method 609—Nitroaromatics and Isophorone,” Special letter report for EPA Contract 68-03-2624, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, June 1980.
11. “EPA Method Study 19, Method 609 (Nitroaromatics and Isophorone),” EPA 600/4-84-018, National Technical Information Service, PB84-176908, Springfield, Virginia 22161, March 1984.
1.1This method covers the determination of certain polynuclear aromatic hydrocarbons (PAH). The following parameters can be determined by this method:
1.2This is a chromatographic method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compounds above, compound identifications should be supported by at least one additional qualitative technique. Method 625 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for many of the parameters listed above, using the extract produced by this method.
1.3This method provides for both high performance liquid chromatographic (HPLC) and gas chromatographic (GC) approaches for the determination of PAHs. The gas chromatographic procedure does not adequately resolve the following four pairs of compounds: Anthracene and phenanthrene; chrysene and benzo(a)anthracene; benzo(b)fluoranthene and benzo(k)fluoranthene; and dibenzo(a,h) anthracene and indeno (1,2,3-cd)pyrene. Unless the purpose for the analysis can be served by reporting the sum of an unresolved pair, the liquid chromatographic approach must be used for these compounds. The liquid chromatographic method does resolve all 16 of the PAHs listed.
1.4The method detection limit (MDL, defined in Section 15.1)
1.5The sample extraction and concentration steps in this method are essentially the same as in Methods 606, 608, 609, 611, and 612. Thus, a single sample may be extracted to measure the parameters included in the scope of each of these methods. When cleanup is required, the concentration levels must be high enough to permit selecting aliquots, as necessary, to apply appropriate cleanup procedures. Selection of the aliquots must be made prior to the solvent exchange steps of this method. The analyst is allowed the latitude, under Sections 12 and 13, to select chromatographic conditions appropriate for the simultaneous measurement of combinations of these parameters.
1.6Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.7This method is restricted to use by or under the supervision of analysts experienced in the use of HPLC and GC systems and in the interpretation of liquid and gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is extracted with methylene chloride using a separatory funnel. The methylene chloride extract is dried and concentrated to a volume of 10 mL or less. The extract is then separated by HPLC or GC. Ultraviolet (UV) and fluorescence detectors are used with HPLC to identify and measure the PAHs. A flame ionization detector is used with GC.
2.2The method provides a silica gel column cleanup procedure to aid in the elimination of interferences that may be encountered.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardward that lead to discrete artifacts and/or elevated baselines in the chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. The cleanup procedure in Section 11 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Table 1.
3.3The extent of interferences that may be encountered using liquid chromatographic techniques has not been fully assessed. Although the HPLC conditions described allow for a unique resolution of the specific PAH compounds covered by this method, other PAH compounds may interfere.
4.1The toxicity or carcinogenicity of each reagent used in this method have not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
4.2The following parameters covered by this method have been tentatively classified as known or suspected, human or mammalian carcinogens: benzo(a)anthracene, benzo(a)pyrene, and dibenzo(a,h)-anthracene. Primary standards of these toxic compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles high concentrations of these toxic compounds.
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flow meter is required to collect flow proportional composites.
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnel—2-L, with Teflon stopcock.
5.2.2Drying column—Chromatographic column, approximately 400 mm long × 19 mm ID, with coarse frit filter disc.
5.2.3Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.4Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.5Snyder column, Kuderna-Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.6Snyder column, Kuderna-Danish—Two-ball micro (Kontes K-569001-0219 or equivalent).
5.2.7Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.8Chromatographic column—250 mm long × 10 mm ID, with coarse frit filter disc at bottom and Teflon stopcock.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2 °C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighing 0.0001 g.
5.6High performance liquid chromatograph (HPLC)—An analytical system complete with column supplies, high pressure syringes, detectors, and compatible strip-chart recorder. A data system is recommended for measuring peak areas and retention times.
5.6.1Gradient pumping system—Constant flow.
5.6.2Reverse phase column—HC-ODS Sil-X, 5 micron particle diameter, in a 25 cm × 2.6 mm ID stainless steel column (Perkin Elmer No. 089-0716 or equivalent). This column was used to develop the method performance statements in Section 15. Guidelines for the use of alternate column packings are provided in Section 12.2.
5.6.3Detectors—Fluorescence and/or UV detectors. The fluorescence detector is used for excitation at 280 nm and emission greater than 389 nm cutoff (Corning 3-75 or equivalent). Fluorometers should have dispersive optics for excitation and can utilize either filter or dispersive optics at the emission detector. The UV detector is used at 254 nm and should be coupled to the fluorescence detector. These detectors were used to develop the method performance statements in Section 15. Guidelines for the use of alternate detectors are provided in Section 12.2.
5.7Gas chromatograph—An analytical system complete with temperature programmable gas chromatograph suitable for on-column or splitless injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.7.1Column—1.8 m long × 2 mm ID glass, packed with 3% OV-17 on Chromosorb W-AW-DCMS (100/120 mesh) or equivalent. This column was used to develop the retention time data in Table 2. Guidelines for the use of alternate column packings are provided in Section 13.3.
5.7.2Detector—Flame ionization detector. This detector has proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1), excluding the four pairs of unresolved compounds listed in Section 1.3. Guidelines for the use of alternate detectors are provided in Section 13.3.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Sodium thiosulfate—(ACS) Granular.
6.3Cyclohexane, methanol, acetone, methylene chloride, pentane—Pesticide quality or equivalent.
6.4Acetonitrile—HPLC quality, distilled in glass.
6.5Sodium sulfate—(ACS) Granular, anhydrous. Purify by heating at 400 °C for 4 h in a shallow tray.
6.6Silica gel—100/200 mesh, desiccant, Davison, grade-923 or equivalent. Before use, activate for at least 16 h at 130 °C in a shallow glass tray, loosely covered with foil.
6.7Stock standard solutions (1.00 μg/μL)—Stock standard solutions can be prepared from pure standard materials or purchased as certified solutions.
6.7.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in acetonitrile and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When com-pound purity is assayed to be 96% or greater, -the weight can be used without cor-rection to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.7.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4 °C and protect from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.7.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.8Quality control check sample concentrate—See Section 8.2.1.
7.1Establish liquid or gas chroma-tog-ra-phic operating conditions equivalent to those given in Table 1 or 2. The chromatographic system can be calibrated using the external standard technique (Section 7.2) or the internal standard technique (Section 7.3).
7.2External standard calibration procedure:
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with acetonitrile. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using injections of 5 to 25 μL for HPLC and 2 to 5 μL for GC, analyze each calibration standard according to Section 12 or 13, as appropriate. Tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with acetonitrile. One of the standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using injections of 5 to 25 μL for HPLC and 2 to 5 μL for GC, analyze each calibration standard according to Section 12 or 13, as appropriate. Tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, the test must be repeated using a fresh calibration standard. Alternatively, a new calibration curve must be prepared for that compound.
7.5Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.4, 11.1, 12.2, and 13.3) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at the following concentrations in acetonitrile: 100 μg/mL of any
8.2.2Using a pipet, prepare QC check samples at the test concentrations shown in Table 3 by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
The large number of parameters in Table 3 present a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.
8.2.6When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.
8.2.6.1Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2Beginning with Section 8.2.2, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compounds of interest beginning with Section 8.2.2.
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at the test concentration in Section 8.2.2 or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none, (2) the larger of either 5 times higher than the expected background concentration or the test concentration in Section 8.2.2.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100 (A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 3. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory. If the entire list of parameters in Table 3 must be measured in the sample in Section 8.3, the probability that the analysis of a QC check standard will be required is high. In this case the QC check standard should be routinely analyzed with the spike sample.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as gas chromatography with a dissimilar column, specific element detector, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All samples must be iced or refrigerated at 4 °C from the time of collection until extraction. PAHs are known to be light sensitive; therefore, samples, extracts, and standards should be stored in amber or foil-wrapped bottles in order to minimize photolytic decomposition. Fill the sample bottles and, if residual chlorine is present, add 80 mg of sodium thiosulfate per liter of sample and mix well. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine.
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel.
10.2Add 60 mL of methylene chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min. with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner.
10.4Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.5Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.6Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
10.7Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of methylene chloride. A 5-mL syringe is recommended for this operation. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial and protected from light. If the sample extract requires no further cleanup, proceed with gas or liquid chromatographic analysis (Section 12 or 13). If the sample requires further cleanup, proceed to Section 11.
10.8Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use of a cleanup procedure, the analyst may use the procedure below or any other appropriate procedure. However, the analyst first must demonstrate that the requirements of Section 8.2 can be met using the methods as revised to incorporate the cleanup procedure.
11.2Before the silica gel cleanup technique can be utilized, the extract solvent must be exchanged to cyclohexane. Add 1 to 10 mL of the sample extract (in methylene chloride) and a boiling chip to a clean K-D concentrator tube. Add 4 mL of cyclohexane and attach a two-ball micro-Snyder column. Prewet the column by adding 0.5 mL of methylene chloride to the top. Place the micro-K-D apparatus on a boiling (100 °C) water bath so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood. When the apparent volume of the liquid reaches 0.5 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min. Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with a minimum amount of cyclohexane. Adjust the extract volume to about 2 mL.
11.3Silica gel column cleanup for PAHs:
11.3.1Prepare a slurry of 10 g of activiated silica gel in methylene chloride and place this into a 10-mm ID chromatographic column. Tap the column to settle the silica gel and elute the methylene chloride. Add 1 to 2 cm of anhydrous sodium sulfate to the top of the silica gel.
11.3.2Preelute the column with 40 mL of pentane. The rate for all elutions should be about 2 mL/min. Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, transfer the 2-mL cyclohexane sample extract onto the column using an additional 2 mL cyclohexane to complete the transfer. Just prior to exposure of the sodium sulfate layer to the air, add 25 mL of pentane and continue the elution of the column. Discard this pentane eluate.
11.3.3Next, elute the column with 25 mL of methylene chloride/pentane (4+6)(V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator tube. Concentrate the collected fraction to less than 10 mL as in Section 10.6. When the apparatus is cool, remove the Snyder column and rinse the flask and its lower joint with pentane. Proceed with HPLC or GC analysis.
12.1To the extract in the concentrator tube, add 4 mL of acetonitrile and a new boiling chip, then attach a two-ball micro-Snyder column. Concentrate the solvent as in Section 10.6, except set the water bath at 95 to 100 °C. When the apparatus is cool, remove the micro-Snyder column and rinse its lower joint into the concentrator tube with about 0.2 mL of acetonitrile. Adjust the extract volume to 1.0 mL.
12.2Table 1 summarizes the recommended operating conditions for the HPLC. Included in this table are retention times, capacity factors, and MDL that can be achieved under
12.3Calibrate the system daily as described in Section 7.
12.4If the internal standard calibration procedure is being used, the internal standard must be added to the sample extract and mixed thoroughly immediately before injection into the instrument.
12.5Inject 5 to 25 μL of the sample extract or standard into the HPLC using a high pressure syringe or a constant volume sample injection loop. Record the volume injected to the nearest 0.1 μL, and the resulting peak size in area or peak height units. Re-equilibrate the HPLC column at the initial gradient conditions for at least 10 min between injections.
12.6Identify the parameters in the sam-ple by comparing the retention time of -the peaks in the sample chromatogram with those of -the peaks in standard chromatograms. The -width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
12.7If the response for a peak exceeds the working range of the system, dilute the extract with acetonitrile and reanalyze.
12.8If the measurement of the peak response is prevented by the presence of interferences, further cleanup is required.
13.1The packed column GC procedure will not resolve certain isomeric pairs as indicated in Section 1.3 and Table 2. The liquid chromatographic procedure (Section 12) must be used for these parameters.
13.2To achieve maximum sensitivity with this method, the extract must be concentrated to 1.0 mL. Add a clean boiling chip to the methylene chloride extract in the concentrator tube. Attach a two-ball micro-Snyder column. Prewet the micro-Snyder column by adding about 0.5 mL of methylene chloride to the top. Place the micro-K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 5 to 10 min. At the proper rate of distillation the balls will actively chatter but the chambers will not flood. When the apparent volume of liquid reaches 0.5 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min. Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with a minimum amount of methylene chloride. Adjust the final volume to 1.0 mL and stopper the concentrator tube.
13.3Table 2 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times that were obtained under these conditions. An example of the separations achieved by this column is shown in Figure 3. Other packed or capillary (open-tubular) columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met.
13.4Calibrate the gas chromatographic system daily as described in Section 7.
13.5If the internal standard calibration procedure is being used, the internal standard must be added to the sample extract and mixed thoroughly immediately before injection into the gas chromatograph.
13.6Inject 2 to 5 μL of the sample extract or standard into the gas chromatograph using the solvent-flush technique.
13.7Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
13.8If the response for a peak exceeds the working range of the system, dilute the extract and reanalyze.
13.9If the measurement of the peak response is prevented by the presence of interferences, further cleanup is required.
14.1Determine the concentration of individual compounds in the sample.
14.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
14.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
15.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
15.2This method has been tested for linearity of spike recovery from reagent water and has been demonstrated to be applicable over the concentration range from 8 × MDL to 800 × MDL
15.3This method was tested by 16 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations over the range 0.1 to 425 μg/L.
1. 40 CFR part 136, appendix B.
2. “Determination of Polynuclear Aromatic Hydrocarbons in Industrial and Municipal Wastewaters,” EPA 600/4-82-025, National Technical Information Service, PB82-258799, Springfield, Virginia 22161, June 1982.
3. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
9. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
10. Burke, J.A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
11. Cole, T., Riggin, R., and Glaser, J. “Evaluation of Method Detection Limits and Analytical Curve for EPA Method 610—PNAs,” International Symposium on Polynuclear Aromatic Hydrocarbons, 5th, Battelle's Columbus Laboratories, Columbus, Ohio (1980).
12. “EPA Method Study 20, Method 610 (PNA's),” EPA 600/4-84-063, National Technical Information Service, PB84-211614, Springfield, Virginia 22161, June 1984.
1.1This method covers the determination of certain haloethers. The following parameters can be determined by this method:
1.2This is a gas chromatographic (GC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compounds above, compound identifications should be supported by at least one additional qualitative technique. This method describes analytical conditions for a second gas chromatographic column that can be used to confirm measurements made with the primary column. Method 625 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for all of the parameters listed above, using the extract produced by this method.
1.3The method detection limit (MDL, defined in Section 14.1)
1.4The sample extraction and concentration steps in this method are essentially the same as in Methods 606, 608, 609, and 612. Thus, a single sample may be extracted to measure the parameters included in the scope of each of these methods. When cleanup is required, the concentration levels must be high enough to permit selecting aliquots, as necessary, to apply appropriate cleanup procedures. The analyst is allowed the latitude, under Section 12, to select
1.5Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.6This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is extracted with methylene chloride using a separatory funnel. The methylene chloride extract is dried and exchanged to hexane during concentration to a volume of 10 mL or less. The extract is separated by gas chromatography and the parameters are then measured with a halide specific detector.
2.2The method provides a Florisil column cleanup procedure to aid in the elimination of interferences that may be encountered.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in gas chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. The cleanup procedure in Section 11 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Table 1.
3.3Dichlorobenzenes are known to coelute with haloethers under some gas chromatographic conditions. If these materials are present together in a sample, it may be necessary to analyze the extract with two different column packings to completely resolve all of the compounds.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnel—2-L, with Teflon stopcock.
5.2.2Drying column—Chromatographic col-umn, approximately 400 mm long × 19 mm ID, -with coarse frit filter disc.
5.2.3Chromatographic column—400 mm long × 19 mm ID, with Teflon stopcock and coarse frit filter disc at bottom (Kontes K-420540-0224 or equivalent).
5.2.4Concentrator tube, Kuderna-Danish—-10-mL, graduated (Kontes K-570050-1025 or equival-ent). Calibration must be checked at the volumes em-ployed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.5Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.6Snyder column, Kuderna-Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.7Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2°C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighing 0.0001 g.
5.6Gas chromatograph—An analytical system complete with temperature programmable gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.6.1Column 1—1.8 m long × 2 mm ID glass, -packed with 3% SP-1000 on Supel-co-port (100/120 mesh) or equivalent. This column was used to develop the method performance statements in Section 14. Guidelines for the use of alternate column packings are provided in Section 12.1.
5.6.2Column 2—1.8 m long × 2 mm ID glass, packed with 2,6-diphenylene oxide polymer (60/80 mesh), Tenax, or equivalent.
5.6.3Detector—Halide specific detector: electrolytic conductivity or microcoulo-metric. These detectors have proven effec-tive in the analysis of wastewaters for -the parameters listed in the scope (Section 1.1). The Hall conductivity detector was used to develop the method performance statements in Section 14. Guidelines for the use of alternate detectors are provided in Section 12.1. Although less selective, an electron capture detector is an acceptable alternative.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Sodium thiosulfate—(ACS) Granular.
6.3Acetone, hexane, methanol, methylene chloride, petroleum ether (boiling range 30-60 °C)—Pesticide quality or equivalent.
6.4Sodium sulfate—(ACS) Granular, anhydrous. Purify by heating at 400 °C for 4 h in a shallow tray.
6.5Florisil—PR Grade (60/100 mesh). Purchase activated at 1250 °F and store in the dark in glass containers with ground glass stoppers or foil-lined screw caps. Before use, activate each batch at least 16 h at 130 °C in a foil-covered glass container and allow to cool.
6.6Ethyl ether—Nanograde, redistilled in glass if necessary.
6.6.1Ethyl ether must be shown to be free of peroxides before it is used as indicated by EM Laboratories Quant test strips. (Available from Scientific Products Co., Cat. No. P1126-8, and other suppliers.)
6.6.2Procedures recommended for removal of peroxides are provided with the test strips. After cleanup, 20 mL of ethyl alcohol preservative must be added to each liter of ether.
6.7Stock standard solutions (1.00 μg/μL)—Stock standard solutions can be prepared from pure standard materials or purchased as certified solutions.
6.7.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in acetone and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.7.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4 °C and protect from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.7.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.8Quality control check sample concentrate—See Section 8.2.1.
7.1Establish gas chromatographic operating conditions equivalent to those given in Table 1. The gas chromatographic system
7.2External standard calibration procedure:
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with hexane. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples.
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with hexane. One of the standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, a new calibration curve must be prepared for that compound.
7.5The cleanup procedure in Section 11 utilizes Florisil column chromatography. Florisil from different batches or sources may vary in adsorptive capacity. To standardize the amount of Florisil which is used, the use of lauric acid value
7.6Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.4, 11.1, and 12.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate ac-cepta-ble accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 100 μg/mL in acetone. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at a concentration of 100 μg/L by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check sam-ples according to the method beginning -in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1.The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 100 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none (2) the larger of either 5 times higher than the expected background concentration or 100 μg/L.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory.
8.4.1Prepare the QC check standard by adding 1.0 m/L of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the -chromatogram, confirmatory techniques such as gas -chromatography with a dissimilar column, specific element detector, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1Grab samples must be collected in glass containers. Conventional sampling prac-tices
9.2All samples must be iced or refrigerated at 4
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel.
10.2Add 60 mL methylene chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer
10.4Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.5Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.6Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
Some of the haloethers are very volatile and significant losses will occur in concentration steps if care is not exercised. It is important to maintain a constant gentle evaporation rate and not to allow the liquid volume to fall below 1 to 2 mL before removing the K-D apparatus from the hot water bath.
10.7Momentarily remove the Snyder column, add 50 mL of hexane and a new boiling chip, and reattach the Snyder column. Raise the temperature of the water bath to 85 to 90 °C. Concentrate the extract as in Section 10.6, except use hexane to prewet the column. The elapsed time of concentration should be 5 to 10 min.
10.8Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL syringe is recommended for this operation. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw--cap vial. If the sample extract requires no -further cleanup, proceed with gas -chromatographic analysis (Section 12). If the sam-ple requires further cleanup, -proceed to Section 11.
10.9Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use of a cleanup procedure, the analyst may use the procedure below or any other appropriate procedure. However, the analyst first must demonstrate that the requirements of Section 8.2 can be met using the method as revised to incorporate the cleanup procedure.
11.2Florisil column cleanup for haloethers:
11.2.1Adjust the sample extract volume to 10 mL.
11.2.2Place a weight of Florisil (nominally 20 g) predetermined by calibration (Section 7.5), into a chromatographic column. Tap the column to settle the Florisil and add 1 to 2 cm of anhydrous sodium sulfate to the top.
11.2.3Preelute the column with 50 to 60 mL of petroleum ether. Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the sample extract onto the column by decantation and subsequent petroleum ether washings. Discard the eluate. Just prior to exposure of the sodium sulfate layer to the air, begin eluting the column with 300 mL of ethyl ether/petroleum ether (6+94) (V/V). Adjust the elution rate to approximately 5 mL/min and collect the eluate in a 500-mL K-D flask equipped with a 10-mL concentrator tube. This fraction should contain all of the haloethers.
11.2.4Concentrate the fraction as in Section 10.6, except use hexane to prewet the column. When the apparatus is cool, remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with hexane. Adjust the volume of the cleaned up extract to 10 mL with hexane and analyze by gas chromatography (Section 12).
12.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. Examples of the separations achieved by Columns 1 and 2 are shown in Figures 1 and 2, respectively. Other packed or capillary (open-tubular) columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met.
12.2Calibrate the system daily as described in Section 7.
12.3If the internal standard calibration procedure is being used, the internal standard must be added to the sample extract and mixed thoroughly immediately before injection into the gas chromatrograph.
12.4Inject 2 to 5 μL of the sample extract or standard into the gas chromatograph using the solvent-flush technique.
12.5Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weight heavily in the interpretation of chromatograms.
12.6If the response for a peak exceeds the working range of the system, dilute the extract and reanalyze.
12.7If the measurement of the peak response is prevented by the presence of interferences, further cleanup is required.
13.1Determine the concentration of individual compounds in the sample.
13.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
13.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method has been tested for linearity of spike recovery from reagent water and has been demonstrated to be applicable over the concentration range from 4 × MDL to 1000 × MDL.
14.3This method was tested by 20 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations over the range 1.0 to 626 μ/L.
1. 40 CFR part 136, appendix B.
2. “Determination of Haloethers in Industrial and Municipal Wastewaters,” EPA 600/4-81-062, National Technical Information Service, PB81-232290, Springfield, Virginia 22161, July 1981.
3. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constitutents,” American Society for Testing and Materials, Philadelphia.
4. “Carcinogens—Working Carcinogens, ” Department of Health, Education, and Welfare, Public Health Services, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Mills., P.A. “Variation of Florisil Activity: Simple Method for Measuring Absorbent Capacity and Its Use in Standardizing
8. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
9. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
10. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
11. Burke, J.A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
12. “EPA Method Study 21, Method 611, Haloethers,” EPA 600/4-84-052, National Technical Information Service, PB84-205939, Springfield, Virginia 22161, June 1984.
1.1This method covers the determination of certain chlorinated hydrocarbons. The following parameters can be determined by this method:
1.2This is a gas chromatographic (GC) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1. When this method is used to analyze unfamiliar samples for any or all of the compounds above, compound identifications should be supported by at least one additional qualitative technique. This method describes a second gas chromatographic column that can be used to confirm measurements made with the primary column. Method 625 provides gas chromatograph/mass spectrometer (GC/MS) conditions appropriate for the qualitative and quantitative confirmation of results for all of the parameters listed above, using the extract produced by this method.
1.3The method detection limit (MDL, defined in Section 14.1)
1.4The sample extraction and concentration steps in this method are essentially the same as in Methods 606, 608, 609, and 611. Thus, a single sample may be extracted to measure the parameters included in the scope of each of these methods. When cleanup is required, the concentration levels must be high enough to permit selecting aliquots, as necessary, to apply appropriate cleanup procedures. The analyst is allowed the latitude, under Section 12, to select chromatographic conditions appropriate for the simultaneous measurement of combinations of these parameters.
1.5Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.6This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph and in the interpretation of gas chromatograms. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is extracted with methylene chloride using a separatory funnel. The methylene chloride extract is dried and exchanged to hexane during concentration to a volume of 10 mL or less. The extract is separated by gas chromatography and the parameters are then measured with an electron capture detector.
2.2The method provides a Florisil column cleanup procedure to aid in the elimination of interferences that may be encountered.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in gas chromatograms. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. The cleanup procedure in Section 11 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Table 1.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1cL or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flow meter is required to collect flow proportional composites.
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnel—2-L, with Teflon stopcock.
5.2.2Drying column—Chromatographic column, approximately 400 mm long × 19 mm ID, with coarse frit filter disc.
5.2.3Chromatographic column—300 long × 10 mm ID, with Teflon stopcock and coarse frit filter disc at bottom.
5.2.4Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.5Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.6Snyder column, Kuderna-Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.7Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2 °C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighing 0.0001 g.
5.6Gas chromatograph—An analytical system complete with gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, gases, detector, and strip-chart recorder. A data system is recommended for measuring peak areas.
5.6.1Column 1—1.8 m long × 2 mm ID glass, packed with 1% SP-1000 on Supelcoport (100/120 mesh) or equivalent. Guidelines for the use of alternate column packings are provide in Section 12.1.
5.6.2Column 2—1.8 m long ×2 mm ID glass, packed with 1.5% OV-1/2.4% OV-225 on Supelcoport (80/100 mesh) or equivalent. This column was used to develop the method performance statements in Section 14.
5.6.3Detector— Electron capture detector. This detector has proven effective in the analysis of wastewaters for the parameters listed in the scope (Section 1.1), and was used to develop the method performance statements in Section 14. Guidelines for the use of alternate detectors are provided in Section 12.1.
6.1Reagent water— Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Acetone, hexane, isooctane, methanol, methylene chloride, petroleum ether (boiling range 30 to 60 °C)—Pesticide quality or equivalent.
6.3Sodium sulfate—(ACS) Granular, anhydrous. Purify heating at 400 °C for 4 h in a shallow tray.
6.4Florisil—PR grade (60/100 mesh). Purchase activated at 1250 °F and store in the dark in glass containers with ground glass stoppers or foil-lined screw caps. Before use, activate each batch at least 16 h at 130 °C in a foil-covered glass container and allow to cool.
6.5Stock standard solution (1.00 μg/μL)—Stock standard solutions can be prepared from pure standard materials or purchased as certified solutions.
6.5.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in isooctane and dilute to volume in a 120-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When compound purity is assayed to be 96% or greater, the weight can be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards can be used at any concentration if they are certified by the manufacturer or by an independent source.
6.5.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4
6.5.3Stock standard solutions must be replaced after six months, or sooner if comparision with check standards indicates a problem.
6.6Quality control check sample concentrate—See Section 8.2.1.
7.1Establish gas chromatographic operating conditions equivalent to those given in Table 1. The gas chromatographic system can be calibrated using the external standard technique (Section 7.2) or the internal standard technique (Section 7.3).
7.2External standard calibration procedure:
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask and diluting to volume with isooctane. One of the external standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.2.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against the mass injected. The results can be used to prepare a calibration curve for each compound. Alternatively, if the ratio of response to amount injected (calibration factor) is a constant over the working range (<10% relative standard deviation, RSD), linearity through the origin can be assumed and the average ratio or calibration factor can be used in place of a calibration curve.
7.3Internal standard calibration procedure—To use this approach, the analyst must select one or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Because of these limitations, no internal standard can be suggested that is applicable to all samples.
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding volumes of one or more stock standards to a volumetric flask. To each calibration standard, add a known constant amount of one or more internal standards, and dilute to volume with isooctane. One of the standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the detector.
7.3.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 12 and tabulate peak height or area responses against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
7.4The working calibration curve, calibration factor, or RF must be verified on each working day by the measurement of one or more calibration standards. If the response for any parameter varies from the predicted response by more than ±15%, a new calibration curve must be prepared for that compound.
7.5Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When the results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.4, 11.1, and 12.1) to improve the separations or lower the cost of measurements. Each time such modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at the following concentrations in acetone: Hexachloro-substituted parameters, 10 μg/mL; any other chlorinated hydrocarbon, 100 μg/mL. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at the test concentrations shown in Table 2 by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
The large number of parameters in Table 2 presents a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.
8.2.6When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.
8.2.6.1Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2Beginning with Section 8.2.2, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compounds of interest beginning with Section 8.2.2.
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spike sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at the test concentration in Section 8.2.2 or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none by (2) the larger of either 5 times higher than the expected background concentration or the test concentration in Section 8.2.2.
8.3.2 Analyze one sample aliquot to determine the background concentration (B) of each parameter. In necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100 (A-B)%/T, where T is the known true value of the spike.
8.3.3 Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4 If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4. If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory.
8.4.1 Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Sections 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak on the chromatogram, confirmatory techniques such as gas chromatography with a dissimilar column, specific element detector, or mass spectrometer must be used. Whenever possible, the laboratory should analyze standard reference materials and participate in relevent performance evaluation studies.
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All samples must be iced or refrigerated at 4 °C from the time of collection until extraction.
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel.
10.2Add 60 mL of methylele chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
10.3Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner.
10.4Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.5Pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.6Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 to 2 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
The dichloribenzenes have a sufficiently high volatility that significant losses may occur in concentration steps if care is not exercised. It is important to maintain a constant gentle evaporation rate and not to allow the liquid volume to fall below 1 to 2 mL before removing the K-D apparatus from the hot water bath.
10.7Momentarily remove the Snyder column, add 50 mL of hexane and a new boiling chip, and reattach the Snyder column. Raise the tempeature of the water bath to 85 to 90 °C. Concentrate the extract as in Section 10.6, except use hexane to prewet the column. The elapsed time of concentration should be 5 to 10 min.
10.8Romove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL syringe is recommended for this operation. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extract will be stored longer than two days, it should be transferred to a Teflon-sealed screw-cap vial. If the sample extract requires no further cleanup, proceed with gas chromatographic analysis (Section 12). If the sample requires further cleanup, proceed to Section 11.
10.9Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use of a cleanup procedure, the analyst may use the procedure below or any other appropriate procedure. However, the analyst first must demonstrate that the requirements of Section 8.2 can be met using the method as revised to incorporate the cleanup procedure.
11.2Florisil column cleanup for chlorinated hydrocarbons:
11.2.1Adjust the sample extract to 10 mL with hexane.
11.2.2Place 12 g of Florisil into a chromatographic column. Tap the column to settle the Florisil and add 1 to 2 cm of anhydrous sodium sulfate to the top.
11.2.3Preelute the column with 100 mL of petroleum ether. Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the sample extract onto the column by decantation and subsequent petroleum ether washings. Discard the eluate. Just prior to exposure of the sodium sulfate layer to the air, begin eluting the column with 200 mL of petroleum ether and collect the eluate in a 500-mL K-D flask equipped with a 10-mL concentrator tube. This fraction should contain all of the chlorinated hydrocarbons.
11.2.4Concentrate the fraction as in Section 10.6, except use hexane to prewet the column. When the apparatus is cool, remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with hexane. Analyze by gas chromatography (Section 12).
12.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. Examples of the separations achieved by Columl 2 are shown in Figures 1 and 2. Other packed or capillary (open-tubular) columns, chromatographic conditions, or detectors may be used if the requirements of Section 8.2 are met.
12.2Calibrate the system daily as described in Section 7.
12.3If the internal standard calibration procedure is being used, the internal standard must be added to the sample extract and mixed throughly immediately before injection into the gas chromatograph.
12.4Inject 2 to 5 μL of the sample extract or standard into the gas chromatograph using the solvent-flush techlique.
12.5Identify the parameters in the sample by comparing the retention times of the peaks in the sample chromatogram with those of the peaks in standard chromatograms. The width of the retention time window used to make identifications should be based upon measurements of actual retention time variations of standards over the course of a day. Three times the standard deviation of a retention time for a compound can be used to calculate a suggested window size; however, the experience of the analyst should weigh heavily in the interpretation of chromatograms.
12.6If the response for a peak exceeds the working range of the system, dilute the extract and reanalyze.
12.7If the measurement of the peak response is prevented by the presence of interferences, further cleanup is required.
13.1Determine the concentration of individual compounds in the sample.
13.1.1If the external standard calibration procedure is used, calculate the amount of material injected from the peak response using the calibration curve or calibration factor determined in Section 7.2.2. The concentration in the sample can be calculated from Equation 2.
13.1.2If the internal standard calibration procedure is used, calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.2 and Equation 3.
13.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method has been tested for linearity of spike recovery from reagent water and has been demonstrated to be applicable over the concentration range from 4×MDL to 1000×MDL.
14.3This method was tested by 20 laboratories using reagent water, drinking water, surface water, and three industrial wastewaters spiked at six concentrations over the range 1.0 to 356 μg/L.
1. 40 CFR part 136, appendix B.
2. “Determination of Chlorinated Hydrocarbons In Industrial and Municipal Wastewaters, “EPA 6090/4-84-ABC, National Technical Information Service, PBXYZ, Springfield, Virginia, 22161 November 1984.
3. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American
4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
9. Burke, J.A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
10. “Development of Detection Limits, EPA Method 612, Chlorinated Hydrocarbons,” Special letter report for EPA Contract 68-03-2625, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
11. “EPA Method Study Method 612—Chlorinated Hydrocarbons,” EPA 600/4-84-039, National Technical Information Service, PB84-187772, Springfield, Virginia 22161, May 1984.
12. “Method Performance for Hexachlorocyclopentadiene by Method 612,” Memorandum from R. Slater, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, December 7, 1983.
1.1This method covers the determination of 2,3,7,8-tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD). The following parameter may be determined by this method:
1.2This is a gas chromatographic/mass spectrometer (GC/MS) method applicable to the determination of 2,3,7,8-TCDD in municipal and industrial discharges as provided under 40 CFR 136.1. Method 625 may be used to screen samples for 2,3,7,8-TCDD. When the screening test is positive, the final qualitative confirmation and quantification must be made using Method 613.
1.3The method detection limit (MDL, defined in Section 14.1)
1.4Because of the extreme toxicity of this compound, the analyst must prevent exposure to himself, of to others, by materials knows or believed to contain 2,3,7,8-TCDD. Section 4 of this method contains guidelines and protocols that serve as minimum safe-handling standards in a limited-access laboratory.
1.5Any modification of this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.6This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph/mass spectrometer and in the interpretation of mass spectra. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1A measured volume of sample, approximately 1-L, is spiked with an internal standard of labeled 2,3,7,8-TCDD and extracted with methylene chloride using a separatory funnel. The methylene chloride extract is exchanged to hexane during concentration to a volume of 1.0 mL or less. The extract is then analyzed by capillary column GC/MS to separate and measure 2,3,7,8-TCDD.
2.2The method provides selected column chromatographic cleanup proceudres to aid in the elimination of interferences that may be encountered.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated backgrounds at the masses (m/z) monitored. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to mininmize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are coextracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled. 2,3,7,8-TCDD is often associated with other interfering chlorinated compounds which are at concentrations several magnitudes higher than that of 2,3,7,8-TCDD. The cleanup producers in Section 11 can be used to overcome many of these interferences, but unique samples may require additional cleanup approaches
3.3The primary column, SP-2330 or equivalent, resolves 2,3,7,8-TCDD from the other 21 TCDD insomers. Positive results using any other gas chromatographic column must be confirmed using the primary column.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to
4.2Each laboratory must develop a strict safety program for handling 2,3,7,8-TCDD. The following laboratory practices are recommended:
4.2.1Contamination of the laboratory will be minimized by conducting all manipulations in a hood.
4.2.2The effluents of sample splitters for the gas chromatograph and roughing pumps on the GC/MS should pass through either a column of activated charcoal or be bubbled through a trap containing oil or high-boiling alcohols.
4.2.3Liquid waste should be dissolved in methanol or ethanol and irradiated with ultraviolet light with a wavelength greater than 290 nm for several days. (Use F 40 BL lamps or equivalent). Analyze liquid wastes and dispose of the solutions when 2,3,7,8-TCDD can no longer be detected.
4.3Dow Chemical U.S.A. has issued the following precautimns (revised November 1978) for safe handling of 2,3,7,8-TCDD in the laboratory:
4.3.1The following statements on safe handling are as complete as possible on the basis of available toxicological information. The precautions for safe handling and use are necessarily general in nature since detailed, specific recommendations can be made only for the particular exposure and circumstances of each individual use. Inquiries about specific operations or uses may be addressed to the Dow Chemical Company. Assistance in evaluating the health hazards of particular plant conditions may be obtained from certain consulting laboratories and from State Departments of Health or of Labor, many of which have an industrial health service. 2,3,7,8-TCDD is extremely toxic to laboratory animals. However, it has been handled for years without injury in analytical and biological laboratories. Techniques used in handling radioactive and infectious materials are applicable to 2,3,7,8,-TCDD.
4.3.1.1Protective equipment—Throw--away plas-tic gloves, apron or lab coat, safety glasses, and a lab hood adequate for radioactive work.
4.3.1.2Training—Workers must be trained in the proper method of removing contaminated gloves and clothing without contacting the exterior surfaces.
4.3.1.3Personal hygiene—Thorough washing of hands and forearms after each manipulation and before breaks (coffee, lunch, and shift).
4.3.1.4Confinement—Isolated work area, posted with signs, segregated glassware and tools, plastic-backed absorbent paper on benchtops.
4.3.1.5Waste—Good technique includes mini-miz-ing contaminated waste. Plastic bag liners should be used in waste cans. Janitors must be trained in the safe handling of waste.
4.3.1.6Disposal of wastes—2,3,7,8-TCDD decomposes above 800 °C. Low-level waste such as absorbent paper, tissues, animal remains, and plastic gloves may be burned in a good incinerator. Gross quantities (milligrams) should be packaged securely and disposed through commercial or governmental channels which are capable of handling high-level radioactive wastes or extremely toxic wastes. Liquids should be allowed to evaporate in a good hood and in a disposable container. Residues may then be handled as above.
4.3.1.7Decontamination—For personal decontamination, use any mild soap with plenty of scrubbing action. For decontamination of glassware, tools, and surfaces, Chlorothene NU Solvent (Trademark of the Dow Chemical Company) is the least toxic solvent shown to be effective. Satisfactory cleaning may be accomplished by rinsing with Chlorothene, then washing with any detergent and water. Dishwater may be disposed to the sewer. It is prudent to minimize solvent wastes because they may require special disposal through commercial sources which are expensive.
4.3.1.8Laundry—Clothing known to be contaminated should be disposed with the precautions described under Section 4.3.1.6. Lab coats or other clothing worn in 2,3,7,8-TCDD work areas may be laundered.
Clothing should be collected in plastic bags. Persons who convey the bags and launder the clothing should be advised of the hazard and trained in proper handling. The clothing may be put into a washer without contact if the launderer knows the problem. The washer should be run through a cycle before being used again for other clothing.
4.3.1.9Wipe tests—A useful method of determining cleanliness of work surfaces and tools is to wipe the surface with a piece of filter paper. Extraction and analysis by gas chromatography can achieve a limit of sensitivity of 0.1 μg per wipe. Less than 1 μg of 2,3,7,8-TCDD per sample indicates acceptable cleanliness; anything higher warrants further cleaning. More than 10 μg on a wipe sample constitutes an acute hazard and requires prompt cleaning before further use of the equipment or work space. A high (>10 μg)
4.3.1.10Inhalation—Any procedure that may produce airborne contamination must be done with good ventilation. Gross losses to a ventilation system must not be allowed. Handling of the dilute solutions normally used in analytical and animal work presents no inhalation hazards except in the case of an accident.
4.3.1.11Accidents—Remove contaminated clothing immediately, taking precautions not to contaminate skin or other articles. Wash exposed skin vigorously and repeatedly until medical attention is obtained.
5.1Sampling equipment, for discrete or composite sampling.
5.1.1Grab sample bottle—1-L or 1-qt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. Before use, however, the compressible tubing should be thoroughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flow meter is required to collect flow proportional composites.
5.1.3Clearly label all samples as “POISON” and ship according to U.S. Department of Transportation regulations.
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnels—2-L and 125-mL, with Teflon stopcock.
5.2.2Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.3Evaporative flask, Kuderna-Danish—500-mL (Kontes K-570001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.4Snyder column, Kuderna-Danish—Three-ball macro (Kontes K-503000-0121 or equivalent).
5.2.5Snyder column, Kuderna-Danish—Two--ball micro (Kontes K-569001-0219 or equivalent).
5.2.6Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.7Chromatographic column—300 mm long × 10 mm ID, with Teflon stopcock and coarse frit filter disc at bottom.
5.2.8Chromatographic column—400 mm long × 11 mm ID, with Teflon stopcock and coarse frit filter disc at bottom.
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min or Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2 °C). The bath should be used in a hood.
5.5GC/MS system:
5.5.1Gas chromatograph—An analytical system complete with a temperature programmable gas chromatograph and all required accessories including syringes, analytical columns, and gases. The injection port must be designed for capillary columns. Either split, splitless, or on-column injection techniques may be employed, as long as the requirements of Section 7.1.1 are achieved.
5.5.2Column—60 m long × 0.25 mm ID glass or fused silica, coated with SP-2330 (or equivalent) with a film thickness of 0.2 μm. Any equivalent column must resolve 2, 3, 7, 8-TCDD from the other 21 TCDD isomers.
5.5.3Mass spectrometer—Either a low resolution mass spectrometer (LRMS) or a high resolution mass spectrometer (HRMS) may be used. The mass spectrometer must be equipped with a 70 V (nominal) ion source and be capable of aquiring m/z abundance data in real time selected ion monitoring (SIM) for groups of four or more masses.
5.5.4GC/MS interface—Any GC to MS interface can be used that achieves the requirements of Section 7.1.1. GC to MS interfaces constructed of all glass or glass-lined materials are recommended. Glass surfaces can be deactivated by silanizing with dichlorodimethylsilane. To achieve maximum sensitivity, the exit end of the capillary column should be placed in the ion source. A short piece of fused silica capillary can be used as the interface to overcome problems associated with straightening the exit end of glass capillary columns.
5.5.5The SIM data acquired during the chromatographic program is defined as the Selected Ion Current Profile (SICP). The SICP can be acquired under computer control or as a real time analog output. If computer control is used, there must be software available to plot the SICP and report peak height or area data for any m/z in the SICP between specified time or scan number limits.
5.6Balance—Analytical, capable of accurately weighing 0.0001 g.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of 2, 3, 7, 8-TCDD.
6.2Sodium hydroxide solution (10 N)—Dissolve 40 g of NaOH (ACS) in reagent water and dilute to 100 mL. Wash the solution with methylene chloride and hexane before use.
6.3Sodium thiosulfate—(ACS) Granular.
6.4Sulfuric acid—Concentrated (ACS, sp. gr. 1.84).
6.5Acetone, methylene chloride, hexane, benzene, ortho-xylene, tetradecane—Pesticide quality or equivalent.
6.6Sodium sulfate—(ACS) Granular, anhydrous. Purify by heating at 400 °C for 4 h in a shallow tray.
6.7Alumina—Neutral, 80/200 mesh (Fisher Scientific Co., No. A-540 or equivalent). Before use, activate for 24 h at 130 °C in a foil-covered glass container.
6.8Silica gel—High purity grade, 100/120 mesh (Fisher Scientific Co., No. S-679 or equivalent).
6.9Stock standard solutions (1.00 μg/μL)—Stock standard solutimns can be prepared from pure standard materials or purchased as certified solutions. Acetone should be used as the solvent for spiking solutions; ortho-xylene is recommended for calibration standards for split injectors; and tetradecane is recommended for splitless or on-colum injectors. Analyze stock internal standards to verify the absence of native 2,3,7,8-TCDD.
6.9.1Prepare stock standard solutions of 2,3,7,8-TCDD (mol wt 320) and either
6.9.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store in an isolated refrigerator protected from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards or spiking solutions from them.
6.9.3Stock standard solutions must be replaced after six months, or sooner if comparison with check standards indicates a problem.
6.10Internal standard spiking solution (25 ng/mL)—Using stock standard solution, prepare a spiking solution in acetone of either
6.11Quality control check sample concentrate—See Section 8.2.1.
7.1Establish gas chromatograhic operating conditions equivalent to those given in Table 1 and SIM conditions for the mass spectrometer as described in Section 12.2 The GC/MS system must be calibrated using the internal standard technique.
7.1.1Using stock standards, prepare calibration standards that will allow measurement of relative response factors of at least three concentration ratios of 2,3,7,8-TCDD to internal standard. Each calibration standard must be prepared to contain the internal standard at a concentration of 25 ng/mL. If any interferences are contributed by the internal standard at m/z 320 and 322, its concentration may be reduced in the calibration standards and in the internal standard spiking solution (Section 6.10). One of the calibration standards should contain 2,3,7,8-TCDD at a concentration near, but above, the MDL and the other 2,3,7,8-TCDD concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the GC/MS system.
7.1.2Using injections of 2 to 5 μL, analyze each calibration standardaccording to Section 12 and tabulate peak height or area response against the concentration of 2,3,7,8-TCDD and internal standard. Calculate response factors (RF) for 2,3,7,8-TCDD using Equation 1.
7.1.3The working calibration curve or RF must be verified on each working day by the measurement of one or more 2,3,7,8-TCDD calibration standards. If the response for 2,3,7,8-TCDD varies from the predicted response by more than ±15%, the test must be repeated using a fresh calibration standard. Alternatively, a new calibration curve must be prepared.
7.2Before using any cleanup procedure, the analyst must process a series of calibration standards through the procedure to validate elution patterns and the absence of interferences from the reagents.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Sections 10.5, 11.1, and 12.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 10% of all samples with native 2,3,7,8-TCDD to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 10% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing 2,3,7,8-TCDD at a concentration of 0.100 μg/mL in acetone. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at a concentration of 0.100 μg/L (100 ng/L) by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5Compare s and (X
8.3The laboratory must, on an ongoing basis, spike at least 10% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing one to ten samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of 2,3,7,8-TCDD in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of 2,3,7,8-TCDD in the sample is not being checked against a limit specific to that parameter, the spike should be at 0.100 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the
8.3.2Analyze one sample aliquot to determine the background concentration (B) of 2,3,7,8-TCDD. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentration in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of 2,3,7,8-TCDD. Calculate percent recovery (P) as 100(A-B)%T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for 2,3,7,8-TCDD with the corresponding QC acceptance criteria found in Table 2. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If the recovery of 2,3,7,8-TCDD falls outside the designated range for recovery, a check standard must be analyzed as described in Section 8.4.
8.4If the recovery of 2,3,7,8-TCDD fails the acceptance criteria for recovery in Section 8.3, a QC check standard must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the complexity of the sample matrix and the performance of the laboratory.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of 2,3,7,8-TCDD. Calculate the percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6It is recommended that the lab-o-ra-tory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All samples must be iced or refrigerated at 4 °C and protected from light from the time of collection until extraction. Fill the sample bottles and, if residual chlorine is present, add 80 mg of sodium thiosulfate per liter of sample and mix well. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine.
9.3Label all samples and containers “POISON” and ship according to applicable U.S. Department of Transportation regulations.
9.4All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel.
10.2Add 1.00 mL of internal standard spiking solution to the sample in the separatory funnel. If the final extract will be concentrated to a fixed volume below 1.00 mL (Section 12.3), only that volume of spiking solution should be added to the sample so that the final extract will contain 25 ng/mL of internal standard at the time of analysis.
10.3Add 60 mL of methylene chloride to the sample bottle, seal, and shake 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min. with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the vmlume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask.
10.4Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner.
10.5Assemble a Kuderna-Danish (K-D) con-cen-tra-tor by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.6Pour the combined extract into the K-D concentrator. Rinse the Erlenmeyer flask with 20 to 30 mL of methylele chloride to complete the quantitative transfer.
10.7Add one or two clean boiling chips to the evaporative flask and attach a three-ball Snyder column. Prewet the Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min.
10.8Momentarily remove the Snyder column, add 50 mL of hexane and a new boiling chip, and reattach the Snyder column. Raise the temperature of the water bath to 85 to 90°C. Concentrate the extract as in Section 10.7, except use hexane to prewet the column. Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of hexane. A 5-mL syringe is recommended for this operation. Set aside the K-D glassware for reuse in Section 10.14.
10.9Pour the hexane extract from the concentrator tube into a 125-mL separatory funnel. Rinse the concentrator tube four times with 10-mL aliquots of hexane. Combine all rinses in the 125-mL separatory funnel.
10.10Add 50 mL of sodium hydroxide solution to the funnel and shake for 30 to 60 s. Discard the aqueous phase.
10.11Perform a second wash of the organic layer with 50 mL of reagent water. Discard the aqueous phase.
10.12Wash the hexane layer with a least two 50-mL aliquots of concentrated sulfuric acid. Continue washing the hexane layer with 50-mL aliquots of concentrated sulfuric acid until the acid layer remains colorless. Discard all acid fractions.
10.13Wash the hexane layer with two 50-mL aliquots of reagent water. Discard the aqueous phases.
10.14Transfer the hexane extract into a 125-mL Erlenmeyer flask containing 1 to 2 g of anhydrous sodium sulfate. Swirl the flask for 30 s and decant the hexane extract into the reassembled K-D apparatus. Complete the quantitative transfer with two 10-mL hexane rinses of the Erlenmeyer flask.
10.15Replace the one or two clean boiling chips and concentrate the extract to 6 to 10 mL as in Section 10.8.
10.16Add a clean boiling chip to the concentrator tube and attach a two-ball micro-Snyder column. Prewet the column by adding about 1 mL of hexane to the top. Place the micro-K-D apparatus on the water bath so that the concentrator tube is partially immersed in the hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood. When the apparent volume of liquid reaches about 0.5 mL, remove the K-D apparatus and allow it to drain and cool for at least 10 min. Remove the micro-Snyder column and rinse its lower joint into the concentrator tube with 0.2 mL of hexane.
Adjust the extract volume to 1.0 mL with hexane. Stopper the concentrator tube and store refrigerated and protected from light if further processing will not be performed immediately. If the extract will be stored
10.17Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1Cleanup procedures may not be necessary for a relatively clean sample matrix. If particular circumstances demand the use of a cleanup procedure, the analyst may use either procedure below or any other appropriate procedure.
11.2Alumina column cleanup for 2,3,7,8-TCDD:
11.2.1Fill a 300 mm long × 10 mm ID chromatographic column with activated alumina to the 150 mm level. Tap the column gently to settle the alumina and add 10 mm of anhydrous sodium sulfate to the top.
11.2.2Preelute the column with 50 mL of hexane. Adjust the elution rate to 1 mL/min. Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the 1.0-mL sample extract onto the column using two 2-mL portions of hexane to complete the transfer.
11.2.3Just prior to exposure of the sodium sulfate layer to the air, add 50 mL of 3% methylene chloride/95% hexane (V/V) and continue the elution of the column. Discard the eluate.
11.2.4Next, elute the column with 50 mL of 20% methylene chloride/80% hexane (V/V) into a 500-mL K-D flask equipped with a 10-mL concentrator tube. Concentrate the collected fraction to 1.0 mL as in Section 10.16 and analyze by GC/MS (Section 12).
11.3Silica gel column cleanup for 2,3,7,8-TCDD:
11.3.1Fill a 400 mm long × 11 mm ID chromatmgraphic column with silica gel to the 300 mm level. Tap the column gently to settle the silica gel and add 10 mm of anhydrous sodium sulfate to the top.
11.3.2Preelute the column with 50 mL of 20% benzene/80% hexane (V/V). Adjust the elution rate to 1 mL/min. Discard the eluate and just prior to exposure of the sodium sulfate layer to the air, quantitatively transfer the 1.0-mL sample extract onto the column using two 2-mL portions of 20% benzene/80% hexane to complete the transfer.
11.3.3Just prior to exposure of the sodium sulfate layer to the air, add 40 mL of 20% benzene/80% hexane to the column. Collect the eluate in a clean 500-mL K-D flask equipped with a 10-mL concentrator tube. Concentrate the collected fraction to 1.0 mL as in Section 10.16 and analyze by GC/MS.
12.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. Other capillary columns or chromatographic conditions may be used if the requirements of Sections 5.5.2 and 8.2 are met.
12.2Analyze standards and samples with the mass spectrometer operating in the selected ion monitoring (SIM) mode using a dwell time to give at least seven points per peak. For LRMS, use masses at m/z 320, 322, and 257 for 2,3,7,8-TCDD and either m/z 328 for
12.3If lower detection limits are required, the extract may be carefully evaporated to dryness under a gentle stream of nitrogen with the concentrator tube in a water bath at about 40 °C. Conduct this operation immediately before GC/MS analysis. Redissolve the extract in the desired final volume of ortho-xylene or tetradecane.
12.4Calibrate the system daily as described in Section 7.
12.5Inject 2 to 5 μL of the sample extract into the gas chromatograph. The volume of calibration standard injected must be measured, or be the same as all sample injection volumes.
12.6The presence of 2,3,7,8-TCDD is qualitatively confirmed if all of the following criteria are achieved:
12.6.1The gas chromatographic column must resolve 2,3,7,8-TCDD from the other 21 TCDD isomers.
12.6.2The masses for native 2,3,7,8-TCDD (LRMS-m/z 320, 322, and 257 and HRMS-m/z 320 and 322) and labeled 2,3,7,8-TCDD (m/z 328 or 332) must exhibit a simultaneous maximum at a retention time that matches that of native 2,3,7,8-TCDD in the calibration standard, with the performance specifications of the analytical system.
12.6.3The chlorine isotope ratio at m/z 320 and m/z 322 must agree to within±10% of that in the calibration standard.
12.6.4The signal of all peaks must be greater than 2.5 times the noise level.
12.7For quantitation, measure the response of the m/z 320 peak for 2,3,7,8-TCDD
12.8Co-eluting impurities are suspected if all criteria are achieved except those in Section 12.6.3. In this case, another SIM analysis using masses at m/z 257, 259, 320 and either m/a 328 or m/z 322 can be performed. The masses at m/z 257 and m/z 259 are indicative of the loss of one chlorine and one carbonyl group from 2,3,7,8-TCDD. If masses m/z 257 and m/z 259 give a chlorine isotope ratio that agrees to within ±10% of the same cluster in the calibration standards, then the presence of TCDD can be confirmed. Co-eluting DDD, DDE, and PCB residues can be confirmed, but will require another injection using the appropriate SIM masses or full repetitive mass scans. If the response for
12.9If broad background interference restricts the sensitivity of the GC/MS analysis, the analyst should employ additional cleanup procedures and reanalyze by GC/MS.
12.10In those circumstances where these procedures do not yield a definitive conclusion, the use of high resolution mass spectrometry is suggested.
13.1Calculate the concentration of 2,3,7,8-TCDD in the sample using the response factor (RF) determined in Section 7.1.2 and Equation 2.
13.2For each sample, calculate the percent recovery of the internal standard by comparing the area of the m/z peak measured in the sample to the area of the same peak in the calibration standard. If the recovery is below 50%, the analyst should review all aspects of his analytical technique.
13.3Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method was tested by 11 laboratories using reagent water, drinking water, surface water, and three industrial waste-waters spiked at six concentrations over -the range 0.02 to 0.20 μg/L.
1. 40 CFR part 136, appendix B.
2. “Determination of TCDD in Industrial and Municipal Wastewaters,” EPA 600/4-82-028, National Technical Information Service, PB82-196882, Springfield, Virginia 22161, April 1982.
3. Buser, H.R., and Rappe, C. “High Resolution Gas Chromatography of the 22 Tetrachlorodibenzo-p-dioxin Isomers,”
4. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
5. Harless, R. L., Oswald, E. O., and Wilkinson, M. K. “Sample Preparation and Gas Chromatography/Mass Spectrometry Determination of 2,3,7,8-Tetrachlorodibenzo-p-dioxin,”
6. Lamparski, L. L., and Nestrick, T. J. “Determination of Tetra-, Hepta-, and Octachlorodibenzo-p-dioxin Isomers in Particulate Samples at Parts per Trillion Levels,”
7. Longhorst, M. L., and Shadoff, L. A. “Determination of Parts-per-Trillion Concentrations of Tetra-, Hexa-, and Oc-ta-chloro-di-benzo--p-dioxins in Human Milk,”
8. “Carcinogens—Working with Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
9. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occuptional Safety and Health Administration, OSHA 2206 (Revised, January 1976).
10. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
11. Provost, L. P., and Elder, R. S., “In-terpretation of Percent Recovery Data,” -
12. ASTM Annual Book of Standards, Part 31, D3370-76, “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
13. “Methods, 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
14. Wong, A.S. et al. “The Determination of 2,3,7,8-TCDD in Industrial and Municipal Wastewaters, Method 613, Part 1—Development and Detection Limits,” G. Choudhay, L. Keith, and C. Ruppe, ed., Butterworth Inc., (1983).
15. “EPA Method Study 26, Method 613: 2,3,7,8-Tetrachlorodibenzo-p-dioxin,” EPA 600/4-84-037, National Technical Information Service, PB84-188879, Springfield, Virginia 22161, May 1984.
1.1This method covers the determination of a number of purgeable organics. The following parameters may be determined by this method:
1.2The method may be extended to screen samples for acrolein (STORET No. 34210, CAS No. 107-02-8) and acrylonitrile (STORET No. 34215, CAS No. 107-13-1), however, the preferred method for these two compounds in Method 603.
1.3This is a purge and trap gas chro-ma-to-graphic/-mass spectrometer (GC/MS) method applicable to the determination of the compounds listed above in municipal and industrial discharges as provided under 40 CFR 136.1.
1.4The method detection limit (MDL, defined in Section 14.1)
1.5Any modification to this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5. Depending upon the nature of the modification and the extent of intended use, the applicant may be required to demonstrate that the modifications will produce equivalent results when applied to relevant wastewaters.
1.6This method is restricted to use by or under the supervision of analysts experienced in the operation of a purge and trap system and a gas chromatograph/mass spectrometer and in the interpretation of mass spectra. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1An inert gas is bubbled through a 5-mL water sample contained in a specially-designed purging chamber at ambient temperature. The purgeables are efficiently transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbent trap where the purgeables are trapped. After purging is completed, the trap is heated and backflushed with the inert gas to desorb the purgeables onto a gas chromatographic column. The gas chromatograph is temperature programmed to separate the purgeables which are then detected with a mass spectrometer.
3.1Impurities in the purge gas, organic compounds outgassing from the plumbing ahead of the trap, and solvent vapors in the laboratory account for the majority of contamination problems. The analytical system must be demonstated to be free from contamination under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3. The use of non-Teflon plastic tubing, non-Teflon thread sealants, or flow controllers with rubber components in the purge and trap system should be avoided.
3.2Samples can be contaminated by diffusion of volatile organics (particularly fluorocarbons and methylene chloride) through the septum seal into the sample during shipment and storage. A field reagent blank prepared from reagent water and carried through the sampling and handling protocol can serve as a check on such contamination.
3.3Contamination by carry-over can occur -whenever high level and low level samples are sequentially analyzed. To reduce carry-over, the purging device and sample syringe must be rinsed with reagent water between sample analyses. Whenever an unusually concentrated sample is encountered, it should be followed by an analysis of reagent water to check for cross contamination. For samples containing large amounts of water-soluble materials, suspended solids, high boiling compounds or high pureeable levels, it may be necessary to wash the purging device with a detergent solution, rinse it with distilled water, and then dry it in a 105 °C oven between analyses. The trap and other parts of the system are also subject to contamination; therefore, frequent bakeout and purging of the entire system may be required.
4.1The toxicity or carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this methmd. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
4.2.The following parameters covered by this method have been tentatively classified as known or suspected, human or mammalian carcinogens: benzene, carbon tetrachloride, chloroform, 1,4-dichlorobenzene, and vinyl chloride. Primary standards of these toxic compounds should be prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be worn when the analyst handles high concentrations of these toxic compounds.
5.1Sampling equipment, for discrete sampling.
5.1.1Vial—25-mL capacity or larger, equipped -with a screw cap with a hole in the center (Pierce #13075 or equivalent). Detergent wash, rinse with tap and distilled water, and dry at 105 °C before use.
5.1.2Septum—Teflon-faced silicane (Pierce #12722 or equivalent). Detergent wash, rinse with tap and distilled water, and dry at 105 °C for 1 h before use.
5.2Purge and trap system—The purge and trap system consists of three separate pieces of equipment: A purging device, trap, and desorber. Several complete systems are now commercially available.
5.2.1The purging device must be designed to accept 5-mL samples with a water column at least 3 cm deep. The gaseous head space between the water column and the trap must have a total volume of less than 15 mL. The purge gas must pass though the water column as finely divided bubbles with a diameter of less than 3 mm at the origin. The purge gas must be introduced no more than 5 mm from the base of the water column. The purging device illustrated in Figure 1 meets these design criteria.
5.2.2The trap must be at least 25 cm long and have an inside diameter of at least 0.105 in. The trap must be packed to contain the following minimum lengths of adsorbents: 1.0 cm of methyl silicone coated packing (Section 6.3.2), 15 cm of 2,6-dyphenylene oxide polymer (Section 6.3.1), and 8 cm of silica gel (Section 6.3.3). The minimum specifications for the trap are illustrated in Figure 2.
5.2.3The desorber should be capable of rapidly heating the trap to 180 °C. The polymer section of the trap should not be heated higher than 180 °C and the remaining sections should not exceed 200 °C. The desorber illustrated in Figure 2 meets these design criteria.
5.2.4The purge and trap system may be assembled as a separate unit or be coupled to a gas chromatograph as illustrated in Figures 3 and 4.
5.3GC/MS system:
5.3.1Gas chromatograph—An analytical system complete with a temperature programmable gas chromatograph suitable for on-column injection and all required accessories including syringes, analytical columns, and gases.
5.3.2Column—6 ft long × 0.1 in ID stainless steel or glass, packed with 1% SP-1000 on Carbopack B (60/80 mesh) or equivalent. This column was used to develop the method performance statements in Section 14. Guidelines for the use of alternate column packings are provided in Section 11.1.
5.3.3Mass spectrometer—Capable of scanning from 20 to 260 amu every 7 s or less, utilizing 70 V (nominal) electron energy in the electron impact ionization mode, and producing a mass spectrum which meets all the criteria in Table 2 when 50 ng of 4-bromo-flu-o-ro-ben-zene (BFB) is injected through the GC inlet.
5.3.4GC/MS interface—Any GC to MS interface that gives acceptable calibration points at 50 ng or less per injection for each of the parameters of interest and achieves all acceptable performance criteria (Section 10) may be used. GC to MS interfaces constructed of all glass or glass-lined materials are recommended. Glass can be deactivated by silanizing with dichlorodimethylsilane.
5.3.5Data system—A computer system must be interfaced to the mass spectrometer that allows the continuous acquisition and storage on machine-readable media of all mass spectra obtained throughout the duration of the chromatographic program. The computer must have software that allows searching any GC/MS data file for specific m/z (masses) and plotting such m/z abundances versus time or scan number. This type of plot is defined as an Extracted Ion Current Profile (EICP). Software must also be available that allows integrating the abundance in any EICP between specified time or scan number limits.
5.4Syringes—5-mL, glass hypodermic with Luerlok -tip (two each), if applicable to the purging device.
5.5Micro syringes—25-μL, 0.006 in. ID needle.
5.6Syringe valve—2-way, with Luer ends (three each).
5.7Syringe—5-mL, gas-tight with shut-off valve.
5.8Bottle—15-mL, screw-cap, with Teflon cap liner.
5.9Balance—Analytical, capable of accurately weighing 0.0001 g.
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.1.1Reagent water can be generated by passing tap water through a carbon filter bed containing about 1 lb of activated carbon (Filtrasorb-300, Calgon Corp., or equivalent).
6.1.2A water purification system (Millipore Super-Q or equivalent) may be used to generate reagent water.
6.1.3Reagent water may also be prepared by boiling water for 15 min. Subsequently, while maintaining the temperature at 90 °C, bubble a contaminant-free inert gas through the water for 1 h. While still hot, transfer the water to a narrow mouth screw-cap bottle and seal with a Teflon-lined septum and cap.
6.2Sodium thiosulfate—(ACS) Granular.
6.3Trap materials:
6.3.12,6-Diphenylene oxide polymer—Tenax, (60/80 mesh), chromatographic grade or equivalent.
6.3.2Methyl silicone packing—3% OV-1 on Chromosorb-W (60/80 mesh) or equivalent.
6.3.3Silica gel—35/60 mesh, Davison, grade-15 or equivalent.
6.4Methanol—Pesticide quality or equivalent.
6.5Stock standard solutions—Stock stand-ard solutions may be prepared from pure -standard materials or purchased as certi-fied solutions. Prepare stock standard solutions in methanol using assayed liquids or gases as appropriate. Because of the toxicity of some of the compounds, primary dilutions of these materials should be prepared in a hood. A NIOSH/MESA approved toxic gas respirator should be used when the analyst handles high concentrations of such materials.
6.5.1Place about 9.8 mL of methanol into a 10-mL ground glass stoppered volumetric flask. Allow the flask to stand, unstoppered, for about 10 min or until all alcohol wetted surfaces have dried. Weigh the flask to the nearest 0.1 mg.
6.5.2Add the assayed reference material:
6.5.2.1Liquids—Using a 100-μL syringe, immediately add two or more drops of assayed reference material to the flask, then reweigh. Be sure that the drops fall directly into the alcohol without contacting the neck of the flask.
6.5.2.2Gases—To prepare standards for any of the four halocarbons that boil below 30 °C (bromomethane, chloroethane, chloromethane, and vinyl chloride), fill a 5-mL valved gas-tight syringe with the reference standard to the 5.0-mL mark. Lower the needle to 5 mm above the methanol meniscus. Slowly introduce the reference standard above the surface of the liquid (the heavy gas will rapidly dissolve in the methanol).
6.5.3Reweigh, dilute to volume, stopper, then mix by inverting the flask several times. Calculate the concentration in μg/μL from the net gain in weight. When compound purity is assayed to be 96% or greater, the weight may be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards may be used at any concentration if they are certified by the manufacturer or by an independent source.
6.5.4Transfer the stock standard solution into a Teflon-sealed screw-cap bottle. Store, with minimal headspace, at −10 to −20 °C and protect from light.
6.5.5Prepare fresh standards weekly for the four gases and 2-chloroethylvinyl ether. All other standards must be replaced after one month, or sooner if comparison with check standards indicates a problem.
6.6Secondary dilution standards—Using stock solutions, prepare secondary dilution standards in methanol that contain the compounds of interest, either singly or mixed together. The secondary dilution standards should be prepared at concentrations such that the aqueous calibration standards prepared in Section 7.3 will bracket the working range of the analytical system. Secondary dilution standards should be stored with minimal headspace and should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.7Surrogate standard spiking solution—Select a minimum of three surrogate compounds from Table 3. Prepare stock standard solutions for each surrogate standard in methanol as described in Section 6.5. Prepare a surrogate standard spiking solution from these stock standards at a concentration of 15 μg/mL in water. Store the solutions at 4 °C in Teflon-sealed glass containers with a minimum of headspace. The solutions should be checked frequently for stability. The addition of 10 μL of this solution of 5 mL of sample or standard is equivalent to a concentration of 30 μg/L of each surrogate standard.
6.8BFB Standard—Prepare a 25 μg/mL solution of BFB in methanol.
6.9Quality control check sample concentrate—See Section 8.2.1.
7.1Assemble a purge and trap system that meets the specifications in Section 5.2. Condition the trap overnight at 180 °C by backflushing with an inert gas flow of at least 20 mL/min. Condition the trap for 10 min once daily prior to use.
7.2Connect the purge and trap system to a gas chromatograph. The gas chromatograph must be operated using temperature and flow rate conditions equivalent to those given in Table 1.
7.3Internal standard calibration procedure—To use this approach, the analyst must select three or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standard is not affected by method or matrix interferences. Some recommended internal standards are listed in Table 3.
7.3.1Prepare calibration standards at a minimum of three concentration levels for each parameter by carefully adding 20.0 μL of one or more secondary dilution standards to 50, 250, or 500 mL of reagent water. A 25-μL syringe with a 0.006 in. ID needle should be used for this operation. One of the calibration standards should be at a concentration near, but above, the MDL (Table 1) and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the GC/MS system. These aqueous standards can be stored up to 24 h, if held in sealed vials with zero headspace as described in Section 9.2. If not so stored, they must be discarded after 1 h.
7.3.2Prepare a spiking solution containing each of the internal standards using the procedures described in Sections 6.5 and
7.3.3Analyze each calibration standard according to Section 11, adding 10 μL of internal standard spiking solution directly to the syringe (Section 11.4). Tabulate the area response of the characteristic m/z against concentration for each compound and internal standard, and calculate response factors (RF) for each compound using Equation 1.
7.4The working calibration curve or RF must be verified on each working day by the measurement of a QC check sample.
7.4.1Prepare the QC check sample as described in Section 8.2.2.
7.4.2Analyze the QC check sample according to the method beginning in Section 10.
7.4.3For each parameter, compare the response (Q) with the corresponding calibration acceptance criteria found in Table 5. If the responses for all parameters of interest fall within the designated ranges, analysis of actual samples can begin. If any individual Q falls outside the range, proceed according to Section 7.4.4.
The large number of parameters in Table 5 present a substantial probability that one or more will not meet the calibration acceptance criteria when all parameters are analyzed.
7.4.4Repeat the test only for those parameters that failed to meet the calibration acceptance criteria. If the response for a parameter does not fall within the range in this second test, a new calibration curve or RF must be prepared for that parameter according to Section 7.3.
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occurring in chromatography, the analyst is permitted certain options (detailed in Section 11.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Each day, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system are under control.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 5% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 5% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must spike all samples with surrogate standards to monitor continuing laboratory performance. This procedure is described in Section 8.5.
8.1.7The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.6.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 10 μg/mL in methanol. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample
8.2.2Prepare a QC check sample to contain 20 μg/L of each parameter by adding 200 μL of QC check sample concentrate to 100 mL of reagent water.
8.2.3Analyze four 5-mL aliquots of the well-mixed QC check sample according to the method beginning in Section 10.
8.2.4Calculate the average recovery (X
8.2.5For each parameter compare s and X
The large number of parameters in Table 5 present a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.
8.2.6When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.
8.2.6.1Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.3.
8.2.6.2Beginning with Section 8.2.3, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compounds of interest beginning with Section 8.2.3.
8.3The laboratory must, on an ongoing basis, spike at least 5% of the samples from each sample site being monitored to assess accuracy. For laboratories analyzing 1 to 20 samples per month, at least one spiked sample per month is required.
8.3.1The concentration of the spike in the sample should be determined as follows:
8.3.1.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 20 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.2Analyze one 5-mL sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second 5-mL sample aliquot with 10 μL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 5. These acceptance criteria wer calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required anlaysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory. If the entire list of parameters in Table 5 must be measured in the sample in Section 8.3, the probability that the analysis of a QC check standard will be required is high. In this case the QC check standard should be routinely analyzed with the spiked sample.
8.4.1Prepare the QC check standard by adding 10 μL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 5 mL of reagent water. The QC check standard needs only to
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As a quality control check, the laboratory must spike all samples with the surrogate standard spiking solutions as described in Section 11.4, and calculate the percent recovery of each surrogate compound.
8.6As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.7It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of the samples. Field duplicates may be analyzed to assess the precision of the environmental measurements. Whenever possible, the laboratory should analyze standard reference materials and participate in relevant performance evaluation studies.
9.1All samples must be iced or refrigerated from the time of collection until analysis. If the sample contains residual chlorine, add sodium thiosulfate preservative (10 mg/40 mL is sufficient for up to 5 ppm Cl
9.2Grab samples must be collected in glass containers having a total volume of at least 25 mL. Fill the sample bottle just to overflowing in such a manner that no air bubbles pass through the sample as the bottle is being filled. Seal the bottle so that no air bubbles are entrapped in it. If preservative has been added, shake vigorously for 1 min. Maintain the hermetic seal on the sample bottle until time of analysis.
9.3Experimental evidence indicates that some aromatic compounds, notably benzene, toluene, and ethyl benzene are susceptible to rapid biological degradation under certain environmental conditions.
9.4All samples must be analyzed within 14 days of collection.
10.1At the beginning of each day that analyses are to be performed, the GC/MS system must be checked to see if acceptable performance criteria are achieved for BFB.
10.2These performance tests require the following instrumental parameters:
10.3At the beginning of each day, inject 2 μL of BFB solution directly on the column. Alternatively, add 2 μL of BFB solution to 5.0 mL of reagent water or standard solution and analyze the solution according to section 11. Obtain a background-corrected mass spectrum of BFB and confirm that all the key m/z criteria in Table 2 are achieved. If all the criteria are not achieved, the analyst must retune the mass spectrometer and repeat the test until all criteria are achieved.
11.1Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and MDL that can be achieved under these conditions. An example of the separations achieved by this column is shown in Figure 5. Other packed columns or chromatographic conditions may be used if the requirements of Section 8.2 are met.
11.2After achieving the key m/z abundance criteria in Section 10, calibrate the system daiy as described in Section 7.
11.3Adjust the purge gas (helium) flow rate to 40 mL/min. Attach the trap inlet to the purging device, and set the purge and trap system to purge (Figure 3). Open the syringe valve located on the purging device sample introduction needle.
11.4Allow the sample to come to ambient temperature prior to introducing it into the syringe. Remove the plunger from a 5-mL syringe and attach a closed syringe valve. Open the sample bottle (or standard) and carefully pour the sample into the syringe barrel to just short of overflowing. Replace the syringe plunger and compress the sample. Open the syringe valve and vent any residual air while adjusting the sample volume to 5.0 mL. Since this process of taking an aliquot destroys the validity of the sample for future analysis, the analyst should fill a second syringe at this time to protect against possible loss of data. Add 10.0 μL of the surrogate spiking solution (Section 6.7) and 10.0 μL of the internal standard spiking solution (Section 7.3.2) through the valve bore, then close the valve. The surrogate and internal standards may be mixed and added as a single spiking solution.
11.5Attach the syringe-syringe valve assembly to the syringe valve on the purging device. Open the syringe valves and inject the sample into the purging chamber.
11.6Close both valves and purge the sample for 11.0±0.1 min at ambient temperature.
11.7After the 11-min purge time, attach the trap to the chromatograph, adjust the purge and trap system to the desorb mode (Figure 4), and begin to temperature program the gas chromatograph. Introduce the trapped materials to the GC column by rapidly heating the trap to 180 °C while backflushing the trap with an inert gas between 20 and 60 mL/min for 4 min. If rapid heating of the trap cannot be achieved, the GC cloumn must be used as a secondary trap by cooling it to 30 °C (subambient temperature, if problems persist) instead of the initial program temperature of 45 °C.
11.8While the trap is being desorbed into the gas chromatograph, empty the purging chamber using the sample introduction syringe. Wash the chamber with two 5-mL flushes of reagent water.
11.9After desorbing the sample for 4 min, recondition the trap by returning the purge and trap system to the purge mode. Wait 15 s then close the syringe valve on the purging device to begin gas flow through the trap. The trap temperature should be maintained at -180 °C. After approximately 7 min, turn off the trap heater and open the syringe valve to stop the gas flow through the trap. When the trap is cool, the next sample can be analyzed.
11.10If the response for any m/z exceeds the working range of the system, prepare a dilution of the sample with reagent water from the aliquot in the second syringe and reanalyze.
12.1Obtain EICPs for the primary m/z (Table 4) and at least two secondary masses for each parameter of interest. The following criteria must be met to make a qualitative identification:
12.1.1The characteristic masses of each parameter of interest must maximize in the same or within one scan of each other.
12.1.2The retention time must fall within ±30 s of the retention time of the authentic compound.
12.1.3The relative peak heights of the three characteristic masses in the EICPs must fall within ±20% of the relative intensities of these masses in a reference mass spectrum. The reference mass spectrum can be obtained from a standard analyzed in the GC/MS system or from a reference library.
12.2Structural isomers that have very similar mass spectra and less than 30 s difference in retention time, can be explicitly identified only if the resolution between authentic isomers in a standard mix is acceptable. Acceptable resolution is achieved if the baseline to valley height between the isomers is less than 25% of the sum of the two peak heights. Otherwise, structural isomers are identified as isomeric pairs.
13.1When a parameter has been identified, the quantitation of that parameter should be based on the integrated abundance from the EICP of the primary characteristic m/z given in Table 4. If the sample produces an interference for the primary m/z, use a secondary characteristic m/z to quantitate.
Calculate the concentration in the sample using the response factor (RF) determined in Section 7.3.3 and Equation 2.
13.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
14.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
14.2This method was tested by 15 laboratories using reagent water, drinking water, surface water, and industrial wastewaters spiked at six concentrations over the range 5-600 μg/L.
1. 40 CFR part 136, appendix B.
2. Bellar, T.A., and Lichtenberg, J.J. “Determining Volatile Organics at Microgram-per-Litre Levels by Gas Chromatography,”
3. Bellar, T.A., and Lichtenberg, J.J. “Semi-Automated Headspace Analysis of Drinking Waters and Industrial Waters for Purgeable Volatile Organic Compounds, ” Measurement of Organic Pollutants in Water and Wastewater, C.E. Van Hall, editor, American Society for Testing and Materials, Philadelphia, PA. Special Technical Publication 686, 1978.
4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
9. Budde, W.L., and Eichelberger, J.W. “Performance Tests for the Evaluation of Computerized Eas Chromatography/Mass Spectrometry Equipment and Laboratories,” EPA-600/4-80-025, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, April 1980.
10. Eichelberger, J.W., Harris, L.E., and Budde, W.L. “Reference Compound to Calibrate Ion Abundance Measurement in Gas Chromatography—Mass Spectrometry Systems,”
11. “Method Detection Limit for Methods 624 and 625,” Olynyk, P., Budde, W.L., and Eichelberger, J.W. Unpublished report, May 14, 1980.
12. “EPA Method Study 29 EPA Method 624—Purgeables,” EPA 600/4-84-054, National Technical Information Service, PB84-209915, Springfield, Virginia 22161, June 1984.
13.“Method Performance Data for Method 624,” Memorandum from R. Slater and T. Pressley, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, January 17, 1984.
1.1This method covers the determination of a number of organic compounds that are partitioned into an organic solvent and are amenable to gas chromatography. The parameters listed in Tables 1 and 2 may be qualitatively and quantitatively determined using this method.
1.2The method may be extended to include the parameters listed in Table 3. Benzidine can be subject to oxidative losses during solvent concentration. Under the alkaline conditions of the extraction step, α-BHC, γ-BHC, endosulfan I and II, and endrin are subject to decomposition. Hexachlorocyclopentadiene is subject to thermal decomposition in the inlet of the gas chromatograph, chemical reaction in acetone solution, and photochemical decomposition. N-nitrosodimethylamine is difficult to separate from the solvent under the chromatographic conditions described. N-nitrosodiphenylamine decomposes in the gas chromatographic inlet and cannot be separated from diphenylamine. The preferred method for each of these parameters is listed in Table 3.
1.3This is a gas chromatographic/mass spectrometry (GC/MS) method
1.4The method detection limit (MDL, defined in Section 16.1)
1.5Any modification to this method, beyond those expressly permitted, shall be considered as a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5. Depending upon the nature of the modification and the extent of intended use, the applicant may be required to demonstrate that the modifications will produce equivalent results when applied to relevant wastewaters.
1.6This method is restricted to use by or under the supervision of analysts experienced in the use of a gas chromatograph/mass spectrometer and in the interpretation of mass spectra. Each analyst must demonstrate the ability to generate acceptable results with this method using the procedure described in Section 8.2.
2.1 A measured volume of sample, approximately 1-L, is serially extracted with methylene chloride at a pH greater than 11 and again at a pH less than 2 using a separatory funnel or a continuous extractor.
3.1Method interferences may be caused by contaminants in solvents, reagents, glassware, and other sample processing hardware that lead to discrete artifacts and/or elevated baselines in the total ion current profiles. All of these materials must be routinely demonstrated to be free from interferences under the conditions of the analysis by running laboratory reagent blanks as described in Section 8.1.3.
3.1.1Glassware must be scrupulously cleaned.
3.1.2The use of high purity reagents and solvents helps to minimize interference problems. Purification of solvents by distillation in all-glass systems may be required.
3.2Matrix interferences may be caused by contaminants that are co-extracted from the sample. The extent of matrix interferences will vary considerably from source to source, depending upon the nature and diversity of the industrial complex or municipality being sampled.
3.3The base-neutral extraction may cause significantly reduced recovery of phenol, 2-methylphenol, and 2,4-dimethylphenol. The analyst must recognize that results obtained under these conditions are minimum concentrations.
3.4The packed gas chromatographic columns recommended for the basic fraction may not exhibit sufficient resolution for certain isomeric pairs including the following: anthracene and phenanthrene; chrysene and ben-zo-(a)-an-thra-cene; and ben-zo-(b)-flu-o-ran-thene and ben-zo-(k)-flu-o-ran-thene. The gas chromatographic reten-tion time and mass spectra for these -pairs of compounds are not suf-fi-ciently different to make an unambiguous identification. Alternative techniques should be used to identify and quantify these specific compounds, such as Method 610.
3.5In samples that contain an inordinate number of interferences, the use of chemical ionization (CI) mass spectrometry may make identification easier. Tables 6 and 7 give characteristic CI ions for most of the compounds covered by this method. The use of CI mass spectrometry to support electron ionization (EI) mass spectrometry is encouraged but not required.
4.1The toxicity or carcinogenicity of each reagent used in this method have not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
4.2The following parameters covered by this method have been tentatively classified as known or suspected, human or mammalian carcinogens: benzo(a)anthracene, benzidine, 3,3′-dichlorobenzidine, benzo(a)pyrene,
5.1Sampling equipment, for discrete or composit sampling.
5.1.1Grab sample bottle—1-L or 1-gt, amber glass, fitted with a screw cap lined with Teflon. Foil may be substituted for Teflon if the sample is not corrosive. If amber bottles are not available, protect samples from light. The bottle and cap liner must be washed, rinsed with acetone or methylene chloride, and dried before use to minimize contamination.
5.1.2Automatic sampler (optional)—The sampler must incorporate glass sample containers for the collection of a minimum of 250 mL of sample. Sample containers must be kept refrigerated at 4 °C and protected from light during compositing. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used. before use, however, the compressible tubing should be throughly rinsed with methanol, followed by repeated rinsings with distilled water to minimize the potential for contamination of the sample. An integrating flow meter is required to collect flow proportional composites.
5.2Glassware (All specifications are suggested. Catalog numbers are included for illustration only.):
5.2.1Separatory funnel—2-L, with Teflon stopcock.
5.2.2Drying column—Chromatographic column, 19 mm ID, with coarse frit
5.2.3Concentrator tube, Kuderna-Danish—10-mL, graduated (Kontes K-570050-1025 or equivalent). Calibration must be checked at the volumes employed in the test. Ground glass stopper is used to prevent evaporation of extracts.
5.2.4Evaporative flask, Kuderna-Danish—500-mL (Kontes K-57001-0500 or equivalent). Attach to concentrator tube with springs.
5.2.5Snyder column, Kuderna-Danish—Three all macro (Kontes K-503000-0121 or equivalent).
5.2.6Snyder column, Kuderna-Danish—Two--ball macro (Kontes K-569001-0219 or equivalent).
5.2.7Vials—10 to 15-mL, amber glass, with Teflon-lined screw cap.
5.2.8Continuous liquid—liquid extractor—Equipped with Teflon or glass connecting joints and stopcocks requiring no lubrication. (Hershberg-Wolf Extractor, Ace Glass Company, Vineland, N.J., P/N 6841-10 or equivalent.)
5.3Boiling chips—Approximately 10/40 mesh. Heat to 400 °C for 30 min of Soxhlet extract with methylene chloride.
5.4Water bath—Heated, with concentric ring cover, capable of temperature control (±2°C). The bath should be used in a hood.
5.5Balance—Analytical, capable of accurately weighing 0.0001 g.
5.6GC/MS system:
5.6.1Gas Chromatograph—An analytical system complete with a temperature programmable gas chromatograph and all required accessores including syringes, analytical columns, and gases. The injection port must be designed for on-column injection when using packed columns and for splitless injection when using capillary columns.
5.6.2Column for base/neutrals—1.8 m long × 2 mm ID glass, packed with 3% SP-2250 on Supelcoport (100/120 mesh) or equivalent. This column was used to develop the method performance statements in Section 16. Guide-lines for the use of alternate column pack-ings are provided in Section 13.1.
5.6.3Column for acids—1.8 m long × 2 mm ID glass, packed with 1% SP-1240DA on Supelcoport (100/120 mesh) or equivalent. This column was used to develop the method performance statements in Section 16. Guidelines for the use of alternate column packings are given in Section 13.1.
5.6.4Mass spectrometer—Capable of scanning from 35 to 450 amu every 7 s or less, utilizing a 70 V (nominal) electron energy in the electron impact ionization mode, and producing a mass spectrum which meets all the criteria in Table 9 when 50 ng of decafluorotriphenyl phosphine (DFTPP; bis(perfluorophenyl) phenyl phosphine) is injected through the GC inlet.
5.6.5GC/MS interface—Any GC to MS interface that gives acceptable calibration points at 50 ng per injection for each of the parameters of interest and achieves all acceptable performance criteria (Section 12) may be used. GC to MS interfaces constructed of all glass or glass-lined materials are recommended. Glass can be deactivated by silanizing with dichlorodimethylsilane.
5.6.6Data system—A computer system must be interfaced to the mass spectrometer that allows the contiluous acquisition and storage on machine-readable media of all mass spectra obtained throughout the duration of the chromatographic program. The computer must have software that allows searching any GC/MS data file for specific m/z and plotting such m/z abundances versus time or scan number. This type of plot is defined as an Extracted Ion Current Profile (EICP). Software must also be available that
6.1Reagent water—Reagent water is defined as a water in which an interferent is not observed at the MDL of the parameters of interest.
6.2Sodium hydroxide solution (10 N)—Dissolve 40 g of NaOH (ACS) in reagent water and dilute to 100 mL.
6.3Sodium thiosulfate—(ACS) Granular.
6.4Sulfuric acid (1+1)—Slowly, add 50 mL of H
6.5Acetone, methanol, methlylene chloride—Pesticide quality or equivalent.
6.6Sodium sulfate—(ACS) Granular, anhydrous. Purify by heating at 400 °C for 4 h in a shallow tray.
6.7Stock standard solutions (1.00 μg/μL)—standard solutions can be prepared from pure standard materials or purchased as certified solutions.
6.7.1Prepare stock standard solutions by accurately weighing about 0.0100 g of pure material. Dissolve the material in pesticide quality acetone or other suitable solvent and dilute to volume in a 10-mL volumetric flask. Larger volumes can be used at the convenience of the analyst. When compound purity is assayed to be 96% or greater, the weight may be used without correction to calculate the concentration of the stock standard. Commercially prepared stock standards may be used at any concentration if they are certified by the manufacturer or by an independent source.
6.7.2Transfer the stock standard solutions into Teflon-sealed screw-cap bottles. Store at 4 °C and protect from light. Stock standard solutions should be checked frequently for signs of degradation or evaporation, especially just prior to preparing calibration standards from them.
6.7.3Stock standard solutions must be replaced after six months, or sooner if comparison with quality control check samples indicate a problem.
6.8Surrogate standard spiking solution—Select a minimum of three surrogate compounds from Table 8. Prepare a surrogate standard spiking solution containing each selected surrogate compound at a concentration of 100 μg/mL in acetone. Addition of 1.00 mL of this solution to 1000 mL of sample is equivalent to a concentration of 100 μg/L of each surrogate standard. Store the spiking solution at 4 °C in Teflon-sealed glass container. The solution should be checked frequently for stability. The solution must be replaced after six months, or sooner if comparison with quality control check standards indicates a problem.
6.9DFTPP standard—Prepare a 25 μg/mL solution of DFTPP in acetone.
6.10Quality control check sample concentrate—See Section 8.2.1.
7.1Establish gas chromatographic operating parameters equivalent to those indicated in Table 4 or 5.
7.2Internal standard calibration procedure—To use this approach, the analyst must select three or more internal standards that are similar in analytical behavior to the compounds of interest. The analyst must further demonstrate that the measurement of the internal standards is not affected by method or matrix interferences. Some recommended internal standards are listed in Table 8. Use the base peak m/z as the primary m/z for quantification of the standards. If interferences are noted, use one of the next two most intense m/z quantities for quantification.
7.2.1Prepare calibration standards at a minimum of three concentration levels for each parameter of interest by adding appropriate volumes of one or more stock standards to a volumetric flask. To each calibration standard or standard mixture, add a known constant amount of one or more internal standards, and and dilute to volume with acetone. One of the calibration standards should be at a concentration near, but above, the MDL and the other concentrations should correspond to the expected range of concentrations found in real samples or should define the working range of the GC/MS system.
7.2.2Using injections of 2 to 5 μL, analyze each calibration standard according to Section 13 and tabulate the area of the primary characteristic m/z (Tables 4 and 5) against concentration for each compound and internal standard. Calculate response factors (RF) for each compound using Equation 1.
7.3The working calibration curve or RF must be verified on each working day by the
8.1Each laboratory that uses this method is required to operate a formal quality control program. The minimum requirements of this program consist of an initial demonstration of laboratory capability and an ongoing analysis of spiked samples to evaluate and document data quality. The laboratory must maintain records to document the quality of data that is generated. Ongoing data quality checks are compared with established performance criteria to determine if the results of analyses meet the performance characteristics of the method. When results of sample spikes indicate atypical method performance, a quality control check standard must be analyzed to confirm that the measurements were performed in an in-control mode of operation.
8.1.1The analyst must make an initial, one-time, demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2In recognition of advances that are occuring in chromatography, the analyst is permitted certain options (detailed in Sections 10.6 and 13.1) to improve the separations or lower the cost of measurements. Each time such a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2.
8.1.3Before processing any samples, the analyst must analyze a reagent water blank to demonstrate that interferences from the analytical system and glassware are under control. Each time a set of samples is extracted or reagents are changed, a reagent water blank must be processed as a safeguard against laboratory contamination.
8.1.4The laboratory must, on an ongoing basis, spike and analyze a minimum of 5% of all samples to monitor and evaluate laboratory data quality. This procedure is described in Section 8.3.
8.1.5The laboratory must, on an ongoing basis, demonstrate through the analyses of quality control check standards that the operation of the measurement system is in control. This procedure is described in Section 8.4. The frequency of the check standard analyses is equivalent to 5% of all samples analyzed but may be reduced if spike recoveries from samples (Section 8.3) meet all specified quality control criteria.
8.1.6The laboratory must maintain performance records to document the quality of data that is generated. This procedure is described in Section 8.5.
8.2To establish the ability to generate acceptable accuracy and precision, the analyst must perform the following operations.
8.2.1A quality control (QC) check sample concentrate is required containing each parameter of interest at a concentration of 100 μg/mL in acetone. Multiple solutions may be required. PCBs and multicomponent pesticides may be omitted from this test. The QC check sample concentrate must be obtained from the U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory in Cincinnati, Ohio, if available. If not available from that source, the QC check sample concentrate must be obtained from another external source. If not available from either source above, the QC check sample concentrate must be prepared by the laboratory using stock standards prepared independently from those used for calibration.
8.2.2Using a pipet, prepare QC check samples at a concentration of 100 μg/L by adding 1.00 mL of QC check sample concentrate to each of four 1-L aliquots of reagent water.
8.2.3Analyze the well-mixed QC check samples according to the method beginning in Section 10 or 11.
8.2.4Calculate the average recovery (X) in μg/L, and the standard deviation of the recovery (s) in μg/L, for each parameter using the four results.
8.2.5For each parameter compare s and X with the corresponding acceptance criteria for precision and accuracy, respectively, found in Table 6. If s and X for all parameters of interest meet the acceptance criteria, the system performance is acceptable and analysis of actual samples can begin. If any individual s exceeds the precision limit or any individual X falls outside the range for accuracy, the system performance is unacceptable for that parameter.
The large number of parameters in Table 6 present a substantial probability that one or more will fail at least one of the acceptance criteria when all parameters are analyzed.
8.2.6When one or more of the parameters tested fail at least one of the acceptance criteria, the analyst must proceed according to Section 8.2.6.1 or 8.2.6.2.
8.2.6.1Locate and correct the source of the problem and repeat the test for all parameters of interest beginning with Section 8.2.2.
8.2.6.2Beginning with Section 8.2.2, repeat the test only for those parameters that failed to meet criteria. Repeated failure, however, will confirm a general problem with the measurement system. If this occurs, locate and correct the source of the problem and repeat the test for all compounds of interest beginning with Section 8.2.2.
8.3The laboratory must, on an ongoing basis, spike at least 5% of the samples from each sample site being monitored to assess
8.3.1.The concentration of the spike in the sample should be determined as follows:
8.3.1If, as in compliance monitoring, the concentration of a specific parameter in the sample is being checked against a regulatory concentration limit, the spike should be at that limit or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.2If the concentration of a specific parameter in the sample is not being checked against a limit specific to that parameter, the spike should be at 100 μg/L or 1 to 5 times higher than the background concentration determined in Section 8.3.2, whichever concentration would be larger.
8.3.1.3If it is impractical to determine background levels before spiking (e.g., maximum holding times will be exceeded), the spike concentration should be (1) the regulatory concentration limit, if any; or, if none (2) the larger of either 5 times higher than the expected background concentration or 100 μg/L.
8.3.2Analyze one sample aliquot to determine the background concentration (B) of each parameter. If necessary, prepare a new QC check sample concentrate (Section 8.2.1) appropriate for the background concentrations in the sample. Spike a second sample aliquot with 1.0 mL of the QC check sample concentrate and analyze it to determine the concentration after spiking (A) of each parameter. Calculate each percent recovery (P) as 100(A-B)%/T, where T is the known true value of the spike.
8.3.3Compare the percent recovery (P) for each parameter with the corresponding QC acceptance criteria found in Table 6. These acceptance criteria were calculated to include an allowance for error in measurement of both the background and spike concentrations, assuming a spike to background ratio of 5:1. This error will be accounted for to the extent that the analyst's spike to background ratio approaches 5:1.
8.3.4If any individual P falls outside the designated range for recovery, that parameter has failed the acceptance criteria. A check standard containing each parameter that failed the criteria must be analyzed as described in Section 8.4.
8.4If any parameter fails the acceptance criteria for recovery in Section 8.3, a QC check standard containing each parameter that failed must be prepared and analyzed.
The frequency for the required analysis of a QC check standard will depend upon the number of parameters being simultaneously tested, the complexity of the sample matrix, and the performance of the laboratory. If the entire list of single-component parameters in Table 6 must be measured in the sample in Section 8.3, the probability that the analysis of a QC check standard will be required is high. In this case the QC check standard should be routinely analyzed with the spike sample.
8.4.1Prepare the QC check standard by adding 1.0 mL of QC check sample concentrate (Section 8.2.1 or 8.3.2) to 1 L of reagent water. The QC check standard needs only to contain the parameters that failed criteria in the test in Section 8.3.
8.4.2Analyze the QC check standard to determine the concentration measured (A) of each parameter. Calculate each percent recovery (P
8.4.3Compare the percent recovery (P
8.5As part of the QC program for the laboratory, method accuracy for wastewater samples must be assessed and records must be maintained. After the analysis of five spiked wastewater samples as in Section 8.3, calculate the average percent recovery (P
8.6As a quality control check, the laboratory must spike all samples with the surrogate standard spiking solution as described in Section 10.2, and calculate the percent recovery of each surrogate compound.
8.7It is recommended that the laboratory adopt additional quality assurance practices for use with this method. The specific practices that are most productive depend upon the needs of the laboratory and the nature of
9.1Grab samples must be collected in glass containers. Conventional sampling practices
9.2All sampling must be iced or refrigerated at 4 °C from the time of collection until extraction. Fill the sample bottles and, if residual chlorine is present, add 80 mg of sodium thiosulfate per liter of sample and mix well. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine.
9.3All samples must be extracted within 7 days of collection and completely analyzed within 40 days of extraction.
10.1Samples are usually extracted using separatory funnel techniques. If emulsions will prevent achieving acceptable solvent recovery with separatory funnel extractions, continuous extraction (Section 11) may be used. The separatory funnel extraction scheme described below assumes a sample volume of 1 L. When sample volumes of 2 L are to be extracted, use 250, 100, and 100-mL volumes of methylene chloride for the serial extraction of the base/neutrals and 200, 100, and 100-mL volumes of methylene chloride for the acids.
10.2Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Pour the entire sample into a 2-L separatory funnel. Pipet 1.00 mL of the surrogate standard spiking solution into the separatory funnel and mix well. Check the pH of the sample with wide-range pH paper and adjust to pH>11 with sodium hydroxide solution.
10.3Add 60 mL of methylene chloride to the sample bottle, seal, and shake for 30 s to rinse the inner surface. Transfer the solvent to the separatory funnel and extract the sample by shaking the funnel for 2 min. with periodic venting to release excess pressure. Allow the organic layer to separate from the water phase for a minimum of 10 min. If the emulsion interface between layers is more than one-third the volume of the solvent layer, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration of the emulsion through glass wool, centrifugation, or other physical methods. Collect the methylene chloride extract in a 250-mL Erlenmeyer flask. If the emulsion cannot be broken (recovery of less than 80% of the methylene chloride, corrected for the water solubility of methylene chloride), transfer the sample, solvent, and emulsion into the extraction chamber of a continuous extractor and proceed as described in Section 11.3.
10.4Add a second 60-mL volume of methylene chloride to the sample bottle and repeat the extraction procedure a second time, combining the extracts in the Erlenmeyer flask. Perform a third extraction in the same manner. Label the combined extract as the base/neutral fraction.
10.5Adjust the pH of the aqueous phase to less than 2 using sulfuric acid. Serially extract the acidified aqueous phase three times with 60-mL aliquots of methylene chloride. Collect and combine the extracts in a 250-mL Erlenmeyer flask and label the combined extracts as the acid fraction.
10.6For each fraction, assemble a Kuderna-Danish (K-D) concentrator by attaching a 10-mL concentrator tube to a 500-mL evaporative flask. Other concentration devices or techniques may be used in place of the K-D concentrator if the requirements of Section 8.2 are met.
10.7For each fraction, pour the combined extract through a solvent-rinsed drying column containing about 10 cm of anhydrous sodium sulfate, and collect the extract in the K-D concentrator. Rinse the Erlenmeyer flask and column with 20 to 30 mL of methylene chloride to complete the quantitative transfer.
10.8Add one or two clean boiling chips and attach a three-ball Snyder column to the evaporative flask for each fraction. Prewet each Snyder column by adding about 1 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in the hot water, and the entire lower rounded surface of the flask is bathed with hot vapor. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches 1 mL, remove the K-D apparatus from the water bath and allow it to drain and cool for at least 10 min. Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1 to 2 mL of methylene chloride. A 5-mL syringe is recommended for this operation.
10.9Add another one or two clean boiling chips to the concentrator tube for each fraction and attach a two-ball micro-Snyder column. Prewet the Snyder column by adding about 0.5 mL of methylene chloride to the top. Place the K-D apparatus on a hot water bath (60 to 65 °C) so that the concentrator tube is partially immersed in hot water. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will not flood with condensed solvent. When the apparent volume of liquid reaches about 0.5 mL, remove the K-D apparatus from the water bath and allow it to drain and cool for at least 10 min. Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with approximately 0.2 mL of acetone or methylene chloride. Adjust the final volume to 1.0 mL with the solvent. Stopper the concentrator tube and store refrigerated if further processing will not be performed immediately. If the extracts will be stored longer than two days, they should be transferred to Teflon-sealed screw-cap vials and labeled base/neutral or acid fraction as appropriate.
10.10Determine the original sample volume by refilling the sample bottle to the mark and transferring the liquid to a 1000-mL graduated cylinder. Record the sample volume to the nearest 5 mL.
11.1When experience with a sample from a given source indicates that a serious emulsion problem will result or an emulsion is encountered using a separatory funnel in Section 10.3, a continuous extractor should be used.
11.2Mark the water meniscus on the side of the sample bottle for later determination of sample volume. Check the pH of the sample with wide-range pH paper and adjust to pH >11 with sodium hydroxide solution. Transfer the sample to the continuous extractor and using a pipet, add 1.00 mL of surrogate standard spiking solution and mix well. Add 60 mL of methylene chloride to the sample bottle, seal, and shake for 30 s to rinse the inner surface. Transfer the solvent to the extractor.
11.3Repeat the sample bottle rinse with an additional 50 to 100-mL portion of methylene chloride and add the rinse to the extractor.
11.4Add 200 to 500 mL of methylene chloride to the distilling flask, add sufficient reagent water to ensure proper operation, and extract for 24 h. Allow to cool, then detach the distilling flask. Dry, concentrate, and seal the extract as in Sections 10.6 through 10.9.
11.5Charge a clean distilling flask with 500 mL of methylene chloride and attach it to the continuous extractor. Carefully, while stirring, adjust the pH of the aqueous phase to less than 2 using sulfuric acid. Extract for 24 h. Dry, concentrate, and seal the extract as in Sections 10.6 through 10.9.
12.1At the beginning of each day that analyses are to be performed, the GC/MS system must be checked to see if acceptable performance criteria are achieved for DFTPP.
12.2These performance tests require the following instrumental parameters:
12.3DFTPP performance test—At the beginning of each day, inject 2 μL (50 ng) of DFTPP standard solution. Obtain a background-corrected mass spectra of DFTPP and confirm that all the key m/z criteria in Table 9 are achieved. If all the criteria are not achieved, the analyst must retune the mass spectrometer and repeat the test until all criteria are achieved. The performance criteria must be achieved before any samples, blanks, or standards are analyzed. The taililg factor tests in Sections 12.4 and 12.5 may be performed simultaneously with the DFTPP test.
12.4Column performance test for base/neutrals—At the beginning of each day that the base/neutral fraction is to be analyzed for benzidine, the benzidine tailing factor must be calculated. Inject 100 ng of benzidine either separately or as a part of a standard mixture that may contain DFTPP and calculate the tailing factor. The benzidine tailing factor must be less than 3.0. Calculation of the tailing factor is illustrated in Figure 13.
12.5Column performance test for acids—At the beginning of each day that the acids are to be determined, inject 50 ng of pentachlorophenol either separately or as a part of a standard mix that may contain DFTPP. The tailing factor for pentachlorophenol must be less than 5. Calculation of the tailing factor is illustrated in Figure 13.
13.1Table 4 summarizes the recommended gas chromatographic operating conditions for the base/neutral fraction. Table 5 summarizes the recommended gas chromatographic
13.2After conducting the GC/MS performance tests in Section 12, calibrate the system daily as described in Section 7.
13.3The internal standard must be added to sample extract and mixed thoroughly immediately before it is injected into the instrument. This procedure minimizes losses due to adsorption, chemical reaction or evaporation.
13.4Inject 2 to 5 μL of the sample extract or standard into the GC/MS system using the solvent-flush technique.
13.5If the response for any m/z exceeds the working range of the GC/MS system, dilute the extract and reanalyze.
13.6Perform all qualitative and quantitative measurements as described in Sections 14 and 15. When the extracts are not being used for analyses, store them refrigerated at 4°C, protected from light in screw-cap vials equipped with unpierced Teflon-lined septa.
14.1Obtain EICPs for the primary m/z and the two other masses listed in Tables 4 and 5. See Section 7.3 for masses to be used with internal and surrogate standards. The following criteria must be met to make a qualitative identification:
14.1.1The characteristic masses of each parameter of interest must maximize in the same or within one scan of each other.
14.1.2The retention time must fall within ±30 s of the retention time of the authentic compound.
14.1.3The relative peak heights of the three characteristic masses in the EICPs must fall within ±20% of the relative intensities of these masses in a reference mass spectrum. The reference mass spectrum can be obtained from a standard analyzed in the GC/MS system or from a reference library.
14.2Structural isomers that have very similar mass spectra and less than 30 s difference in retention time, can be explicitly identified only if the resolution between authentic isomers in a standard mix is acceptable. Acceptable resolution is achieved if the baseline to valley height between the isomers is less than 25% of the sum of the two peak heights. Otherwise, structural isomers are identified as isomeric pairs.
15.1When a parameter has been identified, the quantitation of that parameter will be based on the integrated abundance from the EICP of the primary characteristic m/z in Tables 4 and 5. Use the base peak m/z for internal and surrogate standards. If the sample produces an interference for the primary m/z, use a secondary characteristic m/z to quantitate.
Calculate the concentration in the sample using the response factor (RF) determined in Section 7.2.2 and Equation 3.
15.2Report results in μg/L without correction for recovery data. All QC data obtained should be reported with the sample results.
16.1The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero.
16.2This method was tested by 15 laboratories using reagent water, drinking water, surface water, and industrial wastewaters spiked at six concentrations over the range 5 to 1300 μg/L.
17.1If the sample must be screened for the presence of 2,3,7,8-TCDD, it is recommended that the reference material not be handled in the laboratory unless extensive safety precautions are employed. It is sufficient to analyze the base/neutral extract by selected ion monitoring (SIM) GC/MS techniques, as follows:
17.1.1Concentrate the base/neutral extract to a final volume of 0.2 ml.
17.1.2Adjust the temperature of the base/neutral column (Section 5.6.2) to 220 °C.
17.1.3Operate the mass spectrometer to acquire data in the SIM mode using the ions at m/z 257, 320 and 322 and a dwell time no greater than 333 milliseconds per mass.
17.1.4Inject 5 to 7 μL of the base/neutral extract. Collect SIM data for a total of 10 min.
17.1.5The possible presence of 2,3,7,8-TCDD is indicated if all three masses exhibit simultaneous peaks at any point in the selected ion current profiles.
17.1.6For each occurrence where the possible presence of 2,3,7,8-TCDD is indicated, calculate and retain the relative abundances of each of the three masses.
17.2False positives to this test may be caused by the presence of single or coeluting combinations of compounds whose mass spectra contain all of these masses.
17.3Conclusive results of the presence and concentration level of 2,3,7,8-TCDD can be obtained only from a properly equipped laboratory through the use of EPA Method 613 or other approved alternate test procedures.
1. 40 CFR part 136, appendix B.
2. “Sampling and Analysis Procedures for Screening of Industrial Effluents for Priority Pollutants,” U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1977, Revised April 1977. Available from Effluent Guidelines Division, Washington, DC 20460.
3. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American Society for Testing and Materials, Philadelphia.
4. “Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
5. “OSHA Safety and Health Standards, General Industry,” (29 CFR part 1910), Occupational Safety and Health Administration, OSHA 2206 (Revised, January 1976).
6. “Safety in Academic Chemistry Laboratories,”American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
7. Provost, L.P., and Elder, R.S. “Interpretation of Percent Recovery Data,”
8. ASTM Annual Book of Standards, Part 31, D3370-76. “Standard Practices for Sampling Water,” American Society for Testing and Materials, Philadelphia.
9. “Methods 330.4 (Titrimetric, DPD-FAS) and 330.5 (Spectrophotometric, DPD) for Chlorine, Total Residual,” Methods for Chemical Analysis of Water and Wastes, EPA-600/4-79-020, U.S. Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268, March 1979.
10. Eichelberger, J.W., Harris, L.E., and Budde, W.L. “Reference Compound to Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectometry,”
11. McNair, N.M. and Bonelli, E.J. “Basic Chromatography,” Consolidated Printing, Berkeley, California, p. 52, 1969.
12. Burke, J.A. “Gas Chromatography for Pesticide Residue Analysis; Some Practical Aspects,”
13. Olynyk, P., Budde, W.L., and Eichelberger, J.W. “Method Detection Limit for Methods 624 and 625,” Unpublished report, May 14, 1980.
14. “EPA Method Study 30, Method 625, Base/Neutrals, Acids, and Pesticides,” EPA 600/4-84-053, National Technical Information Service, PB84-206572, Springfield, Virginia 22161, June 1984.
To support measurement of several semivolatile pollutants, EPA has developed this attachment to EPA Method 625.
The additional semivolatile organic compounds listed in Tables 1 and 2 are added to all applicable calibration, spiking, and other solutions utilized in the determination of base/neutral and acid compounds by EPA Method 625. The instrument is to be calibrated with these compounds, using a capillary column, and all procedures and quality control tests stated in the Method must be performed.
All section and figure numbers in this Attachment reference section and figure numbers in EPA Method 625 unless noted otherwise. Sections not listed here remain unchanged.
1.1This method is for determination of tetra- through octa-chlorinated dibenzo-p-dioxins (CDDs) and dibenzofurans (CDFs) in water, soil, sediment, sludge, tissue, and other sample matrices by high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS). The method is for use in EPA's data gathering and monitoring programs associated with the Clean Water Act, the Resource Conservation and Recovery Act, the Comprehensive Environmental Response, Compensation and Liability Act, and the Safe Drinking Water Act. The method is based on a compilation of EPA, industry, commercial laboratory, and academic methods (References 1-6).
1.2The seventeen 2,3,7,8-substituted CDDs/CDFs listed in Table 1 may be determined by this method. Specifications are also provided for separate determination of 2,3,7,8-tetrachloro-dibenzo-p-dioxin (2,3,7,8-TCDD) and 2,3,7,8-tetrachloro-dibenzofuran (2,3,7,8-TCDF).
1.3The detection limits and quantitation levels in this method are usually dependent on the level of interferences rather than instrumental limitations. The minimum levels (MLs) in Table 2 are the levels at which the CDDs/CDFs can be determined with no interferences present. The Method Detection
1.4The GC/MS portions of this method are for use only by analysts experienced with HRGC/HRMS or under the close supervision of such qualified persons. Each laboratory that uses this method must demonstrate the ability to generate acceptable results using the procedure in Section 9.2.
1.5This method is “performance-based”. The analyst is permitted to modify the method to overcome interferences or lower the cost of measurements, provided that all performance criteria in this method are met. The requirements for establishing method equivalency are given in Section 9.1.2.
1.6Any modification of this method, beyond those expressly permitted, shall be considered a major modification subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
Flow charts that summarize procedures for sample preparation, extraction, and analysis are given in Figure 1 for aqueous and solid samples, Figure 2 for multi-phase samples, and Figure 3 for tissue samples.
2.1Extraction.
2.1.1Aqueous samples (samples containing less than 1% solids)—Stable isotopically labeled analogs of 15 of the 2,3,7,8-substituted CDDs/CDFs are spiked into a 1 L sample, and the sample is extracted by one of three procedures:
2.1.1.1Samples containing no visible particles are extracted with methylene chloride in a separatory funnel or by the solid-phase extraction technique summarized in Section 2.1.1.3. The extract is concentrated for cleanup.
2.1.1.2Samples containing visible particles are vacuum filtered through a glass-fiber filter. The filter is extracted in a Soxhlet/Dean-Stark (SDS) extractor (Reference 7), and the filtrate is extracted with methylene chloride in a separatory funnel. The methylene chloride extract is concentrated and combined with the SDS extract prior to cleanup.
2.1.1.3The sample is vacuum filtered through a glass-fiber filter on top of a solid-phase extraction (SPE) disk. The filter and disk are extracted in an SDS extractor, and the extract is concentrated for cleanup.
2.1.2Solid, semi-solid, and multi-phase samples (but not tissue)—The labeled compounds are spiked into a sample containing 10 g (dry weight) of solids. Samples containing multiple phases are pressure filtered and any aqueous liquid is discarded. Coarse solids are ground or homogenized. Any non-aqueous liquid from multi-phase samples is combined with the solids and extracted in an SDS extractor. The extract is concentrated for cleanup.
2.1.3Fish and other tissue—The sample is extracted by one of two procedures:
2.1.3.1Soxhlet or SDS extraction—A 20 g aliquot of sample is homogenized, and a 10 g aliquot is spiked with the labeled compounds. The sample is mixed with sodium sulfate, allowed to dry for 12-24 hours, and extracted for 18-24 hours using methylene chloride:hexane (1:1) in a Soxhlet extractor. The extract is evaporated to dryness, and the lipid content is determined.
2.1.3.2HCl digestion—A 20 g aliquot is homogenized, and a 10 g aliquot is placed in a bottle and spiked with the labeled compounds. After equilibration, 200 mL of hydrochloric acid and 200 mL of methylene chloride:hexane (1:1) are added, and the bottle is agitated for 12-24 hours. The extract is evaporated to dryness, and the lipid content is determined.
2.2After extraction,
2.3After cleanup, the extract is concentrated to near dryness. Immediately prior to injection, internal standards are added to each extract, and an aliquot of the extract is injected into the gas chromatograph. The analytes are separated by the GC and detected by a high-resolution (≥10,000) mass spectrometer. Two exact m/z's are monitored for each analyte.
2.4An individual CDD/CDF is identified by comparing the GC retention time and ion-abundance ratio of two exact m/z's with the corresponding retention time of an authentic standard and the theoretical or acquired ion-abundance ratio of the two exact m/z's. The non-2,3,7,8 substituted isomers and congeners are identified when retention times and ion-abundance ratios agree within predefined limits. Isomer specificity for 2,3,7,8-TCDD and 2,3,7,8-TCDF is achieved using GC columns that resolve these isomers from the other tetra-isomers.
2.5Quantitative analysis is performed using selected ion current profile (SICP) areas, in one of three ways:
2.5.1For the 15 2,3,7,8-substituted CDDs/CDFs with labeled analogs (see Table 1), the GC/MS system is calibrated, and the concentration of each compound is determined using the isotope dilution technique.
2.5.2For 1,2,3,7,8,9-HxCDD, OCDF, and the labeled compounds, the GC/MS system is calibrated and the concentration of each compound is determined using the internal standard technique.
2.5.3For non-2,3,7,8-substituted isomers and for all isomers at a given level of chlorination (i.e., total TCDD), concentrations are determined using response factors from calibration of the CDDs/CDFs at the same level of chlorination.
2.6The quality of the analysis is assured through reproducible calibration and testing of the extraction, cleanup, and GC/MS systems.
Definitions are given in the glossary at the end of this method.
4.1Solvents, reagents, glassware, and other sample processing hardware may yield artifacts and/or elevated baselines causing misinterpretation of chromatograms (References 8-9). Specific selection of reagents and purification of solvents by distillation in all-glass systems may be required. Where possible, reagents are cleaned by extraction or solvent rinse.
4.2Proper cleaning of glassware is extremely important, because glassware may not only contaminate the samples but may also remove the analytes of interest by adsorption on the glass surface.
4.2.1Glassware should be rinsed with solvent and washed with a detergent solution as soon after use as is practical. Sonication of glassware containing a detergent solution for approximately 30 seconds may aid in cleaning. Glassware with removable parts, particularly separatory funnels with fluoropolymer stopcocks, must be disassembled prior to detergent washing.
4.2.2After detergent washing, glassware should be rinsed immediately, first with methanol, then with hot tap water. The tap water rinse is followed by another methanol rinse, then acetone, and then methylene chloride.
4.2.3Do not bake reusable glassware in an oven as a routine part of cleaning. Baking may be warranted after particularly dirty samples are encountered but should be minimized, as repeated baking of glassware may cause active sites on the glass surface that will irreversibly adsorb CDDs/CDFs.
4.2.4Immediately prior to use, the Soxhlet apparatus should be pre-extracted with toluene for approximately three hours (see Sections 12.3.1 through 12.3.3). Separatory funnels should be shaken with methylene chloride/toluene (80/20 mixture) for two minutes, drained, and then shaken with pure methylene chloride for two minutes.
4.3All materials used in the analysis shall be demonstrated to be free from interferences by running reference matrix method blanks initially and with each sample batch (samples started through the extraction process on a given 12-hour shift, to a maximum of 20 samples).
4.3.1The reference matrix must simulate, as closely as possible, the sample matrix under test. Ideally, the reference matrix should not contain the CDDs/CDFs in detectable amounts, but should contain potential interferents in the concentrations expected to be found in the samples to be analyzed. For example, a reference sample of human adipose tissue containing pentachloronaphthalene can be used to exercise the cleanup systems when samples containing pentachloronaphthalene are expected.
4.3.2When a reference matrix that simulates the sample matrix under test is not available, reagent water (Section 7.6.1) can be used to simulate water samples; playground sand (Section 7.6.2) or white quartz sand (Section 7.3.2) can be used to simulate soils; filter paper (Section 7.6.3) can be used to simulate papers and similar materials; and corn oil (Section 7.6.4) can be used to simulate tissues.
4.4Interferences coextracted from samples will vary considerably from source to source, depending on the diversity of the site being sampled. Interfering compounds may be present at concentrations several orders of magnitude higher than the CDDs/CDFs. The most frequently encountered interferences are chlorinated biphenyls, methoxy biphenyls, hydroxydiphenyl ethers, benzylphenyl ethers, polynuclear aromatics, and pesticides. Because very low levels of CDDs/CDFs are measured by this method, the elimination of interferences is essential. The cleanup steps given in Section 13 can be used to reduce or eliminate these interferences and thereby permit reliable determination of the CDDs/CDFs at the levels shown in Table 2.
4.5Each piece of reusable glassware should be numbered to associate that glassware with the processing of a particular sample. This will assist the laboratory in tracking possible sources of contamination for individual samples, identifying glassware associated with highly contaminated samples that may require extra cleaning, and determining when glassware should be discarded.
4.6Cleanup of tissue—The natural lipid content of tissue can interfere in the analysis of tissue samples for the CDDs/CDFs. The lipid contents of different species and portions of tissue can vary widely. Lipids are soluble to varying degrees in various organic solvents and may be present in sufficient quantity to overwhelm the column chromatographic cleanup procedures used for cleanup of sample extracts. Lipids must
5.1The toxicity or carcinogenicity of each compound or reagent used in this method has not been precisely determined; however, each chemical compound should be treated as a potential health hazard. Exposure to these compounds should be reduced to the lowest possible level.
5.1.1The 2,3,7,8-TCDD isomer has been found to be acnegenic, carcinogenic, and teratogenic in laboratory animal studies. It is soluble in water to approximately 200 ppt and in organic solvents to 0.14%. On the basis of the available toxicological and physical properties of 2,3,7,8-TCDD, all of the CDDs/CDFs should be handled only by highly trained personnel thoroughly familiar with handling and cautionary procedures and the associated risks.
5.1.2It is recommended that the laboratory purchase dilute standard solutions of the analytes in this method. However, if primary solutions are prepared, they shall be prepared in a hood, and a NIOSH/MESA approved toxic gas respirator shall be worn when high concentrations are handled.
5.2The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material safety data sheets (MSDSs) should also be made available to all personnel involved in these analyses. It is also suggested that the laboratory perform personal hygiene monitoring of each analyst who uses this method and that the results of this monitoring be made available to the analyst. Additional information on laboratory safety can be found in References 10-13. The references and bibliography at the end of Reference 13 are particularly comprehensive in dealing with the general subject of laboratory safety.
5.3The CDDs/CDFs and samples suspected to contain these compounds are handled using essentially the same techniques employed in handling radioactive or infectious materials. Well-ventilated, controlled access laboratories are required. Assistance in evaluating the health hazards of particular laboratory conditions may be obtained from certain consulting laboratories and from State Departments of Health or Labor, many of which have an industrial health service. The CDDs/CDFs are extremely toxic to laboratory animals. Each laboratory must develop a strict safety program for handling these compounds. The practices in References 2 and 14 are highly recommended.
5.3.1Facility—When finely divided samples (dusts, soils, dry chemicals) are handled, all operations (including removal of samples from sample containers, weighing, transferring, and mixing) should be performed in a glove box demonstrated to be leak tight or in a fume hood demonstrated to have adequate air flow. Gross losses to the laboratory ventilation system must not be allowed. Handling of the dilute solutions normally used in analytical and animal work presents no inhalation hazards except in the case of an accident.
5.3.2Protective equipment—Disposable plastic gloves, apron or lab coat, safety glasses or mask, and a glove box or fume hood adequate for radioactive work should be used. During analytical operations that may give rise to aerosols or dusts, personnel should wear respirators equipped with activated carbon filters. Eye protection equipment (preferably full face shields) must be worn while working with exposed samples or pure analytical standards. Latex gloves are commonly used to reduce exposure of the hands. When handling samples suspected or known to contain high concentrations of the CDDs/CDFs, an additional set of gloves can also be worn beneath the latex gloves.
5.3.3Training—Workers must be trained in the proper method of removing contaminated gloves and clothing without contacting the exterior surfaces.
5.3.4Personal hygiene—Hands and forearms should be washed thoroughly after each manipulation and before breaks (coffee, lunch, and shift).
5.3.5Confinement—Isolated work areas posted with signs, segregated glassware and tools, and plastic absorbent paper on bench tops will aid in confining contamination.
5.3.6Effluent vapors—The effluents of sample splitters from the gas chromatograph (GC) and from roughing pumps on the mass spectrometer (MS) should pass through either a column of activated charcoal or be bubbled through a trap containing oil or high-boiling alcohols to condense CDD/CDF vapors.
5.3.7Waste Handling—Good technique includes minimizing contaminated waste. Plastic bag liners should be used in waste cans. Janitors and other personnel must be trained in the safe handling of waste.
5.3.8Decontamination
5.3.8.1Decontamination of personnel—Use any mild soap with plenty of scrubbing action.
5.3.8.2Glassware, tools, and surfaces—Chlorothene NU Solvent is the least toxic solvent shown to be effective. Satisfactory cleaning may be accomplished by rinsing with Chlorothene, then washing with any detergent and water. If glassware is first rinsed
5.3.9Laundry—Clothing known to be contaminated should be collected in plastic bags. Persons who convey the bags and launder the clothing should be advised of the hazard and trained in proper handling. The clothing may be put into a washer without contact if the launderer knows of the potential problem. The washer should be run through a cycle before being used again for other clothing.
5.3.10Wipe tests—A useful method of determining cleanliness of work surfaces and tools is to wipe the surface with a piece of filter paper. Extraction and analysis by GC with an electron capture detector (ECD) can achieve a limit of detection of 0.1 μg per wipe; analysis using this method can achieve an even lower detection limit. Less than 0.1 μg per wipe indicates acceptable cleanliness; anything higher warrants further cleaning. More than 10 μg on a wipe constitutes an acute hazard and requires prompt cleaning before further use of the equipment or work space, and indicates that unacceptable work practices have been employed.
5.3.11Table or wrist-action shaker—The use of a table or wrist-action shaker for extraction of tissues presents the possibility of breakage of the extraction bottle and spillage of acid and flammable organic solvent. A secondary containment system around the shaker is suggested to prevent the spread of acid and solvents in the event of such a breakage. The speed and intensity of shaking action should also be adjusted to minimize the possibility of breakage.
Brand names, suppliers, and part numbers are for illustration purposes only and no endorsement is implied. Equivalent performance may be achieved using apparatus and materials other than those specified here. Meeting the performance requirements of this method is the responsibility of the laboratory.
6.1Sampling Equipment for Discrete or Composite Sampling
6.1.1Sample bottles and caps
6.1.1.1Liquid samples (waters, sludges and similar materials containing 5% solids or less)—Sample bottle, amber glass, 1.1 L minimum, with screw cap.
6.1.1.2Solid samples (soils, sediments, sludges, paper pulps, filter cake, compost, and similar materials that contain more than 5% solids)—Sample bottle, wide mouth, amber glass, 500 mL minimum.
6.1.1.3If amber bottles are not available, samples shall be protected from light.
6.1.1.4Bottle caps—Threaded to fit sample bottles. Caps shall be lined with fluoropolymer.
6.1.1.5Cleaning
6.1.1.5.1Bottles are detergent water washed, then solvent rinsed before use.
6.1.1.5.2Liners are detergent water washed, rinsed with reagent water (Section 7.6.1) followed by solvent, and baked at approximately 200 °C for a minimum of 1 hour prior to use.
6.1.2Compositing equipment—Automatic or manual compositing system incorporating glass containers cleaned per bottle cleaning procedure above. Only glass or fluoropolymer tubing shall be used. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used in the pump only. Before use, the tubing shall be thoroughly rinsed with methanol, followed by repeated rinsing with reagent water to minimize sample contamination. An integrating flow meter is used to collect proportional composite samples.
6.2Equipment for Glassware Cleaning—Laboratory sink with overhead fume hood.
6.3Equipment for Sample Preparation
6.3.1Laboratory fume hood of sufficient size to contain the sample preparation equipment listed below.
6.3.2Glove box (optional).
6.3.3Tissue homogenizer—VirTis Model 45 Macro homogenizer (American Scientific Products H-3515, or equivalent) with stainless steel Macro-shaft and Turbo-shear blade.
6.3.4Meat grinder—Hobart, or equivalent, with 3-5 mm holes in inner plate.
6.3.5Equipment for determining percent moisture
6.3.5.1Oven—Capable of maintaining a temperature of 110 ±5 °C.
6.3.5.2Dessicator.
6.3.6Balances
6.3.6.1Analytical—Capable of weighing 0.1 mg.
6.3.6.2Top loading—Capable of weighing 10 mg.
6.4Extraction Apparatus
6.4.1Water samples
6.4.1.1pH meter, with combination glass electrode.
6.4.1.2pH paper, wide range (Hydrion Papers, or equivalent).
6.4.1.3Graduated cylinder, 1 L capacity.
6.4.1.4Liquid/liquid extraction—Separatory funnels, 250 mL, 500 mL, and 2000 mL, with fluoropolymer stopcocks.
6.4.1.5Solid-phase extraction
6.4.1.5.1One liter filtration apparatus, including glass funnel, glass frit support, clamp, adapter, stopper, filtration flask, and vacuum tubing (Figure 4). For wastewater samples, the apparatus should accept 90 or 144 mm disks. For drinking water or other samples containing low solids, smaller disks may be used.
6.4.1.5.2Vacuum source capable of maintaining 25 in. Hg, equipped with shutoff valve and vacuum gauge.
6.4.1.5.3Glass-fiber filter—Whatman GMF 150 (or equivalent), 1 micron pore size, to fit filtration apparatus in Section 6.4.1.5.1.
6.4.1.5.4Solid-phase extraction disk containing octadecyl (C
6.4.2Soxhlet/Dean-Stark (SDS) extractor (Figure 5)—For filters and solid/sludge samples.
6.4.2.1Soxhlet—50 mm ID, 200 mL capacity with 500 mL flask (Cal-Glass LG-6900, or equivalent, except substitute 500 mL round-bottom flask for 300 mL flat-bottom flask).
6.4.2.2Thimble—43 × 123 to fit Soxhlet (Cal-Glass LG-6901-122, or equivalent).
6.4.2.3Moisture trap—Dean Stark or Barret with fluoropolymer stopcock, to fit Soxhlet.
6.4.2.4Heating mantle—Hemispherical, to fit 500 mL round-bottom flask (Cal-Glass LG-8801-112, or equivalent).
6.4.2.5Variable transformer—Powerstat (or equivalent), 110 volt, 10 amp.
6.4.3Apparatus for extraction of tissue.
6.4.3.1Bottle for extraction (if digestion/extraction using HCl is used)” 500-600 mL wide-mouth clear glass, with fluoropolymer-lined cap.
6.4.3.2Bottle for back-extraction—100-200 mL narrow-mouth clear glass with fluoropolymer-lined cap.
6.4.3.3Mechanical shaker—Wrist-action or platform-type rotary shaker that produces vigorous agitation (Sybron Thermolyne Model LE “Big Bill” rotator/shaker, or equivalent).
6.4.3.4Rack attached to shaker table to permit agitation of four to nine samples simultaneously.
6.4.4Beakers—400-500 mL.
6.4.5Spatulas—Stainless steel.
6.5Filtration Apparatus.
6.5.1Pyrex glass wool—Solvent-extracted by SDS for three hours minimum.
Baking glass wool may cause active sites that will irreversibly adsorb CDDs/CDFs.
6.5.2Glass funnel—125-250 mL.
6.5.3Glass-fiber filter paper—Whatman GF/D (or equivalent), to fit glass funnel in Section 6.5.2.
6.5.4Drying column—15-20 mm ID Pyrex chromatographic column equipped with coarse-glass frit or glass-wool plug.
6.5.5Buchner funnel—15 cm.
6.5.6Glass-fiber filter paper—to fit Buchner funnel in Section 6.5.5.
6.5.7Filtration flasks—1.5-2.0 L, with side arm.
6.5.8Pressure filtration apparatus—Millipore YT30 142 HW, or equivalent.
6.6Centrifuge Apparatus.
6.6.1Centrifuge—Capable of rotating 500 mL centrifuge bottles or 15 mL centrifuge tubes at 5,000 rpm minimum.
6.6.2Centrifuge bottles—500 mL, with screw-caps, to fit centrifuge.
6.6.3Centrifuge tubes—12-15 mL, with screw-caps, to fit centrifuge.
6.7Cleanup Apparatus.
6.7.1Automated gel permeation chromatograph (Analytical Biochemical Labs, Inc, Columbia, MO, Model GPC Autoprep 1002, or equivalent).
6.7.1.1Column—600-700 mm long × 25 mm ID, packed with 70 g of
6.7.1.2Syringe—10 mL, with Luer fitting.
6.7.1.3Syringe filter holder—stainless steel, and glass-fiber or fluoropolymer filters (Gelman 4310, or equivalent).
6.7.1.4UV detectors—254 nm, preparative or semi-preparative flow cell (Isco, Inc., Type 6; Schmadzu, 5 mm path length; Beckman-Altex 152W, 8 μL micro-prep flow cell, 2 mm path; Pharmacia UV-1, 3 mm flow cell; LDC Milton-Roy UV-3, monitor #1203; or equivalent).
6.7.2Reverse-phase high-performance liquid chromatograph.
6.7.2.1Column oven and detector—Perkin-Elmer Model LC-65T (or equivalent) operated at 0.02 AUFS at 235 nm.
6.7.2.2Injector—Rheodyne 7120 (or equivalent) with 50 μL sample loop.
6.7.2.3Column—Two 6.2 mm × 250 mm Zorbax-ODS columns in series (DuPont Instruments Division, Wilmington, DE, or equivalent), operated at 50 °C with 2.0 mL/min methanol isocratic effluent.
6.7.2.4Pump—Altex 110A (or equivalent).
6.7.3Pipets.
6.7.3.1Disposable, pasteur—150 mm long × 5-mm ID (Fisher Scientific 13-678-6A, or equivalent).
6.7.3.2Disposable, serological—10 mL (6 mm ID).
6.7.4Glass chromatographic columns.
6.7.4.1150 mm long × 8-mm ID, (Kontes K-420155, or equivalent) with coarse-glass frit or glass-wool plug and 250 mL reservoir.
6.7.4.2200 mm long × 15 mm ID, with coarse-glass frit or glass-wool plug and 250 mL reservoir.
6.7.4.3300 mm long × 25 mm ID, with 300 mL reservoir and glass or fluoropolymer stopcock.
6.7.5Stirring apparatus for batch silica cleanup of tissue extracts.
6.7.5.1Mechanical stirrer—Corning Model 320, or equivalent.
6.7.5.2Bottle—500-600 mL wide-mouth clear glass.
6.7.6Oven—For baking and storage of adsorbents, capable of maintaining a constant temperature (±5 °C) in the range of 105-250 °C.
6.8Concentration Apparatus.
6.8.1Rotary evaporator—Buchi/Brinkman-American Scientific No. E5045-10 or equivalent, equipped with a variable temperature water bath.
6.8.1.1Vacuum source for rotary evaporator equipped with shutoff valve at the evaporator and vacuum gauge.
6.8.1.2A recirculating water pump and chiller are recommended, as use of tap water for cooling the evaporator wastes large volumes of water and can lead to inconsistent performance as water temperatures and pressures vary.
6.8.1.3Round-bottom flask—100 mL and 500 mL or larger, with ground-glass fitting compatible with the rotary evaporator.
6.8.2Kuderna-Danish (K-D) Concentrator.
6.8.2.1Concentrator tube—10 mL, graduated (Kontes K-570050-1025, or equivalent) with calibration verified. Ground-glass stopper (size 19/22 joint) is used to prevent evaporation of extracts.
6.8.2.2Evaporation flask—500 mL (Kontes K-570001-0500, or equivalent), attached to concentrator tube with springs (Kontes K-662750-0012 or equivalent).
6.8.2.3Snyder column—Three-ball macro (Kontes K-503000-0232, or equivalent).
6.8.2.4Boiling chips.
6.8.2.4.1Glass or silicon carbide—Approximately 10/40 mesh, extracted with methylene chloride and baked at 450 °C for one hour minimum.
6.8.2.4.2Fluoropolymer (optional)—Extracted with methylene chloride.
6.8.2.5Water bath—Heated, with concentric ring cover, capable of maintaining a temperature within ±2 °C, installed in a fume hood.
6.8.3Nitrogen blowdown apparatus—Equipped with water bath controlled in the range of 30-60 °C (N-Evap, Organomation Associates, Inc., South Berlin, MA, or equivalent), installed in a fume hood.
6.8.4Sample vials.
6.8.4.1Amber glass—2-5 mL with fluoropolymer-lined screw-cap.
6.8.4.2Glass—0.3 mL, conical, with fluoropolymer-lined screw or crimp cap.
6.9Gas Chromatograph—Shall have splitless or on-column injection port for capillary column, temperature program with isothermal hold, and shall meet all of the performance specifications in Section 10.
6.9.1GC column for CDDs/CDFs and for isomer specificity for 2,3,7,8-TCDD—60±5 m long × 0.32±0.02 mm ID; 0.25 μm 5% phenyl, 94% methyl, 1% vinyl silicone bonded-phase fused-silica capillary column (J&W DB-5, or equivalent).
6.9.2GC column for isomer specificity for 2,3,7,8-TCDF—30±5 m long × 0.32±0.02 mm ID; 0.25 μm bonded-phase fused-silica capillary column (J&W DB-225, or equivalent).
6.10Mass Spectrometer—28-40 eV electron impact ionization, shall be capable of repetitively selectively monitoring 12 exact m/z's minimum at high resolution (≥10,000) during a period of approximately one second, and shall meet all of the performance specifications in Section 10.
6.11GC/MS Interface—The mass spectrometer (MS) shall be interfaced to the GC such that the end of the capillary column terminates within 1 cm of the ion source but does not intercept the electron or ion beams.
6.12Data System—Capable of collecting, recording, and storing MS data.
7.1pH Adjustment and Back-Extraction.
7.1.1Potassium hydroxide—Dissolve 20 g reagent grade KOH in 100 mL reagent water.
7.1.2Sulfuric acid—Reagent grade (specific gravity 1.84).
7.1.3Hydrochloric acid—Reagent grade, 6N.
7.1.4Sodium chloride—Reagent grade, prepare at 5% (w/v) solution in reagent water.
7.2Solution Drying and Evaporation.
7.2.1Solution drying—Sodium sulfate, reagent grade, granular, anhydrous (Baker 3375, or equivalent), rinsed with methylene chloride (20 mL/g), baked at 400 °C for one hour minimum, cooled in a dessicator, and stored in a pre-cleaned glass bottle with screw-cap that prevents moisture from entering. If, after heating, the sodium sulfate develops a noticeable grayish cast (due to the presence of carbon in the crystal matrix), that batch of reagent is not suitable for use and should be discarded. Extraction with methylene chloride (as opposed to simple rinsing) and baking at a lower temperature may produce sodium sulfate that is suitable for use.
7.2.2Tissue drying—Sodium sulfate, reagent grade, powdered, treated and stored as above.
7.2.3Prepurified nitrogen.
7.3Extraction.
7.3.1Solvents—Acetone, toluene, cyclohexane, hexane, methanol, methylene chloride, and nonane; distilled in glass, pesticide quality, lot-certified to be free of interferences.
7.3.2White quartz sand, 60/70 mesh—For Soxhlet/Dean-Stark extraction (Aldrich Chemical, Cat. No. 27-437-9, or equivalent). Bake at 450 °C for four hours minimum.
7.4GPC Calibration Solution—Prepare a solution containing 300 mg/mL corn oil, 15 mg/mL bis(2-ethylhexyl) phthalate, 1.4 mg/mL pentachlorophenol, 0.1 mg/mL perylene, and 0.5 mg/mL sulfur.
7.5Adsorbents for Sample Cleanup.
7.5.1Silica gel.
7.5.1.1Activated silica gel—100-200 mesh, Supelco 1-3651 (or equivalent), rinsed with methylene chloride, baked at 180 °C for a minimum of one hour, cooled in a dessicator, and stored in a precleaned glass bottle with
7.5.1.2Acid silica gel (30% w/w)—Thoroughly mix 44.0 g of concentrated sulfuric acid with 100.0 g of activated silica gel in a clean container. Break up aggregates with a stirring rod until a uniform mixture is obtained. Store in a bottle with a fluoropolymer-lined screw-cap.
7.5.1.3Basic silica gel—Thoroughly mix 30 g of 1N sodium hydroxide with 100 g of activated silica gel in a clean container. Break up aggregates with a stirring rod until a uniform mixture is obtained. Store in a bottle with a fluoropolymer-lined screw-cap.
7.5.1.4Potassium silicate.
7.5.1.4.1Dissolve 56 g of high purity potassium hydroxide (Aldrich, or equivalent) in 300 mL of methanol in a 750-1000 mL flat-bottom flask.
7.5.1.4.2Add 100 g of silica gel and a stirring bar, and stir on a hot plate at 60-70 °C for one to two hours.
7.5.1.4.3Decant the liquid and rinse the potassium silicate twice with 100 mL portions of methanol, followed by a single rinse with 100 mL of methylene chloride.
7.5.1.4.4Spread the potassium silicate on solvent-rinsed aluminum foil and dry for two to four hours in a hood.
7.5.1.4.5Activate overnight at 200-250 °C.
7.5.2Alumina—Either one of two types of alumina, acid or basic, may be used in the cleanup of sample extracts, provided that the laboratory can meet the performance specifications for the recovery of labeled compounds described in Section 9.3. The same type of alumina must be used for all samples, including those used to demonstrate initial precision and recovery (Section 9.2) and ongoing precision and recovery (Section 15.5).
7.5.2.1Acid alumina—Supelco 19996-6C (or equivalent). Activate by heating to 130 °C for a minimum of 12 hours.
7.5.2.2Basic alumina—Supelco 19944-6C (or equivalent). Activate by heating to 600 °C for a minimum of 24 hours. Alternatively, activate by heating in a tube furnace at 650-700 °C under an air flow rate of approximately 400 cc/minute. Do not heat over 700 °C, as this can lead to reduced capacity for retaining the analytes. Store at 130 °C in a covered flask. Use within five days of baking.
7.5.3Carbon.
7.5.3.1Carbopak C—(Supelco 1-0258, or equivalent).
7.5.3.2Celite 545—(Supelco 2-0199, or equivalent).
7.5.3.3Thoroughly mix 9.0 g Carbopak C and 41.0 g Celite 545 to produce an 18% w/w mixture. Activate the mixture at 130 °C for a minimum of six hours. Store in a dessicator.
7.5.4Anthropogenic isolation column—Pack the column in Section 6.7.4.3 from bottom to top with the following:
7.5.4.12 g silica gel (Section 7.5.1.1).
7.5.4.22 g potassium silicate (Section 7.5.1.4).
7.5.4.32 g granular anhydrous sodium sulfate (Section 7.2.1).
7.5.4.410 g acid silica gel (Section 7.5.1.2).
7.5.4.52 g granular anhydrous sodium sulfate.
7.5.5Florisil column.
7.5.5.1Florisil—60-100 mesh, Floridin Corp (or equivalent). Soxhlet extract in 500 g portions for 24 hours.
7.5.5.2Insert a glass wool plug into the tapered end of a graduated serological pipet (Section 6.7.3.2). Pack with 1.5 g (approx 2 mL) of Florisil topped with approx 1 mL of sodium sulfate (Section 7.2.1) and a glass wool plug.
7.5.5.3Activate in an oven at 130-150 °C for a minimum of 24 hours and cool for 30 minutes. Use within 90 minutes of cooling.
7.6Reference Matrices—Matrices in which the CDDs/CDFs and interfering compounds are not detected by this method.
7.6.1Reagent water—Bottled water purchased locally, or prepared by passage through activated carbon.
7.6.2High-solids reference matrix—Playground sand or similar material. Prepared by extraction with methylene chloride and/or baking at 450 °C for a minimum of four hours.
7.6.3Paper reference matrix—Glass-fiber filter, Gelman Type A, or equivalent. Cut paper to simulate the surface area of the paper sample being tested.
7.6.4Tissue reference matrix—Corn or other vegetable oil. May be prepared by extraction with methylene chloride.
7.6.5Other matrices—This method may be verified on any reference matrix by performing the tests given in Section 9.2. Ideally, the matrix should be free of the CDDs/CDFs, but in no case shall the background level of the CDDs/CDFs in the reference matrix exceed three times the minimum levels in Table 2. If low background levels of the CDDs/CDFs are present in the reference matrix, the spike level of the analytes used in Section 9.2 should be increased to provide a spike-to-background ratio in the range of 1:1 to 5:1 (Reference 15).
7.7Standard Solutions—Purchased as solutions or mixtures with certification to their purity, concentration, and authenticity, or prepared from materials of known purity and composition. If the chemical purity is 98% or greater, the weight may be used without correction to compute the concentration of the standard. When not being used, standards are stored in the dark at room temperature in screw-capped vials with fluoropolymer-lined caps. A mark is placed on the vial at the level of the solution so that solvent loss by evaporation can be detected. If solvent loss has occurred, the solution should be replaced.
7.8Stock Solutions.
7.8.1Preparation—Prepare in nonane per the steps below or purchase as dilute solutions (Cambridge Isotope Laboratories (CIL), Woburn, MA, or equivalent). Observe the safety precautions in Section 5, and the recommendation in Section 5.1.2.
7.8.2Dissolve an appropriate amount of assayed reference material in solvent. For example, weigh 1-2 mg of 2,3,7,8-TCDD to three significant figures in a 10 mL ground-glass-stoppered volumetric flask and fill to the mark with nonane. After the TCDD is completely dissolved, transfer the solution to a clean 15 mL vial with fluoropolymer-lined cap.
7.8.3Stock standard solutions should be checked for signs of degradation prior to the preparation of calibration or performance test standards. Reference standards that can be used to determine the accuracy of calibration standards are available from CIL and may be available from other vendors.
7.9PAR Stock Solution
7.9.1All CDDs/CDFs—Using the solutions in Section 7.8, prepare the PAR stock solution to contain the CDDs/CDFs at the concentrations shown in Table 3. When diluted, the solution will become the PAR (Section 7.14).
7.9.2If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, prepare the PAR stock solution to contain these compounds only.
7.10Labeled-Compound Spiking Solution.
7.10.1All CDDs/CDFs—From stock solutions, or from purchased mixtures, prepare this solution to contain the labeled compounds in nonane at the concentrations shown in Table 3. This solution is diluted with acetone prior to use (Section 7.10.3).
7.10.2If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, prepare the labeled-compound solution to contain these compounds only. This solution is diluted with acetone prior to use (Section 7.10.3).
7.10.3Dilute a sufficient volume of the labeled compound solution (Section 7.10.1 or 7.10.2) by a factor of 50 with acetone to prepare a diluted spiking solution. Each sample requires 1.0 mL of the diluted solution, but no more solution should be prepared than can be used in one day.
7.11Cleanup Standard—Prepare
7.12Internal Standard(s).
7.12.1All CDDs/CDFs—Prepare the internal standard solution to contain
7.12.2If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, prepare the internal standard solution to contain
7.13Calibration Standards (CS1 through CS5)—Combine the solutions in Sections 7.9 through 7.12 to produce the five calibration solutions shown in Table 4 in nonane. These solutions permit the relative response (labeled to native) and response factor to be measured as a function of concentration. The CS3 standard is used for calibration verification (VER). If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, combine the solutions appropriate to these compounds.
7.14Precision and Recovery (PAR) Standard—Used for determination of initial (Section 9.2) and ongoing (Section 15.5) precision and recovery. Dilute 10 μL of the precision and recovery standard (Section 7.9.1 or 7.9.2) to 2.0 mL with acetone for each sample matrix for each sample batch. One mL each are required for the blank and OPR with each matrix in each batch.
7.15GC Retention Time Window Defining Solution and Isomer Specificity Test Standard—Used to define the beginning and ending retention times for the dioxin and furan isomers and to demonstrate isomer specificity of the GC columns employed for determination of 2,3,7,8-TCDD and 2,3,7,8-TCDF. The standard must contain the compounds listed in Table 5 (CIL EDF—4006, or equivalent), at a minimum. It is not necessary to monitor the window-defining compounds if only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined. In this case, an isomer-specificity test standard containing the most closely eluted isomers listed in Table 5 (CIL EDF-4033, or equivalent) may be used.
7.16QC Check Sample—A QC Check Sample should be obtained from a source independent of the calibration standards. Ideally, this check sample would be a certified reference material containing the CDDs/CDFs in known concentrations in a sample matrix similar to the matrix under test.
7.17Stability of Solutions—Standard solutions used for quantitative purposes (Sections 7.9 through 7.15) should be analyzed periodically, and should be assayed against reference standards (Section 7.8.3) before further use.
8.1Collect samples in amber glass containers following conventional sampling practices (Reference 16). Aqueous samples that flow freely are collected in refrigerated bottles using automatic sampling equipment. Solid samples are collected as grab samples using wide-mouth jars.
8.2Maintain aqueous samples in the dark at 0-4 °C from the time of collection until receipt at the laboratory. If residual chlorine is present in aqueous samples, add 80 mg sodium thiosulfate per liter of water. EPA
Maintain solid, semi-solid, oily, and mixed-phase samples in the dark at <4 °C from the time of collection until receipt at the laboratory.
Store aqueous samples in the dark at 0-4 °C. Store solid, semi-solid, oily, mixed-phase, and tissue samples in the dark at <−10 °C.
8.3Fish and Tissue Samples.
8.3.1Fish may be cleaned, filleted, or processed in other ways in the field, such that the laboratory may expect to receive whole fish, fish fillets, or other tissues for analysis.
8.3.2Fish collected in the field should be wrapped in aluminum foil, and must be maintained at a temperature less than 4 °C from the time of collection until receipt at the laboratory.
8.3.3Samples must be frozen upon receipt at the laboratory and maintained in the dark at <−10 °C until prepared. Maintain unused sample in the dark at <−10 °C.
8.4Holding Times.
8.4.1There are no demonstrated maximum holding times associated with CDDs/CDFs in aqueous, solid, semi-solid, tissues, or other sample matrices. If stored in the dark at 0-4 °C and preserved as given above (if required), aqueous samples may be stored for up to one year. Similarly, if stored in the dark at <−10 °C, solid, semi-solid, multi-phase, and tissue samples may be stored for up to one year.
8.4.2Store sample extracts in the dark at <−10 °C until analyzed. If stored in the dark at <−10 °C, sample extracts may be stored for up to one year.
9.1Each laboratory that uses this method is required to operate a formal quality assurance program (Reference 18). The minimum requirements of this program consist of an initial demonstration of laboratory capability, analysis of samples spiked with labeled compounds to evaluate and document data quality, and analysis of standards and blanks as tests of continued performance. Laboratory performance is compared to established performance criteria to determine if the results of analyses meet the performance characteristics of the method.
If the method is to be applied to sample matrix other than water (e.g., soils, filter cake, compost, tissue) the most appropriate alternate matrix (Sections 7.6.2 through 7.6.5) is substituted for the reagent water matrix (Section 7.6.1) in all performance tests.
9.1.1The analyst shall make an initial demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 9.2.
9.1.2In recognition of advances that are occurring in analytical technology, and to allow the analyst to overcome sample matrix interferences, the analyst is permitted certain options to improve separations or lower the costs of measurements. These options include alternate extraction, concentration, cleanup procedures, and changes in columns and detectors. Alternate determinative techniques, such as the substitution of spectroscopic or immuno-assay techniques, and changes that degrade method performance, are not allowed. If an analytical technique other than the techniques specified in this method is used, that technique must have a specificity equal to or better than the specificity of the techniques in this method for the analytes of interest.
9.1.2.1Each time a modification is made to this method, the analyst is required to repeat the procedure in Section 9.2. If the detection limit of the method will be affected by the change, the laboratory is required to demonstrate that the MDL (40 CFR Part 136, Appendix B) is lower than one-third the regulatory compliance level or one-third the ML in this method, whichever is higher. If calibration will be affected by the change, the analyst must recalibrate the instrument per Section 10.
9.1.2.2The laboratory is required to maintain records of modifications made to this method. These records include the following, at a minimum:
9.1.2.2.1The names, titles, addresses, and telephone numbers of the analyst(s) who performed the analyses and modification, and of the quality control officer who witnessed and will verify the analyses and modifications.
9.1.2.2.2A listing of pollutant(s) measured, by name and CAS Registry number.
9.1.2.2.3A narrative stating reason(s) for the modifications.
9.1.2.2.4Results from all quality control (QC) tests comparing the modified method to this method, including:
(a) Calibration (Section 10.5 through 10.7).
(b) Calibration verification (Section 15.3).
(c) Initial precision and recovery (Section 9.2).
(d) Labeled compound recovery (Section 9.3).
(e) Analysis of blanks (Section 9.5).
(f) Accuracy assessment (Section 9.4).
9.1.2.2.5Data that will allow an independent reviewer to validate each determination by tracing the instrument output (peak height, area, or other signal) to the final result. These data are to include:
(a) Sample numbers and other identifiers.
(b) Extraction dates.
(c) Analysis dates and times.
(d) Analysis sequence/run chronology.
(e) Sample weight or volume (Section 11).
(f) Extract volume prior to each cleanup step (Section 13).
(g) Extract volume after each cleanup step (Section 13).
(h) Final extract volume prior to injection (Section 14).
(i) Injection volume (Section 14.3).
(j) Dilution data, differentiating between dilution of a sample or extract (Section 17.5).
(k) Instrument and operating conditions.
(l) Column (dimensions, liquid phase, solid support, film thickness, etc).
(m) Operating conditions (temperatures, temperature program, flow rates).
(n) Detector (type, operating conditions, etc).
(o) Chromatograms, printer tapes, and other recordings of raw data.
(p) Quantitation reports, data system outputs, and other data to link the raw data to the results reported.
9.1.3Analyses of method blanks are required to demonstrate freedom from contamination (Section 4.3). The procedures and criteria for analysis of a method blank are described in Sections 9.5 and 15.6.
9.1.4The laboratory shall spike all samples with labeled compounds to monitor method performance. This test is described in Section 9.3. When results of these spikes indicate atypical method performance for samples, the samples are diluted to bring method performance within acceptable limits. Procedures for dilution are given in Section 17.5.
9.1.5The laboratory shall, on an ongoing basis, demonstrate through calibration verification and the analysis of the ongoing precision and recovery aliquot that the analytical system is in control. These procedures are described in Sections 15.1 through 15.5.
9.1.6The laboratory shall maintain records to define the quality of data that is generated. Development of accuracy statements is described in Section 9.4.
9.2Initial Precision and Recovery (IPR)—To establish the ability to generate acceptable precision and recovery, the analyst shall perform the following operations.
9.2.1For low solids (aqueous) samples, extract, concentrate, and analyze four 1 L aliquots of reagent water spiked with the diluted labeled compound spiking solution (Section 7.10.3) and the precision and recovery standard (Section 7.14) according to the procedures in Sections 11 through 18. For an alternative sample matrix, four aliquots of the alternative reference matrix (Section 7.6) are used. All sample processing steps that are to be used for processing samples, including preparation (Section 11), extraction (Section 12), and cleanup (Section 13), shall be included in this test.
9.2.2Using results of the set of four analyses, compute the average concentration (X) of the extracts in ng/mL and the standard deviation of the concentration (s) in ng/mL for each compound, by isotope dilution for CDDs/CDFs with a labeled analog, and by internal standard for 1,2,3,7,8,9-HxCDD, OCDF, and the labeled compounds.
9.2.3For each CDD/CDF and labeled compound, compare s and X with the corresponding limits for initial precision and recovery in Table 6. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, compare s and X with the corresponding limits for initial precision and recovery in Table 6a. If s and X for all compounds meet the acceptance criteria, system performance is acceptable and analysis of blanks and samples may begin. If, however, any individual s exceeds the precision limit or any individual X falls outside the range for accuracy, system performance is unacceptable for that compound. Correct the problem and repeat the test (Section 9.2).
9.3The laboratory shall spike all samples with the diluted labeled compound spiking solution (Section 7.10.3) to assess method performance on the sample matrix.
9.3.1Analyze each sample according to the procedures in Sections 11 through 18.
9.3.2Compute the percent recovery of the labeled compounds and the cleanup standard using the internal standard method (Section 17.2).
9.3.3The recovery of each labeled compound must be within the limits in Table 7 when all 2,3,7,8-substituted CDDs/CDFs are determined, and within the limits in Table 7a when only 2,3,7,8-TCDD and 2,3,7,8-TCDF are determined. If the recovery of any compound falls outside of these limits, method performance is unacceptable for that compound in that sample. To overcome such difficulties, water samples are diluted and smaller amounts of soils, sludges, sediments, and other matrices are reanalyzed per Section 18.4.
9.4Recovery of labeled compounds from samples should be assessed and records should be maintained.
9.4.1After the analysis of five samples of a given matrix type (water, soil, sludge, pulp, etc.) for which the labeled compounds pass the tests in Section 9.3, compute the average percent recovery (R) and the standard deviation of the percent recovery (SR) for the labeled compounds only. Express the assessment as a percent recovery interval from R−2S
9.4.2Update the accuracy assessment for each labeled compound in each matrix on a regular basis (e.g., after each 5-10 new measurements).
9.5Method Blanks—Reference matrix method blanks are analyzed to demonstrate freedom from contamination (Section 4.3).
9.5.1Prepare, extract, clean up, and concentrate a method blank with each sample batch (samples of the same matrix started through the extraction process on the same 12-hour shift, to a maximum of 20 samples). The matrix for the method blank shall be similar to sample matrix for the batch, e.g., a 1 L reagent water blank (Section 7.6.1), high-solids reference matrix blank (Section 7.6.2), paper matrix blank (Section 7.6.3); tissue blank (Section 7.6.4) or alternative reference matrix blank (Section 7.6.5). Analyze the blank immediately after analysis of the OPR (Section 15.5) to demonstrate freedom from contamination.
9.5.2If any 2,3,7,8-substituted CDD/CDF (Table 1) is found in the blank at greater than the minimum level (Table 2) or one-third the regulatory compliance level, whichever is greater; or if any potentially interfering compound is found in the blank at the minimum level for each level of chlorination given in Table 2 (assuming a response factor of 1 relative to the
9.6QC Check Sample—Analyze the QC Check Sample (Section 7.16) periodically to assure the accuracy of calibration standards and the overall reliability of the analytical process. It is suggested that the QC Check Sample be analyzed at least quarterly.
9.7The specifications contained in this method can be met if the apparatus used is calibrated properly and then maintained in a calibrated state. The standards used for calibration (Section 10), calibration verification (Section 15.3), and for initial (Section 9.2) and ongoing (Section 15.5) precision and recovery should be identical, so that the most precise results will be obtained. A GC/MS instrument will provide the most reproducible results if dedicated to the settings and conditions required for the analyses of CDDs/CDFs by this method.
9.8Depending on specific program requirements, field replicates may be collected to determine the precision of the sampling technique, and spiked samples may be required to determine the accuracy of the analysis when the internal standard method is used.
10.1Establish the operating conditions necessary to meet the minimum retention times for the internal standards in Section 10.2.4 and the relative retention times for the CDDs/CDFs in Table 2.
10.1.1Suggested GC operating conditions:
All portions of the column that connect the GC to the ion source shall remain at or above the interface temperature specified above during analysis to preclude condensation of less volatile compounds.
Optimize GC conditions for compound separation and sensitivity. Once optimized, the same GC conditions must be used for the analysis of all standards, blanks, IPR and OPR aliquots, and samples.
10.1.2Mass spectrometer (MS) resolution—Obtain a selected ion current profile (SICP) of each analyte in Table 3 at the two exact m/z's specified in Table 8 and at ≥10,000 resolving power by injecting an authentic standard of the CDDs/CDFs either singly or as part of a mixture in which there is no interference between closely eluted components.
10.1.2.1The analysis time for CDDs/CDFs may exceed the long-term mass stability of the mass spectrometer. Because the instrument is operated in the high-resolution mode, mass drifts of a few ppm (e.g., 5 ppm in mass) can have serious adverse effects on instrument performance. Therefore, a mass-drift correction is mandatory and a lock-mass m/z from PFK is used for drift correction. The lock-mass m/z is dependent on the exact m/z's monitored within each descriptor, as shown in Table 8. The level of PFK metered into the HRMS during analyses should be adjusted so that the amplitude of the most intense selected lock-mass m/z signal (regardless of the descriptor number) does not exceed 10% of the full-scale deflection for a given set of detector parameters. Under those conditions, sensitivity changes that might occur during the analysis can be more effectively monitored.
Excessive PFK (or any other reference substance) may cause noise problems and contamination of the ion source necessitating increased frequency of source cleaning.
10.1.2.2If the HRMS has the capability to monitor resolution during the analysis, it is acceptable to terminate the analysis when the resolution falls below 10,000 to save reanalysis time.
10.1.2.3Using a PFK molecular leak, tune the instrument to meet the minimum required resolving power of 10,000 (10% valley) at m/z 304.9824 (PFK) or any other reference signal close to m/z 304 (from TCDF). For each
10.2Ion Abundance Ratios, Minimum Levels, Signal-to-Noise Ratios, and Absolute Retention Times—Choose an injection volume of either 1 μL or 2 μL, consistent with the capability of the HRGC/HRMS instrument. Inject a 1 μL or 2 μL aliquot of the CS1 calibration solution (Table 4) using the GC conditions from Section 10.1.1. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, the operating conditions and specifications below apply to analysis of those compounds only.
10.2.1Measure the SICP areas for each analyte, and compute the ion abundance ratios at the exact m/z's specified in Table 8. Compare the computed ratio to the theoretical ratio given in Table 9.
10.2.1.1The exact m/z's to be monitored in each descriptor are shown in Table 8. Each group or descriptor shall be monitored in succession as a function of GC retention time to ensure that all CDDs/CDFs are detected. Additional m/z's may be monitored in each descriptor, and the m/z's may be divided among more than the five descriptors listed in Table 8, provided that the laboratory is able to monitor the m/z's of all the CDDs/CDFs that may elute from the GC in a given retention-time window. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, the descriptors may be modified to include only the exact m/z's for the tetra-and penta-isomers, the diphenyl ethers, and the lock m/z's.
10.2.1.2The mass spectrometer shall be operated in a mass-drift correction mode, using perfluorokerosene (PFK) to provide lock m/z's. The lock-mass for each group of m/z's is shown in Table 8. Each lock mass shall be monitored and shall not vary by more than ±20% throughout its respective retention time window. Variations of the lock mass by more than 20% indicate the presence of coeluting interferences that may significantly reduce the sensitivity of the mass spectrometer. Reinjection of another aliquot of the sample extract will not resolve the problem. Additional cleanup of the extract may be required to remove the interferences.
10.2.2All CDDs/CDFs and labeled compounds in the CS1 standard shall be within the QC limits in Table 9 for their respective ion abundance ratios; otherwise, the mass spectrometer shall be adjusted and this test repeated until the m/z ratios fall within the limits specified. If the adjustment alters the resolution of the mass spectrometer, resolution shall be verified (Section 10.1.2) prior to repeat of the test.
10.2.3Verify that the HRGC/HRMS instrument meets the minimum levels in Table 2. The peaks representing the CDDs/CDFs and labeled compounds in the CS1 calibration standard must have signal-to-noise ratios (S/N) greater than or equal to 10.0. Otherwise, the mass spectrometer shall be adjusted and this test repeated until the minimum levels in Table 2 are met.
10.2.4The absolute retention time of
10.4Isomer Specificity.
10.4.1Analyze the isomer specificity test standards (Section 7.15) using the procedure in Section 14 and the optimized conditions for sample analysis (Section 10.1.1).
10.4.2Compute the percent valley between the GC peaks that elute most closely to the 2,3,7,8-TCDD and TCDF isomers, on their respective columns, per Figures 6 and 7.
10.4.3Verify that the height of the valley between the most closely eluted isomers and the 2,3,7,8-substituted isomers is less than 25% (computed as 100 x/y in Figures 6 and 7). If the valley exceeds 25%, adjust the analytical conditions and repeat the test or replace the GC column and recalibrate (Sections 10.1.2 through 10.7).
10.5Calibration by Isotope Dilution—Isotope dilution calibration is used for the 15 2,3,7,8-substituted CDDs/CDFs for which labeled compounds are added to samples prior to extraction. The reference compound for each CDD/CDF compound is shown in Table 2.
10.5.1A calibration curve encompassing the concentration range is prepared for each compound to be determined. The relative response (RR) (labeled to native) vs. concentration in standard solutions is plotted or computed using a linear regression. Relative response is determined according to the procedures described below. Five calibration points are employed.
10.5.2The response of each CDD/CDF relative to its labeled analog is determined using the area responses of both the primary and secondary exact m/z's specified in Table 8, for each calibration standard, as follows:
10.5.3To calibrate the analytical system by isotope dilution, inject a volume of calibration standards CS1 through CS5 (Section 7.13 and Table 4) identical to the volume chosen in Section 10.2, using the procedure in Section 14 and the conditions in Section 10.1.1 and Table 2. Compute the relative response (RR) at each concentration.
10.5.4Linearity—If the relative response for any compound is constant (less than 20% coefficient of variation) over the five-point calibration range, an averaged relative response may be used for that compound; otherwise, the complete calibration curve for that compound shall be used over the five-point calibration range.
10.6Calibration by Internal Standard—The internal standard method is applied to determination of 1,2,3,7,8,9-HxCDD (Section 17.1.2), OCDF (Section 17.1.1), the non 2,3,7,8-substituted compounds, and to the determination of labeled compounds for intralaboratory statistics (Sections 9.4 and 15.5.4).
10.6.1Response factors—Calibration requires the determination of response factors (RF) defined by the following equation:
There is only one m/z for
10.6.2To calibrate the analytical system by internal standard, inject 1.0 μL or 2.0 μL of calibration standards CS1 through CS5 (Section 7.13 and Table 4) using the procedure in Section 14 and the conditions in Section 10.1.1 and Table 2. Compute the response factor (RF) at each concentration.
10.6.3Linearity—If the response factor (RF) for any compound is constant (less than 35% coefficient of variation) over the five-point calibration range, an averaged response factor may be used for that compound; otherwise, the complete calibration curve for that compound shall be used over the five-point range.
10.7Combined Calibration—By using calibration solutions (Section 7.13 and Table 4) containing the CDDs/CDFs and labeled compounds and the internal standards, a single set of analyses can be used to produce calibration curves for the isotope dilution and internal standard methods. These curves are verified each shift (Section 15.3) by analyzing the calibration verification standard (VER, Table 4). Recalibration is required if any of the calibration verification criteria (Section 15.3) cannot be met.
10.8Data Storage—MS data shall be collected, recorded, and stored.
10.8.1Data acquisition—The signal at each exact m/z shall be collected repetitively throughout the monitoring period and stored on a mass storage device.
10.8.2Response factors and multipoint calibrations—The data system shall be used to record and maintain lists of response factors (response ratios for isotope dilution) and multipoint calibration curves. Computations of relative standard deviation (coefficient of variation) shall be used to test calibration linearity. Statistics on initial performance (Section 9.2) and ongoing performance (Section 15.5) should be computed and maintained, either on the instrument data system, or on a separate computer system.
11.1Sample preparation involves modifying the physical form of the sample so that the CDDs/CDFs can be extracted efficiently. In general, the samples must be in a liquid form or in the form of finely divided solids in order for efficient extraction to take place. Table 10 lists the phases and suggested quantities for extraction of various sample matrices.
For samples known or expected to contain high levels of the CDDs/CDFs, the smallest sample size representative of the entire sample should be used (see Section 17.5).
For all samples, the blank and IPR/OPR aliquots must be processed through the same steps as the sample to check for contamination and losses in the preparation processes.
11.1.1For samples that contain particles, percent solids and particle size are determined using the procedures in Sections 11.2 and 11.3, respectively.
11.1.2Aqueous samples—Because CDDs/CDFs may be bound to suspended particles, the preparation of aqueous samples is dependent on the solids content of the sample.
11.1.2.1Aqueous samples visibly absent particles are prepared per Section 11.4 and extracted directly using the separatory funnel or SPE techniques in Sections 12.1 or 12.2, respectively.
11.1.2.2Aqueous samples containing visible particles and containing one percent suspended solids or less are prepared using the procedure in Section 11.4. After preparation, the sample is extracted directly using the SPE technique in 12.2 or filtered per Section 11.4.3. After filtration, the particles and filter are extracted using the SDS procedure in Section 12.3 and the filtrate is extracted using the separatory funnel procedure in Section 12.1.
11.1.2.3For aqueous samples containing greater than one percent solids, a sample aliquot sufficient to provide 10 g of dry solids is used, as described in Section 11.5.
11.1.3Solid samples are prepared using the procedure described in Section 11.5 followed by extraction via the SDS procedure in Section 12.3.
11.1.4Multiphase samples—The phase(s) containing the CDDs/CDFs is separated from the non-CDD/CDF phase using pressure filtration and centrifugation, as described in Section 11.6. The CDDs/CDFs will be in the organic phase in a multiphase sample in which an organic phase exists.
11.1.5Procedures for grinding, homogenization, and blending of various sample phases are given in Section 11.7.
11.1.6Tissue samples—Preparation procedures for fish and other tissues are given in Section 11.8.
11.2Determination of Percent Suspended Solids.
This aliquot is used for determining the solids content of the sample, not for determination of CDDs/CDFs.
11.2.1Aqueous liquids and multi-phase samples consisting of mainly an aqueous phase.
11.2.1.1Dessicate and weigh a GF/D filter (Section 6.5.3) to three significant figures.
11.2.1.2Filter 10.0±0.02 mL of well-mixed sample through the filter.
11.2.1.3Dry the filter a minimum of 12 hours at 110±5 °C and cool in a dessicator.
11.2.1.4Calculate percent solids as follows:
11.2.2Non-aqueous liquids, solids, semi-solid samples, and multi-phase samples in which the main phase is not aqueous; but not tissues.
11.2.2.1Weigh 5-10 g of sample to three significant figures in a tared beaker.
11.2.2.2Dry a minimum of 12 hours at 110±5 °C, and cool in a dessicator.
11.2.2.3Calculate percent solids as follows:
11.3Determination of Particle Size.
11.3.1Spread the dried sample from Section 11.2.2.2 on a piece of filter paper or aluminum foil in a fume hood or glove box.
11.3.2Estimate the size of the particles in the sample. If the size of the largest particles is greater than 1 mm, the particle size must be reduced to 1 mm or less prior to extraction using the procedures in Section 11.7.
11.4Preparation of Aqueous Samples Containing 1% Suspended Solids or Less.
11.4.1Aqueous samples visibly absent particles are prepared per the procedure below and extracted directly using the separatory funnel or SPE techniques in Sections 12.1 or 12.2, respectively. Aqueous samples containing visible particles and one percent suspended solids or less are prepared using the procedure below and extracted using either the SPE technique in Section 12.2 or further prepared using the filtration procedure in Section 11.4.3. The filtration procedure is followed by SDS extraction of the filter and particles (Section 12.3) and separatory funnel extraction of the filtrate (Section 12.1). The SPE procedure is followed by SDS extraction of the filter and disk.
11.4.2Preparation of sample and QC aliquots.
11.4.2.1Mark the original level of the sample on the sample bottle for reference. Weigh the sample plus bottle to ± 1.
11.4.2.2Spike 1.0 mL of the diluted labeled-compound spiking solution (Section 7.10.3) into the sample bottle. Cap the bottle and mix the sample by careful shaking. Allow the sample to equilibrate for one to two hours, with occasional shaking.
11.4.2.3For each sample or sample batch (to a maximum of 20 samples) to be extracted during the same 12-hour shift, place two 1.0 L aliquots of reagent water in clean sample bottles or flasks.
11.4.2.4Spike 1.0 mL of the diluted labeled-compound spiking solution (Section 7.10.3) into both reagent water aliquots. One of these aliquots will serve as the method blank.
11.4.2.5Spike 1.0 mL of the PAR standard (Section 7.14) into the remaining reagent water aliquot. This aliquot will serve as the OPR (Section 15.5).
11.4.2.6If SPE is to be used, add 5 mL of methanol to the sample, cap and shake the sample to mix thoroughly, and proceed to Section 12.2 for extraction. If SPE is not to be used, and the sample is visibly absent particles, proceed to Section 12.1 for extraction. If SPE is not to be used and the sample contains visible particles, proceed to the following section for filtration of particles.
11.4.3Filtration of particles.
11.4.3.1Assemble a Buchner funnel (Section 6.5.5) on top of a clean filtration flask. Apply vacuum to the flask, and pour the entire contents of the sample bottle through a glass-fiber filter (Section 6.5.6) in the Buchner funnel, swirling the sample remaining in the bottle to suspend any particles.
11.4.3.2Rinse the sample bottle twice with approximately 5 mL portions of reagent water to transfer any remaining particles onto the filter.
11.4.3.3Rinse any particles off the sides of the Buchner funnel with small quantities of reagent water.
11.4.3.4Weigh the empty sample bottle to ±1 g. Determine the weight of the sample by difference. Save the bottle for further use.
11.4.3.5Extract the filtrate using the separatory funnel procedure in Section 12.1.
11.4.3.6Extract the filter containing the particles using the SDS procedure in Section 12.3.
11.5Preparation of Samples Containing Greater Than 1% Solids.
11.5.1Weigh a well-mixed aliquot of each sample (of the same matrix type) sufficient to provide 10 g of dry solids (based on the solids determination in Section 11.2) into a clean beaker or glass jar.
11.5.2Spike 1.0 mL of the diluted labeled compound spiking solution (Section 7.10.3) into the sample.
11.5.3For each sample or sample batch (to a maximum of 20 samples) to be extracted during the same 12-hour shift, weigh two 10 g aliquots of the appropriate reference matrix (Section 7.6) into clean beakers or glass jars.
11.5.4Spike 1.0 mL of the diluted labeled compound spiking solution (Section 7.10.3) into each reference matrix aliquot. One aliquot will serve as the method blank. Spike 1.0 mL of the PAR standard (Section 7.14) into the other reference matrix aliquot. This aliquot will serve as the OPR (Section 15.5).
11.5.5Stir or tumble and equilibrate the aliquots for one to two hours.
11.5.6Decant excess water. If necessary to remove water, filter the sample through a glass-fiber filter and discard the aqueous liquid.
11.5.7If particles >1mm are present in the sample (as determined in Section 11.3.2), spread the sample on clean aluminum foil in a hood. After the sample is dry, grind to reduce the particle size (Section 11.7).
11.5.8Extract the sample and QC aliquots using the SDS procedure in Section 12.3.
11.6Multiphase Samples.
11.6.1Using the percent solids determined in Section 11.2.1 or 11.2.2, determine the volume of sample that will provide 10 g of solids, up to 1 L of sample.
11.6.2Pressure filter the amount of sample determined in Section 11.6.1 through Whatman GF/D glass-fiber filter paper (Section 6.5.3). Pressure filter the blank and OPR aliquots through GF/D papers also. If necessary to separate the phases and/or settle the solids, centrifuge these aliquots prior to filtration.
11.6.3Discard any aqueous phase (if present). Remove any non-aqueous liquid present and reserve the maximum amount filtered from the sample (Section 11.6.1) or 10 g, whichever is less, for combination with the solid phase (Section 12.3.5).
11.6.4If particles >1mm are present in the sample (as determined in Section 11.3.2) and the sample is capable of being dried, spread the sample and QC aliquots on clean aluminum foil in a hood. After the aliquots are dry or if the sample cannot be dried, reduce the particle size using the procedures in Section 11.7 and extract the reduced particles using the SDS procedure in Section 12.3. If particles >1mm are not present, extract the particles and filter in the sample and QC aliquots directly using the SDS procedure in Section 12.3.
11.7Sample grinding, homogenization, or blending—Samples with particle sizes greater than 1 mm (as determined in Section 11.3.2) are subjected to grinding, homogenization, or blending. The method of reducing particle size to less than 1 mm is matrix-dependent. In general, hard particles can be reduced by grinding with a mortar and pestle. Softer particles can be reduced by grinding in a Wiley mill or meat grinder, by homogenization, or in a blender.
11.7.1Each size-reducing preparation procedure on each matrix shall be verified by running the tests in Section 9.2 before the procedure is employed routinely.
11.7.2The grinding, homogenization, or blending procedures shall be carried out in a glove box or fume hood to prevent particles from contaminating the work environment.
11.7.3Grinding—Certain papers and pulps, slurries, and amorphous solids can be ground in a Wiley mill or heavy duty meat grinder. In some cases, reducing the temperature of the sample to freezing or to dry ice or liquid nitrogen temperatures can aid in the grinding process. Grind the sample aliquots from Section 11.5.7 or 11.6.4 in a clean grinder. Do not allow the sample temperature to exceed 50 °C. Grind the blank and reference matrix aliquots using a clean grinder.
11.7.4Homogenization or blending—Particles that are not ground effectively, or particles greater than 1 mm in size after grinding, can often be reduced in size by high speed homogenization or blending. Homogenize and/or blend the particles or filter from Section 11.5.7 or 11.6.4 for the sample, blank, and OPR aliquots.
11.7.5Extract the aliquots using the SDS procedure in Section 12.3.
11.8Fish and Other Tissues—Prior to processing tissue samples, the laboratory must determine the exact tissue to be analyzed. Common requests for analysis of fish tissue include whole fish—skin on, whole fish—skin removed, edible fish fillets (filleted in the field or by the laboratory), specific organs, and other portions. Once the appropriate tissue has been determined, the sample must be homogenized.
11.8.1Homogenization.
11.8.1.1Samples are homogenized while still frozen, where practical. If the laboratory must dissect the whole fish to obtain the appropriate tissue for analysis, the unused tissues may be rapidly refrozen and stored in a clean glass jar for subsequent use.
11.8.1.2Each analysis requires 10 g of tissue (wet weight). Therefore, the laboratory should homogenize at least 20 g of tissue to allow for re-extraction of a second aliquot of the same homogenized sample, if re-analysis is required. When whole fish analysis is necessary, the entire fish is homogenized.
11.8.1.3Homogenize the sample in a tissue homogenizer (Section 6.3.3) or grind in a meat grinder (Section 6.3.4). Cut tissue too large to feed into the grinder into smaller pieces. To assure homogeneity, grind three times.
11.8.1.4Transfer approximately 10 g (wet weight) of homogenized tissue to a clean, tared, 400-500 mL beaker. For the alternate HCl digestion/extraction, transfer the tissue to a clean, tared 500-600 mL wide-mouth bottle. Record the weight to the nearest 10 mg.
11.8.1.5Transfer the remaining homogenized tissue to a clean jar with a fluoropolymer-lined lid. Seal the jar and store the tissue at <−10 °C. Return any tissue that was not homogenized to its original container and store at <−10 °C.
11.8.2QC aliquots.
11.8.2.1Prepare a method blank by adding approximately 10 g of the oily liquid reference matrix (Section 7.6.4) to a 400-500 mL beaker. For the alternate HCl digestion/extraction, add the reference matrix to a 500-600 mL wide-mouth bottle. Record the weight to the nearest 10 mg.
11.8.2.2Prepare a precision and recovery aliquot by adding approximately 10 g of the oily liquid reference matrix (Section 7.6.4) to a separate 400-500 mL beaker or wide-mouth bottle, depending on the extraction procedure to be used. Record the weight to the nearest 10 mg. If the initial precision and recovery test is to be performed, use four aliquots; if the ongoing precision and recovery test is to be performed, use a single aliquot.
11.8.3Spiking
11.8.3.1Spike 1.0 mL of the labeled compound spiking solution (Section 7.10.3) into the sample, blank, and OPR aliquot.
11.8.3.2Spike 1.0 mL of the PAR standard (Section 7.14) into the OPR aliquot.
11.8.4Extract the aliquots using the procedures in Section 12.4.
Extraction procedures include separatory funnel (Section 12.1) and solid phase (Section 12.2) for aqueous liquids; Soxhlet/Dean-Stark (Section 12.3) for solids, filters, and SPE disks; and Soxhlet extraction (Section 12.4.1) and HCl digestion (Section 12.4.2) for tissues. Acid/base back-extraction (Section 12.5) is used for initial cleanup of extracts.
Macro-concentration procedures include rotary evaporation (Section 12.6.1), heating mantle (Section 12.6.2), and Kuderna-Danish (K-D) evaporation (Section 12.6.3). Micro-concentration uses nitrogen blowdown (Section 12.7).
12.1Separatory funnel extraction of filtrates and of aqueous samples visibly absent particles.
12.1.1Pour the spiked sample (Section 11.4.2.2) or filtrate (Section 11.4.3.5) into a 2 L separatory funnel. Rinse the bottle or flask twice with 5 mL of reagent water and add these rinses to the separatory funnel.
12.1.2Add 60 mL methylene chloride to the empty sample bottle (Section 12.1.1), seal, and shake 60 seconds to rinse the inner surface. Transfer the solvent to the separatory funnel, and extract the sample by shaking the funnel for two minutes with periodic venting. Allow the organic layer to separate from the aqueous phase for a minimum of 10 minutes. If an emulsion forms and is more than one-third the volume of the solvent layer, employ mechanical techniques to complete the phase separation (see note below). Drain the methylene chloride extract
If an emulsion forms, the analyst must employ mechanical techniques to complete the phase separation. The optimum technique depends upon the sample, but may include stirring, filtration through glass wool, use of phase separation paper, centrifugation, use of an ultrasonic bath with ice, addition of NaCl, or other physical methods. Alternatively, solid-phase or other extraction techniques may be used to prevent emulsion formation. Any alternative technique is acceptable so long as the requirements in Section 9 are met.
Experience with aqueous samples high in dissolved organic materials (e.g., paper mill effluents) has shown that acidification of the sample prior to extraction may reduce the formation of emulsions. Paper industry methods suggest that the addition of up to 400 mL of ethanol to a 1 L effluent sample may also reduce emulsion formation. However, studies by EPA suggest that the effect may be a result of sample dilution, and that the addition of reagent water may serve the same function. Mechanical techniques may still be necessary to complete the phase separation. If either acidification or addition of ethanol is utilized, the laboratory must perform the startup tests described in Section 9.2 using the same techniques.
12.1.3Extract the water sample two more times with 60 mL portions of methylene chloride. Drain each portion through the sodium sulfate into the concentrator. After the third extraction, rinse the separatory funnel with at least 20 mL of methylene chloride, and drain this rinse through the sodium sulfate into the concentrator. Repeat this rinse at least twice. Set aside the funnel with sodium sulfate if the extract is to be combined with the extract from the particles.
12.1.4Concentrate the extract using one of the macro-concentration procedures in Section 12.6.
12.1.4.1If the extract is from a sample visibly absent particles (Section 11.1.2.1), adjust the final volume of the concentrated extract to approximately 10 mL with hexane, transfer to a 250 mL separatory funnel, and back-extract using the procedure in Section 12.5.
12.1.4.2If the extract is from the aqueous filtrate (Section 11.4.3.5), set aside the concentration apparatus for addition of the SDS extract from the particles (Section 12.3.9.1.2).
12.2SPE of Samples Containing Less Than 1% Solids (References 19-20).
12.2.1Disk preparation.
12.2.1.1Place an SPE disk on the base of the filter holder (Figure 4) and wet with toluene. While holding a GMF 150 filter above the SPE disk with tweezers, wet the filter with toluene and lay the filter on the SPE disk, making sure that air is not trapped between the filter and disk. Clamp the filter and SPE disk between the 1 L glass reservoir and the vacuum filtration flask.
12.2.1.2Rinse the sides of the filtration flask with approx 15 mL of toluene using a squeeze bottle or syringe. Apply vacuum momentarily until a few drops appear at the drip tip. Release the vacuum and allow the filter/disk to soak for approx one minute. Apply vacuum and draw all of the toluene through the filter/disk. Repeat the wash step with approx 15 mL of acetone and allow the filter/disk to air dry.
12.2.1.3Re-wet the filter/disk with approximately 15 mL of methanol, allowing the filter/disk to soak for approximately one minute. Pull the methanol through the filter/disk using the vacuum, but retain a layer of methanol approximately 1 mm thick on the filter. Do not allow the disk to go dry from this point until the end of the extraction.
12.2.1.4Rinse the filter/disk with two 50-mL portions of reagent water by adding the water to the reservoir and pulling most through, leaving a layer of water on the surface of the filter.
12.2.2Extraction.
12.2.2.1Pour the spiked sample (Section 11.4.2.2), blank (Section 11.4.2.4), or IPR/OPR aliquot (Section 11.4.2.5) into the reservoir and turn on the vacuum to begin the extraction. Adjust the vacuum to complete the extraction in no less than 10 minutes. For samples containing a high concentration of particles (suspended solids), filtration times may be eight hours or longer.
12.2.2.2Before all of the sample has been pulled through the filter/disk, rinse the sample bottle with approximately 50 mL of reagent water to remove any solids, and pour into the reservoir. Pull through the filter/disk. Use additional reagent water rinses until all visible solids are removed.
12.2.2.3Before all of the sample and rinses have been pulled through the filter/disk, rinse the sides of the reservoir with small portions of reagent water.
12.2.2.4Allow the filter/disk to dry, then remove the filter and disk and place in a glass Petri dish. Extract the filter and disk per Section 12.3.
12.3SDS Extraction of Samples Containing Particles, and of Filters and/or Disks.
12.3.1Charge a clean extraction thimble (Section 6.4.2.2) with 5.0 g of 100/200 mesh silica (Section 7.5.1.1) topped with 100 g of quartz sand (Section 7.3.2).
Do not disturb the silica layer throughout the extraction process.
12.3.2Place the thimble in a clean extractor. Place 30-40 mL of toluene in the receiver and 200-250 mL of toluene in the flask.
12.3.3Pre-extract the glassware by heating the flask until the toluene is boiling. When properly adjusted, one to two drops of toluene will fall per second from the condenser tip into the receiver. Extract the apparatus for a minimum of three hours.
12.3.4After pre-extraction, cool and disassemble the apparatus. Rinse the thimble with toluene and allow to air dry.
12.3.5Load the wet sample, filter, and/or disk from Section 11.4.3.6, 11.5.8, 11.6.4, 11.7.3, 11.7.4, or 12.2.2.4 and any nonaqueous liquid from Section 11.6.3 into the thimble and manually mix into the sand layer with a clean metal spatula, carefully breaking up any large lumps of sample.
12.3.6Reassemble the pre-extracted SDS apparatus, and add a fresh charge of toluene to the receiver and reflux flask. Apply power to the heating mantle to begin refluxing. Adjust the reflux rate to match the rate of percolation through the sand and silica beds until water removal lessens the restriction to toluene flow. Frequently check the apparatus for foaming during the first two hours of extraction. If foaming occurs, reduce the reflux rate until foaming subsides.
12.3.7Drain the water from the receiver at one to two hours and eight to nine hours, or sooner if the receiver fills with water. Reflux the sample for a total of 16-24 hours. Cool and disassemble the apparatus. Record the total volume of water collected.
12.3.8Remove the distilling flask. Drain the water from the Dean-Stark receiver and add any toluene in the receiver to the extract in the flask.
12.3.9Concentrate the extract using one of the macro-concentration procedures in Section 12.6 per the following:
12.3.9.1Extracts from the particles in an aqueous sample containing less than 1% solids (Section 11.4.3.6).
12.3.9.1.1Concentrate the extract to approximately 5 mL using the rotary evaporator or heating mantle procedures in Section 12.6.1 or 12.6.2.
12.3.9.1.2Quantitatively transfer the extract through the sodium sulfate (Section 12.1.3) into the apparatus that was set aside (Section 12.1.4.2) and reconcentrate to the level of the toluene.
12.3.9.1.3Adjust to approximately 10 mL with hexane, transfer to a 250 mL separatory funnel, and proceed with back-extraction (Section 12.5).
12.3.9.2Extracts from particles (Sections 11.5 through 11.6) or from the SPE filter and disk (Section 12.2.2.4)—Concentrate to approximately 10 mL using the rotary evaporator or heating mantle (Section 12.6.1 or 12.6.2), transfer to a 250 mL separatory funnel, and proceed with back-extraction (Section 12.5).
12.4Extraction of Tissue—Two procedures are provided for tissue extraction.
12.4.1Soxhlet extraction (Reference 21).
12.4.1.1Add 30-40 g of powdered anhydrous sodium sulfate to each of the beakers (Section 11.8.4) and mix thoroughly. Cover the beakers with aluminum foil and allow to equilibrate for 12-24 hours. Remix prior to extraction to prevent clumping.
12.4.1.2Assemble and pre-extract the Soxhlet apparatus per Sections 12.3.1 through 12.3.4, except use the methylene chloride:hexane (1:1) mixture for the pre-extraction and rinsing and omit the quartz sand. The Dean-Stark moisture trap may also be omitted, if desired.
12.4.1.3Reassemble the pre-extracted Soxhlet apparatus and add a fresh charge of methylene chloride:hexane to the reflux flask.
12.4.1.4Transfer the sample/sodium sulfate mixture (Section 12.4.1.1) to the Soxhlet thimble, and install the thimble in the Soxhlet apparatus.
12.4.1.5 Rinse the beaker with several portions of solvent mixture and add to the thimble. Fill the thimble/receiver with solvent. Extract for 18-24 hours.
12.4.1.6After extraction, cool and disassemble the apparatus.
12.4.1.7Quantitatively transfer the extract to a macro-concentration device (Section 12.6), and concentrate to near dryness. Set aside the concentration apparatus for re-use.
12.4.1.8Complete the removal of the solvent using the nitrogen blowdown procedure (Section 12.7) and a water bath temperature of 60 °C. Weigh the receiver, record the weight, and return the receiver to the blowdown apparatus, concentrating the residue until a constant weight is obtained.
12.4.1.9Percent lipid determination—The lipid content is determined by extraction of tissue with the same solvent system (methylene chloride:hexane) that was used in EPA's National Dioxin Study (Reference 22) so that lipid contents are consistent with that study.
12.4.1.9.1Redissolve the residue in the receiver in hexane and spike 1.0 mL of the cleanup standard (Section 7.11) into the solution.
12.4.1.9.2Transfer the residue/hexane to the anthropogenic isolation column (Section 13.7.1) or bottle for the acidified silica gel batch cleanup (Section 13.7.2), retaining the boiling chips in the concentration apparatus. Use several rinses to assure that all material is transferred. If necessary, sonicate or heat the receiver slightly to assure that all material is re-dissolved. Allow the receiver to dry. Weigh the receiver and boiling chips.
12.4.1.9.3Calculate the lipid content to the nearest three significant figures as follows:
12.4.1.9.4It is not necessary to determine the lipid content of the blank, IPR, or OPR aliquots.
12.4.2HCl digestion/extraction and concentration (References 23-26).
12.4.2.1Add 200 mL of 6 N HCl and 200 mL of methylene chloride:hexane (1:1) to the sample and QC aliquots (Section 11.8.4).
12.4.2.2Cap and shake each bottle one to three times. Loosen the cap in a hood to vent excess pressure. Shake each bottle for 10-30 seconds and vent.
12.4.2.3Tightly cap and place on shaker. Adjust the shaker action and speed so that the acid, solvent, and tissue are in constant motion. However, take care to avoid such violent action that the bottle may be dislodged from the shaker. Shake for 12-24 hours.
12.4.2.4After digestion, remove the bottles from the shaker. Allow the bottles to stand so that the solvent and acid layers separate.
12.4.2.5Decant the solvent through a glass funnel with glass-fiber filter (Sections 6.5.2 through 6.5.3) containing approximately 10 g of granular anhydrous sodium sulfate (Section 7.2.1) into a macro-concentration apparatus (Section 12.6). Rinse the contents of the bottle with two 25 mL portions of hexane and pour through the sodium sulfate into the apparatus.
12.4.2.6Concentrate the solvent to near dryness using a macro-concentration procedure (Section 12.6).
12.4.2.7Complete the removal of the solvent using the nitrogen blowdown apparatus (Section 12.7) and a water bath temperature of 60 °C. Weigh the receiver, record the weight, and return the receiver to the blowdown apparatus, concentrating the residue until a constant weight is obtained.
12.4.2.8Percent lipid determination—The lipid content is determined in the same solvent system [methylene chloride:hexane (1:1)] that was used in EPA's National Dioxin Study (Reference 22) so that lipid contents are consistent with that study.
12.4.2.8.1Redissolve the residue in the receiver in hexane and spike 1.0 mL of the cleanup standard (Section 7.11) into the solution.
12.4.2.8.2Transfer the residue/hexane to the narrow-mouth 100-200 mL bottle retaining the boiling chips in the receiver. Use several rinses to assure that all material is transferred, to a maximum hexane volume of approximately 70 mL. Allow the receiver to dry. Weigh the receiver and boiling chips.
12.4.2.8.3Calculate the percent lipid per Section 12.4.1.9.3. It is not necessary to determine the lipid content of the blank, IPR, or OPR aliquots.
12.4.2.9Clean up the extract per Section 13.7.3.
12.5Back-Extraction with Base and Acid.
12.5.1Spike 1.0 mL of the cleanup standard (Section 7.11) into the separatory funnels containing the sample and QC extracts from Section 12.1.4.1, 12.3.9.1.3, or 12.3.9.2.
12.5.2Partition the extract against 50 mL of potassium hydroxide solution (Section 7.1.1). Shake for two minutes with periodic venting into a hood. Remove and discard the aqueous layer. Repeat the base washing until no color is visible in the aqueous layer, to a maximum of four washings. Minimize contact time between the extract and the base to prevent degradation of the CDDs/CDFs. Stronger potassium hydroxide solutions may be employed for back-extraction, provided that the laboratory meets the specifications for labeled compound recovery and demonstrates acceptable performance using the procedure in Section 9.2.
12.5.3Partition the extract against 50 mL of sodium chloride solution (Section 7.1.4) in the same way as with base. Discard the aqueous layer.
12.5.4Partition the extract against 50 mL of sulfuric acid (Section 7.1.2) in the same way as with base. Repeat the acid washing until no color is visible in the aqueous layer, to a maximum of four washings.
12.5.5Repeat the partitioning against sodium chloride solution and discard the aqueous layer.
12.5.6Pour each extract through a drying column containing 7-10 cm of granular anhydrous sodium sulfate (Section 7.2.1). Rinse the separatory funnel with 30-50 mL of solvent, and pour through the drying column. Collect each extract in a round-bottom flask. Re-concentrate the sample and QC aliquots per Sections 12.6 through 12.7, and clean up the samples and QC aliquots per Section 13.
12.6Macro-Concentration—Extracts in toluene are concentrated using a rotary evaporator or a heating mantle; extracts in methylene chloride or hexane are concentrated using a rotary evaporator, heating mantle, or Kuderna-Danish apparatus.
12.6.1Rotary evaporation—Concentrate the extracts in separate round-bottom flasks.
12.6.1.1Assemble the rotary evaporator according to manufacturer's instructions, and warm the water bath to 45 °C. On a daily basis, preclean the rotary evaporator by concentrating 100 mL of clean extraction solvent through the system. Archive both the concentrated solvent and the solvent in the catch flask for a contamination check if necessary. Between samples, three 2-3 mL aliquots of solvent should be rinsed down the feed tube into a waste beaker.
12.6.1.2Attach the round-bottom flask containing the sample extract to the rotary evaporator. Slowly apply vacuum to the system, and begin rotating the sample flask.
12.6.1.3Lower the flask into the water bath, and adjust the speed of rotation and the temperature as required to complete concentration in 15-20 minutes. At the proper rate of concentration, the flow of solvent into the receiving flask will be steady, but no bumping or visible boiling of the extract will occur.
If the rate of concentration is too fast, analyte loss may occur.
12.6.1.4When the liquid in the concentration flask has reached an apparent volume of approximately 2 mL, remove the flask from the water bath and stop the rotation. Slowly and carefully admit air into the system. Be sure not to open the valve so quickly that the sample is blown out of the flask. Rinse the feed tube with approximately 2 mL of solvent.
12.6.1.5Proceed to Section 12.6.4 for preparation for back-extraction or micro-concentration and solvent exchange.
12.6.2Heating mantle—Concentrate the extracts in separate round-bottom flasks.
12.6.2.1Add one or two clean boiling chips to the round-bottom flask, and attach a three-ball macro Snyder column. Prewet the column by adding approximately 1 mL of solvent through the top. Place the round-bottom flask in a heating mantle, and apply heat as required to complete the concentration in 15-20 minutes. At the proper rate of distillation, the balls of the column will actively chatter, but the chambers will not flood.
12.6.2.2When the liquid has reached an apparent volume of approximately 10 mL, remove the round-bottom flask from the heating mantle and allow the solvent to drain and cool for at least 10 minutes. Remove the Snyder column and rinse the glass joint into the receiver with small portions of solvent.
12.6.2.3Proceed to Section 12.6.4 for preparation for back-extraction or micro-concentration and solvent exchange.
12.6.3Kuderna-Danish (K-D)—Concentrate the extracts in separate 500 mL K-D flasks equipped with 10 mL concentrator tubes. The K-D technique is used for solvents such as methylene chloride and hexane. Toluene is difficult to concentrate using the K-D technique unless a water bath fed by a steam generator is used.
12.6.3.1Add one to two clean boiling chips to the receiver. Attach a three-ball macro Snyder column. Prewet the column by adding approximately 1 mL of solvent through the top. Place the K-D apparatus in a hot water bath so that the entire lower rounded surface of the flask is bathed with steam.
12.6.3.2Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15-20 minutes. At the proper rate of distillation, the balls of the column will actively chatter but the chambers will not flood.
12.6.3.3When the liquid has reached an apparent volume of 1 mL, remove the K-D apparatus from the bath and allow the solvent to drain and cool for at least 10 minutes. Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1-2 mL of solvent. A 5 mL syringe is recommended for this operation.
12.6.3.4Remove the three-ball Snyder column, add a fresh boiling chip, and attach a two-ball micro Snyder column to the concentrator tube. Prewet the column by adding approximately 0.5 mL of solvent through the top. Place the apparatus in the hot water bath.
12.6.3.5Adjust the vertical position and the water temperature as required to complete the concentration in 5-10 minutes. At the proper rate of distillation, the balls of the column will actively chatter but the chambers will not flood.
12.6.3.6When the liquid reaches an apparent volume of 0.5 mL, remove the apparatus from the water bath and allow to drain and cool for at least 10 minutes.
12.6.3.7Proceed to 12.6.4 for preparation for back-extraction or micro-concentration and solvent exchange.
12.6.4Preparation for back-extraction or micro-concentration and solvent exchange.
12.6.4.1For back-extraction (Section 12.5), transfer the extract to a 250 mL separatory funnel. Rinse the concentration vessel with small portions of hexane, adjust the hexane volume in the separatory funnel to 10-20 mL, and proceed to back-extraction (Section 12.5).
12.6.4.2For determination of the weight of residue in the extract, or for clean-up procedures other than back-extraction, transfer the extract to a blowdown vial using two to three rinses of solvent. Proceed with micro-concentration and solvent exchange (Section 12.7).
12.7Micro-Concentration and Solvent Exchange.
12.7.1Extracts to be subjected to GPC or HPLC cleanup are exchanged into methylene chloride. Extracts to be cleaned up using silica gel, alumina, carbon, and/or Florisil are exchanged into hexane.
12.7.2Transfer the vial containing the sample extract to a nitrogen blowdown device. Adjust the flow of nitrogen so that the surface of the solvent is just visibly disturbed.
A large vortex in the solvent may cause analyte loss.
12.7.3Lower the vial into a 45 °C water bath and continue concentrating.
12.7.3.1If the extract is to be concentrated to dryness for weight determination (Sections 12.4.1.8, 12.4.2.7, and 13.7.1.4), blow dry until a constant weight is obtained.
12.7.3.2If the extract is to be concentrated for injection into the GC/MS or the
12.7.4When the volume of the liquid is approximately 100 L, add 2-3 mL of the desired solvent (methylene chloride for GPC and HPLC, or hexane for the other cleanups) and continue concentration to approximately 100 μL. Repeat the addition of solvent and concentrate once more.
12.7.5If the extract is to be cleaned up by GPC, adjust the volume of the extract to 5.0 mL with methylene chloride. If the extract is to be cleaned up by HPLC, further concentrate the extract to 30 μL. Proceed with GPC or HPLC cleanup (Section 13.2 or 13.6, respectively).
12.7.6If the extract is to be cleaned up by column chromatography (alumina, silica gel, Carbopak/Celite, or Florisil), bring the final volume to 1.0 mL with hexane. Proceed with column cleanups (Sections 13.3 through 13.5 and 13.8).
12.7.7If the extract is to be concentrated for injection into the GC/MS (Section 14), quantitatively transfer the extract to a 0.3 mL conical vial for final concentration, rinsing the larger vial with hexane and adding the rinse to the conical vial. Reduce the volume to approximately 100 μL. Add 10 μL of nonane to the vial, and evaporate the solvent to the level of the nonane. Seal the vial and label with the sample number. Store in the dark at room temperature until ready for GC/MS analysis. If GC/MS analysis will not be performed on the same day, store the vial at <−10 °C.
13.1Cleanup may not be necessary for relatively clean samples (e.g., treated effluents, groundwater, drinking water). If particular circumstances require the use of a cleanup procedure, the analyst may use any or all of the procedures below or any other appropriate procedure. Before using a cleanup procedure, the analyst must demonstrate that the requirements of Section 9.2 can be met using the cleanup procedure. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, the cleanup procedures may be optimized for isolation of these two compounds.
13.1.1Gel permeation chromatography (Section 13.2) removes high molecular weight interferences that cause GC column performance to degrade. It should be used for all soil and sediment extracts and may be used for water extracts that are expected to contain high molecular weight organic compounds (e.g., polymeric materials, humic acids).
13.1.2Acid, neutral, and basic silica gel (Section 13.3), alumina (Section 13.4), and Florisil (Section 13.8) are used to remove nonpolar and polar interferences. Alumina and Florisil are used to remove chlorodiphenyl ethers.
13.1.3Carbopak/Celite (Section 13.5) is used to remove nonpolar interferences.
13.1.4HPLC (Section 13.6) is used to provide specificity for the 2,3,7,8-substituted and other CDD and CDF isomers.
13.1.5The anthropogenic isolation column (Section 13.7.1), acidified silica gel batch adsorption procedure (Section 13.7.2), and sulfuric acid and base back-extraction (Section 13.7.3) are used for removal of lipids from tissue samples.
13.2Gel Permeation Chromatography (GPC).
13.2.1Column packing.
13.2.1.1Place 70-75 g of SX-3 Bio-beads (Section 6.7.1.1) in a 400-500 mL beaker.
13.2.1.2Cover the beads with methylene chloride and allow to swell overnight (a minimum of 12 hours).
13.2.1.3Transfer the swelled beads to the column (Section 6.7.1.1) and pump solvent through the column, from bottom to top, at 4.5-5.5 mL/minute prior to connecting the column to the detector.
13.2.1.4After purging the column with solvent for one to two hours, adjust the column head pressure to 7-10 psig and purge for four to five hours to remove air. Maintain a head pressure of 7-10 psig. Connect the column to the detector (Section 6.7.1.4).
13.2.2Column calibration.
13.2.2.1Load 5 mL of the calibration solution (Section 7.4) into the sample loop.
13.2.2.2Inject the calibration solution and record the signal from the detector. The elution pattern will be corn oil, bis(2-ethyl hexyl)phthalate, pentachlorophenol, perylene, and sulfur.
13.2.2.3Set the “dump time” to allow >85% removal of the corn oil and >85% collection of the phthalate.
13.2.2.4Set the “collect time” to the peak minimum between perylene and sulfur.
13.2.2.5Verify the calibration with the calibration solution after every 20 extracts. Calibration is verified if the recovery of the pentachlorophenol is greater than 85%. If calibration is not verified, the system shall be recalibrated using the calibration solution, and the previous 20 samples shall be re-extracted and cleaned up using the calibrated GPC system.
13.2.3Extract cleanup—GPC requires that the column not be overloaded. The column specified in this method is designed to handle a maximum of 0.5 g of high molecular weight material in a 5 mL extract. If the extract is known or expected to contain more than 0.5 g, the extract is split into aliquots for GPC, and the aliquots are combined after elution from the column. The residue content of the extract may be obtained gravimetrically by evaporating the solvent from a 50 μL aliquot.
13.2.3.1Filter the extract or load through the filter holder (Section 6.7.1.3) to remove the particles. Load the 5.0 mL extract onto the column.
13.2.3.2Elute the extract using the calibration data determined in Section 13.2.2. Collect the eluate in a clean 400-500 mL beaker.
13.2.3.3Rinse the sample loading tube thoroughly with methylene chloride between extracts to prepare for the next sample.
13.2.3.4If a particularly dirty extract is encountered, a 5.0 mL methylene chloride blank shall be run through the system to check for carry-over.
13.2.3.5Concentrate the eluate per Sections 12.6 and 12.7 for further cleanup or injection into the GC/MS.
13.3Silica Gel Cleanup.
13.3.1Place a glass-wool plug in a 15 mm ID chromatography column (Section 6.7.4.2). Pack the column bottom to top with: 1 g silica gel (Section 7.5.1.1), 4 g basic silica gel (Section 7.5.1.3), 1 g silica gel, 8 g acid silica gel (Section 7.5.1.2), 2 g silica gel, and 4 g granular anhydrous sodium sulfate (Section 7.2.1). Tap the column to settle the adsorbents.
13.3.2Pre-elute the column with 50-100 mL of hexane. Close the stopcock when the hexane is within 1 mm of the sodium sulfate. Discard the eluate. Check the column for channeling. If channeling is present, discard the column and prepare another.
13.3.3Apply the concentrated extract to the column. Open the stopcock until the extract is within 1 mm of the sodium sulfate.
13.3.4Rinse the receiver twice with 1 mL portions of hexane, and apply separately to the column. Elute the CDDs/CDFs with 100 mL hexane, and collect the eluate.
13.3.5Concentrate the eluate per Sections 12.6 and 12.7 for further cleanup or injection into the HPLC or GC/MS.
13.3.6For extracts of samples known to contain large quantities of other organic compounds (such as paper mill effluents), it may be advisable to increase the capacity of the silica gel column. This may be accomplished by increasing the strengths of the acid and basic silica gels. The acid silica gel (Section 7.5.1.2) may be increased in strength to as much as 44% w/w (7.9 g sulfuric acid added to 10 g silica gel). The basic silica gel (Section 7.5.1.3) may be increased in strength to as much as 33% w/w (50 mL 1N NaOH added to 100 g silica gel), or the potassium silicate (Section 7.5.1.4) may be used.
The use of stronger acid silica gel (44% w/w) may lead to charring of organic compounds in some extracts. The charred material may retain some of the analytes and lead to lower recoveries of CDDs/CDFs. Increasing the strengths of the acid and basic silica gel may also require different volumes of hexane than those specified above to elute the analytes off the column. Therefore, the performance of the method after such modifications must be verified by the procedure in Section 9.2.
13.4Alumina Cleanup.
13.4.1Place a glass-wool plug in a 15 mm ID chromatography column (Section 6.7.4.2).
13.4.2If using acid alumina, pack the column by adding 6 g acid alumina (Section 7.5.2.1). If using basic alumina, substitute 6 g basic alumina (Section 7.5.2.2). Tap the column to settle the adsorbents.
13.4.3Pre-elute the column with 50-100 mL of hexane. Close the stopcock when the hexane is within 1 mm of the alumina.
13.4.4Discard the eluate. Check the column for channeling. If channeling is present, discard the column and prepare another.
13.4.5Apply the concentrated extract to the column. Open the stopcock until the extract is within 1 mm of the alumina.
13.4.6Rinse the receiver twice with 1 mL portions of hexane and apply separately to the column. Elute the interfering compounds with 100 mL hexane and discard the eluate.
13.4.7The choice of eluting solvents will depend on the choice of alumina (acid or basic) made in Section 13.4.2.
13.4.7.1If using acid alumina, elute the CDDs/CDFs from the column with 20 mL methylene chloride:hexane (20:80 v/v). Collect the eluate.
13.4.7.2If using basic alumina, elute the CDDs/CDFs from the column with 20 mL methylene chloride:hexane (50:50 v/v). Collect the eluate.
13.4.8Concentrate the eluate per Sections 12.6 and 12.7 for further cleanup or injection into the HPLC or GC/MS.
13.5Carbon Column.
13.5.1Cut both ends from a 10 mL disposable serological pipet (Section 6.7.3.2) to produce a 10 cm column. Fire-polish both ends and flare both ends if desired. Insert a glass-wool plug at one end, and pack the column with 0.55 g of Carbopak/Celite (Section 7.5.3.3) to form an adsorbent bed approximately 2 cm long. Insert a glass-wool plug on top of the bed to hold the adsorbent in place.
13.5.2Pre-elute the column with 5 mL of toluene followed by 2 mL of methylene chloride: methanol:toluene (15:4:1 v/v), 1 mL of methylene chloride:cyclohexane (1:1 v/v), and 5 mL of hexane. If the flow rate of eluate exceeds 0.5 mL/minute, discard the column.
13.5.3When the solvent is within 1 mm of the column packing, apply the sample extract to the column. Rinse the sample container twice with 1 mL portions of hexane and apply separately to the column. Apply 2 mL of hexane to complete the transfer.
13.5.4Elute the interfering compounds with two 3 mL portions of hexane, 2 mL of methylene chloride:cyclohexane (1:1 v/v), and 2 mL of methylene chloride:methanol:toluene (15:4:1 v/v). Discard the eluate.
13.5.5Invert the column, and elute the CDDs/CDFs with 20 mL of toluene. If carbon particles are present in the eluate, filter through glass-fiber filter paper.
13.5.6Concentrate the eluate per Sections 12.6 and 12.7 for further cleanup or injection into the HPLC or GC/MS.
13.6HPLC (Reference 6).
13.6.1Column calibration.
13.6.1.1Prepare a calibration standard containing the 2,3,7,8-substituted isomers and/or other isomers of interest at a concentration of approximately 500 pg/μL in methylene chloride.
13.6.1.2Inject 30 μL of the calibration solution into the HPLC and record the signal from the detector. Collect the eluant for reuse. The elution order will be the tetra- through octa-isomers.
13.6.1.3Establish the collection time for the tetra-isomers and for the other isomers of interest. Following calibration, flush the injection system with copious quantities of methylene chloride, including a minimum of five 50 μL injections while the detector is monitored, to ensure that residual CDDs/CDFs are removed from the system.
13.6.1.4Verify the calibration with the calibration solution after every 20 extracts. Calibration is verified if the recovery of the CDDs/CDFs from the calibration standard (Section 13.6.1.1) is 75-125% compared to the calibration (Section 13.6.1.2). If calibration is not verified, the system shall be recalibrated using the calibration solution, and the previous 20 samples shall be re-extracted and cleaned up using the calibrated system.
13.6.2Extract cleanup—HPLC requires that the column not be overloaded. The column specified in this method is designed to handle a maximum of 30 μL of extract. If the extract cannot be concentrated to less than 30 μL, it is split into fractions and the fractions are combined after elution from the column.
13.6.2.1Rinse the sides of the vial twice with 30 μL of methylene chloride and reduce to 30 μL with the evaporation apparatus (Section 12.7).
13.6.2.2Inject the 30 μL extract into the HPLC.
13.6.2.3Elute the extract using the calibration data determined in Section 13.6.1. Collect the fraction(s) in a clean 20 mL concentrator tube containing 5 mL of hexane:acetone (1:1 v/v).
13.6.2.4If an extract containing greater than 100 ng/mL of total CDD or CDF is encountered, a 30 μL methylene chloride blank shall be run through the system to check for carry-over.
13.6.2.5Concentrate the eluate per Section 12.7 for injection into the GC/MS.
13.7Cleanup of Tissue Lipids—Lipids are removed from the Soxhlet extract using either the anthropogenic isolation column (Section 13.7.1) or acidified silica gel (Section 13.7.2), or are removed from the HCl digested extract using sulfuric acid and base back-extraction (Section 13.7.3).
13.7.1Anthropogenic isolation column (References 22 and 27)—Used for removal of lipids from the Soxhlet/SDS extraction (Section 12.4.1).
13.7.1.1Prepare the column as given in Section 7.5.4.
13.7.1.2Pre-elute the column with 100 mL of hexane. Drain the hexane layer to the top of the column, but do not expose the sodium sulfate.
13.7.1.3Load the sample and rinses (Section 12.4.1.9.2) onto the column by draining each portion to the top of the bed. Elute the CDDs/CDFs from the column into the apparatus used for concentration (Section 12.4.1.7) using 200 mL of hexane.
13.7.1.4Concentrate the cleaned up extract (Sections 12.6 through 12.7) to constant weight per Section 12.7.3.1. If more than 500 mg of material remains, repeat the cleanup using a fresh anthropogenic isolation column.
13.7.1.5Redissolve the extract in a solvent suitable for the additional cleanups to be used (Sections 13.2 through 13.6 and 13.8).
13.7.1.6Spike 1.0 mL of the cleanup standard (Section 7.11) into the residue/solvent.
13.7.1.7Clean up the extract using the procedures in Sections 13.2 through 13.6 and 13.8. Alumina (Section 13.4) or Florisil (Section 13.8) and carbon (Section 13.5) are recommended as minimum additional cleanup steps.
13.7.1.8Following cleanup, concentrate the extract to 10 μL as described in Section 12.7 and proceed with the analysis in Section 14.
13.7.2Acidified silica gel (Reference 28)—Procedure alternate to the anthropogenic isolation column (Section 13.7.1) that is used for removal of lipids from the Soxhlet/SDS extraction (Section 12.4.1).
13.7.2.1Adjust the volume of hexane in the bottle (Section 12.4.1.9.2) to approximately 200 mL.
13.7.2.2Spike 1.0 mL of the cleanup standard (Section 7.11) into the residue/solvent.
13.7.2.3Drop the stirring bar into the bottle, place the bottle on the stirring plate, and begin stirring.
13.7.2.4Add 30-100 g of acid silica gel (Section 7.5.1.2) to the bottle while stirring, keeping the silica gel in motion. Stir for two to three hours.
30 grams of silica gel should be adequate for most samples and will minimize contamination from this source.
13.7.2.5After stirring, pour the extract through approximately 10 g of granular anhydrous sodium sulfate (Section 7.2.1) contained in a funnel with glass-fiber filter into a macro contration device (Section 12.6). Rinse the bottle and sodium sulfate with hexane to complete the transfer.
13.7.2.6Concentrate the extract per Sections 12.6 through 12.7 and clean up the extract using the procedures in Sections 13.2 through 13.6 and 13.8. Alumina (Section 13.4) or Florisil (Section 13.8) and carbon (Section 13.5) are recommended as minimum additional cleanup steps.
13.7.3Sulfuric acid and base back-extraction’Used with HCl digested extracts (Section 12.4.2).
13.7.3.1Spike 1.0 mL of the cleanup standard (Section 7.11) into the residue/solvent (Section 12.4.2.8.2).
13.7.3.2Add 10 mL of concentrated sulfuric acid to the bottle. Immediately cap and shake one to three times. Loosen cap in a hood to vent excess pressure. Cap and shake the bottle so that the residue/solvent is exposed to the acid for a total time of approximately 45 seconds.
13.7.3.3Decant the hexane into a 250 mL separatory funnel making sure that no acid is transferred. Complete the quantitative transfer with several hexane rinses.
13.7.3.4Back extract the solvent/residue with 50 mL of potassium hydroxide solution per Section 12.5.2, followed by two reagent water rinses.
13.7.3.5Drain the extract through a filter funnel containing approximately 10 g of granular anhydrous sodium sulfate in a glass-fiber filter into a macro concentration device (Section 12.6).
13.7.3.6Concentrate the cleaned up extract to a volume suitable for the additional cleanups given in Sections 13.2 through 13.6 and 13.8. Gel permeation chromatography (Section 13.2), alumina (Section 13.4) or Florisil (Section 13.8), and Carbopak/Celite (Section 13.5) are recommended as minimum additional cleanup steps.
13.7.3.7Following cleanup, concentrate the extract to 10 L as described in Section 12.7 and proceed with analysis per Section 14.
13.8Florisil Cleanup (Reference 29).
13.8.1Pre-elute the activated Florisil column (Section 7.5.3) with 10 mL of methylene chloride followed by 10 mL of hexane:methylene chloride (98:2 v/v) and discard the solvents.
13.8.2When the solvent is within 1 mm of the packing, apply the sample extract (in hexane) to the column. Rinse the sample container twice with 1 mL portions of hexane and apply to the column.
13.8.3Elute the interfering compounds with 20 mL of hexane:methylene chloride (98:2) and discard the eluate.
13.8.4Elute the CDDs/CDFs with 35 mL of methylene chloride and collect the eluate. Concentrate the eluate per Sections 12.6 through 12.7 for further cleanup or for injection into the HPLC or GC/MS.
14.1Establish the operating conditions given in Section 10.1.
14.2Add 10 uL of the appropriate internal standard solution (Section 7.12) to the sample extract immediately prior to injection to minimize the possibility of loss by evaporation, adsorption, or reaction. If an extract is to be reanalyzed and evaporation has occurred, do not add more instrument internal standard solution. Rather, bring the extract back to its previous volume (e.g., 19 L) with pure nonane only (18 L if 2 L injections are used).
14.3Inject 1.0 μL or 2.0 μL of the concentrated extract containing the internal standard solution, using on-column or splitless injection. The volume injected must be identical to the volume used for calibration (Section 10). Start the GC column initial isothermal hold upon injection. Start MS data collection after the solvent peak elutes. Stop data collection after the OCDD and OCDF have eluted. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, stop data collection after elution of these compounds. Return the column to the initial temperature for analysis of the next extract or standard.
15.1At the beginning of each 12-hour shift during which analyses are performed, GC/MS system performance and calibration are verified for all CDDs/CDFs and labeled compounds. For these tests, analysis of the CS3 calibration verification (VER) standard (Section 7.13 and Table 4) and the isomer specificity test standards (Section 7.15 and Table 5) shall be used to verify all performance criteria. Adjustment and/or recalibration (Section 10) shall be performed until all performance criteria are met. Only after all performance criteria are met may samples, blanks, IPRs, and OPRs be analyzed.
15.2MS Resolution—A static resolving power of at least 10,000 (10% valley definition) must be demonstrated at the appropriate m/z before any analysis is performed. Static resolving power checks must be performed at the beginning and at the end of each 12-hour shift according to procedures in Section 10.1.2. Corrective actions must be implemented whenever the resolving power does not meet the requirement.
15.3Calibration Verification.
15.3.1Inject the VER standard using the procedure in Section 14.
15.3.2The m/z abundance ratios for all CDDs/CDFs shall be within the limits in Table 9; otherwise, the mass spectrometer shall be adjusted until the m/z abundance ratios fall within the limits specified, and the verification test shall be repeated. If the adjustment alters the resolution of the mass spectrometer, resolution shall be verified (Section 10.1.2) prior to repeat of the verification test.
15.3.3The peaks representing each CDD/CDF and labeled compound in the VER
15.3.4Compute the concentration of each CDD/CDF compound by isotope dilution (Section 10.5) for those compounds that have labeled analogs (Table 1). Compute the concentration of the labeled compounds by the internal standard method (Section 10.6). These concentrations are computed based on the calibration data in Section 10.
15.3.5For each compound, compare the concentration with the calibration verification limit in Table 6. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, compare the concentration to the limit in Table 6a. If all compounds meet the acceptance criteria, calibration has been verified and analysis of standards and sample extracts may proceed. If, however, any compound fails its respective limit, the measurement system is not performing properly for that compound. In this event, prepare a fresh calibration standard or correct the problem causing the failure and repeat the resolution (Section 15.2) and verification (Section 15.3) tests, or recalibrate (Section 10).
15.4Retention Times and GC Resolution.
15.4.1Retention times.
15.4.1.1Absolute—The absolute retention times of the
15.4.1.2Relative—The relative retention times of CDDs/CDFs and labeled compounds in the verification test (Section 15.3) shall be within the limits given in Table 2.
15.4.2GC resolution.
15.4.2.1Inject the isomer specificity standards (Section 7.15) on their respective columns.
15.4.2.2The valley height between 2,3,7,8-TCDD and the other tetra-dioxin isomers at m/z 319.8965, and between 2,3,7,8-TCDF and the other tetra-furan isomers at m/z 303.9016 shall not exceed 25% on their respective columns (Figures 6 and 7).
15.4.3If the absolute retention time of any compound is not within the limits specified or if the 2,3,7,8-isomers are not resolved, the GC is not performing properly. In this event, adjust the GC and repeat the verification test (Section 15.3) or recalibrate (Section 10), or replace the GC column and either verify calibration or recalibrate.
15.5Ongoing Precision and Recovery.
15.5.1Analyze the extract of the ongoing precision and recovery (OPR) aliquot (Section 11.4.2.5, 11.5.4, 11.6.2, 11.7.4, or 11.8.3.2) prior to analysis of samples from the same batch.
15.5.2Compute the concentration of each CDD/CDF by isotope dilution for those compounds that have labeled analogs (Section 10.5). Compute the concentration of 1,2,3,7,8,9-HxCDD, OCDF, and each labeled compound by the internal standard method (Section 10.6).
15.5.3For each CDD/CDF and labeled compound, compare the concentration to the OPR limits given in Table 6. If only 2,3,7,8-TCDD and 2,3,7,8-TCDF are to be determined, compare the concentration to the limits in Table 6a. If all compounds meet the acceptance criteria, system performance is acceptable and analysis of blanks and samples may proceed. If, however, any individual concentration falls outside of the range given, the extraction/concentration processes are not being performed properly for that compound. In this event, correct the problem, re-prepare, extract, and clean up the sample batch and repeat the ongoing precision and recovery test (Section 15.5).
15.5.4Add results that pass the specifications in Section 15.5.3 to initial and previous ongoing data for each compound in each matrix. Update QC charts to form a graphic representation of continued laboratory performance. Develop a statement of laboratory accuracy for each CDD/CDF in each matrix type by calculating the average percent recovery (R) and the standard deviation of percent recovery (S
15.6Blank—Analyze the method blank extracted with each sample batch immediately following analysis of the OPR aliquot to demonstrate freedom from contamination and freedom from carryover from the OPR analysis. The results of the analysis of the blank must meet the specifications in Section 9.5.2 before sample analyses may proceed.
A CDD, CDF, or labeled compound is identified in a standard, blank, or sample when all of the criteria in Sections 16.1 through 16.4 are met.
16.1The signals for the two exact m/z's in Table 8 must be present and must maximize within the same two seconds.
16.2The signal-to-noise ratio (S/N) for the GC peak at each exact m/z must be greater than or equal to 2.5 for each CDD or CDF detected in a sample extract, and greater than or equal to 10 for all CDDs/CDFs in the calibration standard (Sections 10.2.3 and 15.3.3).
16.3The ratio of the integrated areas of the two exact m/z's specified in Table 8 must be within the limit in Table 9, or within ±10% of the ratio in the midpoint (CS3) calibration or calibration verification (VER), whichever is most recent.
16.4The relative retention time of the peak for a 2,3,7,8-substituted CDD or CDF must be within the limit in Table 2. The retention time of peaks representing non-
16.5Confirmatory Analysis—Isomer specificity for 2,3,7,8-TCDF cannot be achieved on the DB-5 column. Therefore, any sample in which 2,3,7,8-TCDF is identified by analysis on a DB-5 column must have a confirmatory analysis performed on a DB-225, SP-2330, or equivalent GC column. The operating conditions in Section 10.1.1 may be adjusted to optimize the analysis on the second GC column, but the GC/MS must meet the mass resolution and calibration specifications in Section 10.
16.6If the criteria for identification in Sections 16.1 through 16.5 are not met, the CDD or CDF has not been identified and the results may not be reported for regulatory compliance purposes. If interferences preclude identification, a new aliquot of sample must be extracted, further cleaned up, and analyzed.
17.0Quantitative Determination
17.1Isotope Dilution Quantitation—By adding a known amount of a labeled compound to every sample prior to extraction, correction for recovery of the CDD/CDF can be made because the CDD/CDF and its labeled analog exhibit similar effects upon extraction, concentration, and gas chromatography. Relative response (RR) values are used in conjunction with the initial calibration data described in Section 10.5 to determine concentrations directly, so long as labeled compound spiking levels are constant, using the following equation:
17.1.1Because of a potential interference, the labeled analog of OCDF is not added to the sample. Therefore, OCDF is quantitated against labeled OCDD. As a result, the concentration of OCDF is corrected for the recovery of the labeled OCDD. In instances where OCDD and OCDF behave differently during sample extraction, concentration, and cleanup procedures, this may decrease the accuracy of the OCDF results. However, given the low toxicity of this compound relative to the other dioxins and furans, the potential decrease in accuracy is not considered significant.
17.1.2Because
17.1.3Any peaks representing non-2,3,7,8-substituted CDDs/CDFs are quantitated using an average of the response factors from all of the labeled 2,3,7,8-isomers at the same level of chlorination.
17.2Internal Standard Quantitation and Labeled Compound Recovery.
17.2.1Compute the concentrations of 1,2,3,7,8,9--HxCDD, OCDF, the
There is only one m/z for the
17.2.2 Using the concentration in the extract determined above, compute the percent recovery of the
17.3The concentration of a CDD/CDF in the solid phase of the sample is computed using the concentration of the compound in the extract and the weight of the solids (Section 11.5.1), as follows:
17.4The concentration of a CDD/CDF in the aqueous phase of the sample is computed using the concentration of the compound in the extract and the volume of water extracted (Section 11.4 or 11.5), as follows:
17.5If the SICP area at either quantitation m/z for any compound exceeds the calibration range of the system, a smaller sample aliquot is extracted.
17.5.1For aqueous samples containing 1% solids or less, dilute 100 mL, 10 mL, etc., of sample to 1 L with reagent water and re-prepare, extract, clean up, and analyze per Sections 11 through 14.
17.5.2For samples containing greater than 1% solids, extract an amount of sample equal to
17.5.3If a smaller sample size will not be representative of the entire sample, dilute the sample extract by a factor of 10, adjust the concentration of the instrument internal standard to 100 pg/μL in the extract, and analyze an aliquot of this diluted extract by the internal standard method.
17.6Results are reported to three significant figures for the CDDs/CDFs and labeled compounds found in all standards, blanks, and samples.
17.6.1Reporting units and levels.
17.6.1.1Aqueous samples—Report results in pg/L (parts-per-quadrillion).
17.6.1.2Samples containing greater than 1% solids (soils, sediments, filter cake, compost)—Report results in ng/kg based on the dry weight of the sample. Report the percent solids so that the result may be corrected.
17.6.1.3Tissues—Report results in ng/kg of wet tissue, not on the basis of the lipid content of the sample. Report the percent lipid content, so that the data user can calculate the concentration on a lipid basis if desired.
17.6.1.4Reporting level.
17.6.1.4.1Standards (VER, IPR, OPR) and samples—Report results at or above the minimum level (Table 2). Report results below the minimum level as not detected or as required by the regulatory authority.
17.6.1.4.2Blanks—Report results above one-third the ML.
17.6.2Results for CDDs/CDFs in samples that have been diluted are reported at the least dilute level at which the areas at the quantitation m/z's are within the calibration range (Section 17.5).
17.6.3For CDDs/CDFs having a labeled analog, results are reported at the least dilute level at which the area at the quantitation m/z is within the calibration range (Section 17.5) and the labeled compound recovery is within the normal range for the method (Section 9.3 and Tables 6, 6a, 7, and 7a).
17.6.4Additionally, if requested, the total concentration of all isomers in an individual level of chlorination (i.e., total TCDD, total TCDF, total Paced, etc.) may be reported by summing the concentrations of all isomers identified in that level of chlorination, including both 2,3,7,8-substituted and non-2,3,7,8-substituted isomers.
18.1Some samples may contain high levels (>10 ng/L; >1000 ng/kg) of the compounds of interest, interfering compounds, and/or polymeric materials. Some extracts will not concentrate to 10 μL (Section 12.7); others may overload the GC column and/or mass spectrometer.
18.2Analyze a smaller aliquot of the sample (Section 17.5) when the extract will not concentrate to 10 μL after all cleanup procedures have been exhausted.
18.3Chlorodiphenyl Ethers—If chromatographic peaks are detected at the retention time of any CDDs/CDFs in any of the m/z channels being monitored for the
18.4Recovery of Labeled Compounds—In most samples, recoveries of the labeled compounds will be similar to those from reagent water or from the alternate matrix (Section 7.6).
18.4.1If the recovery of any of the labeled compounds is outside of the normal range (Table 7), a diluted sample shall be analyzed (Section 17.5).
18.4.2If the recovery of any of the labeled compounds in the diluted sample is outside of normal range, the calibration verification standard (Section 7.13) shall be analyzed and calibration verified (Section 15.3).
18.4.3If the calibration cannot be verified, a new calibration must be performed and the original sample extract reanalyzed.
18.4.4If the calibration is verified and the diluted sample does not meet the limits for labeled compound recovery, the method does not apply to the sample being analyzed and the result may not be reported for regulatory compliance purposes. In this case, alternate extraction and cleanup procedures in this method must be employed to resolve the interference. If all cleanup procedures in this method have been employed and labeled compound recovery remains outside of the normal range, extraction and/or cleanup procedures that are beyond this scope of this method will be required to analyze these samples.
19.1The solvents used in this method pose little threat to the environment when managed properly. The solvent evaporation techniques used in this method are amenable to solvent recovery, and it is recommended that the laboratory recover solvents wherever feasible.
19.2Standards should be prepared in volumes consistent with laboratory use to minimize disposal of standards.
20.1It is the laboratory's responsibility to comply with all federal, state, and local regulations governing waste management, particularly the hazardous waste identification rules and land disposal restrictions, and to protect the air, water, and land by minimizing and controlling all releases from fume hoods and bench operations. Compliance is also required with any sewage discharge permits and regulations.
20.2Samples containing HCl to pH <2 are hazardous and must be neutralized before being poured down a drain or must be handled as hazardous waste.
20.3The CDDs/CDFs decompose above 800 °C. Low-level waste such as absorbent paper, tissues, animal remains, and plastic gloves may be burned in an appropriate incinerator. Gross quantities (milligrams) should be packaged securely and disposed of through commercial or governmental channels that are capable of handling extremely toxic wastes.
20.4Liquid or soluble waste should be dissolved in methanol or ethanol and irradiated with ultraviolet light with a wavelength shorter than 290 nm for several days. Use F40 BL or equivalent lamps. Analyze liquid wastes, and dispose of the solutions when the CDDs/CDFs can no longer be detected.
20.5For further information on waste management, consult “The Waste Management Manual for Laboratory Personnel” and “Less is Better—Laboratory Chemical Management for Waste Reduction,” available from the American Chemical Society's Department of Government Relations and Science Policy, 1155 16th Street N.W., Washington, D.C. 20036.
Method performance was validated and performance specifications were developed using data from EPA's international interlaboratory validation study (References 30-31) and the EPA/paper industry Long-Term Variability Study of discharges from the pulp and paper industry (58 FR 66078).
1. Tondeur, Yves. “Method 8290: Analytical Procedures and Quality Assurance for Multimedia Analysis of Polychlorinated Dibenzo-
2. “Measurement of 2,3,7,8-Tetrachlorinated Dibenzo-
3. “NCASI Procedures for the Preparation and Isomer Specific Analysis of Pulp and Paper Industry Samples for 2,3,7,8-TCDD and 2,3,7,8-TCDF,” National Council of the Paper Industry for Air and Stream Improvement Inc., 260 Madison Avenue, New York, NY 10016, Technical Bulletin No. 551, Pre-Release Copy, July 1988.
4. “Analytical Procedures and Quality Assurance Plan for the Determination of PCDD/PCDF in Fish,” USEPA, Environmental Research Laboratory, 6201 Congdon Boulevard, Duluth, MN 55804, April 1988.
5. Tondeur, Yves. “Proposed GC/MS Methodology for the Analysis of PCDDs and
6. Lamparski, L.L. and Nestrick, T.J. “Determination of Tetra-, Hexa-, Hepta-, and Octachlorodibenzo-
7. Lamparski, L.L. and Nestrick, T.J. “Novel Extraction Device for the Determination of Chlorinated Dibenzo-
8. Patterson, D.G., et. al. “Control of Interferences in the Analysis of Human Adipose Tissue for 2,3,7,8-Tetrachlorodibenzo-
9. Stanley, John S. and Sack, Thomas M. “Protocol for the Analysis of 2,3,7,8-Tetrachlorodibenzo-
10. “Working with Carcinogens,” Department of Health, Education, & Welfare, Public Health Service, Centers for Disease Control, NIOSH, Publication 77-206, August 1977, NTIS PB-277256.
11. “OSHA Safety and Health Standards, General Industry,” OSHA 2206, 29 CFR 1910.
12. “Safety in Academic Chemistry Laboratories,” ACS Committee on Chemical Safety, 1979.
13. “Standard Methods for the Examination of Water and Wastewater,” 18th edition and later revisions, American Public Health Association, 1015 15th St, N.W., Washington, DC 20005, 1-35: Section 1090 (Safety), 1992.
14. “Method 613—2,3,7,8-Tetrachlorodibenzo-p-dioxin,” 40 CFR 136 (49 FR 43234), October 26, 1984, Section 4.1.
15. Provost, L.P. and Elder, R.S. “Interpretation of Percent Recovery Data,” American Laboratory, 15: 56-83, 1983.
16. “Standard Practice for Sampling Water,” ASTM Annual Book of Standards, ASTM, 1916 Race Street, Philadelphia, PA 19103-1187, 1980.
17. “Methods 330.4 and 330.5 for Total Residual Chlorine,” USEPA, EMSL, Cincinnati, OH 45268, EPA 600/4-79-020, March 1979.
18. “Handbook of Analytical Quality Control in Water and Wastewater Laboratories,” USEPA EMSL, Cincinnati, OH 45268, EPA-600/4-79-019, March 1979.
19. Williams, Rick. Letter to Bill Telliard, June 4, 1993, available from the EPA Sample Control Center operated by DynCorp Viar, Inc., 300 N Lee St, Alexandria, VA 22314, 703-519-1140.
20. Barkowski, Sarah. Fax to Sue Price, August 6, 1992, available from the EPA Sample Control Center operated by DynCorp Viar, Inc., 300 N Lee St, Alexandria VA 22314, 703-519-1140.
21. “Analysis of Multi-media, Multi-concentration Samples for Dioxins and Furans, PCDD/PCDF Analyses Data Package”, Narrative for Episode 4419, MRI Project No. 3091-A, op.cit. February 12, 1993, Available from the EPA Sample Control Center operated by DynCorp Viar Inc, 300 N Lee St, Alexandria, VA 22314 (703-519-1140).
22. “Analytical Procedures and Quality Assurance Plan for the Determination of PCDD/PCDF in Fish”, U.S. Environmental Protection Agency, Environmental Research Laboratory, Duluth, MN 55804, EPA/600/3-90/022, March 1990.
23. Afghan, B.K., Carron, J., Goulden, P.D., Lawrence, J., Leger, D., Onuska, F., Sherry, J., and Wilkenson, R.J., “Recent Advances in Ultratrace Analysis of Dioxins and Related Halogenated Hydrocarbons”, Can J. Chem., 65: 1086-1097, 1987.
24. Sherry, J.P. and Tse, H. “A Procedure for the Determination of Polychlorinated Dibenzo-p-dioxins in Fish”, Chemosphere, 20: 865-872, 1990.
25. “Preliminary Fish Tissue Study”, Results of Episode 4419, available from the EPA Sample Control Center operated by DynCorp Viar, Inc., 300 N Lee St, Alexandria, VA 22314, 703-519-1140.
26. Nestrick, Terry L. DOW Chemical Co., personal communication with D.R. Rushneck, April 8, 1993. Details available from the U.S. Environmental Protection Agency Sample Control Center operated by DynCorp Viar Inc, 300 N Lee St, Alexandria, VA 22314, 703-519-1140.
27. Barnstadt, Michael. “Big Fish Column”, Triangle Laboratories of RTP, Inc., SOP 129-90, 27 March 27, 1992.
28. “Determination of Polychlorinated Dibenzo-p-Dioxins (PCDD) and Dibenzofurans (PCDF) in Environmental Samples Using EPA Method 1613”, Chemical Sciences Department, Midwest Research Institute, 425 Volker Boulevard, Kansas City, MO 44110-2299, Standard Operating Procedure No. CS-153, January 15, 1992.
29. Ryan, John J. Raymonde Lizotte and William H. Newsome, J. Chromatog. 303 (1984) 351-360.
30. Telliard, William A., McCarty, Harry B., and Riddick, Lynn S. “Results of the Interlaboratory Validation Study of USEPA Method 1613 for the Analysis of Tetra-through Octachlorinated Dioxins and Furans by Isotope Dilution GC/MS,” Chemosphere, 27, 41-46 (1993).
31. “Results of the International Interlaboratory Validation Study of USEPA Method 1613”, October 1994, available from the EPA Sample Control Center operated by DynCorp
These definitions and purposes are specific to this method but have been conformed to common usage as much as possible.
24.1Units of weight and Measure and Their Abbreviations.
24.1.1Symbols:
24.2Definitions and Acronyms (in Alphabetical Order).
Analyte—A CDD or CDF tested for by this method. The analytes are listed in Table 1.
Calibration Standard (CAL)—A solution prepared from a secondary standard and/or stock solutions and used to calibrate the response of the instrument with respect to analyte concentration.
Calibration Verification Standard (VER)—The mid-point calibration standard (CS3) that is used in to verify calibration. See Table 4.
CDD—Chlorinated Dibenzo-p-ioxin—The isomers and congeners of tetra-through octa-chlorodibenzo-p-dioxin.
CDF—Chlorinated Dibenzofuran—The isomers and congeners of tetra-through octa-chlorodibenzofuran.
CS1, CS2, CS3, CS4, CS5—See Calibration standards and Table 4.
Field Blank—An aliquot of reagent water or other reference matrix that is placed in a sample container in the laboratory or the field, and treated as a sample in all respects, including exposure to sampling site conditions, storage, preservation, and all analytical procedures. The purpose of the field blank is to determine if the field or sample transporting procedures and environments have contaminated the sample.
GC—Gas chromatograph or gas chromatography.
GPC—Gel permeation chromatograph or gel permeation chromatography.
HPLC—High performance liquid chromatograph or high performance liquid chromatography.
HRGC—High resolution GC.
HRMS—High resolution MS.
IPR—Initial precision and recovery; four aliquots of the diluted PAR standard analyzed to establish the ability to generate acceptable precision and accuracy. An IPR is performed prior to the first time this method is used and any time the method or instrumentation is modified.
K-D—Kuderna-Danish concentrator; a device used to concentrate the analytes in a solvent.
Laboratory Blank—See method blank.
Laboratory Control sample (LCS)—See ongoing precision and recovery standard (OPR).
Laboratory Reagent Blank—See method blank.
May—This action, activity, or procedural step is neither required nor prohibited.
May Not—This action, activity, or procedural step is prohibited.
Method Blank—An aliquot of reagent water that is treated exactly as a sample including exposure to all glassware, equipment, solvents, reagents, internal standards, and surrogates that are used with samples. The method blank is used to determine if analytes or interferences are present in the laboratory environment, the reagents, or the apparatus.
Minimum Level (ML)—The level at which the entire analytical system must give a recognizable signal and acceptable calibration point for the analyte. It is equivalent to the concentration of the lowest calibration standard, assuming that all method-specified sample weights, volumes, and cleanup procedures have been employed.
MS—Mass spectrometer or mass spectrometry.
Must—This action, activity, or procedural step is required.
OPR—Ongoing precision and recovery standard (OPR); a laboratory blank spiked with known quantities of analytes. The OPR is analyzed exactly like a sample. Its purpose is to assure that the results produced by the laboratory remain within the limits specified in this method for precision and recovery.
PAR—Precision and recovery standard; secondary standard that is diluted and spiked to form the IPR and OPR.
PFK—Perfluorokerosene; the mixture of compounds used to calibrate the exact m/z scale in the HRMS.
Preparation Blank—See method blank.
Primary Dilution Standard—A solution containing the specified analytes that is purchased or prepared from stock solutions and diluted as needed to prepare calibration solutions and other solutions.
Quality Control Check Sample (QCS)—A sample containing all or a subset of the analytes at known concentrations. The QCS is obtained from a source external to the laboratory or is prepared from a source of standards different from the source of calibration standards. It is used to check laboratory performance with test materials prepared external to the normal preparation process.
Reagent Water—Water demonstrated to be free from the analytes of interest and potentially interfering substances at the method detection limit for the analyte.
Relative Standard Deviation (RSD)—The standard deviation times 100 divided by the mean. Also termed “coefficient of variation.”
RF—Response factor. See Section 10.6.1.
RR—Relative response. See Section 10.5.2.
RSD—See relative standard deviation.
SDS—Soxhlet/Dean-Stark extractor; an extraction device applied to the extraction of solid and semi-solid materials (Reference 7).
Should—This action, activity, or procedural step is suggested but not required.
SICP—Selected ion current profile; the line described by the signal at an exact m/z.
SPE—Solid-phase extraction; an extraction technique in which an analyte is extracted from an aqueous sample by passage over or through a material capable of reversibly adsorbing the analyte. Also termed liquid-solid extraction.
Stock Solution—A solution containing an analyte that is prepared using a reference material traceable to EPA, the National Institute of Science and Technology (NIST), or a source that will attest to the purity and authenticity of the reference material.
TCDD—Tetrachlorodibenzo-p-dioxin.
TCDF—Tetrachlorodibenzofuran.
VER—See calibration verification standard.
1.1This method is designed to determine the volatile toxic organic pollutants associated with the 1976 Consent Decree and additional compounds amenable to purge and trap gas chromatography-mass spectrometry (GC/MS).
1.2The chemical compounds listed in table 1 may be determined in municipal and industrial discharges by this method. The methmd is designed to meet the survey requirements of Effluent Guidelines Division (EGD) and the National Pollutants Discharge Elimination System (NPDES) under 40 CFR 136.1 and 136.5. Any modifications of this method, beyond those expressly permitted, shall be considered as major modifications subject to application and approval of alternate test procedures under 40 CFR 136.4 and 136.5.
1.3The detection limit of this method is usually dependent on the level of interfer-ences -rather than instrumental limitations. The limits in table 2 represent the minimum quantity that can be detected with no interferences present.
1.4The GC/MS portions of this method are for use only by analysts experienced with GC/MS or under the close supervision of such qualified persons. Laboratories unfamiliar with the analyses of environmental samples by GC/MS should run the performance tests in reference 1 before beginning.
2.1Stable isotopically labeled analogs of the compounds of interest are added to a 5 mL water sample. The sample is purged at 20-25 °C with an inert gas in a specially designed chamber. The volatile organic compounds are transferred from the aqueous phase into the gaseous phase where they are passed into a sorbent column and trapped. After purging is completed, the trap is backflushed and heated rapidly to desorb the compounds into a gas chromatograph (GC). The compounds are separated by the GC and detected by a mass spectrometer (MS) (references 2 and 3). The labeled compounds serve to correct the variability of the analytical technique.
2.2Identification of a compound (qualitative analysis) is performed by comparing the GC retention time and the background corrected characteristic spectral masses with those of authentic standards.
2.3Quantitative analysis is performed by GC/MS using extracted ion current profile (EICP) areas. Isotope dilution is used when labeled compounds are available; otherwise, an internal standard method is used.
2.4Quality is assured through reproducible calibration and testing of the purge and trap and GC/MS systems.
3.1Impurities in the purge gas, organic compounds out-gassing from the plumbing upstream of the trap, and solvent vapors in the laboratory account for the majority of contamination problems. The analytical system is demonstrated to be free from interferences under conditions of the analysis by analyzing blanks initially and with each sample lot (samples analyzed on the same 8 hr shift), as described in Section 8.5.
3.2Samples can be contaminated by diffusion of volatile organic compounds (particularly methylene chloride) through the bottle seal during shipment and storage. A field blank prepared from reagent water and carried through the sampling and handling protocol serves as a check on such contamination.
3.3Contamination by carry-over can occur when high level and low level samples are analyzed sequentially. To reduce carry-over, the purging device and sample syringe are rinsed between samples with reagent water. When an unusually concentrated sample is encountered, it is followed by analysis of a reagent water blank to check for carry-over. For samples containing large amounts of water soluble materials, suspended solids, high boiling compounds, or high levels or purgeable compounds, the purge device is washed with soap solution, rinsed with tap and distilled water, and dried in an oven at 100-125 °C. The trap and other parts of the system are also subject to contamination; therefore, frequent bakeout and purging of the entire system may be required.
3.4Interferences resulting from samples will vary considerably from source to source, depending on the diversity of the industrial complex or municipality being sampled.
4.1The toxicity or carcinogenicity of each com-pound or reagent used in this method -has not been precisely determined; how-ever, each chemical compound should be treated as a potential health hazard. Exposure to these compounds should be reduced to the lowest possible level. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of data handling sheets should also be made available to all personnel involved in these analyses. Additional information on laboratory safety can be found in references 4-6.
4.2The following compounds covered by this method have been tentatively classified as known or suspected human or mammalian carcinogens: benzene, carbon tetrachloride, chloroform, and vinyl chloride. Primary standards of these toxic compounds should be prepared in a hood, and a NIOSH/MESA approved toxic gas respirator should be worn when high concentrations are handled.
5.1Sample bottles for discrete sampling.
5.1.1Bottle—25 to 40 mL with screw cap (Pierce 13075, or equivalent). Detergent wash, rinse with tap and distilled water, and dry at >105 °C for one hr minimum before use.
5.1.2Septum—Teflon-faced silicone (Pierce -12722, or equivalent), cleaned as above -and baked at 100-200 °C, for one hour mini-mum.
5.2Purge and trap device—consists of purging device, trap, and desorber. Complete devices are commercially available.
5.2.1Purging device—designed to accept 5 mL samples with water column at least 3 cm deep. The volume of the gaseous head space between the water and trap shall be less than 15 mL. The purge gas shall be introduced less than 5 mm from the base of the water column and shall pass through the water as bubbles with a diameter less than 3 mm. The purging device shown in Figure 1 meets these criteria.
5.2.2Trap—25 to 30 cm × 2.5 mm i.d. minimum, containing the following:
5.2.2.1Methyl silicone packing—one ±0.2 cm, 3 percent OV-1 on 60/80 mesh Chromosorb W, or equivalent.
5.2.2.2Porous polymer—15 ±1.0 cm, Tenax GC (2,6-diphenylene oxide polymer), 60/80 mesh, chromatographic grade, or equivalent.
5.2.2.3Silica gel—8 ±1.0 cm, Davison Chemical, 35/60 mesh, grade 15, or equivalent. The trap shown in Figure 2 meets these specifications.
5.2.3Desorber—shall heat the trap to 175 ±5 °C in 45 seconds or less. The polymer section of the trap shall not exceed 180 °C, and the remaining sections shall not exceed 220 °C. The desorber shown in Figure 2 meets these specifications.
5.2.4The purge and trap device may be a separate unit or coupled to a GC as shown in Figures 3 and 4.
5.3Gas chromatograph—shall be linearly temperature programmable with initial and final holds, shall contain a glass jet separator as the MS interface, and shall produce results which meet the calibration (Section 7), quality assurance (Section 8), and performance tests (Section 11) of this method.
5.3.1Column—2.8 ±0.4 m × 2 ±0.5 mm i. d. glass, packekd with one percent SP-1000 on Carbopak B, 60/80 mesh, or equivalent.
5.4Mass spectrometer—70 eV electron impact ionization; shall repetitively scan from 20 to 250 amu every 2-3 seconds, and produce a unit resolution (valleys between m/z 174-176 less than 10 percent of the height of the m/z 175 peak), background corrected mass spectrum from 50 ng 4-bromo-fluorobenzene (BFB) injected into the GC. The BFB spectrum shall meet the mass-intensity criteria in Table 3. All portions of the GC column, transfer lines, and separator which connect the GC column to the ion source shall remain at or above the column temperature during analysis to preclude condensation of less volatile compounds.
5.5Data system—shall collect and record MS data, store mass intensity data in spectral libraries, process GC/MS data and generate reports, and shall calculate and record response factors.
5.5.1Data acquisition—mass spectra shall be collected continuously throughout the analysis and stored on a mass storage device.
5.5.2Mass spectral libraries—user created libraries containing mass spectra obtained from analysis of authentic standards shall be employed to reverse search GC/MS runs for the compounds of interest (Section 7.2).
5.5.3Data processing—the data system shall be used to search, locate, identify, and quantify the compounds of interest in each GC/MS analysis. Software routines shall be employed to compute retention times and EICP areas. Displays of spectra, mass chromatograms, and library comparisons are required to verify results.
5.5.4Response factors and multipoint calibrations—the data system shall be used to record and maintain lists of response factors (response ratios for isotope dilution) and generate multi-point calibration curves (Section 7). Computations of relative standard deviation (coefficient of variation) are useful for testing calibration linearity. Statistics on initial and on-going performance shall be maintained (Sections 8 and 11).
5.6Syringes—5 mL glass hypodermic, with Luer-lok tips.
5.7Micro syringes—10, 25, and 100 uL.
5.8Syringe valves—2-way, with Luer ends (Telfon or Kel-F).
5.9Syringe—5 mL, gas-tight, with shut-off valve.
5.10Bottles—15 mL., screw-cap with Telfon -liner.
5.11Balance—analytical, capable of weighing 0.1 -mg.
6.1Reagent water—water in which the compounds of interest and interfering compounds are not detected by this method (Section 11.7). It may be generated by any of the following methods:
6.1.1Activated carbon—pass tap water through a carbon bed (Calgon Filtrasorb-300, or equivalent).
6.1.2Water purifier—pass tap water through -a purifier (Millipore Super Q, or equivalent).
6.1.3Boil and purge—heat tap water to 90-100 °C and bubble contaminant free inert gas through it for approx one hour. While still hot, transfer the water to screw-cap bottles and seal with a Teflon-lined cap.
6.2Sodium thiosulfate—ACS granular.
6.3Methanol—pesticide quality or equivalent.
6.4Standard solutions—purchased as solution or mixtures with certification to their purity, concentration, and authenticity, or prepared from materials of known purity and composition. If compound purity is 96 percent or greater, the weight may be used without correction to calculate the concentration of the standard.
6.5Preparation of stock solutions—prepare in methanol using liquid or gaseous standards per the steps below. Observe the safety precautions given in Section 4.
6.5.1Place approx 9.8 mL of methanol in a 10 mL ground glass stoppered volumetric flask. Allow the flask to stand unstoppered for approximately 10 minutes or until all methanol wetted surfaces have dried. In each case, weigh the flask, immediately add the compound, then immediately reweigh to prevent evaporation losses from affecting the measurement.
6.5.1.1Liquids—using a 100 μL syringe, permit 2 drops of liquid to fall into the methanol without contacting the leck of the flask. Alternatively, inject a known volume of the compound into the methanol in the flask using a micro-syringe.
6.5.1.2Gases (chloromethane, bromome-thane, chloro-ethane, vinyl chloride)—fill a valved 5 mL gas-tight syringe with the compound. Lower the needle to approximately 5 mm above the methanol meniscus. Slowly introduce the compound above the surface of the meniscus. The gas will dissolve rapidly in the methanol.
6.5.2Fill the flask to volume, stopper, then mix by inverting several times. Calculate the concentration in mg/mL (μg/μL ) from the weight gain (or density if a known volume was injected).
6.5.3Transfer the stock solution to a Teflon sealed screw-cap-bottle. Store, with minimal headspace, in the dark at −10 to −20 °C.
6.5.4Prepare fresh standards weekly for the gases and 2-chloroethylvinyl ether. All other standards are replaced after one month, or sooner if comparison with check standards indicate a change in concentration. Quality control check standards that can be used to determine the accuracy of calibration standards are available from the US Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio.
6.6Labeled compound spiking solution—from stock standard solutions prepared as above, or from mixtures, prepare the spiking solution to contain a concentration such that a 5-10 μL spike into each 5 mL sample, blank, or aqueous standard analyzed will result in a concentration of 20 μg/L of each labeled compound. For the gases and for the water soluble compounds (acrolein, acrylonitrile, acetone, diethyl ether, and MEK), a concentration of 100 μg/L may be used. Include the internal standards (Section 7.5) in this solution so that a concentration of 20 μg/L in each sample, blank, or aqueous standard will be produced.
6.7Secondary standards—using stock solutions, prepare a secondary standard in methanol to contain each pollutant at a concentration of 500 μg/mL For the gases and water soluble compounds (Section 6.6), a concentration of 2.5 mg/mL may be used.
6.7.1Aqueous calibration standards—using a 25 μL syringe, add 20 μL of the secondary standard (Section 6.7) to 50, 100, 200, 500, and 1000 mL of reagent water to produce concentrations of 200, 100, 50, 20, and 10 μg/L, respectively. If the higher concentration standard for the gases and water soluble compounds was chosen (Section 6.6), these compounds will be at concentrations of 1000, 500, 250, 100, and 50 μg/L in the aqueous calibration standards.
6.7.2Aqueous performance standard—an aqueous standard containing all pollutants, internal standards, labeled compounds, and BFB is prepared daily, and analyzed each shift to demonstrate performance (Section 11). This standard shall contain either 20 or 100 μg/L of the labeled and pollutant gases and water soluble compounds, 10 μg/L BFB, and 20 μg/L of all other pollutants, labeled compounds, and internal standards. It may be the nominal 20 μg/L aqueous calibration standard (Section 6.7.1).
6.7.3A methanolic standard containing all pollutants and internal standards is prepared to demonstrate recovery of these compounds when syringe injection and purge and trap analyses are compared. This standard shall contain either 100 μg/mL or 500 μg/mL of the gases and water soluble compounds, and 100 μg/mL of the remaining pollutants
6.7.4Other standards which may be needed are those for test of BFB performance (Section 7.1) and for collection of mass spectra for storage in spectral libraries (Section 7.2).
7.1Assemble the gas chromatographic apparatus and establish operating conditions given in table 2. By injecting standards into the GC, demonstrate that the analytical system meets the detection limits in table 2 and the mass-intensity criteria in table 3 for 50 ng BFB.
7.2Mass spectral libraries—detection and identification of the compound of interest are dependent upon the spectra stored in user created libraries.
7.2.1Obtain a mass spectrum of each pollutant and labeled compound and each internal standard by analyzing an authentic standard either singly or as part of a mixture in which there is no interference between closely eluted components. That only a single compound is present is determined by examination of the spectrum. Fragments not attributable to the compound under study indicate the presence of an interfering compound. Adjust the analytical conditions and scan rate (for this test only) to produce an undistorted spectrum at the GC peak maximum. An undistorted spectrum will usually be obtained if five complete spectra are collected across the upper half of the GC peak. Software algorithms designed to “enhance” the spectrum may eliminate distortion, but may also eliminate authentic m/z's or introduce other distortion.
7.2.3The authentic reference spectrum is obtained under BFB tuning conditions (Section 7.1 and table 3) to normalize it to spectra from other instruments.
7.2.4The spectrum is edited by saving the 5 most intense mass spectral peaks and all other mass spectral peaks greater than 10 percent of the base peak. This spectrum is stored for reverse search and for compound confirmation.
7.3Assemble the purge and trap device. Pack the trap as shown in Figure 2 and condition overnight at 170-180 °C by backflushing with an inert gas at a flow rate of 20-30 mL/min. Condition traps daily for a minimum of 10 minutes prior to use.
7.3.1Analyze the aqueous performance standard (Section 6.7.2) according to the purge and trap procedure in Section 10. Compute the area at the primary m/z (table 4) for each compound. Compare these areas to those obtained by injecting one μL of the methanolic standard (Section 6.7.3) to determine compound recovery. The recovery shall be greater than 20 percent for the water soluble compounds, and 60-110 percent for all other compounds. This recovery is demonstrated initially for each purge and trap GC/MS system. The test is repeated only if the purge and trap or GC/MS systems are modified in any way that might result in a change in recovery.
7.3.2Demonstrate that 100 ng toluene (or toluene-d8) produces an area at m/z 91 (or 99) approx one-tenth that required to exceed the linear range of the system. The exact value must be determined by experience for each instrument. It is used to match the calibration range of the instrument to the analytical range and detection limits required.
7.4Calibration by isotope dilution—the isotope dilution approach is used for the purgeable organic compounds when appropriate labeled compounds are available and when interferences do not preclude the analysis. If labeled compounds are not available, or interferences are present, internal standard methods (Section 7.5 or 7.6) are used. A calibration curve encompassing the concentration range of interest is prepared for each compound determined. The relative response (RR) vs concentration (μg/L) is plotted or computed using a linear regression. An example of a calibration curve for toluene using toluene-d8 is given in figure 5. Also shown are the ±10 percent error limits (dotted lines). Relative response is determined according to the procedures described below. A minimum of five data points are required for calibration (Section 7.4.4).
7.4.1The relative response (RR) of pollutant to labeled compound is determined from isotope ratio values calculated from acquired data. Three isotope ratios are used in this process:
The correct way to calculate RR is: RR=(R
7.4.2In most cases, the retention times of the pollutant and labeled compound are the same and isotope ratios (R's) can be calculated from the EICP areas, where: R=(area at m
R
7.4.3An example of the above calculations can be taken from the data plotted in figure 6 for toluene and toluene-d8. For these data, R
Not all labeled compounds elute before their pollutant analogs.
7.4.4To calibrate the analytical system by isotope dilution, analyze a 5 mL aliquot of each of the aqueous calibration standards (Section 6.7.1) spiked with an appropriate constant amount of the labeled compound spiking solution (Section 6.6), using the purge and trap procedure in section 10. Compute the RR at each concentration.
7.4.5Linearity—if the ratio of relative response to concentration for any compound is constant (less than 20 percent coefficient of variation) over the 5 point calibration range, an averaged relative response/concentration ratio may be used for that compound; otherwise, the complete calibration curve for that compound shall be used over the 5 point calibration range.
7.5Calibration by internal standard—used when criteria for isotope dilution (Section 7.4) cannot be met. The method is applied -to pollutants having no labeled analog and -to the labeled compounds. The internal stand-ards used for volatiles analyses are brom-o-chlor-o-methane, 2-bromo-1-chloropropane, and 1,4-dichlorobutane. Concentrations of the labeled compounds and pollutants without labeled analogs are computed relative to the nearest eluted internal standard, as shown in table 2.
7.5.1Response factors—calibration requires the determination of response factors (RF) which are defined by the following equation:
RF=(A
C
C
7.5.2The response factor is determined at 10, 20, 50, 100, and 200 ug/L for the pollutants (optionally at five times these concentrations for gases and water soluble pollutants—see Section 6.7), in a way analogous to that for calibration by isotope dilution (Section 7.4.4). The RF is plotted against concentration for each compound in the standard (C
7.5.3Linearity—if the response factor (RF) for any compound is constant (less than 35 percent coefficient of variation) over the 5 point calibration range, an averaged response factor may be used for that compound; otherwise, the complete calibration curve for that compound shall be used over the 5 point range.
7.6Combined calibration—by adding the isotopically labeled compounds and internal standards (Section 6.6) to the aqueous calibration standards (Section 6.7.1), a single set of analyses can be used to produce calibration curves for the isotope dilution and internal standard methods. These curves are verified each shift (Section 11.5) by purging the aqueous performance standard (Section 6.7.2). Recalibration is required only if calibration and on-going performance (Section 11.5) criteria cannot be met.
8.1Each laboratory that uses this method is required to operate a formal quality assurance program. The minimum requirements of this program consist of an initial demonstration of laboratory capability, analysis of samples spiked with labeled compounds to evaluate and document data quality, and analysis of standards and blanks as tests of continued performance. Laboratory performance is compared to established performance criteria to determine if the results of analyses meet the performance characteristics of the method.
8.1.1The analyst shall make an initial demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2The analyst is permitted to modify this method to improve separations or lower the costs of measurements, provided all performance specifications are met. Each time a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2 to demonstrate method performance.
8.1.3Analyses of blanks are required to demonstrate freedom from contamination and that the compounds of interest and interfering compounds have not been carried over from a previous analysis (Section 3). The procedures and criteria for analysis of a blank are described in Sections 8.5 and 11.7.
8.1.4The laboratory shall spike all samples with labeled compounds to monitor method performance. This test is described in Section 8.3. When results of these spikes indicate atypical method performance for samples, the samples are diluted to bring method performance within acceptable limits (Section 14.2).
8.1.5The laboratory shall, on an on-going basis, demonstrate through the analysis of the aqueous performance standard (Section 6.7.2) that the analysis system is in control. This procedure is described in Sections 11.1 and 11.5.
8.1.6The laboratory shall maintain rec-ords to define the quality of data -that is generated. Development of accuracy statements is described in Sections 8.4 and 11.5.2.
8.2Initial precision and accuracy—to establish the ability to generate acceptable precision and accuracy, the analyst shall perform the following operations:
8.2.1Analyze two sets of four 5-mL aliquots (8 aliquots total) of the aqueous performance standard (Section 6.7.2) according to the method beginning in Section 10.
8.2.2Using results of the first set of four analyses in Section 8.2.1, compute the average recovery (X
8.2.3For each compound, compare s and X
The large number of compounds in table 5 present a substantial probability that one or more will fail one of the acceptance criteria when all compoulds are analyzed. To determine if the analytical system is out of control, or if the failure can be attributed to probability, proceed as follows:
8.2.4Using the results of the second set of four analyses, compute s and X
8.3The laboratory shall spike all samples with labeled compounds to assess method performance on the sample matrix.
8.3.1Spike and analyze each sample according to the method beginning in Section 10.
8.3.2Compute the percent recovery (P) of the labeled compounds using the internal standard method (Section 7.5).
8.3.3Compare the percent recovery for each compound with the corresponding labeled compound recovery limit in table 5. If the recovery of any compound falls outside its warning limit, method performance is unacceptable for that compound in that sample. Therefore, the sample matrix is complex and the sample is to be diluted and reanalyzed, per Section 14.2.
8.4As part of the QA program for the laboratory, method accuracy for wastewater samples shall be assessed and records shall be maintained. After the analysis of five wastewater samples for which the labeled compounds pass the tests in Section 8.3.3, compute the average percent recovery (P) and the standard deviation of the percent recovery (s
8.5Blanks—reagent water blanks are analyzed to demonstrate freedom from carry-over (Section 3) and contamination.
8.5.1The level at which the purge and trap system will carry greater than 5 μg/L of a pollutant of interest (table 1) into a succeeding blank shall be determined by analyzing successively larger concentrations of these compounds. When a sample contains this concentration or more, a blank shall be analyzed immediately following this sample to demonstrate no carry-over at the 5 μg/L level.
8.5.2With each sample lot (samples analyzed on the same 8 hr shift), a blank shall be analyzed immediately after analysis of the aqueous performance standard (Section 11.1) to demonstrate freedom from contamination. If any of the compounds of interest (table 1) or any potentially interfering compound is found in a blank at greater than 10 μg/L (assuming a response factor of 1 relative to the nearest eluted internal standard for compounds not listed in table 1), analysis of samples is halted until the source of contamination is eliminated and a blank shows no evidence of contamination at this level.
8.6The specifications contained in this method can be met if the apparatus used is calibrated properly, then maintained in a calibrated state.
The standards used for calibration (Section 7), calibration verification (Section 11.5) and for initial (Section 8.2) and on-going (Section 11.5) precision and accuracy should be identical, so that the most precise results will be obtained. The GC/MS instrument in particular will provide the most reproducible results if dedicated to the settings and conditions required for the analyses of volatiles by this method.
8.7Depending on specific pro-gram requirements, field repli-cates may be collected to determine the precision of the sampling technique, and spiked samples may be required to determine the accuracy of the analysis when internal or external standard methods are used.
9.1Grab samples are collected in glass containers having a total volume greater than 20 mL. Fill sample bottles so that no air bubbles pass through the sample as the bottle is filled. Seal each bottle so that no air bubbles are entrapped. Maintain the hermetic seal on the sample bottle until time of analysis.
9.2Samples are maintained at 0-4 °C from the time of collection until analysis. If the sample contains residual chlorine, add sodium thiosulfate preservative (10 mg/40 mL) to the empty sample bottles just prior to shipment to the sample site. EPA Methods 330.4 and 330.5 may be used for measurement of residual chlorine (Reference 8). If preservative has been added, shake bottle vigorously for one minute immediately after filling.
9.3Experimental evidence indicates that some aromatic compounds, notably benzene, toluene, and ethyl benzene are susceptible to rapid biological degradation under certain environmental conditions. Refrigeration alone may not be adequate to preserve these compounds in wastewaters for more than seven days. For this reason, a separate sample should be collected, acidified, and analyzed when these aromatics are to be determined. Collect about 500 mL of sample in a clean container.
Adjust the pH of the sample to about 2 by adding HCl (1+1) while stirring. Check pH with narrow range (1.4 to 2.8) pH paper. Fill a sample container as described in Section 9.1. If residual chlorine is present, add sodium thiosulfate to a separate sample container and fill as in Section 9.1.
9.4All samples shall be analyzed within 14 days of collection.
10.1Remove standards and samples from cold storage and bring to 20-25 °.
10.2Adjust the purge gas flow rate to 40 ±4 mL/min. Attach the trap inlet to the purging device and set the valve to the purge mode (figure 3). Open the syringe valve located on the purging device sample introduction needle (figure 1).
10.3Remove the plunger from a 5-mL syringe and attach a closed syringe valve. Open the sample bottle and carefully pour the sample into the syringe barrel until it overflows. Replace the plunger and compress the sample. Open the syringe valve and vent any residual air while adjusting the sample volume to 5.0 mL. Because this process of taking an aliquot destroys the validity of the sample for future analysis, fill a second syringe at this time to protect against possible loss of data. Add an appropriate amount of the labeled compound spiking solution (Section 6.6) through the valve bore, then close the valve.
10.4Attach the syringe valve assembly to the syringe valve on the purging device. Open both syringe valves and inject the sample into the purging chamber.
10.5Close both valves and purge the sample for 11.0 ±0.1 minutes at 20-25 °C.
10.6After the 11 minute purge time, attach the trap to the chromatograph and set the purge and trap apparatus to the desorb mode (figure 4). Desorb the trapped compounds into the GC column by heating the trap to 170-180 °C while backflushing with carrier gas at 20-60 mL/min for four minutes. Start MS data acquisition upon start of the desorb cycle, and start the GC column temperature program 3 minutes later. Table 1 summarizes the recommended operating conditions for the gas chromatograph. Included in this table are retention times and detection limits that were achieved under these conditions. Other columns may be used provided the requirements in Section 8 can be met. If the priority pollutant gases produce GC peaks so broad that the precision and recovery specifications (Section 8.2) cannot be met, the column may be cooled to ambient or sub-ambient temperatures to sharpen these peaks.
10.7While analysis of the desorbed compounds proceeds, empty the purging chamber using the sample introduction syringe. Wash the chamber with two 5-mL portions of reagent water. After the purging device has been emptied, allow the purge gas to vent through the chamber until the frit is dry, so that it is ready for the next sample.
10.8After desorbing the sample for four minutes, recondition the trap by returning to the purge mode. Wait 15 seconds, then close the syringe valve on the purging device to begin gas flow through the trap. Maintain the trap temperature at 170-180 °C. After approximately seven minutes, turn off the trap heater and open the syringe valve to stop the gas flow through the trap. When cool, the trap is ready for the next sample.
11.1At the beginning of each 8 hr shift during which analyses are performed, system calibration and performance shall be verified for all pollutants and labeled compounds. For these tests, analysis of the aqueous performance standard (Section 6.7.2) shall be used to verify all performance criteria. Adjustment and/or recalibration (per Section 7) shall be performed until all performance criteria are met. Only after all performance criteria are met may blanks and samples be analyzed.
11.2BFB spectrum validity—the criteria in table 3 shall be met.
11.3Retention times—the absolute retention times of all compounds shall approximate those given in Table 2.
11.4GC resolution—the valley height between toluene and toluene-d8 (at m/z 91 and 99 plotted on the same graph) shall be less than 10 percent of the taller of the two peaks.
11.5Calibration verification and on-going precision and accuracy—compute the concentration of each polutant (Table 1) by isotope dilution (Section 7.4) for those compmunds which have labeled analogs. Compute the concentration of each pollutant (Table 1) which has no labeled analog by the internal standard method (Section 7.5). Compute the concentration of the labeled compounds by the internal standard method. These concentrations are computed based on the calibration data determined in Section 7.
11.5.1For each pollutant and labeled compound, compare the concentration with the corresponding limit for on-going accuracy in Table 5. If all compmunds meet the acceptance criteria, system performance is acceptable and analysis of blanks and samples may continue. If any individual value falls outside the range given, system performance is unacceptable for that compound.
The large number of compounds in Table 5 present a substantial probability that one or more will fail the acceptance criteria when all compounds are analyzed. To determine if the analytical system is out of control, or if the failure may be attributed to probability, proceed as follows:
11.5.1.1Analyze a second aliquot of the aqueous performance standard (Section 6.7.2).
11.5.1.2Compute the concentration for only those compounds which failed the first test (Section 11.5.1). If these compounds now pass, system performance is acceptable for all compounds and analyses of blanks and samples may proceed. If, however, any of the compounds fail again, the measurement system is not performing properly for these compounds. In this event, locate and correct the problem or recalibrate the system (Section 7), and repeat the entire test (Section 11.1) for all compounds.
11.5.2Add results which pass the specification in 11.5.1.2 to initial (Section 8.2) and previous on-going data. Update QC charts to form a graphic representation of laboratory performance (Figure 7). Develop a statement of accuracy for each pollutant and labeled compound by calculating the average percentage recovery (R) and the standard deviation of percent recovery (s
12.1Labeled compounds and pollutants having no labeled analog:
12.1.1The signals for all characteristic masses stored in the spectral library (Section 7.2.4) shall be present and shall maximize within the same two consecutive scans.
12.1.2Either (1) the background corrected EICP areas, or (2) the corrected relative intensities of the mass spectral peaks at the GC peak maximum shall agree within a factor of two (0.5 to 2 times) for all masses stored in the library.
12.1.3The retention time relative to the nearest eluted internal standard shall be within ±7 scans or ±20 seconds, whichever is greater.
12.2Pollutants having a labeled analog:
12.2.1The signals for all characteristic masses stored in the spectral library (Section 7.2.4) shall be present and shall maximize within the same two consecutive scans.
12.2.2Either (1) the background corrected EICP areas, or (2) the corrected relative intensities of the mass spectral peaks at the GC peak maximum shall agree within a factor of two for all masses stored in the spectral library.
12.2.3The retention time difference between the pollutant and its labeled analog shall agree within ±2 scans or ±6 seconds (whichever is greater) of this difference in the shift standard (Section 11.1).
12.3Masses present in the experimental mass spectrum that are not present in the reference mass spectrum shall be accounted for by contaminant or background ions. If the experimental mass spectrum is contaminated, an experienced spectrometrist (Section 1.4) is to determine the presence or absence of the compound.
13.1Isotope dilution—by adding a known amount of a labeled compound to every sample prior to purging, correction for recovery of the pollutant can be made because the pollutant and its labeled analog exhibit the same effects upon purging, desorption, and gas chromatography. Relative response (RR) values for sample mixtures are used in conjunction with calibration curves described in Section 7.4 to determine concentrations directly, so long as labeled compound spiking levels are constant. For the toluene example given in Figure 6 (Section 7.4.3), RR would be equal to 1.174. For this RR value, the toluene
13.2Internal standard—calculate the concentration using the response factor determined from calibration data (Section 7.5) and the following equation:
Concentration =(A
13.3If the EICP area at the quantitation mass for any compound exceeds the calibration range of the system, the sample is diluted by successive factors of 10 and these dilutions are analyzed until the area is within the calibration range.
13.4Report results for all pollutants and labeled compounds (Table 1) found in all standards, blanks, and samples, in μg/L to three significant figures. Results for samples which have been diluted are reported at the least dilute level at which the area at the quantitation mass is within the calibration range (Section 13.3) and the labeled compound recovery is within the normal range for the Method (Section 14.2).
14.1Untreated effluents and other samples frequently contain high levels (>1000 μg/L) of the compounds of interest and of interfering compounds. Some samples will foam excessively when purged; others will overload the trap/or GC column.
14.2Dilute 0.5 mL of sample with 4.5 mL of reagent water and analyze this diluted sample when labeled compound recovery is outside the range given in Table 5. If the recovery remains outside of the range for this diluted sample, the aqueous performance standard shall be analyzed (Section 11) and calibration verified (Section 11.5). If the recovery for the labeled compmund in the aqueous performance standard is outside the range given in Table 5, the analytical system is out of control. In this case, the instrumelt shall be repaired, the performance specifications in Section 11 shall be met, and the analysis of the undiluted sample shall be repeated. If the recovery for the aqueous performance standard is within the range given in Table 5, the method does not work on the sample being analyzed and the result may not be reported for regulatory compliance purposes.
14.3Reverse search computer programs can misinterpret the spectrum of chro-ma-tographically unresolved pollutant and labeled compound pairs with overlapping spectra when a high level of the pollutant is present. Examine each chromatogram for peaks greater than the height of the internal standard peaks. These peaks can obscure the compounds of interest.
15.1The specifications for this method were taken from the inter-laboratory validation of EPA Method 624 (reference 9). Method 1624 has been shown to yield slightly better performance on treated effluents than Method 624. Additional method performance data can be found in Reference 10.
1. “Performance Tests for the Evaluation of Computerized Gas Chromatography/Mass Spectrometry Equipment and Laboratories,” USEPA, EMSL/Cincinnati, OH 45268, EPA-600/4-80-025 (April 1980).
2. Bellar, T.A. and Lichtenberg, J.J., “Journal American Water Works Association,”
3. Bellar, T.A. and Lichtenberg, J.J., “Semi-automated Headspace Analysis of Drinking Waters and Industrial Waters for Purgeable Volatile Organic Compounds,” in
4. “Working with Carcinogens,” DHEW, PHS, NIOSH, Publication 77-206 (1977).
5. “OSHA Safety and Health Standards, General Industry,” 29 CFR part 1910, OSHA 2206, (1976).
6. “Safety in Academic Chemistry Laboratories,” American Chemical Society Publication, Committee on Chemical Safety (1979).
7. “Handbook of Analytical Quality Control in Water and Wastewater Laboratories,” USEPA, EMSL/Cincinnati, OH 45268, EPA-4-79-019 (March 1979).
8. “Methods 330.4 and 330.5 for Total Residual Chlorine,” USEPA, EMSL/Cincinnati, OH 45268, EPA-4-79-020 (March 1979).
9. “EPA Method Study 29 EPA Method 624—Purgeables,” EPA 600/4-84-054, National Technical Information Service, PB84-209915, Springfield, Virginia 22161, June 1984.
10. “Colby, B.N., Beimer, R.G., Rushneck, D.R., and Telliard, W.A., “Isotope Dilution Gas Chromatography-Mass Spectrometry for the Determination of Priority Pollutants in Industrial Effluents,” USEPA, Effluent Guidelines Division, Washington, DC 20460 (1980).
1.1This method is designed to determine the semivolatile toxic organic pollutants associated with the 1976 Consent Decree and additional compounds amenable to extraction and analysis by capillary column gas chromatography-mass spectrometry (GC/MS).
1.2The chemical compounds listed in Tables 1 and 2 may be determined in municipal and industrial discharges by this method. The method is designed to meet the survey
1.3The detection limit of this method is usually dependent on the level of interferences rather than instrumental limitations. The limits listed in Tables 3 and 4 represent the minimum quantity that can be detected with no interferences present.
1.4The GC/MS portions of this method are for use only by analysts experienced with GC/MS or under the close supervision of such qualified persons. Laboratories unfamiliar with analyses of environmental samples by GC/MS should run the performance tests in reference 1 before beginning.
2.1Stable isotopically labeled analogs of the compounds of interest are added to a one liter wastewater sample. The sample is extracted at pH 12-13, then at pH <2 with methylene chloride using continuous extraction techniques. The extract is dried over sodium sulfate and concentrated to a volume of one mL. An internal standard is added to the extract, and the extract is injected into the gas chromatograph (GC). The compounds are separated by GC and detected by a mass spectrometer (MS). The labeled compounds serve to correct the variability of the analytical technique.
2.2Identification of a compound (qualitative analysis) is performed by comparing the GC retention time and background corrected characteristic spectral masses with those of authentic standards.
2.3Quantitative analysis is performed by GC/MS using extracted ion current profile (EICP) areas. Isotope dilution is used when labeled compounds are available; otherwise, an internal standard method is used.
2.4Quality is assured through reproducible calibration and testing of the extraction and GC/MS systems.
3.1Solvents, reagents, glassware, and other sample processing hardware may yield artifacts and/or elevated baselines causing misinterpretation of chromatograms and spectra. All materials shall be demonstrated to be free from interferences under the conditions of analysis by running method blanks initially and with each sample lot (samples started through the extraction process on a given 8 hr shift, to a maximum of 20). Specific selection of reagents and purification of solvents by distillation in all-glass systems may be required. Glassware and, where possible, reagents are cleaned by solvent rinse and baking at 450 °C for one hour minimum.
3.2Interferences coextracted from samples will vary considerably from source to source, depending on the diversity of the industrial complex or municipality being samples.
4.1The toxicity or carcinogenicity of each compound or reagent used in this method has not been precisely determined; however, each chemical compound should be treated as a potential health hazard. Exposure to these compounds should be reduced to the lowest possible level. The laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of data handling sheets should also be made available to all personnel involved in these analyses. Additional information on laboratory safety can be found in references 2-4.
4.2The following compounds covered by this method have been tentatively classified as known or suspected human or mammalian carcinogens: benzidine benzo(a)anthracene, 3,3′-dichlorobenzidine, benzo(a)pyrene, di-ben-zo(a,h)an-thra-cene, N-nitrosodimethylamine, and β-naphtylamine. Primary standards of these compounds shall be prepared in a hood, and a NIOSH/MESA approved toxic gas respirator should be worn when high concentrations are handled.
5.1Sampling equipment for discrete or composite sampling.
5.1.1Sample bottle, amber glass, 1.1 liters minimum. If amber bottles are not available, samples shall be protected from light. Bottles are detergent water washed, then solvent rinsed or baked at 450 °C for one hour minimum before use.
5.1.2Bottle caps—threaded to fit sample bottles. Caps are lined with Teflon. Aluminum foil may be substituted if the sample is not corrosive. Liners are detergent water washed, then reagent water (Section 6.5) and solvent rinsed, and baked at approximately 200 °C for one hour minimum before use.
5.1.3Compositing equipment—automatic or manual compositing system incorporating glass containers for collection of a minimum 1.1 liters. Sample containers are kept at 0 to 4 °C during sampling. Glass or Teflon tubing only shall be used. If the sampler uses a peristaltic pump, a minimum length of compressible silicone rubber tubing may be used in the pump only. Before use, the tubing is thoroughly rinsed with methanol, followed by repeated rinsings with reagent water (Section 6.5) to minimize sample contamination. An integrating flow meter is used to collect proportional composite samples.
5.2Continuous liquid-liquid extractor—Teflon or glass conncecting joints and stopcocks without lubrication (Hershberg-Wolf Extractor) one liter capacity, Ace Glass 6841-10, or equivalent.
5.3Drying column—15 to 20 mm i.d. Pyrex chromatographic column equipped with coarse glass frit or glass wool plug.
5.4Kuderna-Danish (K-D) apparatus
5.4.1Concentrator tube—10mL, graduated (Kontes K-570050-1025, or equivalent) with calibration verified. Ground glass stopper (size 19/22 joint) is used to prevent evaporation of extracts.
5.4.2Evaporation flask—500 mL (Kontes K-570001-0500, or equivalent), attached to concentrator tube with springs (Kontes K-662750-0012).
5.4.3Snyder column—three ball macro (Kontes K-503000-0232, or equivalent).
5.4.4Snyder column—two ball micro (Kontes K-469002-0219, or equivalent).
5.4.5Boiling chips—approx 10/40 mesh, extracted with methylene chloride and baked at 450 °C for one hr minimum.
5.5Water bath—heated, with concentric ring cover, capable of temperature control ±2 °C, installed in a fume hood.
5.6Sample vials—amber glass, 2-5 mL with Teflon-lined screw cap.
5.7Analytical balance—capable of weighing 0.1 mg.
5.8Gas chromatograph—shall have splitless or -on-column injection port for -ca-pil-lary column, temperature program with 30 °C hold, and shall meet all of the performance specifications in Section 12.
5.8.1Column—30±5 m×0.25±0.02 mm i.d. 5% phenyl, 94% methyl, 1% vinyl silicone bonded phase fused silica capillary column (J & W DB-5, or equivalent).
5.9Mass spectrometer—70 eV electron impact ionization, shall repetitively scan from 35 to 450 amu in 0.95 to 1.00 second, and -shall produce a unit resolution (valleys be-tween m/z 441-442 less than 10 percent of -the height of the 441 peak), backgound -cor-rected mass spectrum from 50 ng decaflu-o-ro-tri-phenylphosphine (DFTPP) introduced through the GC inlet. The spectrum shall meet the mass-intensity criteria in Table 5 (reference 5). The mass spectrometer shall be interfaced to the GC such that the end of the capillary column terminates within one centimeter of the ion source but does not intercept the electron or ion beams. All portions of the column which connect the GC to the ion source shall remain at or above the column temperature during analysis to preclude condensation of less volatile compounds.
5.10Data system—shall collect and record MS data, store mass-intensity data in spectral libraries, process GC/MS data, generate reports, and shall compute and record response factors.
5.10.1Data acquisition—mass spectra shall be collected continuously throughout the analysis and stored on a mass storage device.
5.10.2Mass spectral libraries—user created libraries containing mass spectra obtained from analysis of authentic standards shall be employed to reverse search GC/MS runs for the compounds of interest (Section 7.2).
5.10.3Data processing—the data system shall be used to search, locate, identify, and quantify the compounds of interest in each GC/MS analysis. Software routines shall be employed to compute retention times and peak areas. Displays of spectra, mass chromatograms, and library comparisons are required to verify results.
5.10.4Response factors and multipoint calibrations—the data system shall be used to record and maintain lists of response factors (response ratios for isotope dilution) and multipoint calibration curves (Section 7). Computations of relative standard deviation (coefficient of variation) are useful for testing calibration linearity. Statistics on initial (Section 8.2) and on-going (Section 12.7) performance shall be computed and maintained.
6.1Sodium hydroxide—reagent grade, 6N in reagent water.
6.2Sulfuric acid—reagent grade, 6N in reagent water.
6.3Sodium sulfate—reagent grade, granular anhydrous, rinsed with methylene chloride (20 mL/g) and conditioned at 450 °C for one hour minimum.
6.4Methylene chloride—distilled in glass (Burdick and Jackson, or equivalent).
6.5Reagent water—water in which the compounds of interest and interfering compounds are not detected by this method.
6.6Standard solutions—purchased as solutions or mixtures with certification to -their purity, concentration, and authenticity, or pre-pared from materials of known purity and com-position. If compound purity is 96 percent or greater, the weight may be used without correction to compute the concentration of the standard. When not being used, standards are stored in the dark at −20 to −10 °C in screw-capped vials with Teflon-lined lids. A mark is placed on the vial at the level of the solution so that solvent evaporation loss can be detected. The vials are brought to room temperature prior to use. Any precipitate is redissolved and solvent is added if solvent loss has occurred.
6.7Preparation of stock solutions—prepare in methylene chloride, benzene, p-dioxane, or a mixture of these solvents per the steps below. Observe the safety precautions in Section 4. The large number of labeled and unlabeled acid, base/neutral, and Appendix C compounds used for combined calibration (Section 7) and calibration verification (12.5) require high
6.7.1Dissolve an appropriate amount of assayed reference material in a suitable solvent. For example, weigh 400 mg naphthalene in a 10 mL ground glass stoppered volumetric flask and fill to the mark with benzene. After the naphthalene is completely dissolved, transfer the solution to a 15 mL vial with Teflon-lined cap.
6.7.2Stock standard solutions should be checked for signs of degradation prior to the preparation of calibration or performance test standards. Quality control check samples that can be used to determine the accuracy of calibration standards are available from the US Environmental Protection Agency, Environmental Monitoring and Support Laboratory, Cincinnati, Ohio 45268.
6.7.3Stock standard solutions shall be replaced after six months, or sooner if comparison with quality control check samples indicates a change in concentration.
6.8Labeled compound spiking solution—from stock standard solutions prepared as above, or from mixtures, prepare the spiking solution at a concentration of 200 μg/mL, or at a concentration appropriate to the MS response of each compound.
6.9Secondary standard—using stock solutions (Section 6.7), prepare a secondary standard containing all of the compounds in Tables 1 and 2 at a concentration of 400 μg/mL, or higher concentration appropriate to the MS response of the compound.
6.10Internal standard solution—prepare 2,2′-difluorobiphenyl (DFB) at a concentration of 10 mg/mL in benzene.
6.11DFTPP solution—prepare at 50 μg/mL in acetone.
6.12Solutions for obtaining authentic mass spectra (Section 7.2)—prepare mixtures of compounds at concentrations which will assure authentic spectra are obtained for storage in libraries.
6.13Calibration solutions—combine 0.5 mL of the solution in Section 6.8 with 25, 50, 125, 250, and 500 uL of the solution in section 6.9 and bring to 1.00 mL total volume each. This will produce calibration solutions of nominal 10, 20, 50, 100, and 200 μg/mL of the pollutants and a constant nominal 100 μg/mL of the labeled compounds. Spike each solution with 10 μL of the internal standard solution (Section 6.10). These solutions permit the relative response (labeled to unlabeled) to be measured as a function of concentration (Section 7.4).
6.14Precision and recovery standard—used for determination of initial (Section 8.2) and on-going (Section 12.7) precision and recovery. This solution shall contain the pollutants and labeled compounds at a nominal concentration of 100 μg/mL.
6.15Stability of solutions—all standard solutions (Sections 6.8-6.14) shall be analyzed within 48 hours of preparation and on a monthly basis thereafter for signs of degradation. Standards will remain acceptable if the peak area at the quantitation mass relative to the DFB internal standard remains within ±15 percent of the area obtained in the initial analysis of the standard.
7.1Assemble the GC/MS and establish the operating conditions in Table 3. Analyze standards per the procedure in Section 11 to demonstrate that the analytical system meets the detection limits in Tables 3 and 4, and the mass-intensity criteria in Table 5 for 50 ng DFTPP.
7.2Mass spectral libraries—detection and identification of compounds of interest are dependent upon spectra stored in user created libraries.
7.2.1Obtain a mass spectrum of each pollutant, labeled compound, and the internal standard by analyzing an authentic standard either singly or as part of a mixture in which there is no interference between closely eluted components. That only a single compound is present is determined by examination of the spectrum. Fragments not attributable to the compound under study indicate the presence of an interfering compound.
7.2.2Adjust the analytical conditions and scan rate (for this test only) to produce an undistorted spectrum at the GC peak maximum. An undistorted spectrum will usually be obtained if five complete spectra are collected across the upper half of the GC peak. Software algorithms designed to “enhance” the spectrum may eliminate distortion, but may also eliminate authentic masses or introduce other distortion.
7.2.3The authentic reference spectrum is obtained under DFTPP tuning conditions (Section 7.1 and Table 5) to normalize it to spectra from other instruments.
7.2.4The spectrum is edited by saving the 5 most intense mass spectral peaks and all other mass spectral peaks greater than 10 percent of the base peak. This edited spectrum is stored for reverse search and for compound confirmation.
7.3Analytical range—demonstrate that 20 ng anthracene or phenanthrene produces an area at m/z 178 approx one-tenth that required to exceed the linear range of the system. The exact value must be determined by experience for each instrument. It is used to match the calibration range of the instrument to the analytical range and detection limits required, and to diagnose instrument sensitivity problems (Section 15.4). The 20 ug/mL calibration standard (Section 6.13) can be used to demonstrate this performance.
7.3.1Polar compound detection—demonstrate that unlabeled pentachlorophenol and benzidine are detectable at the 50 μg/mL level (per all criteria in Section 13). The 50 μg/mL calibration standard (Section 6.13) can be used to demonstrate this performance.
7.4Calibration with isotope dilution—isotope dilution is used when (1) labeled compounds are available, (2) interferences do not preclude its use, and (3) the quantitation mass extracted ion current profile (EICP) area for the compound is in the calibration range. If any of these conditions preclude isotope dilution, internal standard methods (Section 7.5 or 7.6) are used.
7.4.1A calibration curve encompassing the concentration range is prepared for each compound to be determined. The relative response (pollutant to labeled) vs concentration in standard solutions is plotted or computed using a linear regression. The example in Figure 1 shows a calibration curve for phenol using phenol-d5 as the isotopic diluent. Also shown are the ± 10 percent error limits (dotted lines). Relative Reponse (RR) is determined according to the procedures described below. A minimum of five data points are employed for calibration.
7.4.2The relative response of a pollutant to its labeled analog is determined from isotope ratio values computed from acquired data. Three isotope ratios are used in this process:
R
R
R
The m/z's are selected such that R
7.4.3Capillary columns usually separate the pollutant-labeled pair, with the labeled compound eluted first (Figure 2). For this case, R
7.4.4Special precautions are taken when the pollutant-labeled pair is not separated, or when another labeled compound with interfering spectral masses overlaps the pollutant (a case which can occur with isomeric compounds). In this case, it is necessary to determine the respective contributions of the pollutant and labeled compounds to the respective EICP areas. If the peaks are separated well enough to permit the data system or operator to remove the contributions of the compounds to each other, the equations in Section 7.4.3 apply. This usually occurs when the height of the valley between the two GC peaks at the same m/z is less than 10 percent of the height of the shorter of the two peaks. If significant GC and spectral overlap occur, RR is computed using the following equation:
RR = (R
7.4.5To calibrate the analytical system by isotope dilution, analyze a 1.0 μL aliquot of each of the calibration standards (Section 6.13) using the procedure in Section 11. Compute the RR at each concentration.
7.4.6Linearity—if the ratio of relative response to concentration for any compound is constant (less than 20 percent coefficient of variation) over the 5 point calibration range, and averaged relative response/concentration ratio may be used for that compound; otherwise, the complete calibration curve for that compound shall be used over the 5 point calibration range.
7.5Calibration by internal standard—used when criteria for istope dilution (Section 7.4) cannot be met. The internal standard to be used for both acid and base/neutral analyses is 2,2’-difluorobiphenyl. The internal standard method is also applied to determination of compounds having no labeled analog, and to measurement of labeled compounds for intra-laboratory statistics (Sections 8.4 and 12.7.4).
7.5.1Response factors—calibration requires the determination of response factors (RF) which are defined by the following equation:
7.5.1.1The response factor is determined for at least five concentrations appropriate to the response of each compound (Section 6.13); nominally, 10, 20, 50, 100, and 200 μg/mL. The amount of internal standard added to each extract is the same (100 μg/mL) so that C
7.5.1.2Linearity—if the response factor (RF) for any compound is constant (less than 35 percent coefficient of variation) over the 5 point calibration range, an averaged response factor may be used for that compound; otherwise, the complete calibration
7.6Combined calibration—by using calibration solutions (Section 6.13) containing the pollutants, labeled compounds, and the internal standard, a single set of analyses can be used to produce calibration curves for the isotope dilution and internal standard methods. These curves are verified each shift (Section 12.5) by analyzing the 100 θg/mL calibration standard (Section 6.13). Recalibration is required only if calibration verification (Section 12.5) criteria cannot be met.
8.1Each laboratory that uses this method is required to operate a formal quality assurance program. The minimum requirements of this program consist of an initial demonstration of laboratory capability, analysis of samples spiked with labeled compounds to evaluate and document data quality, and analysis of standards and blanks as tests of continued performance. Laboratory performance is compared to established performance criteria to determine if the results of analyses meet the performance characteristics of the method.
8.1.1The analyst shall make an initial demonstration of the ability to generate acceptable accuracy and precision with this method. This ability is established as described in Section 8.2.
8.1.2The analyst is permitted to modify this method to improve separations or lower the costs of measurements, provided all performance specifications are met. Each time a modification is made to the method, the analyst is required to repeat the procedure in Section 8.2 to demonstrate method performance.
8.1.3Analyses of blanks are required to demonstrate freedom from contamination. The procedures and criteria for analysis of a blank are described in Section 8.5.
8.1.4The laboratory shall spike all samples with labeled compounds to monitor method performance. This test is described in Section 8.3. When results of these spikes indicate atypical method performance for samples, the samples are diluted to bring method performance within acceptable limits (Section 15).
8.1.5The laboratory shall, on an on-going basis, demonstrate through calibration verification and the analysis of the precision and recovery standard (Section 6.14) that the analysis system is in control. These procedures are described in Sections 12.1, 12.5, and 12.7.
8.1.6The laboratory shall maintain records to define the quality of data that is generated. Development of accuracy statements is described in Section 8.4.
8.2Initial precision and accuracy—to establish the ability to generate acceptable precision and accuracy, the analyst shall perform the following operations:
8.2.1Extract, concentrate, and analyze two sets of four one-liter aliquots (8 aliquots total) of the precision and recovery standard (Section 6.14) according to the procedure in Section 10.
8.2.2Using results of the first set of four analyses, compute the average recovery (X
8.2.3For each compound, compare s and X
The large number of compounds in Table 8 present a substantial probability that one or more will fail the acceptance criteria when all compounds are analyzed. To determine if the analytical system is out of control, or if the failure can be attributed to probability, proceed as follows:
8.2.4Using the results of the second set of four analyses, compute s and X
8.3The laboratory shall spike all samples with labeled compounds to assess method performance on the sample matrix.
8.3.1Analyze each sample according to the method in Section 10.
8.3.2Compute the percent recovery (P) of the labeled compounds using the internal standard methmd (Section 7.5).
8.3.3Compare the labeled compound recovery for each compound with the corresponding limits in Table 8. If the recovery of any compounds falls outside its warning limit, method performance is unacceptable for that compound in that sample, Therefore, the sample is complex and is to be diluted and reanalyzed per Section 15.4.
8.4As part of the QA program for the laboratory, method accuracy for wastewater samples shall be assessed and records shall be maintained. After the analysis of five wastewater samples for which the labeled compounds pass the tests in Section 8.3, compute the average percent recovery (P)
8.5Blanks—reagent water blanks are analyzed to demonstrate freedom from contamination.
8.5.1Extract and concentrate a blank with each sample lot (samples started through the extraction process on the same 8 hr shift, to a maximum of 20 samples). Analyze the blank immediately after analysis of the precision and recovery standard (Section 6.14) to demonstrate freedom from contamination.
8.5.2If any of the compounds of interest (Tables 1 and 2) or any potentially interfering compound is found in a blank at greater than 10 μg/L (assuming a response factor of 1 relative to the internal standard for compounds not listed in Tables 1 and 2), analysis of samples is halted until the source of contamination is eliminated and a blank shows no evidence of contamination at this level.
8.6The specifications contained in this method can be met if the apparatus used is calibrated properly, then maintained in a calibrated state. The standards used for calibration (Section 7), calibration verification (Section 12.5), and for initial (Section 8.2) and on-going (Section 12.7) precision and recovery should be identical, so that the most precise results will be obtained. The GC/MS instrument in particular will provide the most reproducible results if dedicated to the settings and conditions required for the analysis of semi-volatiles by this method.
8.7Depending on specific program requirements, field replicates may be collected to determine the precision of the sampling technique, and spiked samples may be required to determine the accuracy of the analysis when internal or external standard methods are used.
9.1Collect samples in glass containers following conventional sampling practices (Reference 7). Composite samples are collected in refrigerated glass containers (Section 5.1.3) in accordance with the requirements of the sampling program.
9.2Maintain samples at 0-4 °C from the time collectimn until extraction. If residual chlorine is present, add 80 mg sodium thiosulfate per liter of water. EPA Methods 330.4 and 330.5 may be used to measure residual chlorine (Reference 8).
9.3Begin sample extraction within seven days of collection, and analyze all extracts within 40 days of extraction.
10.1Labeled compound spiking—measure 1.00 ± 0.01 liter of sample into a glass container. For untreated effluents, and samples which are expected to be difficult to extract and/or concentrate, measure an additional 10.0 ± 0.1 mL and dilute to a final volume of 1.00 ± 0.01 liter with reagent water in a glass container.
10.1.1For each sample or sample lot (to a maximum of 20) to be extracted at the same time, place three 1.00 ± 0.10 liter aliquots of reagent water in glass containers.
10.1.2Spike 0.5 mL of the labeled compound spiking solution (Section 6.8) into all samples and one reagant water aliquot.
10.1.3Spike 1.0 mL of the precision and recovery standard (Section 6.14) into the two remaining reagent water aliquots.
10.1.4Stir and equilibrate all solutions for 1-2 hr.
10.2Base/neutral extraction—place 100-150 mL methylene chloride in each continuous extractor and 200-300 in each distilling flask.
10.2.1Pour the sample(s), blank, and standard aliquots into the extractors. Rinse the glass containers with 50-100 mL methylene chloride and add to the respective extractor.
10.2.2Adjust the pH of the waters in the extractors to 12-13 with 6N NaOH while monitoring with a pH meter. Begin the extraction by heating the flask until the methylene chloride is boiling. When properly adjusted, 1-2 drops of methylene chloride per second will fall from the condensor tip into the water. After 1-2 hours of extraction, test the pH and readjust to 12-13 if required. Extract for 18-24 hours.
10.2.3Remove the distilling flask, estimate and record the volume of extract (to the nearest 100 mL), and pour the contents through a drying column containing 7 to 10 cm anhydrous sodium sulfate. Rinse the distilling flask with 30-50 mL of methylene chloride and pour through the drying column. Collect the solution in a 500 mL K-D evaporator flask equipped with a 10 mL concentrator tube. Seal, label as the base/neutral fraction, and concentrate per Sections 10.4 to 10.5.
10.3Acid extraction—adjust the pH of the waters in the extractors to 2 or less using 6N sulfuric acid. Charge clean distilling flasks with 300-400 mL of methylene chloride. Test and adjust the pH of the waters after the first 1-2 hr of extraction. Extract for 18-24 hours.
10.3.1Repeat Section 10.2.3, except label as the acid fraction.
10.4Concentration—concentrate the extracts in separate 500 mL K-D flasks equipped with 10 mL concentrator tubes.
10.4.1Add 1 to 2 clean boiling chips to the flask and attach a three-ball macro Snyder column. Prewet the column by adding approximately one mL of methylene chloride through the top. Place the K-D apparatus in a hot water bath so that the entire lower rounded surface of the flask is bathed with steam. Adjust the vertical position of the apparatus and the water temperature as required to complete the concentration in 15 to 20 minutes. At the proper rate of distillation, the balls of the column will actively chatter but the chambers will not flood. When the liquid has reached an apparent volume of 1 mL, remove the K-D apparatus from the bath and allow the solvent to drain and cool for at least 10 minutes. Remove the Snyder column and rinse the flask and its lower joint into the concentrator tube with 1-2 mL of methylene chloride. A 5-mL syringe is recommended for this operation.
10.4.2For performance standards (Sections 8.2 and 12.7) and for blanks (Section 8.5), combine the acid and base/neutral extracts for each at this point. Do not combine the acid and base/neutral extracts for samples.
10.5Add a clean boiling chip and attach a two ball micro Snyder column to the concentrator tube. Prewet the column by adding approx 0.5 mL methylene chloride through the top. Place the apparatus in the hot water bath. Adjust the vertical position and the water temperature as required to complete the concentration in 5-10 minutes. At the proper rate of distillation, the balls of the column will actively chatter but the chambers will not flood. When the liquid reaches an apparent volume of approx 0.5 mL, remove the apparatus from the water bath and allow to drain and cool for at least 10 minutes. Remove the micro Snyder column and rinse its lower joint into the concentrator tube with approx 0.2 mL of methylene chloride. Adjust the final volume to 1.0 mL.
10.6Transfer the concentrated extract to a clean screw-cap vial. Seal the vial with a Teflon-lined lid, and mark the level on the vial. Label with the sample number and fraction, and store in the dark at −20 to -−10 °C until ready for analysis.
11.1Establish the operating conditions given in Table 3 or 4 for analysis of the base/neutral or acid extracts, respectively. For analysis of combined extracts (Section 10.4.2), use the operating conditions in Table 3.
11.2Bring the concentrated extract (Section 10.6) or standard (Sections 6.13 through 6.14) to room temperature and verify that any precipitate has redissolved. Verify the level on the extract (Sections 6.6 and 10.6) and bring to the mark with solvent if required.
11.3Add the internal standard solution (Section 6.10) to the extract (use 1.0 uL of solution per 0.1 mL of extract) immediately prior to injection to minimize the possibility of loss by evaporation, adsorption, or reaction. Mix thoroughly.
11.4Inject a volume of the standard solution or extract such that 100 ng of the internal standard will be injected, using on-column or splitless injection. For 1 mL extracts, this volume will be 1.0 uL. Start the GC column initial isothermal hold upon injection. Start MS data collection after the solvent peak elutes. Stop data collection after the benzo (ghi) perylene or pentachlorophenol peak elutes for the base/neutral or acid fraction, respectively. Return the column to the initial temperature for analysis of the next sample.
12.1At the beginning of each 8 hr shift during which analyses are performed, GC/MS system performance and calibration are verified for all pollutants and labeled compounds. For these tests, analysis of the 100 μg/mL calibration standard (Section 6.13) shall be used to verify all performance criteria. Adjustment and/or recalibration (per Section 7) shall be performed until all performance criteria are met. Only after all performance criteria are met may samples, blanks, and precision and recovery standards be analyzed.
12.2DFTPP spectrum validity—inject 1 μL of the DFTPP solution (Section 6.11) either separately or within a few seconds of injection of the standard (Section 12.1) analyzed at the beginning of each shift. The criteria in Table 5 shall be met.
12.3Retention times—the absolute retention time of 2,2′-difluorobiphenyl shall be within the range of 1078 to 1248 seconds and the relative retention times of all pollutants and labeled compounds shall fall within the limits given in Tables 3 and 4.
12.4GC resolution—the valley height between anthracene and phenanthrene at -m/z 178 (or the analogs at -m/z 188) shall not exceed 10 percent of the taller of the two peaks.
12.5Calibration verification—compute the concentration of each pollutant (Tables 1 and 2) by isotope dilution (Section 7.4) for those compounds which have labeled analogs. Compute the concentration of each pollutant which has no labeled analog by the internal standard method (Section 7.5). Compute the concentration of the labeled compounds by the internal standard method. These concentrations are computed based on the calibration data determined in Section 7.
12.5.1For each pollutant and labeled compound being tested, compare the concentration with the calibration verification limit
12.6Multiple peaks—each compound injected shall give a single, distinct GC peak.
12.7On-going precision and accuracy.
12.7.1Analyze the extract of one of the pair of precision and recovery standards (Section 10.1.3) prior to analysis of samples from the same lot.
12.7.2Compute the concentration of each pollutant (Tables 1 and 2) by isotope dilution (Section 7.4) for those compounds which have labeled analogs. Compute the concentration of each pollutant which has no labeled analog by the internal standard method (Section 7.5). Compute the concentration of the labeled compounds by the internal standard method.
12.7.3For each pollutant and labeled compound, compare the concentration with the limits for on-going accuracy in Table 8. If all compounds meet the acceptance criteria, system performance is acceptable and analysis of blanks and samples may proceed. If, however, any individual concentration falls outside of the range given, system performance is unacceptable for that compound.
The large number of compounds in Table 8 present a substantial probability that one or more will fail when all compounds are analyzed. To determine if the extraction/concentration system is out of control or if the failure is caused by probability, proceed as follows:
12.7.3.1Analyze the second aliquot of the pair of precision and recovery standard (Section 10.1.3).
12.7.3.2Compute the concentration of only those pollutants or labeled compounds that failed the previous test (Section 12.7.3). If these compounds now pass, the extraction/concentration processes are in control and analysis of blanks and samples may proceed. If, however, any of the same compounds fail again, the extraction/concentration processes are not being performed properly for these compounds. In this event, correct the problem, re-extract the sample lot (Section 10) and repeat the on-going precision and recovery test (Section 12.7).
12.7.4Add results which pass the specifications in Section 12.7.2 to initial and previous on-going data. Update QC charts to perform a graphic representation of continued laboratory performance (Figure 5). Develop a statement of laboratory accuracy for each pollutant and labeled compound by calculating the average percent recovery (R) and the standard deviation of percent recovery (s
13.1Qualititative determination is accomplished by comparison of data from analysis of a sample or blank with data from analysis of the shift standard (Section 12.1) and with data stored in the spectral libraries (Section 7.2.4). Identification is confirmed when spectra and retention times agree per the criteria below.
13.2Labeled compounds and pollutants having no labeled analog:
13.2.1The signals for all characteristic masses stored in the spectral library (Section 7.2.4) shall be present and shall maximize within the same two consecutive scans.
13.2.2Either (1) the background corrected EICP areas, or (2) the corrected relative intensities of the mass spectral peaks at the GC peak maximum shall agree within a factor of two (0.5 to 2 times) for all masses stored in the library.
13.2.3The retention time relative to the nearest eluted internal standard shall be within ±15 scans or ±15 seconds, whichever is greater of this difference in the shift standard (Section 12.1).
13.3Pollutants having a labled analog:
13.3.1The signals for all characteristic masses stored in the spectral library (Section 7.2.4) shall be present and shall maximize within the same two consecutive scans.
13.3.2.Either (1) the background corrected EICP areas, or (2) the corrected relative intensities of the mass spectral peaks at the GC peak maximum shall agree within a factor of two for all masses stored in the spectral library.
13.3.3.The retention time difference between the pollutant and its labeled analog shall agree within ± 6 scans or ± 6 seconds (whichever is greater) of this difference in the shift standard (Section 12.1).
13.4Masses present in the experimental mass spectrum that are not present in the reference mass spectrum shall be accounted for by contaminant or background ions. If the experimental mass spectrum is contaminated, an experienced spectrometrist (Section 1.4) is to determine the presence or absence of the cmmpound.
14.1Isotope dilution—by adding a known amount of a labeled compound to every sample prior to extraction, correction for recovery of the pollutant can be made because the pollutant and its labeled analog exhibit the same effects upon extraction, concentration, and gas chromatography. Relative response (RR) values for mixtures are used in conjunction with calibration curves described in
14.2Internal standard—compute the concentration in the extract using the response factor determined from calibration data (Section 7.5) and the following equation: C
14.3The concentration of the pollutant in water is computed using the volumes of the original water sample (Section 10.1) and the final extract volume (Section 10.5), as follows: Concentration in water (μg/L)=(C
14.4If the EICP area at the quantitiation mass for any compound exceeds the calibration range of the system, the extract of the dilute aliquot (Section 10.1) is analyzed by isotope dilution; otherwise, the extract is diluted by a factor of 10, 9 μL of internal standard solution (Section 6.10) are added to a 1.0 mL aliquot, and this diluted extract is analyzed by the internal standard method (Section 14.2). Quantify each compound at the highest concentration level within the calibration range.
14.5Report results for all pollutants and labeled compounds (Tables 1 and 2) found in all standards, blanks, and samples in μg/L, to three significant figures. Results for samples which have been diluted are reported at the least dilute level at which the area at the quantitation mass is within the calibration range (Section 14.4) and the labeled compound recovery is within the normal range for the method (Section 15.4).
15.1Untreated effluents and other samples frequently contain high levels (>1000 μg/L) of the compounds of interest, interfering compounds, and/or polymeric materials. Some samples will not concentrate to one mL (Section 10.5); others will overload the GC column and/or mass spectrometer.
15.2Analyze the dilute aliquot (Section 10.1) when the sample will not concentrate to 1.0 mL. If a dilute aliquot was not extracted, and the sample holding time (Section 9.3) has not been exceeded, dilute an aliquot of the sample with reagent water and re-extract (Section 10.1); otherwise, dilute the extract (Section 14.4) and analyze by the internal standard method (Section 14.2).
15.3Recovery of internal standard— the EICP area of the internal standard should be within a factor of two of the area in the shift standard (Section 12.1). If the absolute areas of the labeled compounds are within a factor of two of the respective areas in the shift standard, and the internal standard area is less than one-half of its respective area, then internal standard loss in the extract has occurred. In this case, use one of the labeled compounds (perferably a polynuclear aromatic hydrocarbon) to compute the concentration of a pollutant with no labeled analog.
15.4Recovery of labeled compounds— in most samples, labeled compound recoveries will be similar to those from reagent water (Section 12.7). If the labeled compound recovery is outside the limits given in Table 8, the dilute extract (Section 10.1) is analyzed as in Section 14.4. If the recoveries of all labeled compounds and the internal staldard are low (per the criteria above), then a loss in instrument sensitivity is the most likely cause. In this case, the 100 μg/mL calibration standard (Section 12.1) shall be analyzed and calibration verified (Section 12.5). If a loss in sensitivity has occurred, the instrument shall be repaired, the performance specifications in Section 12 shall be met, and the extract reanalyzed. If a loss in instrument sensitivity has not occurred, the method does not work on the sample being analyzed and the result may not be reported for regulatory compliance purposes.
16.1Interlaboratory performance for this method is detailed in references 9 and 10.
16.2A chromatogram of the 100 μg/mL acid/base/neutral calibration standard (Section 6.13) is shown in Figure 6.
1. “Performance Tests for the Evaluation of Computerized Gas Chromatography/Mass Spectrometry Equipment and Laboratories” USEPA, EMSL/Cincinnati, OH 45268, EPA-600/4-80-025 (April 1980).
2. “Working with Carcinogens,” DHEW, PHS, CDC, NIOSH, Publication 77-206, (August 1977).
3. “OSHA Safety and Health Standards, General Industry” OSHA 2206, 29 CFR part 1910 (January 1976).
4. “Safety in Academic Chemistry Laboratories, ” ACS Committee on Chemical Safety (1979).
5. “Reference Compound to Calibrate Ion Abundance Measurement in Gas Chromatography-Mass Spectrometry Systems,” J.W. Eichelberger, L.E. Harris, and W.L. Budde, Anal. Chem.,
6. “Handbook of Analytical Quality Control in Water and Wastewater Laboratories,” USEPA, EMSL/Cincinnati, OH 45268, EPA-600/4-79-019 (March 1979).
7. “Standard Practice for Sampling Water,” ASTM Annual Book of Standards, ASTM, Philadelphia, PA, 76 (1980).
8. “Methods 330.4 and 330.5 for Total Residual Chlorine,” USEPA, EMSL/ Cincinnati, OH 45268, EPA 600/4-70-020 (March 1979).
9. Colby, B.N., Beimer, R.G., Rushneck, D.R., and Telliard, W.A., “Isotope Dilution Gas Chromatography-Mass Spectrometry for the determination of Priority Pollutants in Industrial Effluents.” USEPA, Effluent Guidelines Division, Washington, DC 20460 (1980).
10. “Inter-laboratory Validation of US Environmental Protection Agency Method 1625,” USEPA, Effluent Guidelines Division, Washington, DC 20460 (June 15, 1984).
To support measurement of several semivolatile pollutants, EPA has developed this attachment to EPA Method 1625B.
The additional semivolatile organic compounds listed in Tables 1 and 2 are added to all applicable calibration, spiking, and other solutions utilized in the determination of semivolatile compounds by EPA Method 1625. The instrument is to be calibrated with these compounds, and all procedures and quality control tests described in the Method must be performed.
All section and figure numbers in this Attachment reference section and figure numbers in EPA Method 1625 Revision B unless noted otherwise. Sections not listed here remain unchanged.
The method detection limit (MDL) is defined as the minimum concentration of a substance that can be measured and reported with 99% confidence that the analyte concentration is greater than zero and is determined from analysis of a sample in a given matrix containing the analyte.
This procedure is designed for applicability to a wide variety of sample types ranging from reagent (blank) water containing analyte to wastewater containing analyte. The MDL for an analytical procedure may vary as a function of sample type. The procedure requires a complete, specific, and well defined analytical method. It is essential that all sample processing steps of the analytical method be included in the determination of the method detection limit.
The MDL obtained by this procedure is used to judge the significance of a single measurement of a future sample.
The MDL procedure was designed for applicability to a broad variety of physical and chemical methods. To accomplish this, the procedure was made device- or instrument-independent.
1. Make an estimate of the detection limit using one of the following:
(a) The concentration value that corresponds to an instrument signal/noise in the range of 2.5 to 5.
(b) The concentration equivalent of three times the standard deviation of replicate instrumental measurements of the analyte in reagent water.
(c) That region of the standard curve where there is a significant change in sensitivity, i.e., a break in the slope of the standard curve.
(d) Instrumental limitations.
It is recognized that the experience of the analyst is important to this process. However, the analyst must include the above considerations in the initial estimate of the detection limit.
2. Prepare reagent (blank) water that is as free of analyte as possible. Reagent or interference free water is defined as a water sample in which analyte and interferent concentrations are not detected at the method detection limit of each analyte of interest. Interferences are defined as systematic errors in the measured analytical signal of an established procedure caused by the presence of interfering species (interferent). The interferent concentration is presupposed to be normally distributed in representative samples of a given matrix.
3. (a) If the MDL is to be determined in reagent (blank) water, prepare a laboratory standard (analyte in reagent water) at a concentration which is at least equal to or in the same concentration range as the estimated method detection limit. (Recommend between 1 and 5 times the estimated method detection limit.) Proceed to Step 4.
(b) If the MDL is to be determined in another sample matrix, analyze the sample. If the measured level of the analyte is in the recommended range of one to five times the estimated detection limit, proceed to Step 4.
If the measured level of analyte is less than the estimated detection limit, add a known amount of analyte to bring the level of analyte between one and five times the estimated detection limit.
If the measured level of analyte is greater than five times the estimated detection limit, there are two options.
(1) Obtain another sample with a lower level of analyte in the same matrix if possible.
(2) The sample may be used as is for determining the method detection limit if the analyte level does not exceed 10 times the MDL of the analyte in reagent water. The variance of the analytical method changes as the analyte concentration increases from the MDL, hence the MDL determined under these circumstances may not truly reflect method variance at lower analyte concentrations.
4. (a) Take a minimum of seven aliquots of the sample to be used to calculate the method detection limit and process each through the entire analytical method. Make all computations according to the defined method with final results in the method reporting units. If a blank measurement is required to calculate the measured level of analyte, obtain a separate blank measurement for each sample aliquot analyzed. The average blank measurement is subtracted from the respective sample measurements.
(b) It may be economically and technically desirable to evaluate the estimated method detection limit before proceeding with 4a. This will: (1) Prevent repeating this entire procedure when the costs of analyses are high and (2) insure that the procedure is being conducted at the correct concentration. It is quite possible that an inflated MDL will be calculated from data obtained at many times the real MDL even though the level of analyte is less than five times the calculated method detection limit. To insure that the estimate of the method detection limit is a good estimate, it is necessary to determine that a lower concentration of analyte will not result in a significantly lower method detection limit. Take two aliquots of the sample to be used to calculate the method detection limit and process each through the entire method, including blank measurements as described above in 4a. Evaluate these data:
(1) If these measurements indicate the sample is in desirable range for determination of the MDL, take five additional aliquots and proceed. Use all seven measurements for calculation of the MDL.
(2) If these measurements indicate the sample is not in correct range, reestimate the MDL, obtain new sample as in 3 and repeat either 4a or 4b.
5. Calculate the variance (S
6. (a) Compute the MDL as follows:
(b) The 95% confidence interval estimates for the MDL derived in 6a are computed according to the following equations derived from percentiles of the chi square over degrees of freedom distribution (
7. Optional iterative procedure to verify the reasonableness of the estimate of the MDL and subsequent MDL determinations.
(a) If this is the initial attempt to compute MDL based on the estimate of MDL formulated in Step 1, take the MDL as calculated in Step 6, spike the matrix at this calculated MDL and proceed through the procedure starting with Step 4.
(b) If this is the second or later iteration of the MDL calculation, use S
(c) Use the S
(d) The 95% confidence limits for MDL derived in 7c are computed according to the following equations derived from precentiles of the chi squared over degrees of freedom distribution.
The analytical method used must be specifically identified by number or title ald the MDL for each analyte expressed in the appropriate method reporting units. If the analytical method permits options which affect the method detection limit, these conditions must be specified with the MDL value. The sample matrix used to determine the MDL must also be identified with MDL value. Report the mean analyte level with the MDL and indicate if the MDL procedure was iterated. If a laboratory standard or a sample that contained a known amount analyte was used for this determination, also report the mean recovery.
If the level of analyte in the sample was below the determined MDL or exceeds 10 times the MDL of the analyte in reagent water, do not report a value for the MDL.
1.1This method may be used for the determination of dissolved, suspended, or total elements in drinking water, surface water, and domestic and industrial wastewaters.
1.2Dissolved elements are determined in filtered and acidified samples. Appropriate steps must be taken in all analyses to ensure that potential interferences are taken into account. This is especially true when dissolved solids exceed 1500 mg/L. (See Section 5.)
1.3Total elements are determined after appropriate digestion procedures are performed. Since digestion techniques increase the dissolved solids content of the samples, appropriate steps must be taken to correct for potential interference effects. (See Section 5.)
1.4Table 1 lists elements for which this method applies along with recommended wavelengths and typical estimated instrumental detection limits using conventional pneumatic nebulization. Actual working detection limits are sample dependent and as the sample matrix varies, these concentrations may also vary. In time, other elements may be added as more information becomes available and as required.
1.5Because of the differences between various makes and models of satisfactory instruments, no detailed instrumental operating instructions can be provided. Instead, the analyst is referred to the instruction provided by the manufacturer of the particular instrument.
2.1The method describes a technique for the simultaneous or sequential multielement determination of trace elements in solution. The basis of the method is the measurement of atomic emission by an optical spectroscopic -technique. Samples are nebulized and the aero-sol that is produced is trans-ported to the plasma torch where excitation occurs. Characteristic atomic-line emission spectra are produced by a radio-frequency inductively coupled plasma (ICP). The spectra are dispersed by a grating spectrometer and the intensities of the lines are monitored by photomultiplier tubes. The photocurrents from the photomultiplier tubes are processed and controlled by a computer system. A background correction technique is required to compensate for variable background contribution to the determination of trace elements. Background must be measured adjacent to analyte lines on samples during analysis. The position selected for the background intensity measurement, on either or both sides of the analytical line, will be determined by the complexity of the spectrum adjacent to the analyte line. The position used must be free of spectral interference and reflect the same change in background intensity as occurs at the analyte wavelength measured. Background correction is not required in cases of line broadening where a background correction measure-ment would actually degrade the analyti-cal result. The possibility of additional interferences named in 5.1 (and tests for their presence as described in 5.2) should also be recognized and appropriate corrections made.
3.1
3.2
3.3
3.4
3.5
3.6
3.7
3.8
3.9
3.10
3.11
3.12
3.13
3.14
4.1The toxicity of carcinogenicity of each reagent used in this method has not been precisely defined; however, each chemical compound should be treated as a potential health hazard. From this viewpoint, exposure to these chemicals must be reduced to the lowest possible level by whatever means available. The laboratory is repsonsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method. A reference file of material data handling sheets should also be made available to all personnel involved in the chemical analysis. Additional references to laboratory safety are available and have been identified
5.1Several types of interference effects may contribute to inaccuracies in the determination of trace elements. They can be summarized as follows:
5.1.1
Only those interferents listed were investigated and the blank spaces in Table 2 indicate that measurable interferences were not observed for the interferent concentrations listed in Table 3. Generally, interferences were discernible if they produced peaks or background shifts corresponding to 2-5% of the peaks generated by the analyte concentrations also listed in Table 3.
At present, information on the listed silver and potassium wavelengths are not available but it has been reported that second order energy from the magnesium 383.231 nm wavelength interferes with the listed potassium line at 766.491 nm.
5.1.2
5.1.3
5.2It is recommended that whenever a new or unusual sample matrix is encountered, a series of tests be performed prior to reporting concentration data for analyte elements. These tests, as outlined in 5.2.1 through 5.2.4, will ensure the analyst that neither positive nor negative interference effects are operative on any of the analyte elements thereby distorting the accuracy of the reported values.
5.2.1
5.2.2
5.2.3
5.2.4
6.1Inductively Coupled Plasma-Atomic Emission Spectrometer.
6.1.1Computer controlled atomic emission spectrometer with background correction.
6.1.2Radiofrequency generator.
6.1.3Argon gas supply, welding grade or better.
6.2Operating conditions—Because of the differences between various makes and models of satisfactory instruments, no detailed operating instructions can be provided. Instead, the analyst should follow the instructions provided by the manufacturer of the particular instrument. Sensitivity, instrumental detection limit, precision, linear dynamic range, and interference effects must be investigated and established for each individual analyte line on that particular instrument. It is the responsibility of the analyst to verify that the instrument configuration and operating conditions used satisfy the analytical requirements and to maintain quality control data confirming instrument performance and analytical results.
7.1Acids used in the preparation of standards and for sample processing must be ultra-high purity grade or equivalent. Redistilled acids are acceptable.
7.1.1
7.1.2
7.1.3
7.1.4
7.1.5
7.2
7.3
(CAUTION: Many metal salts are extremely toxic and may be fatal if swallowed. Wash hands thoroughly after handling.)
Typical stock solution preparation procedures follow:
7.3.1
7.3.2
7.3.3
7.3.4
7.3.5
7.3.6
7.3.7
7.3.8
7.3.9
7.3.10
7.3.11
7.3.12
7.3.13
7.3.14
7.3.15
7.3.16
7.3.17
7.3.18
7.3.19
7.3.20
7.3.21
7.3.22
7.3.23
7.3.24
7.3.25
7.4
7.4.1
7.4.2
7.4.3
7.4.4
7.4.5
1. If the addition of silver to the recommended acid combination results in an initial precipitation, add 15 mL of deionized distilled water and warm the flask until the solution clears. Cool and dilute to 100 mL with deionized, distilled water. For this acid combination the silver concentration should be limited to 2 mg/L. Silver under these conditions is stable in a tap water matrix for 30 days. Higher concentrations of silver require additional HCl.
7.5Two types of blanks are required for the analysis. The calibration blank (3.13) is used in establishing the analytical curve while the reagent blank (3.12) is used to correct for possible contamination resulting from varying amounts of the acids used in the sample processing.
7.5.1
7.5.2
7.6In addition to the calibration standards, an instrument check standard (3.7), an interference check sample (3.8) and a quality control sample (3.9) are also required for the analyses.
7.6.1The
7.6.2The
7.6.3The
8.1For the determination of trace elements, contamination and loss are of prime concern. Dust in the laboratory environment, impurities in reagents and impurities on laboratory apparatus which the sample contacts are all sources of potential contamination. Sample containers can introduce either positive or negative errors in the measurement of trace elements by (a) contributing contaminants through leaching or surface desorption and (b) by depleting concentrations through adsorption. Thus the collection and treatment of the sample prior to analysis requires particular attention. Laboratory glassware including the sample bottle (whether polyethylene, polyproplyene or FEP-fluorocarbon) should be thoroughly washed with detergent and tap water; rinsed with (1+1) nitric acid, tap water, (1+1) hydrochloric acid, tap and finally deionized, distilled water in that order (See Notes 2 and 3).
2. Chromic acid may be useful to remove organic deposits from glassware; however, the analyst should be cautioned that the glassware must be thoroughly rinsed with water to remove the last traces of chromium. This is especially important if -chromium is to be included in the analytical scheme. A commercial product, NOCHROMIX, -available from Godax Laboratories, -6 Varick St., New York, NY 10013, may -be used in place of chromic acid. Chromic acid should not be used with plastic bottles.
3. If it can be documented through an active analytical quality control program using spiked samples and reagent blanks, that certain steps in the cleaning procedure are not required for routine samples, those steps may be eliminated from the procedure.
8.2Before collection of the sample a decision must be made as to the type of data desired, that is dissolved, suspended or total, so that the appropriate preservation and pretreatment steps may be accomplished. Filtration, acid preservation, etc., are to be performed at the time the sample is collected or as soon as possible thereafter.
8.2.1For the determination of dissolved elements the sample must be filtered through a 0.45-μm membrane filter as soon as practical after collection. (Glass or plastic filtering apparatus are recommended to avoid possible contamination.) Use the first 50-100 mL to rinse the filter flask. Discard this portion and collect the required volume of filtrate. Acidify the filtrate with (1+1) HNO
8.2.2For the determination of suspended elements a measured volume of unpreserved sample must be filtered through a 0.45-μm membrane filter as soon as practical after collection. The filter plus suspended material should be transferred to a suitable container for storage and/or shipment. No preservative is required.
8.2.3For the determination of total or total recoverable elements, the sample is acidified with (1+1) HNO
9.1For the determinations of dissolved elements, the filtered, preserved sample may often be analyzed as received. The acid matrix and concentration of the samples and calibration standards must be the same. (See Note 6.) If a precipitate formed upon acidification of the sample or during transit or storage, it must be redissolved before the analysis by adding additional acid and/or by heat as described in 9.3.
9.2For the determination of suspended elements, transfer the membrane filter containing the insoluble material to a 150-mL Griffin beaker and add 4 mL conc. HNO
4. In place of filtering, the sample after diluting and mixing may be centrifuged or allowed to settle by gravity overnight to remove insoluble material.
9.3For the determination of total elements, choose a measured volume of the well mixed acid preserved sample appropriate for the expected level of elements and transfer to a Griffin beaker. (See Note 5.) Add 3 mL of conc. HNO
5. If low determinations of boron are critical, quartz glassware should be used.
6. If the sample analysis solution has a different acid concentration from that given in 9.4, but does not introduce a physical interference or affect the analytical result, the same calibration standards may be used.
9.4For the determination of total recoverable elements, choose a measured volume of a well mixed, acid preserved sample appropriate for the expected level of elements and transfer to a Griffin beaker. (See Note 5.) Add 2 mL of (1+1) HNO
10.1Set up instrument with proper operating parameters established in Section 6.2. The instrument must be allowed to become thermally stable before beginning. This usually requires at least 30 min. of operation prior to calibration.
10.2Initiate appropriate operating configuration of computer.
10.3Profile and calibrate instrument according to instrument manufacturer's recommended procedures, using the typical mixed calibration standard solutions described in Section 7.4. Flush the system with the calibration blank (7.5.1) between each standard. (See Note 7.) (The use of the average intensity of multiple exposures for both standardization and sample analysis has been found to reduce random error.)
7. For boron concentrations greater than 500 μg/L extended flush times of 1 to 2 minutes may be required.
10.4Before beginning the sample run, reanalyze the highest mixed calibration standard as if it were a sample. Concentration values obtained should not deviate from the actual values by more than ±5 percent (or the established control limits whichever is lower). If they do, follow the recommendations of the instrument manufacturer to correct for this condition.
10.5Begin the sample run flushing the system with the calibration blank solution (7.5.1) between each sample. (See Note 7.) Analyze the instrument check standard (7.6.1) and the calibration blank (7.5.1) each 10 samples.
10.6If it has been found that methods of standard addition are required, the following procedure is recommended.
10.6.1The standard addition technique (14.2) involves preparing new standards in the sample matrix by adding known amounts of standard to one or more aliquots of the processed sample solution. This technique compensates for a sample constitutent that enhances or depresses the analyte signal thus producing a different slope from that of the calibration standards. It will not correct for additive interference which causes a baseline shift. The simplest version of this technique is the single-addition method. The procedure is as follows. Two identical aliquots of the sample solution, each of volume V
1. The analytical curve must be linear.
2. The chemical form of the analyte added must respond the same as the analyte in the sample.
3. The interference effect must be constant over the working range of concern.
4. The signal must be corrected for any additive interference.
11.1Reagent blanks (7.5.2) should be subtracted from all samples. This is particularly important for digested samples requiring large quantities of acids to complete the digestion.
11.2If dilutions were performed, the appropriate factor must be applied to sample values.
11.3Data should be rounded to the thousandth place and all results should be reported in mg/L up to three significant figures.
12.1Check the instrument standardization by analyzing appropriate quality control check standards as follow:
12.1.1Analyze and appropriate instrument check standard (7.6.1) containing the elements of interest at a frequency of 10%. This check standard is used to determine instrument drift. If agreement is not within ±5% of the expected values or within the established control limits, whichever is lower, the analysis is out of control. The analysis should be terminated, the problem corrected, and the instrument recalibrated.
Analyze the calibration blank (7.5.1) at a frequency of 10%. The result should be within the established control limits of 2 standard deviations of the meal value. If not, repeat the analysis two more times and average the three results. If the average is not wihin the control limit, terminate the analysis, correct the problem and recalibrate the instrument.
12.1.2To verify interelement and background correction factors analyze the interference check sample (7.6.2) at the beginning,
12.1.3 A quality control sample (7.6.3) obtained from an outside source must first be used for the initial verification of the calibration standards. A fresh dilution of this sample shall be analyzed every week thereafter to monitor their stability. If the results are not within ±5% of the true value listed for the control sample, prepare a new calibration standard and recalibrate the instrument. If this does not correct the problem, prepare a new stock standard and a new calibration standard and repeat the calibration.
13.1An interlaboratory study of metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of the twenty-five elements listed in Table 4 were added to reagent water, surface water, drinking water and three effluents. These samples were digested by both the total digestion procedure (9.3) and the total recoverable procedure (9.4). Results for both digestions for the twenty-five elements in reagent water are given in Table 4; results for the other matrices can be found in Reference 14.10.
14.1Winge, R.K., V.J. Peterson, and V.A. Fassel, “Inductively Coupled Plasma-Atomic Emission Spectroscopy: Prominent Lines, EPA-600/4-79-017.
14.2Winefordner, J.D., “Trace Analysis: Spectroscopic Methods for Elements,”
14.3Handbook for Analytical Quality Control in Water and Wastewater Laboratories, EPA-600/4-79-019.
14.4Garbarino, J.R. and Taylor, H.E., “An Inductively-Coupled Plasma Atomic Emission Spectrometric Method for Routine Water Quality Testing,” Applied Spectroscopy
14.5“Methods for Chemical Analysis of Water and Wastes,” EPA-600/4-79-020.
14.6Annual Book of ASTM Standards, Part 31.
14.7“Carcinogens—Working With Carcinogens,” Department of Health, Education, and Welfare, Public Health Service, Center for Disease Control, National Institute for Occupational Safety and Health, Publication No. 77-206, August 1977.
14.8“OSHA Safety and Health Standards, General Industry,” (29 CFR Part 1910), Occupational Safety and Health Administration, OSHA 2206, (Revised, January 1976).
14.9“Safety in Academic Chemistry Laboratories, American Chemical Society Publication, Committee on Chemical Safety, 3rd Edition, 1979.
14.10Maxfield R. and Minak B., “EPA Method Study 27, Method 200.7 Trace Metals by ICP,” National Technical Information Service, Order No. PB 85-248-656, November 1983.
Twenty-eight selected methods from “Methods for Chemical Analysis of Water and Wastes,” EPA-600/4-79-020 (1979) have been subjected to interlaboratory method validation studies. The following precision and recovery statements are presented in this appendix and incorporated into part 136:
For Aluminum, Method 202.1 (Atomic Absorption, Direct Aspiration) replace the Precision and Accuracy Section with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the -En-vi-ronmental Monitoring Systems Labora-tory—Cincinnati (EMSL-CI). Synthetic concen-trates -containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. The digestion procedure was not specified. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7, Analyses for Trace Methods in water by Atomic Absorption Spectroscopy (Direction Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and Britton, P.W., June, 1986.
For a concentration range of 500-1200 μg/L
For Arsenic, Method 206.4 (Spectrophotometric--SDDC) add the following to the Precision and Accuracy Section:
An interlaboratory study on metal anal-yses by this method was conducted by -the Quality Assurance Branch (QAB) of the -Environmental Monitoring Systems Labor-a-tory—Cincinnati (EMSL-CI). Synthetic concentrates -containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7, Analyses for Trace Methods in Water by Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and Britton, P.W., June, 1986.
For a concentration range of 20-292 -μg/L
For Cadmium, Method 213.1 (Atomic Absorption, Direct Aspiration) replace the Precision and Accuracy Section with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. The digestion procedure was not specified. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7, Analyses for Trace Methods in Water by Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and Britton, P.W., June, 1986.
For a concentration range of 14-78 μg/L
For Chromium, Method 218.1 (Atomic Absorption, Direct Aspiration) replace the Precision and Accuracy Section with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. The digestion procedure was not specified. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7, Analyses for Trace Methods in Water by Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and Britton, P.W., June 1986.
For a concentration range of 74-407 μg/L
For Copper, Method 220.1 (Atomic Absorption, Direct Aspiration) replace the Precision and Accuracy Section with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. The digestion procedure was not specified. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7, Analyses for Trace Methods in Water by Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and Britton, P.W., June, 1986.
For concentration range 60-332 μg/L
For Iron, Method 236.1 (Atomic Absorption, Direct Aspiration) replace the Precision and Accuracy Section with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. The digestion procedure was not specified. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7, Analyses for Trade Methods in Water by Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and Britton, P.W., June, 1986.
For concentration range 350-840 μg/L
For Lead, Method 239.1 (Atomic Absorption, Direct Aspiration) replace Precision and Accuracy Section with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. The digestion procedure was not specified. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7 Analyses for Trace Methods in Water by Atomic Absorption Spectroscopy
For concentration range of 84-367 μg/L
For Manganese, Method 243.1 (Atomic Absorption, Direct Aspiration) replace Precision and Accuracy Section with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. The digestion procedure was not specified. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7, Analyses for Trace Methods in Water by Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J.A. and Britton, P.W., June, 1986.
For concentration range 84-469 μg/L
For Zinc, Method 289.1 (Atomic Absorption, Direct Aspiration) replace the Precision and Accuracy Section with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water and a natural water or effluent of the analyst's choice. The digestion procedure was not specified. Results for the reagent water are given below. Results for other water types and study details are found in “USEPA Method Study 7, Analyses for Trace Methods in Water by Atomic Absorption Spectroscopy (Direct Aspiration) and Colorimetry”, National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB86-208709/AS, Winter, J. A. and Britton, P. W., June, 1986.
For Aluminum, Method 202.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques), “National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Antimony, Method 204.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual as modified by this method. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Arsenic, Method 206.2 (Atomic Absorption, Furnace Technique) add the following to the existing Precision and Accuracy statement:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Barium, Method 208.2 (Atomic Absorption, Furnace Technique) add the following to the existing Precision and Accuracy information:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Beryllium, Method 210.2 (Atomic Absorption, Furnace Technique) replace the existing Precision and Accuracy statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31,
For Cadmium, Method 213.2 (Atomic Absorption, Furnace Technique) add the following to the existing Precision and Accuracy information:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring System Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Chromium, Method 218.2 (Atomic Absorption, Furnace Technique) add the following to the existing Precision and Accuracy Section:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161, Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Cobalt, Method 219.2 (Atomic Absorption, Furnace Technique), replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Copper, Method 220.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Iron, Method 236.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Lead, Method 239.2 (Atomic Absorption, Furnace Technique) add the following to the existing Precisions and Accuracy Section:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Manganese, Method 243.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL—CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents.
For Nickel, Method 249.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL—CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161. Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Selenium, Method 270.2 (Atomic Absorption, Furnace Technique) add the following to the existing Precision and Accuracy Section:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL—CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161. Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Silver, Method 272.2 (Atomic Absorption, Furnace Technique) add the following to the existing Precision and Accuracy Section:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory—Cincinnati (EMSL—CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161. Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Thalliu, Method 279.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Vanadium, Method 286.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
For Zinc, Method 289.2 (Atomic Absorption, Furnace Technique) replace the Precision and Accuracy Section statement with the following:
An interlaboratory study on metal analyses by this method was conducted by the Quality Assurance Branch (QAB) of the Environmental Monitoring Systems Laboratory-Cincinnati (EMSL-CI). Synthetic concentrates containing various levels of this element were added to reagent water, surface water, drinking water and three effluents. These samples were digested by the total digestion procedure, 4.1.3 in this manual. Results for the reagent water are given below. Results for other water types and study details are found in “EPA Method Study 31, Trace Metals by Atomic Absorption (Furnace Techniques),” National Technical Information Service, 5285 Port Royal Road, Springfield, VA 22161 Order No. PB 86-121 704/AS, by Copeland, F.R. and Maney, J.P., January 1986.
33 U.S.C. 1322, as amended.
For the purpose of these standards the following definitions shall apply:
(a)
(b)
(c)
(d)
(e)
(f)
(g)
The standard adopted herein applies only to vessels on which a marine sanitation device has been installed. The standard does not require the installation of a marine sanitation device on any vessel that is not so equipped. The standard applies to vessels owned and operated by the United States unless the Secretary of Defense finds that compliance would not be in the interest of national security.
(a) (1) In freshwater lakes, freshwater reservoirs or other freshwater impoundments whose inlets or outlets are such as to prevent the ingress or egress by vessel traffic subject to this regulation, or in rivers not capable of navigation by interstate vessel traffic subject to this regulation, marine sanitation devices certified by the U.S. Coast Guard (see 33 CFR part 159, published in 40 FR 4622, January 30, 1975), installed on all vessels shall be designed and operated to prevent the overboard discharge of sewage, treated or untreated, or of any waste derived from sewage. This shall not be construed to prohibit the carriage of Coast Guard-certified flow-through treatment devices which have been secured so as to prevent such discharges.
(2) In all other waters, Coast Guard-certified marine sanitation devices installed on all vessels shall be designed and operated to either retain, dispose of, or discharge sewage. If the device has a discharge, subject to paragraph (d) of this section, the effluent shall not have a fecal coliform bacterial count of greater than 1,000 per 100 milliliters nor visible floating solids. Waters where a Coast Guard-certified marine sanitation device permitting discharge is allowed include coastal waters and estuaries, the Great Lakes and inter-connected waterways, fresh-water lakes and impoundments accessible through locks, and other flowing waters that are navigable interstate by vessels subject to this regulation.
(b) This standard shall become effective on January 30, 1977 for new vessels and on January 30, 1980 for existing vessels (or, in the case of vessels owned and operated by the Department of Defense, two years and five years, for new and existing vessels, respectively, after promulgation of implementing regulations by the Secretary of Defense under section 312(d) of the Act).
(c) Any vessel which is equipped as of the date of promulgation of this regulation with a Coast Guard-certified flow-through marine sanitation device meeting the requirements of paragraph (a)(2) of this section, shall not be required to comply with the provisions designed to prevent the overboard discharge of sewage, treated or untreated, in paragraph (a)(1) of this section, for the operable life of that device.
(d) After January 30, 1980, subject to paragraphs (e) and (f) of this section, marine sanitation devices on all vessels on waters that are not subject to a prohibition of the overboard discharge
(e) Any existing vessel on waters not subject to a prohibition of the overboard discharge of sewage in paragraph (a)(1) of this section, and which is equipped with a certified device on or before January 30, 1978, shall not be required to comply with paragraph (d) of this section, for the operable life of that device.
(f) Any new vessel on waters not subject to the prohibition of the overboard discharge of sewage in paragraph (a)(1) of this section, and on which construction is initiated before January 31, 1980, which is equipped with a marine sanitation device before January 31, 1980, certified under paragraph (a)(2) of this section, shall not be required to comply with paragraph (d) of this section, for the operable life of that device.
(g) The degrees of treatment described in paragraphs (a) and (d) of this section are “appropriate standards” for purposes of Coast Guard and Department of Defense certification pursuant to section 312(g)(2) of the Act.
(a) Prohibition pursuant to CWA section 312(f)(3): a State may completely prohibit the discharge from all vessels of any sewage, whether treated or not, into some or all of the waters within such State by making a written application to the Administrator, Environmental Protection Agency, and by receiving the Administrator's affirmative determination pursuant to section 312(f)(3) of the Act. Upon receipt of an application under section 312(f)(3) of the Act, the Administrator will determine within 90 days whether adequate facilities for the safe and sanitary removal and treatment of sewage from all vessels using such waters are reasonably available. Applications made by States pursuant to section 312(f)(3) of the Act shall include:
(1) A certification that the protection and enhancement of the waters described in the petition require greater environmental protection than the applicable Federal standard;
(2) A map showing the location of commercial and recreational pump-out facilities;
(3) A description of the location of pump-out facilities within waters designated for no discharge;
(4) The general schedule of operating hours of the pump-out facilities;
(5) The draught requirements on vessels that may be excluded because of insufficient water depth adjacent to the facility;
(6) Information indicating that treatment of wastes from such pump-out facilities is in conformance with Federal law; and
(7) Information on vessel population and vessel usage of the subject waters.
(b) Prohibition pursuant to CWA section 312(f)(4)(A): a State may make a written application to the Administrator, Environmental Protection Agency, under section 312(f)(4)(A) of the Act, for the issuance of a regulation completely prohibiting discharge from a vessel of any sewage, whether treated or not, into particular waters of the United States or specified portions thereof, which waters are located within the boundaries of such State. Such application shall specify with particularly the waters, or portions thereof, for which a complete prohibition is desired. The application shall include identification of water recreational areas, drinking water intakes, aquatic sanctuaries, identifiable fish-spawning and nursery areas, and areas of intensive boating activities. If, on the basis of the State's application and any other information available to him, the Administrator is unable to make a finding that the waters listed in the application require a complete prohibition of any discharge in the waters or portions thereof covered by the application, he shall state the reasons why he cannot make such a finding, and shall deny the application. If the Administrator makes a finding that the waters listed in the application require a complete prohibition of any
(1) For the following waters the discharge from a vessel of any sewage (whether treated or not) is completely prohibited pursuant to CWA section 312(f)(4)(A):
(i) Boundary Waters Canoe Area, formerly designated as the Superior, Little Indian Sioux, and Caribou Roadless Areas, in the Superior National Forest, Minnesota, as described in 16 U.S.C. 577-577d1.
(ii) Waters of the State of Florida within the boundaries of the Florida Keys National Marine Sanctuary as delineated on a map of the Sanctuary at
(c)(1)
(i) Identify and describe exactly and in detail the location of the drinking water supply intake(s) and the community served by the intake(s), including average and maximum expected amounts of inflow;
(ii) Specify and describe exactly and in detail, the waters, or portions thereof, for which a complete prohibition is desired, and where appropriate, average, maximum and low flows in million gallons per day (MGD) or the metric equivalent;
(iii) Include a map, either a USGS topographic quadrant map or a NOAA nautical chart, as applicable, clearly marking by latitude and longitude the waters or portions thereof to be designated a drinking water intake zone; and
(iv) Include a statement of basis justifying the size of the requested drinking water intake zone, for example, identifying areas of intensive boating activities.
(2) If the Administrator finds that a complete prohibition is appropriate under this paragraph, he or she shall publish notice of such finding together with a notice of proposed rulemaking, and then shall proceed in accordance with 5 U.S.C. 553. If the Administrator's finding is that a complete prohibition covering a more restricted or more expanded area than that applied for by the State is appropriate, he or she shall also include a statement of the reasons why the finding differs in scope from that requested in the State's application.
(3) If the Administrator finds that a complete prohibition is inappropriate under this paragraph, he or she shall deny the application and state the reasons for such denial.
(4) For the following waters the discharge from a vessel of any sewage, whether treated or not, is completely prohibited pursuant to CWA section 312(f)(4)(B):
(i) Two portions of the Hudson River in New York State, the first is bounded by an east-west line through the most northern confluence of the Mohawk River which will be designated by the Troy-Waterford Bridge (126th Street Bridge) on the south and Lock 2 on the north, and the second of which is bounded on the north by the southern end of Houghtaling Island and on the south by a line between the Village of Roseton on the western shore and Low Point on the eastern shore in the vicinity of Chelsea, as described in Items 2 and 3 of 6 NYCRR Part 858.4.
(ii) [Reserved]
In determining the composition and quality of effluent discharge from marine sanitation devices, the procedures contained in 40 CFR part 136, “Guidelines Establishing Test Procedures for the Analysis of Pollutants,” or subsequent revisions or amendments thereto, shall be employed.
42 U.S.C. 300f, 300g-1, 300g-2, 300g-3, 300g-4, 300g-5, 300g-6, 300j-4, 300j-9, and 300j-11.
For community water systems serving 75,000 or more persons,monitoring must begin 1 year following promulation and the effective date of the MCL is 2 years following promulgation. For community water systems serving 10,000 to 75,000 persons, monitoring must begin within 3 years from the date of promulgation and the effective date of the MCL is 4 years from the date of promulgation. Effective immediately, systems that plan to make significant modifications to their treatment processes for the purpose of complying with the TTHM MCL are required to seek and obtain State approval of their treatment modification plans. This note affects §§ 141.2, 141.6, 141.12, 141.24 and 141.30. For additional information see 44 FR 68641, Nov. 29, 1979.
This part establishes primary drinking water regulations pursuant to section 1412 of the Public Health Service Act, as amended by the Safe Drinking Water Act (Pub. L. 93-523); and related regulations applicable to public water systems.
As used in this part, the term:
(1) The water is used exclusively for purposes other than residential uses (consisting of drinking, bathing, and cooking, or other similar uses);
(2) The State determines that alternative water to achieve the equivalent level of public health protection provided by the applicable national primary drinking water regulation is provided for residential or similar uses for drinking and cooking; or
(3) The State determines that the water provided for residential or similar uses for drinking, cooking, and bathing is centrally treated or treated at the point of entry by the provider, a pass-through entity, or the user to achieve the equivalent level of protection provided by the applicable national primary drinking water regulations.
This part shall apply to each public water system, unless the public water system meets all of the following conditions:
(a) Consists only of distribution and storage facilities (and does not have any collection and treatment facilities);
(b) Obtains all of its water from, but is not owned or operated by, a public water system to which such regulations apply:
(c) Does not sell water to any person; and
(d) Is not a carrier which conveys passengers in interstate commerce.
(a) Variances or exemptions from certain provisions of these regulations may be granted pursuant to sections 1415 and 1416 of the Act and subpart K of part 142 of this chapter (for small system variances) by the entity with primary enforcement responsibility, except that variances or exemptions from the MCL for total coliforms and variances from any of the treatment technique requirements of subpart H of this part may not be granted.
(b) EPA has stayed the effective date of this section relating to the total coliform MCL of § 141.63(a) for systems that demonstrate to the State that the violation of the total coliform MCL is
Before a person may enter into a financial commitment for or initiate construction of a new public water system or increase the capacity of an existing public water system, he shall notify the State and, to the extent practicable, avoid locating part or all of the new or expanded facility at a site which:
(a) Is subject to a significant risk from earthquakes, floods, fires or other disasters which could cause a breakdown of the public water system or a portion thereof; or
(b) Except for intake structures, is within the floodplain of a 100-year flood or is lower than any recorded high tide where appropriate records exist. The U.S. Environmental Protection Agency will not seek to override land use decisions affecting public water systems siting which are made at the State or local government levels.
(a) Except as provided in paragraphs (b) through (k) of this section, and in § 141.80(a)(2), the regulations set forth in this part shall take effect on June 24, 1977.
(b) The regulations for total tri-hal-o-methanes set forth in § 141.12(c) shall -take effect 2 years after the date of pro-mul-gation of these regulations for community water systems serving 75,000 or more individuals, and 4 years after the date of promulgation for communities serving 10,000 to 74,999 individuals.
(c) The regulations set forth in §§ 141.11(d); 141.21(a), (c) and (i); 141.22(a) and (e); 141.23(a)(3) and (a)(4); 141.23(f); 141.24(e) and (f); 141.25(e); 141.27(a); 141.28(a) and (b); 141.31(a), (d) and (e); 141.32(b)(3); and 141.32(d) shall take effect immediately upon promulgation.
(d) The regulations set forth in § 141.41 shall take effect 18 months from the date of promulgation. Suppliers must complete the first round of sampling and reporting within 12 months following the effective date.
(e) The regulations set forth in § 141.42 shall take effect 18 months from the date of promulgation. All requirements in § 141.42 must be completed within 12 months following the effective date.
(f) The regulations set forth in § 141.11(c) and § 141.23(g) are effective May 2, 1986. Section 141.23(g)(4) is effective October 2, 1987.
(g) The regulations contained in § 141.6, paragraph (c) of the table in 141.12, and 141.62(b)(1) are effective July 1, 1991. The regulations contained in §§ 141.11(b), 141.23, 141.24, 142.57(b), 143.4(b)(12) and (b)(13), are effective July 30, 1992. The regulations contained in the revisions to §§ 141.32(e) (16), (25) through (27) and (46); 141.61(c)(16); and 141.62(b)(3) are effective January 1, 1993. The effective date of regulations contained in § 141.61(c) (2), (3), and (4) is postponed.
(h) Regulations for the analytic methods listed at § 141.23(k)(4) for measuring antimony, beryllium, cyanide, nickel, and thallium are ef-fective August 17, 1992. Regulations -for the analytic methods listed at -§ 141.24(f)(16) for dichloromethane, 1,2,4-tri-chlor-o-benzene, and 1,1,2-tri-chlor-o-ethane are effective August 17, 1992. Regulations for the analytic methods listed at § 141.24(h)(12) for measuring dalapon, dinoseb, diquat, endothall, endrin, glyphosate, oxamyl, picloram, simazine, benzo(a)pyrene, di(2-ethylhexyl)adipate, di(2-ethylhexyl)ph-thalate, hex-a-chlor-o-ben-zene, hexachlorocyclopentadiene, and 2,3,7,8-TCDD are effective August 17, 1992. The revision to § 141.12(a) promulgated on July 17, 1992 is effective on August 17, 1992.
(i) [Reserved]
(j) The arsenic maximum contaminant levels (MCL) listed in § 141.62 is effective for the purpose of compliance on January 23, 2006. Requirements relating to arsenic set forth in §§ 141.23(i)(4), 141.23(k)(3) introductory text, 141.23(k)(3)(ii), 141.51(b), 141.62(b), 141.62(b)(16), 141.62(c), 141.62(d), and
(k) Regulations set forth in §§ 141.23(i)(1), 141.23(i)(2), 141.24(f)(15), 141.24(f)(22), 141.24(h)(11), 141.24(h)(20), 142.16(e), 142.16(j), and 142.16(k) are effective for the purpose of compliance on January 22, 2004.
(a) The maximum contaminant level for arsenic applies only to community water systems. The analyses and determination of compliance with the 0.05 milligrams per liter maximum contaminant level for arsenic use the requirements of § 141.23.
(b) The maximum contaminant level for arsenic is 0.05 milligrams per liter for community water systems until January 23, 2006.
(c) [Reserved]
(d) At the discretion of the State, nitrate levels not to exceed 20 mg/l may be allowed in a non-community water system if the supplier of water demonstrates to the satisfaction of the State that:
(1) Such water will not be available to children under 6 months of age; and
(2) The non-community water system is meeting the public notification requirements under § 141.209, including continuous posting of the fact that nitrate levels exceed 10 mg/l and the potential health effects of exposure; and
(3) Local and State public health authorities will be notified annually of nitrate levels that exceed 10 mg/l; and
(4) No adverse health effects shall result.
The maximum contaminant level of 0.10 mg/L for total trihalomethanes (the sum of the concentrations of bromodichloromethane, dibromochloromethane, tribromomethane (bromoform), and trichloromethane (chloroform)) applies to subpart H community water systems which serve a population of 10,000 people or more until December 31, 2001. This level applies to community water systems that use only ground water not under the direct influence of surface water and serve a population of 10,000 people or more until December 31, 2003. Compliance with the maximum contaminant level for total trihalomethanes is calculated pursuant to § 141.30. After December 31, 2003, this section is no longer applicable.
The maximum contaminant levels for turbidity are applicable to both community water systems and non-community water systems using surface water sources in whole or in part. The maximum contaminant levels for turbidity in drinking water, measured at a representative entry point(s) to the distribution system, are:
At 54 FR 27527, June 29, 1989, § 141.13 was amended by adding introductory text, effective December 31, 1990, however, introductory text already exists. The added text follows.
The requirements in this section apply to unfiltered systems until December 30, 1991, unless the State has determined prior to that date, in writing pursuant to § 1412(b)(7)(C)(iii), that filtration is required. The requirements
(a) One turbidity unit (TU), as determined by a monthly average pursuant to § 141.22, except that five or fewer turbidity units may be allowed if the supplier of water can demonstrate to the State that the higher turbidity does not do any of the following:
(1) Interfere with disinfection;
(2) Prevent maintenance of an effective disinfectant agent throughout the distribution system; or
(3) Interfere with microbiological determinations.
(b) Five turbidity units based on an average for two consecutive days pursuant to § 141.22.
The following are the maximum contaminant levels for radium-226, radium-228, and gross alpha particle radioactivity:
(a) Combined radium-226 and radium-228—5 pCi/1.
(b) Gross alpha particle activity (including radium-226 but excluding radon and uranium)—15 pCi/1.
At 65 FR 76745, Dec. 7, 2000, § 141.15 was removed, effective Dec. 8, 2003.
(a) The average annual concentration of beta particle and photon radioactivity from man-made radionuclides in drinking water shall not produce an annual dose equivalent to the total body or any internal organ greater than 4 millirem/year.
(b) Except for the radionuclides listed in Table A, the concentration of man-made radionuclides causing 4 mrem total body or organ dose equivalents shall be calculated on the basis of a 2 liter per day drinking water intake using the 168 hour data listed in
At 65 FR 76745, Dec. 7, 2000, § 141.16 was removed, effective Dec. 8, 2003.
(a)
(2) The monitoring frequency for total coliforms for community water systems is based on the population served by the system, as follows:
(3) The monitoring frequency for total coliforms for non-community water systems is as follows:
(i) A non-community water system using only ground water (except ground water under the direct influence of surface water, as defined in § 141.2) and serving 1,000 persons or fewer must monitor each calendar quarter that the system provides water to the public, except that the State may reduce this monitoring frequency, in writing, if a sanitary survey shows that the system is free of sanitary defects. Beginning June 29, 1994, the State cannot reduce the monitoring frequency for a non-community water system using only ground water (except ground water under the direct influence of surface water, as defined in § 141.2) and serving 1,000 persons or fewer to less than once/year.
(ii) A non-community water system using only ground water (except ground water under the direct influence of surface water, as defined in § 141.2) and serving more than 1,000 persons during any month must monitor at the same frequency as a like-sized community water system, as specified in paragraph (a)(2) of this section, except the State may reduce this monitoring frequency, in writing, for any month the system serves 1,000 persons or fewer. The State cannot reduce the monitoring frequency to less than once/year. For systems using ground water under the direct influence of surface water, paragraph (a)(3)(iv) of this section applies.
(iii) A non-community water system using surface water, in total or in part, must monitor at the same frequency as a like-sized community water system, as specified in paragraph (a)(2) of this section, regardless of the number of persons it serves.
(iv) A non-community water system using ground water under the direct -influence of surface water, as defined -in § 141.2, must monitor at the same -frequency as a like-sized community water -system, as specified in paragraph (a)(2) of this section. The system must begin monitoring at this frequency beginning six months after the State determines that the ground water is under the direct influence of surface water.
(4) The public water system must collect samples at regular time intervals throughout the month, except that a system which uses only ground water (except ground water under the direct influence of surface water, as defined in § 141.2), and serves 4,900 persons or fewer, may collect all required samples on a single day if they are taken from different sites.
(5) A public water system that uses surface water or ground water under the direct influence of surface water, as defined in § 141.2, and does not practice filtration in compliance with Subpart
(6) Special purpose samples, such as those taken to determine whether disinfection practices are sufficient following pipe placement, replacement, or repair, shall not be used to determine compliance with the MCL for total coliforms in § 141.63. Repeat samples taken pursuant to paragraph (b) of this section are not considered special purpose samples, and must be used to determine compliance with the MCL for total coliforms in § 141.63.
(b)
(2) The system must collect at least one repeat sample from the sampling tap where the original total coliform-positive sample was taken, and at least one repeat sample at a tap within five service connections upstream and at least one repeat sample at a tap within five service connections downstream of the original sampling site. If a total coliform-positive sample is at the end of the distribution system, or one away from the end of the distribution system, the State may waive the requirement to collect at least one repeat sample upstream or downstream of the original sampling site.
(3) The system must collect all repeat samples on the same day, except that the State may allow a system with a single service connection to collect the required set of repeat samples over a four-day period or to collect a larger volume repeat sample(s) in one or more sample containers of any size, as long as the total volume collected is at least 400 ml (300 ml for systems which collect more than one routine sample/month).
(4) If one or more repeat samples in the set is total coliform-positive, the public water system must collect an additional set of repeat samples in the manner specified in paragraphs (b) (1)-(3) of this section. The additional samples must be collected within 24 hours of being notified of the positive result, unless the State extends the limit as provided in paragraph (b)(1) of this section. The system must repeat this process until either total coliforms are not detected in one complete set of repeat samples or the system determines that the MCL for total coliforms in § 141.63 has been exceeded and notifies the State.
(5) If a system collecting fewer than five routine samples/month has one or more total coliform-positive samples and the State does not invalidate the sample(s) under paragraph (c) of this section, it must collect at least five routine samples during the next month the system provides water to the public, except that the State may waive this requirement if the conditions of paragraph (b)(5) (i) or (ii) of this section are met. The State cannot waive the requirement for a system to collect repeat samples in paragraphs (b) (1)-(4) of this section.
(i) The State may waive the requirement to collect five routine samples the next month the system provides water to the public if the State, or an agent approved by the State, performs
(ii) The State may waive the requirement to collect five routine samples the next month the system provides water to the public if the State has determined why the sample was total coliform-positive and establishes that the system has corrected the problem or will correct the problem before the end of the next month the system serves water to the public. In this case, the State must document this decision to waive the following month's additional monitoring requirement in writing, have it approved and signed by the supervisor of the State official who recommends such a decision, and make this document available to the EPA and public. The written documentation must describe the specific cause of the total coliform-positive sample and what action the system has taken and/or will take to correct this problem. The State cannot waive the requirement to collect five routine samples the next month the system provides water to the public solely on the grounds that all repeat samples are total coliform-negative. Under this paragraph, a system must still take at least one routine sample before the end of the next month it serves water to the public and use it to determine compliance with the MCL for total coliforms in § 141.63, unless the State has determined that the system has corrected the contamination problem before the system took the set of repeat samples required in paragraphs (b) (1)-(4) of this section, and all repeat samples were total coliform-negative.
(6) After a system collects a routine sample and before it learns the results of the analysis of that sample, if it collects another routine sample(s) from within five adjacent service connections of the initial sample, and the initial sample, after analysis, is found to contain total coliforms, then the system may count the subsequent sample(s) as a repeat sample instead of as a routine sample.
(7) Results of all routine and repeat samples not invalidated by the State must be included in determining compliance with the MCL for total coliforms in § 141.63.
(c)
(1) The State may invalidate a total coliform-positive sample only if the conditions of paragraph (c)(1) (i), (ii), or (iii) of this section are met.
(i) The laboratory establishes that improper sample analysis caused the total coliform-positive result.
(ii) The State, on the basis of the results of repeat samples collected as required by paragraphs (b) (1) through (4) of this section, determines that the total coliform-positive sample resulted from a domestic or other non-distribution system plumbing problem. The State cannot invalidate a sample on the basis of repeat sample results unless all repeat sample(s) collected at the same tap as the original total coliform-positive sample are also total coliform-positive, and all repeat samples collected within five service connections of the original tap are total coliform-negative (e.g., a State cannot invalidate a total coliform-positive sample on the basis of repeat samples if all the repeat samples are total coliform-negative, or if the public water system has only one service connection).
(iii) The State has substantial grounds -to believe that a total coliform-positive result is due to a circumstance or condition which does not reflect water quality in the distribution system. In this case, the system must still collect all repeat samples required under paragraphs (b) (1)-(4) of this section, and use them to determine compliance with the MCL for total coliforms in § 141.63. To invalidate a total coliform-positive sample under this paragraph, the decision with the rationale for the decision must be documented in writing, and approved and
(2) A laboratory must invalidate a total coliform sample (unless total coliforms are detected) if the sample produces a turbid culture in the absence of gas production using an analytical method where gas formation is examined (e.g., the Multiple-Tube Fermentation Technique), produces a turbid culture in the absence of an acid reaction in the Presence-Absence (P-A) Coliform Test, or exhibits confluent growth or produces colonies too numerous to count with an analytical method using a membrane filter (e.g., Membrane Filter Technique). If a laboratory invalidates a sample because of such interference, the system must collect another sample from the same location as the original sample within 24 hours of being notified of the interference problem, and have it analyzed for the presence of total coliforms. The system must continue to re-sample within 24 hours and have the samples analyzed until it obtains a valid result. The State may waive the 24-hour time limit on a case-by-case basis.
(d)
(ii) In conducting a sanitary survey of a system using ground water in a State having an EPA-approved wellhead protection program under section 1428 of the Safe Drinking Water Act, information on sources of contamination within the delineated wellhead protection area that was collected in the course of developing and implementing the program should be considered instead of collecting new information, if the information was collected since the last time the system was subject to a sanitary survey.
(2) Sanitary surveys must be performed by the State or an agent approved by the State. The system is responsible for ensuring the survey takes place.
(e)
(2) The State has the discretion to allow a public water system, on a case-by-case basis, to forgo fecal coliform or
(f)
(2) Public water systems need only determine the presence or absence of total coliforms; a determination of total coliform density is not required.
(3) Public water systems must conduct total coliform analyses in accordance with one of the analytical methods in the following table.
(4) [Reserved]
(5) Public water systems must conduct fecal coliform analysis in accordance with the following procedure. When the MTF Technique or Presence-Absence (PA) Coliform Test is used to test for total coliforms, shake the lactose-positive presumptive tube or P-A vigorously and transfer the growth with a sterile 3-mm loop or sterile applicator stick into brilliant green lactose bile broth and EC medium to determine the presence of total and fecal coliforms, respectively. For EPA-approved analytical methods which use a membrane filter, transfer the total coliform-positive culture by one of the following methods: remove the membrane containing the total coliform colonies from the substrate with a sterile forceps and carefully curl and insert the membrane into a tube of EC medium (the laboratory may first remove a small portion of selected colonies for
(6) Public water systems must conduct analysis of
(i) EC medium supplemented with 50 μg/mL of 4-methylumbelliferyl-beta-D-glucuronide (MUG) (final concentration), as described in Method 9222G in Standard Methods for the Examination of Water and Wastewater, 19th edition (1995) and 20th edition (1998). Either edition may be used. Alternatively, the 18th edition (1992) may be used if at least 10 mL of EC medium, as described in paragraph (f)(5) of this section, is supplemented with 50 μg/mL of MUG before autoclaving. The inner inverted fermentation tube may be omitted. If the 18th edition is used, apply the procedure in paragraph (f)(5) of this section for transferring a total coliform-positive culture to EC medium supplemented with MUG, incubate the tube at 44.5 ± 0.2 °C for 24 ± 2 hours, and then observe fluorescence with an ultraviolet light (366 nm) in the dark. If fluorescence is visible, E. coli are present.
(ii) Nutrient agar supplemented with 100 μg/mL of 4-methylumbelliferyl-beta-D-glucuronide (MUG) (final concentration), as described in Method 9222G in Standard Methods for the Examination of Water and Wastewater, 19th edition (1995) and 20th edition (1998). Either edition may be used for determining if a total coliform-positive sample, as determined by a membrane filter technique, contains E. coli. Alternatively, the 18th edition (1992) may be used if the membrane filter containing a total coliform-positive colony(ies) is transferred to nutrient agar, as described in Method 9221B (paragraph 3) of Standard Methods (18th edition), supplemented with 100 μg/mL of MUG. If the 18th edition is used, incubate the agar plate at 35 °C for 4 hours and then observe the colony(ies) under ultraviolet light (366 nm) in the dark for fluorescence. If fluorescence is visible, E. coli are present.
(iii) Minimal Medium ONPG-MUG (MMO-MUG) Test, as set forth in the article “National Field Evaluation of a Defined Substrate Method for the Simultaneous Detection of Total Coliforms and
(iv) The Colisure Test. A description of the Colisure Test may be obtained from the Millipore Corporation, Technical Services Department, 80 Ashby Road, Bedford, MA 01730.
(v) The membrane filter method with MI agar, a description of which is cited in footnote 6 to the table in paragraph (f)(3) of this section.
(vi) E*Colite
(vii) m-ColiBlue24
(viii) Readycult® Coliforms 100 Presence/Absence Test, a description of which is cited in footnote 13 to the table at paragraph (f)(3) of this section.
(ix) Membrane Filter Technique using Chromocult® Coliform Agar, a description of which is cited in footnote 14 to the table at paragraph (f)(3) of this section.
(7) As an option to paragraph (f)(6)(iii) -of this section, a system with a total -coliform-pos-i-tive, MUG-negative, MMO-MUG test may further analyze the culture for the presence of
(8) The following materials are incorporated by reference in this section with the approval of the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of the analytical methods cited in Standard Methods for the Examination of Water and Wastewater (18th, 19th, and 20th editions) may be obtained from the American Public Health Association
(g)
(2) A public water system which has failed to comply with a coliform monitoring requirement, including the sanitary survey requirement, must report the monitoring violation to the State within ten days after the system discovers the violation, and notify the public in accordance with subpart Q.
The requirements in this section apply to unfiltered systems until December 30, 1991, unless the State has determined prior to that date, in writing pursuant to section 1412(b)(7)(iii), that filtration is required. The requirements in this section apply to filtered systems until June 29, 1993. The requirements in this section apply to unfiltered systems that the State has determined, in writing pursuant to section 1412(b)(7)(C)(iii), must install filtration, until June 29, 1993, or until filtration is installed, whichever is later.
(a) Samples shall be taken by suppliers of water for both community and non-community water systems at a representative entry point(s) to the water distribution system at least once per day, for the purposes of making turbidity measurements to determine compliance with § 141.13. If the State determines that a reduced sampling frequency in a non-community will not
(b) If the result of a turbidity analysis indicates that the maximum allowable limit has been exceeded, the sampling and measurement shall be confirmed by resampling as soon as practicable and preferably within one hour. If the repeat sample confirms that the maximum allowable limit has been exceeded, the supplier of water shall report to the State within 48 hours. The repeat sample shall be the sample used for the purpose of calculating the monthly average. If the monthly average of the daily samples exceeds the maximum allowable limit, or if the average of two samples taken on consecutive days exceeds 5 TU, the supplier of water shall report to the State and notify the public as directed in §§ 141.31 and subpart Q.
(c) Sampling for non-community water systems shall begin within two years after the effective date of this part.
(d) The requirements of this § 141.22 shall apply only to public water systems which use water obtained in whole or in part from surface sources.
(e) The State has the authority to determine compliance or initiate enforcement action based upon analytical results or other information compiled by their sanctioned representatives and agencies.
Community water systems shall conduct monitoring to determine compliance with the maximum contaminant levels specified in § 141.62 in accordance with this section. Non-transient, non-community water systems shall conduct monitoring to determine compliance with the maximum contaminant levels specified in § 141.62 in accordance with this section. Transient, non-community water systems shall conduct monitoring to determine compliance with the nitrate and nitrite maximum contaminant levels in §§ 141.11 and 141.62 (as appropriate) in accordance with this section.
(a) Monitoring shall be conducted as follows:
(1) Groundwater systems shall take a minimum of one sample at every entry point to the distribution system which is representative of each well after treatment (hereafter called a sampling point) beginning in the initial compliance period. The system shall take each sample at the same sampling point unless conditions make another sampling point more representative of each source or treatment plant.
(2) Surface water systems shall take a minimum of one sample at every entry point to the distribution system after any application of treatment or in the distribution system at a point which is representative of each source after treatment (hereafter called a sampling point) beginning in the initial compliance period. The system shall take each sample at the same sampling point unless conditions make another sampling point more representative of each source or treatment plant.
For purposes of this paragraph, surface water systems include systems with a combination of surface and ground sources.
(3) If a system draws water from more than one source and the sources are combined before distribution, the system must sample at an entry point to the distribution system during periods of normal operating conditions (i.e., when water is representative of all sources being used).
(4) The State may reduce the total number of samples which must be -analyzed by allowing the use of compositing. -Composite samples from a maximum -of five samples are allowed, provided that -the detection limit of the method used for analysis is less than one-fifth of the MCL.
(i) If the concentration in the composite sample is greater than or equal to one-fifth of the MCL of any inorganic chemical, then a follow-up sample must be taken within 14 days at each sampling point included in the composite. These samples must be analyzed for the contaminants which exceeded one-fifth of the MCL in the composite sample. Detection limits for each analytical method and MCLs for each inorganic contaminant are the following:
(ii) If the population served by the -system is >3,300 persons, then composit-ing may only be permitted by the State at sampling points within a single system. In systems serving ≤3,300 persons, the State may permit compositing among different systems provided the 5-sample limit is maintained.
(iii) If duplicates of the original sample taken from each sampling point used in the composite sample are available, the system may use these instead of resampling. The duplicates must be analyzed and the results reported to the State within 14 days after completing analysis of the composite sample, provided the holding time of the sample is not exceeded.
(5) The frequency of monitoring for asbestos shall be in accordance with paragraph (b) of this section: the frequency of monitoring for antimony, arsenic, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, selenium and thallium shall be in accordance with paragraph (c) of this section; the frequency of monitoring for nitrate shall be in accordance with paragraph (d) of this section; and the frequency of monitoring for nitrite shall be in accordance with paragraph (e) of this section.
(b) The frequency of monitoring conducted to determine compliance with the maximum contaminant level for asbestos specified in § 141.62(b) shall be conducted as follows:
(1) Each community and non-transient, non-community water system is required to monitor for asbestos during the first three-year compliance period of each nine-year compliance cycle beginning in the compliance period starting January 1, 1993.
(2) If the system believes it is not vulnerable to either asbestos contamination in its source water or due to corrosion of asbestos-cement pipe, or both, it may apply to the State for a waiver of the monitoring requirement in paragraph (b)(1) of this section. If the State grants the waiver, the system is not required to monitor.
(3) The State may grant a waiver based on a consideration of the following factors:
(i) Potential asbestos contamination of the water source, and
(ii) The use of asbestos-cement pipe for finished water distribution and the corrosive nature of the water.
(4) A waiver remains in effect until the completion of the three-year compliance period. Systems not receiving a waiver must monitor in accordance with the provisions of paragraph (b)(1) of this section.
(5) A system vulnerable to asbestos contamination due solely to corrosion of asbestos-cement pipe shall take one sample at a tap served by asbestos-cement pipe and under conditions where asbestos contamination is most likely to occur.
(6) A system vulnerable to asbestos contamination due solely to source water shall monitor in accordance with the provision of paragraph (a) of this section.
(7) A system vulnerable to asbestos contamination due both to its source water supply and corrosion of asbestos-cement pipe shall take one sample at a tap served by asbestos-cement pipe and under conditions where asbestos contamination is most likely to occur.
(8) A system which exceeds the maximum contaminant levels as determined in § 141.23(i) of this section shall monitor quarterly beginning in the next quarter after the violation occurred.
(9) The State may decrease the quarterly monitoring requirement to the frequency specified in paragraph (b)(1) of this section pro-vided the State has determined that the sys-tem is reliably and consistently below -the maximum contaminant level. In -no case can a State make this de-term-i-na-tion unless a groundwater system takes a minimum of two quarterly samples and a surface (or combined surface/ground) water system takes a minimum of four quarterly samples.
(10) If monitoring data collected after January 1, 1990 are generally consistent with the requirements of § 141.23(b), then the State may allow systems to use that data to satisfy the monitoring requirement for the initial compliance period beginning January 1, 1993.
(c) The frequency of monitoring conducted to determine compliance with the maximum contaminant levels in § 141.62 for antimony, arsenic, barium,
(1) Groundwater systems shall take one sample at each sampling point during each compliance period. Surface water systems (or combined surface/ground) shall take one sample annually at each sampling point.
(2) The system may apply to the State for a waiver from the monitoring frequencies specified in paragraph (c)(1) of this section. States may grant a public water system a waiver for monitoring of cyanide, provided that the State determines that the system is not vulnerable due to lack of any industrial source of cyanide.
(3) A condition of the waiver shall require that a system shall take a minimum of one sample while the waiver is effective. The term during which the waiver is effective shall not exceed one compliance cycle (i.e., nine years).
(4) The State may grant a waiver provided surface water systems have monitored annually for at least three years and groundwater systems have conducted a minimum of three rounds of monitoring. (At least one sample shall have been taken since January 1, 1990). Both surface and groundwater systems shall demonstrate that all previous analytical results were less than the maximum contaminant level. Systems that use a new water source are not eligible for a waiver until three rounds of monitoring from the new source have been completed.
(5) In determining the appropriate reduced monitoring frequency, the State shall consider:
(i) Reported concentrations from all previous monitoring;
(ii) The degree of variation in reported concentrations; and
(iii) Other factors which may affect contaminant concentrations such as changes in groundwater pumping rates, changes in the system's configuration, changes in the system's operating procedures, or changes in stream flows or characteristics.
(6) A decision by the State to grant a waiver shall be made in writing and shall set forth the basis for the determination. The determination may be initiated by the State or upon an application by the public water system. The public water system shall specify the basis for its request. The State shall review and, where appropriate, revise its determination of the appropriate monitoring frequency when the system submits new monitoring data or when other data relevant to the system's appropriate monitoring frequency become available.
(7) Systems which exceed the maximum contaminant levels as calculated in § 141.23(i) of this section shall monitor quarterly beginning in the next quarter after the violation occurred.
(8) The State may decrease the quarterly monitoring requirement to the frequencies specified in paragraphs (c)(1) and (c)(2) of this section provided it has determined that the system is reliably and consistently below the maximum contaminant level. In no case can a State make this determination unless a groundwater system takes a minimum of two quarterly samples and a surface water system takes a minimum of four quarterly samples.
(d) All public water systems (community; non-transient, non-community; and transient, non-community systems) shall monitor to determine compliance with the maximum contaminant level for nitrate in § 141.62.
(1) Community and non-transient, non-community water systems served by groundwater systems shall monitor annually beginning January 1, 1993; systems served by surface water shall monitor quarterly beginning January 1, 1993.
(2) For community and non-transient, non-community water systems, the repeat monitoring frequency for groundwater systems shall be quarterly for at least one year following any one sample in which the concentration is ≥50 percent of the MCL. The State may allow a groundwater system to reduce the sampling frequency to annually after four consecutive quarterly samples are reliably and consistently less than the MCL.
(3) For community and non-transient, non-community water systems, the State may allow a surface water system to reduce the sampling frequency to annually if all analytical results from four consecutive quarters are <50 percent of the MCL. A surface
(4) Each transient non-community water system shall monitor annually beginning January 1, 1993.
(5) After the initial round of quarterly sampling is completed, each community and non-transient non-community system which is monitoring annually shall take subsequent samples during the quarter(s) which previously resulted in the highest analytical result.
(e) All public water systems (community; non-transient, non-community; and transient, non-community systems) shall monitor to determine compliance with the maximum contaminant level for nitrite in § 141.62(b).
(1) All public water systems shall take one sample at each sampling point in the compliance period beginning January 1, 1993 and ending December 31, 1995.
(2) After the initial sample, systems where an analytical result for nitrite is <50 percent of the MCL shall monitor at the frequency specified by the State.
(3) For community, non-transient, non-community, and transient non-community water systems, the repeat monitoring frequency for any water system shall be quarterly for at least one year following any one sample in which the concentration is ≧50 percent of the MCL. The State may allow a system to reduce the sampling frequency to annually after determining the system is reliably and consistently less than the MCL.
(4) Systems which are monitoring annually shall take each subsequent sample during the quarter(s) which previously resulted in the highest analytical result.
(f) Confirmation samples:
(1) Where the results of sampling for antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, selenium or thallium indicate an exceedance of the maximum contaminant level, the State may require that one additional sample be collected as soon as possible after the initial sample was taken (but not to exceed two weeks) at the same sampling point.
(2) Where nitrate or nitrite sampling results indicate an exceedance of the maximum contaminant level, the system shall take a confirmation sample within 24 hours of the system's receipt of notification of the analytical results of the first sample. Systems unable to comply with the 24-hour sampling requirement must immediately notify persons served by the public water system in accordance with § 141.202 and meet other Tier 1 public notification requirements under Subpart Q of this part. Systems exercising this option must take and analyze a confirmation sample within two weeks of notification of the analytical results of the first sample.
(3) If a State-required confirmation sample is taken for any contaminant, then the results of the initial and -confirmation sample shall be aver-aged. The resulting average shall be -used to determine the system's compliance -in accordance with paragraph (i) of this section. States have the discretion to delete results of obvious sampling errors.
(g) The State may require more frequent monitoring than specified in paragraphs (b), (c), (d) and (e) of this section or may require confirmation samples for positive and negative results at its discretion.
(h) Systems may apply to the State to conduct more frequent monitoring than the minimum monitoring frequencies specified in this section.
(i) Compliance with §§ 141.11 or 141.62(b) (as appropriate) shall be determined based on the analytical result(s) obtained at each sampling point.
(1) For systems which are conducting monitoring at a frequency greater than annual, compliance with the maximum contaminant levels for antimony, asbestos, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, selenium or thallium is determined by a running annual average at any sampling point. If the average at any sampling point is greater than the MCL, then the system is out of compliance. If any one sample would cause the annual average to be exceeded, then the system is out of compliance immediately. Any sample below the method detection limit shall be calculated at zero for the purpose of determining the annual average.
(2) For systems which are monitoring annually, or less frequently, the system is out of compliance with the maximum contaminant levels for asbestos, antimony, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, selenium or thallium if the level of a contaminant at any sampling point is greater than the MCL. If a confirmation sample is required by the State, the determination of compliance will be based on the average of the two samples.
(3) Compliance with the maximum contaminant levels for nitrate and nitrate is determined based on one sample if the levels of these contaminants are below the MCLs. If the levels of nitrate and/or nitrite exceed the MCLs in the initial sample, a confirmation sample is required in accordance with paragraph (f)(2) of this section, and compliance shall be determined based on the average of the initial and confirmation samples.
(4) Arsenic sampling results will be reported to the nearest 0.001 mg/L.
(j) Each public water system shall monitor at the time designated by the State during each compliance period.
(k) Inorganic analysis:
(1) Analysis for the following contaminants shall be conducted in accordance with the methods in the following table, or their equivalent as determined by EPA. Criteria for analyzing arsenic, barium, beryllium, cadmium, calcium, chromium, copper, lead, nickel, selenium, sodium, and thallium with digestion or directly without digestion, and other analytical test procedures are contained in
(2) Sample collection for antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, nitrate, nitrite, selenium, and thallium under this section shall be conducted using the sample preservation, container, and maximum holding time procedures specified in the table below:
(3) Analysis under this section shall only be conducted by laboratories that have been certified by EPA or the State. Laboratories may conduct sample analysis under provisional certification until January 1, 1996. To receive
(i) Analyze Performance Evaluation (PE) samples provided by EPA, the State or by a third party (with the approval of the State or EPA) at least once a year.
(ii) For each contaminant that has been included in the PE sample and for each method for which the laboratory desires certification achieve quantitative results on the analyses that are within the following acceptance limits:
(l) Analyses for the purpose of determining compliance with § 141.11 shall be conducted using the requirements specified in paragraphs (l) through (q) of this section.
(1) Analyses for all community water systems utilizing surface water sources shall be completed by June 24, 1978. These analyses shall be repeated at yearly intervals.
(2) Analyses for all community water systems utilizing only ground water sources shall be completed by June 24, 1979. These analyses shall be repeated at three-year intervals.
(3) For non-community water systems, whether supplied by surface or ground sources, analyses for nitrate shall be completed by December 24, 1980. These analyses shall be repeated at intervals determined by the State.
(4) The State has the authority to determine compliance or initiate enforcement action based upon analytical results and other information compiled by their sanctioned representatives and agencies.
(m) If the result of an analysis made under paragraph (l) of this section indicates that the level of any contaminant listed in § 141.11 exceeds the maximum contaminant level, the supplier of the water shall report to the State within 7 days and initiate three additional analyses at the same sampling point within one month.
(n) When the average of four analyses made pursuant to paragraph (m) of this section, rounded to the same number of significant figures as the maximum contaminant level for the substance in question, exceeds the maximum contaminant level, the supplier of water shall notify the State pursuant to § 141.31 and give notice to the public pursuant to subpart Q. Monitoring after public notification shall be at a frequency designated by the State and shall continue until the maximum contaminant level has not been exceeded in two successive samples or until a monitoring schedule as a condition to a variance, exemption or enforcement action shall become effective.
(o) The provisions of paragraphs (m) and (n) of this section notwithstanding, compliance with the maximum contaminant level for nitrate shall be determined on the basis of the mean of two analyses. When a level exceeding the maximum contaminant level for nitrate is found, a second analysis shall be initiated within 24 hours, and if the mean of the two analyses exceeds the maximum contaminant level, the supplier of water shall report his findings to the State pursuant to § 141.31 and shall notify the public pursuant to subpart Q.
(p) For the initial analyses required by paragraph (l) (1), (2) or (3) of this section, data for surface waters acquired within one year prior to the effective date and data for ground waters acquired within 3 years prior to the effective date of this part may be substituted at the discretion of the State.
(q) [Reserved]
At 66 FR 7061, Jan. 22, 2001, § 141.23 was amended by adding paragraph (c)(9) and revising paragraphs (i)(1) and (i)(2), effective Mar. 23, 2001, except for the amendments to paragraphs (i)(1) and (i)(2) which are effective Jan. 22, 2004. At 66 FR 16134, Mar. 23, 2001, the effective date was delayed until May 22, 2001. At 66 FR 28350, May 22, 2001, the effective date for paragraph (c)(9) was delayed until Jan. 22, 2004. For the convenience of the user, the revised and added text is set forth as follows:
(c) * * *
(9) All new systems or systems that use a new source of water that begin operation after January 22, 2004 must demonstrate compliance with the MCL within a period of time specified by the State. The system must also comply with the initial sampling frequencies specified by the State to ensure a system can demonstrate compliance with the MCL. Routine and increased monitoring frequencies shall be conducted in accordance with the requirements in this section.
(i) * * *
(1) For systems which are conducting monitoring at a frequency greater than annual, compliance with the maximum contaminant levels for antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, selenium or thallium is determined by a running annual average at any sampling point. If the average at any sampling point is greater than the MCL, then the system is out of compliance. If any one sample would cause the annual average to be exceeded, then the system is out of compliance immediately. Any sample below the method detection limit shall be calculated at zero for the purpose of determining the annual average. If a system fails to collect the required number of samples, compliance (average concentration) will be based on the total number of samples collected.
(2) For systems which are monitoring annually, or less frequently, the system is out of compliance with the maximum contaminant levels for antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, selenium or thallium if the level of a contaminant is greater than the MCL. If confirmation samples are required by the State, the determination of compliance will be based on the annual average of the initial MCL exceedance and any State-required confirmation samples. If a system fails to collect the required number of samples, compliance (average concentration) will be based on the total number of samples collected.
(a)-(d) [Reserved]
(e) Analyses for the contaminants in this section shall be conducted using the following EPA methods or their equivalent as approved by EPA.
(1) The following documents are incorporated by reference. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies may be inspected at EPA's Drinking Water Docket, 1301 Constitution Avenue, NW., EPA West, Room B102, Washington DC 20460 (Telephone: 202-566-2426); or at the Office of the Federal Register, 800 North Capitol Street, NW., Suite 700, Washington, DC. Method 508A and 515.1 are in
(2) The following EPA methods will remain available for compliance monitoring until June 1, 2001. The following documents are incorporated by reference. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR Part 51. Copies may be inspected at EPA's Drinking Water Docket, 401 M St., SW., Washington, DC 20460; or at the Office of the Federal Register, 800 North Capitol Street, NW., Suite 700, Washington, DC. EPA methods 502.2 Rev. 2.0, 505 Rev. 2.0, 507 Rev. 2.0, 508 Rev. 3.0, 531.1 Rev. 3.0 are in “Methods for the Determination of Organic Compounds in Drinking Water”, December 1988, revised July 1991; methods 506 and 551 are in “Methods for the Determination of Organic Compounds in Drinking Water—Supplement I”, July 1990; methods 515.2 Rev. 1.0 and 524.2 Rev. 4.0 are in “Methods for the Determination of Organic Compounds in Drinking Water—Supplement II,” August 1992; and methods 504.1 Rev. 1.0, 508.1 Rev. 1.0, 525.2 Rev.1.0 are available from US EPA NERL, Cincinnati, OH 45268
(f) Beginning with the initial compliance period, analysis of the contaminants listed in § 141.61(a) (1) through (21) for the purpose of determining compliance with the maximum contaminant level shall be conducted as follows:
(1) Groundwater systems shall take a minimum of one sample at every entry point to the distribution system which is representative of each well after treatment (hereafter called a sampling point). Each sample must be taken at the same sampling point unless conditions make another sampling point more representative of each source, treatment plant, or within the distribution system.
(2) Surface water systems (or combined surface/ground) shall take a minimum of one sample at points in the distribution system that are representative of each source or at each entry point to the distribution system after treatment (hereafter called a sampling point). Each sample must be taken at the same sampling point unless conditions make another sampling point more representative of each source, treatment plant, or within the distribution system.
(3) If the system draws water from more than one source and the sources are combined before distribution, the system must sample at an entry point to the distribution system during periods of normal operating conditions (i.e., when water representative of all sources is being used).
(4) Each community and non-transient non-community water system shall take four consecutive quarterly samples for each contaminant listed in § 141.61(a) (2) through (21) during each compliance period, beginning in the initial compliance period.
(5) If the initial monitoring for contaminants listed in § 141.61(a) (1) through (8) and the monitoring for the contaminants listed in § 141.61(a) (9) through (21) as allowed in paragraph (f)(18) has been completed by December 31, 1992, and the system did not detect any contaminant listed in § 141.61(a) (1) through (21), then each ground and surface water system shall take one sample annually beginning with the initial compliance period.
(6) After a minimum of three years of annual sampling, the State may allow groundwater systems with no previous detection of any contaiminant listed in § 141.61(a) to take one sample during each compliance period.
(7) Each community and non-transient non-community ground water system which does not detect a contaminant listed in § 141.61(a) (1) through (21) may apply to the State for a waiver from the requirements of paragraphs (f)(5) and (f)(6) of this section after completing the initial monitoring. (For purposes of this section, detection is defined as ≧0.0005 mg/l.) A waiver shall be effective for no more than six years (two compliance periods). States may also issue waivers to small systems for the initial round of monitoring for 1,2,4-trichlorobenzene.
(8) A State may grant a waiver after evaluating the following factor(s):
(i) Knowledge of previous use (including transport, storage, or disposal) of the contaminant within the watershed or zone of influence of the system. If a determination by the State reveals no previous use of the contaminant within the watershed or zone of influence, a waiver may be granted.
(ii) If previous use of the contaminant is unknown or it has been used previously, then the following factors shall be used to determine whether a waiver is granted.
(A) Previous analytical results.
(B) The proximity of the system to a potential point or non-point source of contamination. Point sources include spills and leaks of chemicals at or near a water treatment facility or at manufacturing, distribution, or storage facilities, or from hazardous and municipal waste landfills and other waste handling or treatment facilities.
(C) The environmental persistence and transport of the contaminants.
(D) The number of persons served by the public water system and the proximity of a smaller system to a larger system.
(E) How well the water source is protected against contamination, such as whether it is a surface or groundwater system. Groundwater systems must consider factors such as depth of the
(9) As a condition of the waiver a groundwater system must take one sample at each sampling point during the time the waiver is effective (i.e., one sample during two compliance periods or six years) and update its vulnerability assessment considering the factors listed in paragraph (f)(8) of this section. Based on this vulnerability assessment the State must reconfirm that the system is non-vulnerable. If the State does not make this reconfirmation within three years of the initial determination, then the waiver is invalidated and the system is required to sample annually as specified in paragraph (5) of this section.
(10) Each community and non-transient non-community surface water system which does not detect a contaminant listed in § 141.61(a) (1) through (21) may apply to the State for a waiver from the requirements of (f)(5) of this section after completing the initial monitoring. Composite samples from a maximum of five sampling points are allowed, provided that the detection limit of the method used for analysis is less than one-fifth of the MCL. Systems meeting this criterion must be determined by the State to be non-vulnerable based on a vulnerability assessment during each compliance period. Each system receiving a waiver shall sample at the frequency specified by the State (if any).
(11) If a contaminant listed in § 141.61(a) -(2) through (21) is detected at a -level exceeding 0.0005 mg/l in any sample, then:
(i) The system must monitor quarterly at each sampling point which resulted in a detection.
(ii) The State may decrease the quarterly monitoring requirement spe-ci- fied in paragraph (f)(11)(i) of this section provided it has determined that the system is reliably and consistently below the maximum contaminant level. In no case shall the State make this determination unless a groundwater system takes a minimum of two quarterly samples and a surface water system takes a minimum of four quarterly samples.
(iii) If the State determines that the system is reliably and consistently below the MCL, the State may allow the system to monitor annually. Systems which monitor annually must monitor during the quarter(s) which previously yielded the highest analytical result.
(iv) Systems which have three consecutive annual samples with no detection of a contaminant may apply to the State for a waiver as specified in paragraph (f)(7) of this section.
(v) Groundwater systems which have detected one or more of the following two-carbon organic compounds: trichloroethylene, tetrachloroethylene, 1,2-dichloroethane, 1,1,1-trichloroethane, cis-1,2-dichloroethylene, trans-1,2-dichloroethylene, or 1,1-dichloroethylene shall monitor quarterly for vinyl chloride. A vinyl chloride sample shall be taken at each sampling point at which one or more of the two-carbon organic compounds was detected. If the results of the first analysis do not detect vinyl chloride, the State may reduce the quarterly monitoring frequency of vinyl chloride monitoring to one sample during each compliance period. Surface water systems are required to monitor for vinyl chloride as specified by the State.
(12) Systems which violate the requirements of § 141.61(a) (1) through (21), as determined by paragraph (f)(15) of this section, must monitor quarterly. After a minimum of four consecutive quarterly samples which show the system is in compliance as specified in paragraph (f)(15) of this section the system and the State determines that the system is reliably and consistently below the maximum contaminant level, the system may monitor at the frequency and times specified in paragraph (f)(11)(iii) of this section.
(13) The State may require a confirmation sample for positive or negative results. If a confirmation sample is required by the State, the result must be averaged with the first sampling result and the average is used for the compliance determination as specified by paragraph (f)(15). States have discretion to delete results of obvious sampling errors from this calculation.
(14) The State may reduce the total number of samples a system must analyze by allowing the use of compositing. Composite samples from a maximum of five sampling points are allowed, provided that the detection limit of the method used for analysis is less than one-fifth of the MCL. Compositing of samples must be done in the laboratory and analyzed within 14 days of sample collection.
(i) If the concentration in the composite sample is greater than or equal to 0.0005 mg/l for any contaminant listed in § 141.61(a), then a follow-up sample must be taken within 14 days at each sampling point included in the composite, and be analyzed for that contaminant.
(ii) If duplicates of the original sample taken from each sampling point used in the composite sample are available, the system may use these instead of resampling. The duplicates must be analyzed and the results reported to the State within 14 days after completing analysis of the composite sample, provided the holding time of the sample is not exceeded.
(iii) If the population served by the system is > 3,300 persons, then compositing may only be permitted by the State at sampling points within a single system. In systems serving ≤ 3,300 persons, the State may permit compositing among different systems provided the 5-sample limit is maintained.
(iv) Compositing samples prior to GC analysis.
(A) Add 5 ml or equal larger amounts of each sample (up to 5 samples are allowed) to a 25 ml glass syringe. Special precautions must be made to maintain zero headspace in the syringe.
(B) The samples must be cooled at 4 °C during this step to minimize volatilization losses.
(C) Mix well and draw out a 5-ml aliquot for analysis.
(D) Follow sample introduction, purging, and desorption steps described in the method.
(E) If less than five samples are used for compositing, a proportionately small syringe may be used.
(v) Compositing samples prior to GC/MS analysis.
(A) Inject 5-ml or equal larger amounts of each aqueous sample (up to 5 samples are allowed) into a 25-ml purging device using the sample introduction technique described in the method.
(B) The total volume of the sample in the purging device must be 25 ml.
(C) Purge and desorb as described in the method.
(15) Compliance with § 141.61(a) (1) through (21) shall be determined based on the analytical results obtained at each sampling point.
(i) For systems which are conducting monitoring at a frequency greater than annual, compliance is determined by a running annual average of all samples taken at each sampling point. If the annual average of any sampling point is greater than the MCL, then the system is out of compliance. If the initial sample or a subsequent sample would cause the annual average to be exceeded, then the system is out of compliance immediately.
(ii) If monitoring is conducted annually, or less frequently, the system is out of compliance if the level of a contaminant at any sampling point is greater than the MCL. If a confirmation sample is required by the State, the determination of compliance will be based on the average of two samples.
(16) [Reserved]
(17) Analysis under this section shall only be conducted by laboratories that are certified by EPA or the State according to the following conditions (laboratories may conduct sample analysis under provisional certification until January 1, 1996):
(i) To receive certification to conduct analyses for the contaminants in § 141.61(a) (2) through (21) the laboratory must:
(A) Analyze Performance Evaluation (PE) samples provided by EPA, the State, or by a third party (with the approval of the State or EPA) at least once a year by each method for which the laboratory desires certification.
(B) Achieve the quantitative acceptance limits under paragraphs (f)(17)(i)(C) and (D) of this section for at least 80 percent of the regulated organic contaminants included in the PE sample.
(C) Achieve quantitative results on the analyses performed under paragraph (f)(17)(i)(A) of this section that are within ±20% of the actual amount of the substances in the Performance Evaluation sample when the actual amount is greater than or equal to 0.010 mg/l.
(D) Achieve quantitative results on the analyses performed under paragraph (f)(17)(i)(A) of this section that are within ±40 percent of the actual amount of the substances in the Performance Evaluation sample when the actual amount is less than 0.010 mg/l.
(E) Achieve a method detection limit of 0.0005 mg/l, according to the procedures in appendix B of part 136.
(ii) To receive certification to conduct analyses for vinyl chloride, the laboratory must:
(A) Analyze Performance Evaluation (PE) samples provided by EPA, the State, or by a third party (with the approval of the State or EPA) at least once a year by each method for which the laboratory desires certification.
(B) Achieve quantitative results on the analyses performed under paragraph (f)(17)(ii)(A) of this section that are within ±40 percent of the actual amount of vinyl chloride in the Performance Evaluation sample.
(C) Achieve a method detection limit of 0.0005 mg/l, according to the procedures in appendix B of part 136.
(D) Obtain certification for the contaminants listed in § 141.61(a)(2) through (21).
(18) States may allow the use of monitoring data collected after January 1, 1988, required under section 1445 of the Act for purposes of initial monitoring compliance. If the data are generally consistent with the other requirements of this section, the State may use these data (i.e., a single sample rather than four quarterly samples) to satisfy the initial monitoring requirement of paragraph (f)(4) of this section. Systems which use grandfathered samples and did not detect any contaminant listed § 141.61(a)(2) through (21) shall begin monitoring annually in accordance with paragraph (f)(5) of this section beginning with the initial compliance period.
(19) States may increase required monitoring where necessary to detect variations within the system.
(20) Each certified laboratory must determine the method detection limit (MDL), as defined in appendix B to part 136, at which it is capable of detecting VOCs. The acceptable MDL is 0.0005 mg/l. This concentration is the detection concentration for purposes of this section.
(21) Each public water system shall monitor at the time designated by the State within each compliance period.
(g) [Reserved]
(h) Analysis of the contaminants listed in § 141.61(c) for the purposes of determining compliance with the maximum contaminant level shall be conducted as follows:
(1) Groundwater systems shall take a minimum of one sample at every entry point to the distribution system which is representative of each well after treatment (hereafter called a sampling point). Each sample must be taken at the same sampling point unless conditions make another sampling point more representative of each source or treatment plant.
(2) Surface water systems shall take a minimum of one sample at points in the distribution system that are representative of each source or at each entry point to the distribution system after treatment (hereafter called a sampling point). Each sample must be taken at the same sampling point unless conditions make another sampling point more representative of each source or treatment plant.
For purposes of this paragraph, surface water systems include systems with a combination of surface and ground sources.
(3) If the system draws water from more than one source and the sources are combined before distribution, the system must sample at an entry point to the distribution system during periods of normal operating conditions (i.e., when water representative of all sources is being used).
(4) Monitoring frequency:
(i) Each community and non-transient non-community water system
(ii) Systems serving more than 3,300 persons which do not detect a contaminant in the initial compliance period may reduce the sampling frequency to a minimum of two quarterly samples in one year during each repeat compliance period.
(iii) Systems serving less than or equal to 3,300 persons which do not detect a contaminant in the initial compliance period may reduce the sampling frequency to a minimum of one sample during each repeat compliance period.
(5) Each community and non-transient water system may apply to the State for a waiver from the requirement of paragraph (h)(4) of this section. A system must reapply for a waiver for each compliance period.
(6) A State may grant a waiver after evaluating the following factor(s): Knowledge of previous use (including transport, storage, or disposal) of the contaminant within the watershed or zone of influence of the system. If a determination by the State reveals no previous use of the contaminant within the watershed or zone of influence, a waiver may be granted. If previous use of the contaminant is unknown or it has been used previously, then the following factors shall be used to determine whether a waiver is granted.
(i) Previous analytical results.
(ii) The proximity of the system to a potential point or non-point source of contamination. Point sources include spills and leaks of chemicals at or near a water treatment facility or at manufacturing, distribution, or storage facilities, or from hazardous and municipal waste landfills and other waste handling or treatment facilities. Non-point sources include the use of pesticides to control insect and weed pests on agricultural areas, forest lands, home and gardens, and other land application uses.
(iii) The environmental persistence and transport of the pesticide or PCBs.
(iv) How well the water source is protected against contamination due to such factors as depth of the well and the type of soil and the integrity of the well casing.
(v) Elevated nitrate levels at the water supply source.
(vi) Use of PCBs in equipment used in the production, storage, or distribution of water (i.e., PCBs used in pumps, transformers, etc.).
(7) If an organic contaminant listed in § 141.61(c) is detected (as defined by paragraph (h)(18) of this section) in any sample, then:
(i) Each system must monitor quarterly at each sampling point which resulted in a detection.
(ii) The State may decrease the quarterly monitoring requirement specified in paragraph (h)(7)(i) of this section provided it has determined that the system is reliably and consistently below the maximum contaminant level. In no case shall the State make this determination unless a groundwater system takes a minimum of two quarterly samples and a surface water system takes a minimum of four quarterly samples.
(iii) After the State determines the system is reliably and consistently below the maximum contaminant level the State may allow the system to monitor annually. Systems which monitor annually must monitor during the quarter that previously yielded the highest analytical result.
(iv) Systems which have 3 consecutive annual samples with no detection of a contaminant may apply to the State for a waiver as specified in paragraph (h)(6) of this section.
(v) If monitoring results in detection of one or more of certain related contaminants (aldicarb, aldicarb sulfone, aldicarb sulfoxide and heptachlor, heptachlor epoxide), then subsequent monitoring shall analyze for all related contaminants.
(8) Systems which violate the requirements of § 141.61(c) as determined by paragraph (h)(11) of this section must monitor quarterly. After a minimum of four quarterly samples show the system is in compliance and the State determines the system is reliably and consistently below the MCL, as specified in paragraph (h)(11) of this section, the system shall monitor at the frequency specified in paragraph (h)(7)(iii) of this section.
(9) The State may require a confirmation sample for positive or negative results. If a confirmation sample is required by the State, the result must be averaged with the first sampling result and the average used for the compliance determination as specified by paragraph (h)(11) of this section. States have discretion to delete results of obvious sampling errors from this calculation.
(10) The State may reduce the total number of samples a system must analyze by allowing the use of compositing. Composite samples from a maximum of five sampling points are allowed, provided that the detection limit of the method used for analysis is less than one-fifth of the MCL. Compositing of samples must be done in the laboratory and analyzed within 14 days of sample collection.
(i) If the concentration in the composite sample detects one or more contaminants listed in § 141.61(c), then a follow-up sample must be taken within 14 days at each sampling point included in the composite, and be analyzed for that contaminant.
(ii) If duplicates of the original sample taken from each sampling point used in the composite sample are available, the system may use these instead of resampling. The duplicates must be analyzed and the results reported to the State within 14 days after completion of the composite analysis or before the holding time for the initial sample is exceeded whichever is sooner.
(iii) If the population served by the system is >3,300 persons, then compositing may only be permitted by the State at sampling points within a single system. In systems serving ≤ 3,300 persons, the State may permit compositing among different systems provided the 5-sample limit is maintained.
(11) Compliance with § 141.61(c) shall be determined based on the analytical results obtained at each sampling point.
(i) For systems which are conducting monitoring at a frequency greater than annual, compliance is determined by a running annual average of all samples taken at each sampling point. If the annual average of any sampling point is greater than the MCL, then the system is out of compliance. If the initial sample or a subsequent sample would cause the annual average to be exceeded, then the system is out of compliance immediately. Any samples below the detection limit shall be calculated as zero for purposes of determining the annual average.
(ii) If monitoring is conducted annually, or less frequently, the system is out of compliance if the level of a contaminant at any sampling point is greater than the MCL. If a confirmation sample is required by the State, the determination of compliance will be based on the average of two samples.
(12) [Reserved]
(13) Analysis for PCBs shall be conducted as follows using the methods in paragraph (e) of this section:
(i) Each system which monitors for PCBs shall analyze each sample using either Method 508.1, 525.2, 508 or 505. Users of Method 505 may have more difficulty in achieving the required Aroclor detection limits than users of Methods 508.1, 525.2 or 508.
(ii) If PCBs (as one of seven Aroclors) are detected (as designated in this paragraph) in any sample analyzed using Method 505 or 508, the system shall reanalyze the sample using Method 508A to quantitate PCBs (as decachlorobiphenyl).
(iii) Compliance with the PCB MCL shall be determined based upon the quantitative results of analyses using Method 508A.
(14) If monitoring data collected after January 1, 1990, are generally consistent with the requirements of § 141.24(h), then the State may allow systems to use that data to satisfy the monitoring requirement for the initial compliance period beginning January 1, 1993.
(15) The State may increase the required monitoring frequency, where necessary, to detect variations within
(16) The State has the authority to determine compliance or initiate enforcement action based upon analytical results and other information compiled by their sanctioned representatives and agencies.
(17) Each public water system shall monitor at the time designated by the State within each compliance period.
(18) Detection as used in this paragraph shall be defined as greater than or equal to the following concentrations for each contaminant.
(19) Anaylsis under this section shall only be conducted by laboratories that have received certification by EPA or the State and have met the following conditions:
(i) To receive certification to conduct analyses for the contaminants in § 141.61(c) the laboratory must:
(A) Analyze Performance Evaluation (PE) samples provided by EPA, the State, or by a third party (with the approval of the State or EPA) at least once a year by each method for which the laboratory desires certification.
(B) For each contaminant that has been included in the PE sample achieve quantitative results on the analyses that are within the following acceptance limits:
(ii) [Reserved]
At 66 FR 7063, Jan. 22, 2001, § 141.24 was amended by adding a new sentence to the end of paragraph (f)(15) introductory text; revising paragraphs (f)(15)(i) and (f)(15)(ii) and adding new paragraphs (f)(15)(iii) through (f)(15)(v); adding paragraph (f)(22); adding a new sentence to the end of paragraph (h)(11) introductory text; revising paragraphs (h)(11)(i) and (h)(11)(ii) and adding new paragraphs (h)(11)(iii)
(f) * * *
(15) * * * If one sampling point is in violation of an MCL, the system is in violation of the MCL.
(i) For systems monitoring more than once per year, compliance with the MCL is determined by a running annual average at each sampling point.
(ii) Systems monitoring annually or less frequently whose sample result exceeds the MCL must begin quarterly sampling. The system will not be considered in violation of the MCL until it has completed one year of quarterly sampling.
(iii) If any sample result will cause the running annual average to exceed the MCL at any sampling point, the system is out of compliance with the MCL immediately.
(iv) If a system fails to collect the required number of samples, compliance will be based on the total number of samples collected.
(v) If a sample result is less than the detection limit, zero will be used to calculate the annual average.
(22) All new systems or systems that use a new source of water that begin operation after January 22, 2004 must demonstrate compliance with the MCL within a period of time specified by the State. The system must also comply with the initial sampling frequencies specified by the State to ensure a system can demonstrate compliance with the MCL. Routine and increased monitoring frequencies shall be conducted in accordance with the requirements in this section.
(h) * * *
(11)* * * If one sampling point is in violation of an MCL, the system is in violation of the MCL.
(i) For systems monitoring more than once per year, compliance with the MCL is determined by a running annual average at each sampling point.
(ii) Systems monitoring annually or less frequently whose sample result exceeds the regulatory detection level as defined by paragraph (h)(18) of this section must begin quarterly sampling. The system will not be considered in violation of the MCL until it has completed one year of quarterly sampling.
(iii) If any sample result will cause the running annual average to exceed the MCL at any sampling point, the system is out of compliance with the MCL immediately.
(iv) If a system fails to collect the required number of samples, compliance will be based on the total number of samples collected.
(v) If a sample result is less than the detection limit, zero will be used to calculate the annual average.
(20) All new systems or systems that use a new source of water that begin operation after January 22, 2004 must demonstrate compliance with the MCL within a period of time specified by the State. The system must also comply with the initial sampling frequencies specified by the State to ensure a system can demonstrate compliance with the MCL. Routine and increased monitoring frequencies shall be conducted in accordance with the requirements in this section.
(a) Analysis for the following contaminants shall be conducted to determine compliance with §§ 141.15 and 141.16 (radioactivity) in accordance with the methods in the following table, or their equivalent determined by EPA in accordance with § 141.27.
(b) When the identification and measurement of radionuclides other than those listed in paragraph (a) of this section is required, the following references are to be used, except in cases where alternative methods have been approved in accordance with § 141.27.
(1)
(2)
(c) For the purpose of monitoring radioactivity concentrations in drinking water, the required sensitivity of the radioanalysis is defined in terms of a detection limit. The detection limit shall be that concentration which can be counted with a precision of plus or minus 100 percent at the 95 percent confidence level (1.96σ where σ is the standard deviation of the net counting rate of the sample).
(1) To determine compliance with § 141.15(a) the detection limit shall not exceed 1 pCi/1. To determine compliance with § 141.15(b) the detection limit shall not exceed 3 pCi/1.
(2) To determine compliance with § 141.16 the detection limits shall not exceed the concentrations listed in Table B.
(d) To judge compliance with the maximum contaminant levels listed in §§ 141.15 and 141.16, averages of data shall be used and shall be rounded to the same number of significant figures as the maximum contaminant level for the substance in question.
(e) The State has the authority to determine compliance or initiate enforcement action based upon analytical results or other information compiled by their sanctioned representatives and agencies.
At 65 FR 76745, Dec. 7, 2000, § 141.25 was amended by revising paragraphs (a) introductory text, (c)(1), (c)(2) introductory text, and (d), and by redesignating Table B in paragragh (c)(2) as Table C, effective Dec. 8, 2003. For the convenience of the user, the revised text is set forth as follows:
(a) Analysis for the following contaminants shall be conducted to determine compliance with § 141.66 (radioactivity) in accordance with the methods in the following table, or their equivalent determined by EPA in accordance with § 141.27.
(c) * * *
(1) To determine compliance with § 141.66(b), (c), and (e) the detection limit shall not exceed the concentrations in Table B to this paragraph.
(2) To determine compliance with § 141.66(d) the detection limits shall not exceed the concentrations listed in Table C to this paragraph.
(d) To judge compliance with the maximum contaminant levels listed in § 141.66, averages of data shall be used and shall be rounded to the same number of significant figures as the maximum contaminant level for the substance in question.
(a) Monitoring requirements for gross alpha particle activity, radium-226 and radium-228.
(1) Initial sampling to determine compliance with § 141.15 shall begin within two years of the effective date of these regulations and the analysis shall be completed within three years of the effective date of these regulations. Compliance shall be based on the analysis of an annual composite of four consecutive quarterly samples or the average of the analyses of four samples obtained at quarterly intervals.
(i) A gross alpha particle activity measurement may be substituted for the required radium-226 and radium-228 analysis
(ii) When the gross alpha particle activity exceeds 5 pCi/1, the same or an equivalent sample shall be analyzed for radium-226. If the concentration of radium-226 exceeds 3 pCi/1 the same or an equivalent sample shall be analyzed for radium-228.
(2) For the initial analysis required by paragraph (a)(1) of this section, data acquired within one year prior to the effective date of this part may be substituted at the discretion of the State.
(3) Suppliers of water shall monitor at least once every four years following the procedure required by paragraph (a)(1) of this section. At the discretion of the State, when an annual record taken in conformance with paragraph (a)(1) of this section has established that the average annual concentration is less than half the maximum contaminant levels established by § 141.15, analysis of a single sample may be substituted for the quarterly sampling procedure required by paragraph (a)(1) of this section.
(i) More frequent monitoring shall be conducted when ordered by the State in the vicinity of mining or other operations which may contribute alpha particle radioactivity to either surface or ground water sources of drinking water.
(ii) A supplier of water shall monitor in conformance with paragraph (a)(1) of this section within one year of the introduction of a new water source for a community water system. More frequent monitoring shall be conducted when ordered by the State in the event of possible contamination or when changes in the distribution system or treatment processing occur which may increase the concentration of radioactivity in finished water.
(iii) A community water system using two or more sources having different concentrations of radioactivity shall monitor source water, in addition to water from a free-flowing tap, when ordered by the State.
(iv) Monitoring for compliance with § 141.15 after the initial period need not include radium-228
(v) Suppliers of water shall conduct annual monitoring of any community water system in which the radium-226 concentration exceeds 3 pCi/1, when ordered by the State.
(4) If the average annual maximum contaminant level for gross alpha particle activity or total radium as set forth in § 141.15 is exceeded, the supplier of a community water system shall give notice to the State pursuant to § 141.31 and notify the public as required by subpart Q. Monitoring at quarterly intervals shall be continued until the annual average concentration no longer exceeds the maximum contaminant level or until a monitoring schedule as a condition to a variance, exemption or enforcement action shall become effective.
(b) Monitoring requirements for manmade radioactivity in community water systems.
(1) Within two years of the effective date of this part, systems using surface water sources and serving more than 100,000 persons and such other community water systems as are designated by the State shall be monitored for compliance with § 141.16 by analysis of
(i) If the gross beta particle activity exceeds 50 pCi/1, an analysis of the sample must be performed to identify the major radioactive constituents present and the appropriate organ and total body doses shall be calculated to determine compliance with § 141.16.
(ii) Suppliers of water shall conduct additional monitoring, as ordered by the State, to determine the concentration of man-made radioactivity in principal watersheds designated by the State.
(iii) At the discretion of the State, suppliers of water utilizing only ground waters may be required to monitor for man-made radioactivity.
(2) For the initial analysis required by paragraph (b)(1) of this section data acquired within one year prior to the effective date of this part may be substituted at the discretion of the State.
(3) After the initial analysis required by paragraph (b)(1) of this section suppliers of water shall monitor at least every four years following the procedure given in paragraph (b)(1) of this section.
(4) Within two years of the effective date of these regulations the supplier of any community water system designated by the State as utilizing waters contaminated by effluents from nuclear facilities shall initiate quarterly monitoring for gross beta particle and iodine-131 radioactivity and annual monitoring for strontium-90 and tritium.
(i) Quarterly monitoring for gross beta particle activity shall be based on the analysis of monthly samples or the analysis of a composite of three monthly samples. The former is recommended. If the gross beta particle activity in a sample exceeds 15 pCi/1, the same or an equivalent sample shall be analyzed for strontium-89 and cesium-134. If the gross beta particle activity exceeds 50 pCi/1, an analysis of the sample must be performed to identify the major radioactive constituents present and the appropriate organ and total body doses shall be calculated to determine compliance with § 141.16.
(ii) For iodine-131, a composite of five consecutive daily samples shall be analyzed once each quarter. As ordered by the State, more frequent monitoring shall be conducted when iodine-131 is identified in the finished water.
(iii) Annual monitoring for strontium-90 and tritium shall be conducted by means of the analysis of a composite of four consecutive quarterly samples or analysis of four quarterly samples. The latter procedure is recommended.
(iv) The State may allow the substitution of environmental surveillance data taken in conjunction with a nuclear facility for direct monitoring of manmade radioactivity by the supplier of water where the State determines such data is applicable to a particular community water system.
(5) If the average annual maximum contaminant level for man-made radioactivity set forth in § 141.16 is exceeded, the operator of a community water system shall give notice to the State pursuant to § 141.31 and to the public as required by subpart Q. Monitoring at monthly intervals shall be continued until the concentration no longer exceeds the maximum contaminant level or until a monitoring schedule as a condition to a variance, exemption or enforcement action shall become effective.
At 65 FR 76745, Dec. 7, 2000, § 141.26 was revised, effective Dec. 8, 2003. For the convenience of the user, the revised text is set forth as follows:
(a) Monitoring and compliance requirements for gross alpha particle activity, radium-226, radium-228, and uranium.
(1) Community water systems (CWSs) must conduct initial monitoring to determine
(i) Applicability and sampling location for existing community water systems or sources. All existing CWSs using ground water, surface water or systems using both ground and surface water (for the purpose of this section hereafter referred to as systems) must sample at every entry point to the distribution system that is representative of all sources being used (hereafter called a sampling point) under normal operating conditions. The system must take each sample at the same sampling point unless conditions make another sampling point more representative of each source or the State has designated a distribution system location, in accordance with paragraph(a)(2)(ii)(C) of this section.
(ii) Applicability and sampling location for new community water systems or sources. All new CWSs or CWSs that use a new source of water must begin to conduct initial monitoring for the new source within the first quarter after initiating use of the source. CWSs must conduct more frequent monitoring when ordered by the State in the event of possible contamination or when changes in the distribution system or treatment processes occur which may increase the concentration of radioactivity in finished water.
(2) Initial monitoring: Systems must conduct initial monitoring for gross alpha particle activity, radium-226, radium-228, and uranium as follows:
(i) Systems without acceptable historical data, as defined below, must collect four consecutive quarterly samples at all sampling points before December 31, 2007.
(ii) Grandfathering of data: States may allow historical monitoring data collected at a sampling point to satisfy the initial monitoring requirements for that sampling point, for the following situations.
(A) To satisfy initial monitoring requirements, a community water system having only one entry point to the distribution system may use the monitoring data from the last compliance monitoring period that began between June 2000 and December 8, 2003.
(B) To satisfy initial monitoring requirements, a community water system with multiple entry points and having appropriate historical monitoring data for each entry point to the distribution system may use the monitoring data from the last compliance monitoring period that began between June 2000 and December 8, 2003.
(C) To satisfy initial monitoring requirements, a community water system with appropriate historical data for a representative point in the distribution system may use the monitoring data from the last compliance monitoring period that began between June 2000 and December 8, 2003, provided that the State finds that the historical data satisfactorily demonstrate that each entry point to the distribution system is expected to be in compliance based upon the historical data and reasonable assumptions about the variability of contaminant levels between entry points. The State must make a written finding indicating how the data conforms to the these requirements.
(iii) For gross alpha particle activity, uranium, radium-226, and radium-228 monitoring, the State may waive the final two quarters of initial monitoring for a sampling point if the results of the samples from the previous two quarters are below the detection limit.
(iv) If the average of the initial monitoring results for a sampling point is above the MCL, the system must collect and analyze quarterly samples at that sampling point until the system has results from four consecutive quarters that are at or below the MCL, unless the system enters into another schedule as part of a formal compliance agreement with the State.
(3) Reduced monitoring: States may allow community water systems to reduce the future frequency of monitoring from once every three years to once every six or nine years at each sampling point, based on the following criteria.
(i) If the average of the initial monitoring results for each contaminant (
(ii) For gross alpha particle activity and uranium, if the average of the initial monitoring results for each contaminant is at or above the detection limit but at or below
(iii) For gross alpha particle activity and uranium, if the average of the initial monitoring results for each contaminant is above
(iv) Systems must use the samples collected during the reduced monitoring period to determine the monitoring frequency for subsequent monitoring periods (
(v) If a system has a monitoring result that exceeds the MCL while on reduced monitoring, the system must collect and analyze quarterly samples at that sampling point until the system has results from four consecutive quarters that are below the MCL, unless the system enters into another schedule as part of a formal compliance agreement with the State.
(4) Compositing: To fulfill quarterly monitoring requirements for gross alpha particle activity, radium-226, radium-228, or uranium, a system may composite up to four consecutive quarterly samples from a single entry point if analysis is done within a year of the first sample. States will treat analytical results from the composited as the average analytical result to determine compliance with the MCLs and the future monitoring frequency. If the analytical result from the composited sample is greater than
(5) A gross alpha particle activity measurement may be substituted for the required radium-226 measurement provided that the measured gross alpha particle activity does not exceed 5 pCi/l. A gross alpha particle activity measurement may be substituted for the required uranium measurement provided that the measured gross alpha particle activity does not exceed 15 pCi/l. The gross alpha measurement shall have a confidence interval of 95% (1.65σ, where σ is the standard deviation of the net counting rate of the sample) for radium-226 and uranium. When a system uses a gross alpha particle activity measurement in lieu of a radium-226 and/or uranium measurement, the gross alpha particle activity analytical result will be used to determine the future monitoring frequency for radium-226 and/or uranium. If the gross alpha particle activity result is less than detection,
(b)
(1) Community water systems (both surface and ground water) designated by the State as vulnerable must sample for beta particle and photon radioactivity. Systems must collect quarterly samples for beta emitters and annual samples for tritium and strontium-90 at each entry point to the distribution system (hereafter called a sampling point), beginning within one quarter after being notified by the State. Systems already designated by the State must continue to sample until the State reviews and either reaffirms or removes the designation.
(i) If the gross beta particle activity minus the naturally occurring potassium-40 beta particle activity at a sampling point has a running annual average (computed quarterly) less than or equal to 50 pCi/L (screening level), the State may reduce the frequency of monitoring at that sampling point to once every 3 years. Systems must collect all samples required in paragraph (b)(1) of this section during the reduced monitoring period.
(ii) For systems in the vicinity of a nuclear facility, the State may allow the CWS to utilize environmental surveillance data collected by the nuclear facility in lieu of monitoring at the system's entry point(s), where the State determines if such data is applicable to a particular water system. In the event that there is a release from a nuclear facility, systems which are using surveillance data must begin monitoring at the community water system's entry point(s) in accordance with paragraph (b)(1) of this section.
(2) Community water systems (both surface and ground water) designated by the State as utilizing waters contaminated by effluents from nuclear facilities must sample for beta particle and photon radioactivity. Systems must collect quarterly samples for beta emitters and iodine-131 and annual samples for tritium and strontium-90 at each entry point to the distribution system (hereafter called a sampling point), beginning within one quarter after being notified by the State. Systems already designated by the State as systems using waters contaminated by effluents from nuclear facilities must continue to sample until the State reviews and either reaffirms or removes the designation.
(i) Quarterly monitoring for gross beta particle activity shall be based on the analysis of monthly samples or the analysis of a composite of three monthly samples. The former is recommended.
(ii) For iodine-131, a composite of five consecutive daily samples shall be analyzed once each quarter. As ordered by the State, more frequent monitoring shall be conducted when iodine-131 is identified in the finished water.
(iii) Annual monitoring for strontium-90 and tritium shall be conducted by means of the analysis of a composite of four consecutive quarterly samples or analysis of four quarterly samples. The latter procedure is recommended.
(iv) If the gross beta particle activity beta minus the naturally occurring potassium-40 beta particle activity at a sampling point has a running annual average (computed quarterly) less than or equal to 15 pCi/L, the State may reduce the frequency of monitoring at that sampling point to every 3 years. Systems must collect all samples required in paragraph (b)(2) of this section during the reduced monitoring period.
(v) For systems in the vicinity of a nuclear facility, the State may allow the CWS to utilize environmental surveillance data collected by the nuclear facility in lieu of monitoring at the system's entry point(s), where the State determines if such data is applicable to a particular water system. In the event that there is a release from a nuclear facility, systems which are using surveillance data must begin monitoring at the community water system's entry point(s) in accordance with paragraph (b)(2) of this section.
(3) Community water systems designated by the State to monitor for beta particle and photon radioactivity can not apply to the State for a waiver from the monitoring frequencies specified in paragraph (b)(1) or (b)(2) of this section.
(4) Community water systems may analyze for naturally occurring potassium-40 beta particle activity from the same or equivalent sample used for the gross beta particle activity analysis. Systems are allowed to subtract the potassium-40 beta particle activity value from the total gross beta particle activity value to determine if the screening level is exceeded. The potassium-40 beta particle activity must be calculated by multiplying elemental potassium concentrations (in mg/L) by a factor of 0.82.
(5) If the gross beta particle activity minus the naturally occurring potassium-40 beta particle activity exceeds the screening level, an analysis of the sample must be performed to identify the major radioactive constituents present in the sample and the appropriate doses must be calculated and summed to determine compliance with § 141.66(d)(1), using the formula in § 141.66(d)(2). Doses must also be calculated and combined for measured levels of tritium and strontium to determine compliance.
(6) Systems must monitor monthly at the sampling point(s) which exceed the maximum contaminant level in § 141.66(d) beginning the month after the exceedance occurs. Systems must continue monthly monitoring until the system has established, by a rolling average of 3 monthly samples, that the MCL is being met. Systems who establish that the MCL is being met must return to quarterly monitoring until they meet the requirements set forth in paragraph (b)(1)(ii) or (b)(2)(i) of this section.
(c) General monitoring and compliance requirements for radionuclides.
(1) The State may require more frequent monitoring than specified in paragraphs (a) and (b) of this section, or may require confirmation samples at its discretion. The results of the initial and confirmation samples will be averaged for use in compliance determinations.
(2) Each public water systems shall monitor at the time designated by the State during each compliance period.
(3) Compliance: Compliance with § 141.66 (b) through (e) will be determined based on the analytical result(s) obtained at each sampling point. If one sampling point is in violation of an MCL, the system is in violation of the MCL.
(i) For systems monitoring more than once per year, compliance with the MCL is determined by a running annual average at each sampling point. If the average of any sampling point is greater than the MCL, then the system is out of compliance with the MCL.
(ii) For systems monitoring more than once per year, if any sample result will cause the running average to exceed the MCL at any sample point, the system is out of compliance with the MCL immediately.
(iii) Systems must include all samples taken and analyzed under the provisions of this section in determining compliance, even if that number is greater than the minimum required.
(iv) If a system does not collect all required samples when compliance is based on a running annual average of quarterly samples, compliance will be based on the running average of the samples collected.
(v) If a sample result is less than the detection limit, zero will be used to calculate the annual average, unless a gross alpha particle activity is being used in lieu of radium-226 and/or uranium. If the gross alpha particle activity result is less than detection,
(4) States have the discretion to delete results of obvious sampling or analytic errors.
(5) If the MCL for radioactivity set forth in § 141.66 (b) through (e) is exceeded, the operator of a community water system must give notice to the State pursuant to § 141.31 and to the public as required by subpart Q of this part.
(a) With the written permission of the State, concurred in by the Administrator of the U.S. EPA, an alternate
(a) For the purpose of determining compliance with §§ 141.21 through 141.27, 141.30, 141.40, 141.74 and 141.89, samples may be considered only if they have been analyzed by a laboratory certified by the State except that measurements for alkalinity, calcium, conductivity, disinfectant residual, orthophosphate, pH, silica, temperature and turbidity may be performed by any person acceptable to the State.
(b) Nothing in this part shall be construed to preclude the State or any duly designated representative of the State from taking samples or from using the results from such samples to determine compliance by a supplier of water with the applicable requirements of this part.
When a public water system supplies water to one or more other public water systems, the State may modify the monitoring requirements imposed by this part to the extent that the interconnection of the systems justifies treating them as a single system for monitoring purposes. Any modified monitoring shall be conducted pursuant to a schedule specified by the State and concurred in by the Administrator of the U.S. Environmental Protection Agency.
(a) Community water system which serve a population of 10,000 or more individuals and which add a disinfectant (oxidant) to the water in any part of the drinking water treatment process shall analyze for total trihalomethanes in accordance with this section. For systems serving 75,000 or more individuals, sampling and analyses shall begin not later than 1 year after the date of promulgation of this regulation. For systems serving 10,000 to 74,999 individuals, sampling and analyses shall begin not later than 3 years after the date of promulgation of this regulation. For the purpose of this section, the minimum number of samples required to be taken by the system shall be based on the number of treatment plants used by the system, except that multiple wells drawing raw water from a single aquifer may, with the State approval, be considered one treatment plant for determining the minimum number of samples. All samples taken within an established frequency shall be collected within a 24-hour period.
(b)(1) For all community water systems utilizing surface water sources in whole or in part, and for all community water systems utilizing only ground water sources that have not been determined by the State to qualify for the monitoring requirements of paragraph (c) of this section, analyses for total trihalomethanes shall be performed at quarterly intervals on at least four water samples for each treatment plant used by the system. At least 25 percent of the samples shall be taken at locations within the distribution system reflecting the maximum residence time of the water in the system. The remaining 75 percent shall be taken at representative locations in the distribution system, taking into account number of persons served, different sources of water and different treatment methods employed. The results of all analyses per quarter shall be arithmetically averaged and reported to the State within 30 days of the system's receipt of such results. Results shall also be reported to EPA until such monitoring requirements have been adopted by the State. All samples collected shall be used in the computation of the average, unless the analytical results are invalidated for technical reasons. Sampling and analyses shall be conducted in accordance with the methods listed in paragraph (e) of this section.
(2) Upon the written request of a community water system, the monitoring frequency required by paragraph (b)(1) of this section may be reduced by the State to a minimum of one sample analyzed for TTHMs per quarter taken at a point in the distribution system reflecting the maximum residence time of the water in the system, upon a written determination by the State that the data from at least 1 year of monitoring in accordance with paragraph (b)(1) of this section and local conditions demonstrate that total trihalomethane concentrations will be consistently below the maximum contaminant level.
(3) If at any time during which the reduced monitoring frequency prescribed under this paragraph applies, the results from any analysis exceed 0.10 mg/l of TTHMs and such results are confirmed by at least one check sample taken promptly after such results are received, or if the system makes any significant change to its source of water or treatment program, the system shall immediately begin monitoring in accordance with the requirements of paragraph (b)(1) of this section, which monitoring shall continue for at least 1 year before the frequency may be reduced again. At the option of the State, a system's monitoring frequency may and should be increased above the minimum in those cases where it is necessary to detect variations of TTHM levels within the distribution system.
(c)(1) Upon written request to the State, a community water system utilizing only ground water sources may seek to have the monitoring frequency required by paragraph (b)(1) of this section reduced to a minimum of one sample for maximum TTHM potential per year for each treatment plant used by the system taken at a point in the distribution system reflecting maximum residence time of the water in the system. The system shall submit the results of at least one sample for maximum TTHM potential using the procedure specified in paragraph (g) of this section. A sample must be analyzed from each treatment plant used by the system and be taken at a point in the distribution system reflecting the maximum residence time of the water in the system. The system's monitoring frequency may only be reduced upon a written determination by the State that, based upon the data submitted by the system, the system has a maximum TTHM potential of less than 0.10 mg/l and that, based upon an assessment of the local conditions of the system, the system is not likely to approach or exceed the maximum contaminant level for total TTHMs. The results of all analyses shall be reported to the State within 30 days of the system's receipt of such results. Results shall also be reported to EPA until such monitoring requirements have been adopted by the State. All samples collected shall be used for determining whether the system must comply with the monitoring requirements of paragraph (b) of this section, unless the analytical results are invalidated for technical reasons. Sampling and analyses shall be conducted in accordance with the methods listed in paragraph (e) of this section.
(2) If at any time during which the reduced monitoring frequency prescribed under paragraph (c)(1) of this section applies, the results from any analysis taken by the system for maximum TTHM potential are equal to or greater than 0.10 mg/l, and such results are confirmed by at least one check sample taken promptly after such results are received, the system shall immediately begin monitoring in accordance with the requirements of paragraph (b) of this section and such monitoring shall continue for at least one year before the frequency may be reduced again. In the event of any significant change to the system's raw water or treatment program, the system shall immediately analyze an additional sample for maximum TTHM potential taken at a point in the distribution system reflecting maximum residence time of the water in the system for the purpose of determining whether the system must comply with the monitoring requirements of paragraph (b) of this section. At the option of the State, monitoring frequencies may and should be increased above the minimum in those cases where this is necessary to detect variation of TTHM levels within the distribution system.
(d) Compliance with § 141.12 shall be determined based on a running annual
(e) Sampling and analyses made pursuant to this section shall be conducted by one of the total trihalomethanes methods as directed in § 141.24(e), and the
(f) Before a community water system makes any significant modifications to its existing treatment process for the purposes of achieving compliance with § 141.12, such system must submit and obtain State approval of a detailed plan setting forth its proposed modification and those safeguards that it will implement to ensure that the bacteriological quality of the drinking water served by such system will not be adversely affected by such modification. Each system shall comply with the provisions set forth in the State-approved plan. At a minimum, a State approved plan shall require the system modifying its disinfection practice to:
(1) Evaluate the water system for sanitary defects and evaluate the source water for biological quality;
(2) Evaluate its existing treatment practices and consider improvements that will minimize disinfectant demand and optimize finished water quality throughout the distribution system;
(3) Provide baseline water quality survey data of the distribution system. Such data should include the results from monitoring for coliform and fecal coliform bacteria, fecal streptococci, standard plate counts at 35 °C and 20 °C, phosphate, ammonia nitrogen and total organic carbon. Virus studies should be required where source waters are heavily contaminated with sewage effluent;
(4) Conduct additional monitoring to assure continued maintenance of optimal biological quality in finished water, for example, when chloramines are introduced as disinfectants or when pre-chlorination is being discontinued. Additional monitoring should also be required by the State for chlorate, chlorite and chlorine dioxide when chlorine dioxide is used. Standard plate count analyses should also be required by the State as appropriate before and after any modifications;
(5) Consider inclusion in the plan of provisions to maintain an active disinfectant residual throughout the distribution system at all times during and after the modification.
(g) The water sample for determination of maximum total trihalomethane potential is taken from a point in the distribution system that reflects maximum residence time. Procedures for sample collection and handling are given in the methods. No reducing agent is added to “quench” the chemical reaction producing THMs at the time of sample collection. The intent is to permit the level of THM precursors to be depleted and the concentration of THMs to be maximized for the supply being tested. Four experimental parameters affecting maximum THM production are pH, temperature, reaction time and the presence of a disinfectant residual. These parameters are dealt with as follows: Measure the disinfectant residual at the selected sampling point. Proceed only if a measurable disinfectant residual is present. Collect triplicate 40 ml water samples at the pH prevailing at the time of sampling, and prepare a method blank according to the methods. Seal and store these samples together for seven days at 25 °C or above. After this time period,
(h) The requirements in paragraphs (a) through (g) of this section apply to subpart H community water systems which serve a population of 10,000 or more until December 31, 2001. The requirements in paragraphs (a) through (g) of this section apply to community water systems which use only ground water not under the direct influence of surface water that add a disinfectant (oxidant) in any part of the treatment process and serve a population of 10,000 or more until December 31, 2003. After December 31, 2003, this section is no longer applicable.
(a) Except where a shorter period is specified in this part, the supplier of water shall report to the State the results of any test measurement or analysis required by this part within (1) The first ten days following the month in which the result is received, or (2) the first ten days following the end of the required monitoring period as stipulated by the State, whichever of these is shortest.
(b) Except where a different reporting period is specified in this part, the supplier of water must report to the State within 48 hours the failure to comply with any national primary drinking water regulation (including failure to comply with monitoring requirements) set forth in this part.
(c) The supplier of water is not required to report analytical results to the State in cases where a State laboratory performs the analysis and reports the results to the State office which would normally receive such notification from the supplier.
(d) The public water system, within 10 days of completing the public notification requirements under Subpart Q of this part for the initial public notice and any repeat notices, must submit to the primacy agency a certification that it has fully complied with the public notification regulations. The public water system must include with this certification a representative copy of each type of notice distributed, published, posted, and made available to the persons served by the system and to the media.
(e) The water supply system shall submit to the State within the time stated in the request copies of any records required to be maintained under § 141.33 hereof or copies of any documents then in existence which the State or the Administrator is entitled to inspect pursuant to the authority of section 1445 of the Safe Drinking Water Act or the equivalent provisions of State law.
The requirements in this section apply until the requirements of Subpart Q of this part are applicable. Public water systems where EPA directly implements the public water system supervision program must comply with the requirements in Subpart Q of this part on October 31, 2000. All other public water systems must comply with the requirements in Subpart Q of this part on May 6, 2002 or on the date the State-adopted rule becomes effective, whichever comes first.
(a)
(1) Except as provided in paragraph (a)(3) of this section, the owner or operator of a public water system must give notice:
(i) By publication in a daily newspaper of general circulation in the area served by the system as soon as possible, but in no case later than 14 days after the violation or failure. If the area served by a public water system is not served by a daily newspaper of general circulation, notice shall instead be given by publication in a weekly newspaper of general circulation serving the area; and
(ii) By mail delivery (by direct mail or with the water bill), or by hand delivery, not later than 45 days after the violation or failure. The State may waive mail or hand delivery if it determines that the owner or operator of the public water system in violation has corrected the violation or failure within the 45-day period. The State must make the waiver in writing and within the 45-day period; and
(iii) For violations of the MCLs of contaminants or MRDLs of disinfectants that may pose an acute risk to human health, by furnishing a copy of the notice to the radio and television stations serving the area served by the public water system as soon as possible but in no case later than 72 hours after the violation. The following violations are acute violations:
(A) Any violations specified by the State as posing an acute risk to human health.
(B) Violation of the MCL for nitrate or nitrite as defined in § 141.62 and determined according to § 141.23(i)(3).
(C) Violation of the MCL for total coliforms, when fecal coliforms or
(D) Occurrence of a waterborne disease outbreak, as defined in § 141.2, in an unfiltered system subject to the requirements of subpart H of this part, after December 30, 1991 (see § 141.71(b)(4)).
(E) Violation of the MRDL for chlorine dioxide as defined in § 141.65 and determined according to § 141.133(c)(2).
(2) Except as provided in paragraph (a)(3) of this section, following the initial notice given under paragraph (a)(1) of this section, the owner or operator of the public water system must give notice at least once every three months by mail delivery (by direct mail or with the water bill) or by hand delivery, for as long as the violation or failure exists.
(3)(i) In lieu of the requirements of paragraphs (a) (1) and (2) of this section, the owner or operator of a community water system in an area that is not served by a daily or weekly newspaper of general circulation must give notice by hand delivery or by continuous posting in conspicuous places within the area served by the system. Notice by hand delivery or posting must begin as soon as possible, but no later than 72 hours after the violation or failure for acute violations (as defined in paragraph (a)(1)(iii) of this section), or 14 days after the violation or failure (for any other violation). Posting must continue for as long as the violation or failure exists. Notice by hand delivery must be repeated at least every three months for as long as the violation or failure exists.
(ii) In lieu of the requirements of paragraphs (a) (1) and (2) of this section, the owner or operator of a non-community water system may give notice by hand delivery or by continuous posting in conspicuous places within the area served by the system. Notice by hand delivery or posting must begin as soon as possible, but no later than 72 hours after the violation or failure for acute violations (as defined in paragraph (a)(1)(iii) of this section), or 14 days after the violation or failure (for any other violation). Posting must continue for as long as the violation or failure exists. Notice by hand delivery must be repeated at least every three months for as long as the violation or failure exists.
(b)
(1) Except as provided in paragraph (b)(3) or (b)(4) of this section, the owner or operator of a public water system must give notice within three months of the violation or granting of a variance or exemption by publication in a daily newspaper of general circulation in the area served by the system. If the area served by a public water system is not served by a daily newspaper of general circulation, notice shall instead be given by publication in a weekly newspaper of general circulation serving the area.
(2) Except as provided in paragraph (b)(3) or (b)(4) of this section, following the initial notice given under paragraph (b)(1) of this section, the owner or operator of the public water system must give notice at least once every three months by mail delivery (by direct mail or with the water bill) or by hand delivery, for as long as the violation exists. Repeat notice of the existence of a variance or exemption must be given every three months for as long as the variance or exemption remains in effect.
(3)(i) In lieu of the requirements of paragraphs (b)(1) and (b)(2) of this section, the owner or operator of a community water system in an area that is not served by a daily or weekly newspaper of general circulation must give notice, within three months of the violation or granting of the variance or exemption, by hand delivery or by continuous posting in conspicuous places with the area served by the system. Posting must continue for as long as the violation exists or a variance or exemption remains in effect. Notice by hand delivery must be repeated at least every three months for as long as the violation exists or a variance or exemption remains in effect.
(ii) In lieu of the requirements of paragraphs (b)(1) and (b)(2) of this section, the owner or operator of a non-community water system may give notice, within three months of the violation or the granting of the variance or exemption, by hand delivery or by continuous posting in conspicuous places within the area served by the system. Posting must continue for as long as the violation exists, or a variance or exemption remains in effect. Notice by hand delivery must be repeated at least every three months for as long as the violation exists or a variance or exemption remains in effect.
(4) In lieu of the requirements of paragraphs (b)(1), (b)(2), and (b)(3) of this section, the owner or operator of a public water system, at the discretion of the State, may provide less frequent notice for minor monitoring violations as defined by the State, if EPA has approved the State's application for a program revision under § 142.16. Notice of such violations must be given no less frequently than annually.
(c)
(d)
(e)
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
EPA is not specifying language that must be included in a public notice for a violation of the fluoride maximum contaminant level in this section because § 143.5 of this part includes the necessary information. See paragraph (f) of this section.]
(10)
(11)
(12)
(13)
(14)
(15)
(16)
(17)
(18)
(19)
(20)
(21)
(22)
(23)
(24)
(25)
(26)
(27)
(28)
(29)
(30)
(31)
(32)
(33)
(34)
(35)
(36)
(37)
(38)
(39)
(40)
(41)
(42)
(43)
(44)
(45)
(46)
(47)
(48)
(49)
(50)
(51)
(52)
(53)
(54)
(55)
(56) [Reserved]
(57)
(58)
(59)
(60)
(61)
(62)
(63)
(64)
(65)
(66)
(67)
(68)
(69)
(70)
(71)
(72)
(73)
(74)
(75)
(76)
(77)
(78)
In addition to the language in this introductory text of paragraph (e)(78), systems must include either the language in paragraph (e)(78)(i) or (e)(78)(ii) of this section. Systems with a violation at the treatment plant, but not in the distribution system, are required to use the language in paragraph (e)(78)(i) of this section and treat the violation as a nonacute violation. Systems with a violation in the distribution system are required to use the language in paragraph (e)(78)(ii) of this section and treat the violation as an acute violation.
(i) The chlorine dioxide violations reported today are the result of exceedances at the treatment facility only, and do not include violations within the distribution system serving users of this water supply. Continued compliance with chlorine dioxide levels within the distribution system minimizes the potential risk of these violations to present consumers.
(ii) The chlorine dioxide violations reported today include exceedances of the EPA standard within the distribution system serving water users. Violations of the chlorine dioxide standard within the distribution system may harm human health based on short-term exposures. Certain groups, including pregnant women, infants, and young children, may be especially susceptible to adverse effects of excessive exposure to chlorine dioxide-treated water. The purpose of this notice is to advise that such persons should consider reducing their risk of adverse effects from these chlorine dioxide violations by seeking alternate sources of water for human consumption until such exceedances are rectified. Local and State health authorities are the best sources for information concerning alternate drinking water.
(79)
(80)
(81)
(f)
(g)
Any owner or operator of a public water system subject to the provisions of this part shall retain on its premises or at a convenient location near its premises the following records:
(a) Records of bacteriological analyses made pursuant to this part shall be kept for not less than 5 years. Records of chemical analyses made pursuant to this part shall be kept for not less than 10 years. Actual laboratory reports may be kept, or data may be transferred to tabular summaries, provided that the following information is included:
(1) The date, place, and time of sampling, and the name of the person who collected the sample;
(2) Identification of the sample as to whether it was a routine distribution system sample, check sample, raw or process water sample or other special purpose sample;
(3) Date of analysis;
(4) Laboratory and person responsible for performing analysis;
(5) The analytical technique/method used; and
(6) The results of the analysis.
(b) Records of action taken by the system to correct violations of primary drinking water regulations shall be kept for a period not less than 3 years after the last action taken with respect to the particular violation involved.
(c) Copies of any written reports, summaries or communications relating to sanitary surveys of the system conducted by the system itself, by a private consultant, or by any local, State or Federal agency, shall be kept for a period not less than 10 years after completion of the sanitary survey involved.
(d) Records concerning a variance or exemption granted to the system shall be kept for a period ending not less than 5 years following the expiration of such variance or exemption.
(e) Copies of public notices issued pursuant to Subpart Q of this part and certifications made to the primacy agency pursuant to § 141.31 must be kept for three years after issuance.
(a)
(2)
(b)
(c)
(d)
(i) PWS Technical Contact, the person at your PWS that is responsible for the technical aspects of your unregulated contaminant monitoring regulation (UCMR) activities, such as details concerning sampling and reporting;
(ii) PWS Official, the person at your PWS that is able to function as the official spokesperson for your UCMR activities; and
(iii) Laboratory Contact Person, the person at your laboratory that is able to address questions concerning the analysis that they provided for you.
(2) You must update this information if it changes during the course of UCMR implementation.
(3) You must report the information specified for data elements 1 through 16 in the following table for each sample.
(e)
(2) If you report more than one set of valid results for the same sampling point and the same sampling event (for example, because you have had more than one organization (
(f)
(g)
(a)
(i)
(ii)
(A) You must monitor for the unregulated contaminants on List 1 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section.
(B) You must monitor for the unregulated contaminants on List 2 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, if notified by your State or EPA that you are part of the Screening Surveys.
(C) You must monitor for the unregulated contaminants on List 3 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, if notified by your State or EPA that you are part of the Pre-Screen Testing.
(iii)
(A) You must monitor for the unregulated contaminants on List 1 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, that
(B) You must monitor for the unregulated contaminants on List 2 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, that have a “sampling location” indicated as “distribution system” if notified by your State or EPA that you are part of the Screening Surveys.
(C) You must monitor for the unregulated contaminants on List 3 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, that have a “sampling location” indicated as “distribution system” if notified by your State or EPA that you are part of the Pre-Screen Testing.
(iv)
(A) You must monitor for the unregulated contaminants on List 1 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, if you are notified by your State or EPA that you are part of the State Monitoring Plan for small systems.
(B) You must monitor for the unregulated contaminants on List 2 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, if you are notified by your State or EPA that you are part of the Screening Surveys.
(C) You must monitor for the unregulated contaminants on List 3 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, if you are notified by your State or EPA that you are part of the Pre-Screen Testing.
(v)
(A) You must monitor for the unregulated contaminants on List 1 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, that have a “sampling location” indicated as “distribution system” if you are notified by your State or EPA that you are part of the State Monitoring Plan for small systems.
(B) You must monitor for the unregulated contaminants on List 2 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, that have a “sampling location” indicated as “distribution system” if you are notified by your State or EPA that you are part of the Screening Surveys.
(C) You must monitor for the unregulated contaminants on List 3 of Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, that have a “sampling location” indicated as “distribution system” if you are notified by your State or EPA that you are part of the Pre-Screen Testing.
(2)
(ii)
(iii)
(3)
(4)
(A) Collect samples of the listed contaminants in accordance with paragraph (a)(5) of this section and Appendix A of this section and any other specific instructions provided to you by the State or EPA,
(B) Analyze the additional parameters specified below in Table 2. “Water Quality Parameters to be Monitored with UCMR Contaminants” for each relevant contaminant type. You must analyze the parameters for each sampling event of each sampling point, using the method indicated, and report using the data elements 1 through 10 in Table 1, § 141.35(d), Unregulated Contaminant Monitoring Reporting Requirements;
(C) Review the laboratory testing results to ensure reliability; and
(D) Report the results as specified in § 141.35.
(ii)
(iii)
(A) Properly receive, store, maintain and use the sampling equipment sent to you from the laboratory designated by EPA;
(B) Sample at the times specified by the State or the EPA;
(C) Collect and pack samples in accordance with the instructions sent to you by the laboratory designated by EPA; and
(D) Send the samples to the laboratory designated by EPA.
(5) What specific sampling and quality control requirements must I follow for monitoring of List 1 contaminants?
(A)
(B)
(C)
(ii)
(A)
(B)
(C)
(D)
(E)
(F)
(G)
(
(
(iii)
(A)
(B)
(C)
(D)
(E)
(F)
(G)
(H)
(6)
(7)
(A) Analyze the additional parameters specified in paragraph § 141.40(a)(4)(i), Table 2, “Water Quality Parameters to be Monitored with UCMR Contaminants” for each relevant contaminant type. You must analyze the parameters for each sampling event of each sampling point, using the method indicated, and report the results using the data elements 1 through 10 in Table 1, § 141.35(d), Unregulated Contaminant Monitoring Reporting requirements;
(B) Review the laboratory results to ensure reliability; and
(C) Report the results as specified in § 141.35.
(ii)
(iii)
(8)
(b)
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
(A) First, within ninety (90) days of EPA's letter to you concerning initiation of Pre-Screen Testing for specific contaminants, you can identify from five (5) up to twenty-five (25) systems in your State that you determine to be representative of the most vulnerable systems to these contaminants, modify your State Monitoring Plan to include these most vulnerable systems if any serve 10,000 or fewer persons, and notify EPA of the addition of these systems to the State Plan. These systems must be selected from all community and non-transient noncommunity water systems. EPA will use the State-identified vulnerable systems to select up to 200 systems nationally to be monitored considering the characteristics of the contaminants, precipitation, system operation, and environmental conditions.
(B) Second, within 120 days prior to sampling, EPA will notify you which systems have been selected, sampling dates, the designated laboratory for testing of samples for systems serving 10,000 or fewer persons and approved laboratories for systems serving more than 10,000 persons, and instructions for sampling. You must notify the owners or operators of the selected systems in your State of these Pre-Screen Testing requirements. At least ninety (90) days prior to the sampling date, you must provide the necessary Pre-Screen Testing information to the owners or operators of the selected systems and then inform EPA that you took this action to allow sufficient time for EPA to ensure laboratory readiness.
(ix)
(2) What if I decide not to participate in an MOA? If you decide not to enter into an MOA with EPA to develop the State Monitoring Plan for small systems, the initial monitoring plan that EPA sent you will become the final State Monitoring Plan for your State or Tribe. In that case, you may still notify each public water system of its selection for the plan and instructions for monitoring as long as you notify EPA that you will be undertaking this responsibility at least six (6) months prior to the first unregulated contaminant monitoring.
(3) Can I add contaminants to the Unregulated Contaminant Monitoring List? Yes, the SDWA allows Governors of seven (7) or more States to petition the EPA Administrator to add one or more contaminants to the Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section. The petition must clearly identify the reason(s) for adding the contaminant(s) to the monitoring list in paragraph (a)(3) of this section, including the potential risk to public health, particularly any information that might be available regarding disproportional risks to the health and safety of children, the expected occurrence documented by any available data, any analytical methods known or
(4) Can I waive monitoring requirements? Only with EPA approval and under very limited conditions. Conditions and procedures for obtaining the only type of waiver available under these regulations are as follows:
(i) Application. You may apply to EPA for a State-wide waiver from the unregulated contaminant monitoring requirements for public water systems serving more than 10,000 persons. To apply for such a waiver, you must submit an application to EPA that includes the following information:
(A) the list of contaminants on the Unregulated Contaminant Monitoring List for which you request a waiver, and
(B) documentation for each contaminant in your request demonstrating that the contaminants have not been used, applied, stored, disposed of, released, naturally present or detected in the source waters or distribution systems in your State during the past 15 years, and that it does not occur naturally in your State.
(ii) Approval. EPA will notify you if EPA agrees to waive monitoring requirements.
Your system must ensure that the quality control requirements listed below for testing of samples collected and submitted under § 141.40 are followed:
(1) Sample Collection/Preservation. Follow the sample collection and preservation requirements for the specified method for each of the contaminants in Table 1, UCMR (1999) List, in paragraph (a)(3) of this section. These requirements specify sample containers, collection, dechlorination, preservation, storage, sample holding time, and extract storage and/or holding time that the laboratory must follow.
(2) Detection Limit. Calculate the laboratory detection limit for each contaminant in Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, of paragraph (a)(3) of this section using the appropriate procedure in the specified method with the exception that the contaminant concentration used to fortify reagent water must be less than or equal to the minimum reporting level (MRL) for the contaminants as specified in column 4, Table 1, UCMR (1999) List, in paragraph (a)(3) of this section. The calculated detection limit is equal to the standard deviation times the Student's t value for 99% confidence level with n-1 degrees of freedom. (The detection limit must be less than or equal to one-half of the MRL.)
(3) Calibration. Follow the initial calibration requirements as specified in the method utilized. Calibration must be verified initially with a low-level standard at a concentration at or below the MRL for each contaminant. Perform a continuing calibration verification following every 10th sample. The calibration verification must be performed by alternating low-level and mid-level calibration standards. The low-level standard is defined as a concentration at or below the MRL with an acceptance range of ±40%. The mid-level standard is in the middle of the calibration range with an acceptance range of ±20%.
(4) Reagent Blank Analysis. Analyze one laboratory reagent (method) blank per sample set/batch that is treated exactly as a sample. The maximum allowable background concentration is one-half of the MRL for all contaminants. A field reagent blank is required only for EPA Method 524.2 (or equivalent listed methods, D5790.95, SM6210D, and SM6200B).
(5) Quality Control Sample. Obtain a quality control sample from an external source to check laboratory performance at least once each quarter.
(6) Matrix Spike and Duplicate. Prepare and analyze the sample matrix spike (SMS) for accuracy and matrix spike duplicate (MSD) samples for precision to determine method accuracy and precision for all contaminants in Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section. SMS/MSD samples must be prepared and analyzed at a frequency of 5% (or one SMS/MSD set per every 20 samples) or with each sample batch whichever is more frequent. In addition, the SMS/MSD spike concentrations must be alternated between a low-level spike and mid-level spike approximately 50% of the time. (For example: a set of 40 samples will require preparation and analysis of two SMS/MSD sets. The first set must be spiked at either the low-level or mid level, and the second set must be spiked with the other standard, either the low-level or mid-level, whichever was not used for the initial SMS/MSD set). The low-level SMS/MSD spike concentration must be within ±20% of the MRL for each contaminant. The mid-level SMS/MSD spike concentration must be within ±20% of the
(7) Internal Standard Calibration. As appropriate to a method's requirements to be used, test and obtain an internal standard for the methods for each chemical contaminant in Table 1, Unregulated Contaminant Monitoring Regulation (1999) List, in paragraph (a)(3) of this section, a pure contaminant of known concentration, for calibration and quantitation purposes. The methods specify the percent recovery or response that you must obtain for acceptance.
(8) Method Performance Test. As appropriate to a method's requirements, test for surrogate compounds, a pure contaminant unlikely to be found in any sample, to be used to monitor method performance. The methods specify the percent recovery that you must obtain for acceptance.
(9) Detection Confirmation. Confirm any chemical contaminant analyzed using a gas chromatographic method and detected above the MRL, by gas chromatographic/mass spectrometric (GC/MS) methods. If testing resulted in first analyzing the sample extracts via specified gas chromatographic methods, an initial confirmation by a second column dissimilar to the primary column may be performed. If the contaminant detection is confirmed by the secondary column, then the contaminant must be reconfirmed by GC/MS using three (3) specified ion peaks for contaminant identification. Use one of the following confirming techniques: perform single point calibration of the GC/MS system for confirmation purposes only as long as the calibration standard is at a concentration within ± 50% of the concentration determined by the initial analysis; or perform a three (3) point calibration with single point daily calibration verification of the GC/MS system regardless of whether that verification standard concentration is within ± 50% of sample response. If GC/MS analysis confirms the initial contaminant detection, report results determined from the initial analysis.
(10) Reporting. Report the analytical results and other data, with the required data listed in 40 CFR 141.35, Table 1. Report this data electronically to EPA, unless EPA specifies otherwise, and provide a copy to the State. Systems must coordinate with their laboratories for electronic reporting to EPA to ensure proper formatting and timely data submission.
(11) Method Defined Quality Control. As appropriate to the method's requirements, perform analysis of Laboratory Fortified Blanks and Laboratory Performance Checks as specified in the method. Each method specifies acceptance criteria for these quality control checks.
(a) Suppliers of water for community public water systems shall collect and analyze one sample per plant at the entry point of the distribution system for the determination of sodium concentration levels; samples must be collected and analyzed annually for systems utilizing surface water sources in whole or in part, and at least every three years for systems utilizing solely ground water sources. The minimum number of samples required to be taken by the system shall be based on the number of treatment plants used by the system, except that multiple wells drawing raw water from a single aquifer may, with the State approval, be considered one treatment plant for determining the minimum number of samples. The supplier of water may be required by the State to collect and analyze water samples for sodium more frequently in locations where the sodium content is variable.
(b) The supplier of water shall report to EPA and/or the State the results of the analyses for sodium within the first 10 days of the month following the month in which the sample results were received or within the first 10 days following the end of the required monitoring period as stipulated by the State, whichever of these is first. If more than annual sampling is required the supplier shall report the average sodium concentration within 10 days of the month following the month in which the analytical results of the last sample used for the annual average was received. The supplier of water shall not be required to report the results to EPA where the State has adopted this regulation and results are reported to the State. The supplier shall report the results to EPA where the State has not adopted this regulation.
(c) The supplier of water shall notify appropriate local and State public health officials of the sodium levels by written notice by direct mail within
(d) Analyses for sodium shall be conducted as directed in § 141.23(k)(1).
(a)-(c) [Reserved]
(d) Community water supply systems shall identify whether the following construction materials are present in their distribution system and report to the State:
(a)
(i) Any public water system, or
(ii) Any plumbing in a residential or nonresidential facility providing water for human consumption which is connected to a public water system shall be lead free as defined by paragraph (d) of this section. This paragraph (a)(1) shall not apply to leaded joints necessary for the repair of cast iron pipes.
(2) [Reserved]
(b)
(2) [Reserved]
(c)
(d)
(1) When used with respect to solders and flux refers to solders and flux containing not more than 0.2 percent lead;
(2) When used with respect to pipes and pipe fittings refers to pipes and pipe fittings containing not more than 8.0 percent lead; and
(3) When used with respect to plumbing fittings and fixtures intended by the manufacturer to dispense water for human ingestion refers to fittings and fixtures that are in compliance with standards established in accordance with 42 U.S.C. 300g-6(e).
(a) MCLGs are zero for the following contaminants:
(1) Benzene
(2) Vinyl chloride
(3) Carbon tetrachloride
(4) 1,2-dichloroethane
(5) Trichloroethylene
(6) Acrylamide
(7) Alachlor
(8) Chlordane
(9) Dibromochloropropane
(10) 1,2-Dichloropropane
(11) Epichlorohydrin
(12) Ethylene dibromide
(13) Heptachlor
(14) Heptachlor epoxide
(15) Pentachlorophenol
(16) Polychlorinated biphenyls (PCBs)
(17) Tetrachloroethylene
(18) Toxaphene
(19) Benzo[a]pyrene
(20) Dichloromethane (methylene chloride)
(21) Di(2-ethylhexyl)phthalate
(22) Hexachlorobenzene
(23) 2,3,7,8-TCDD (Dioxin)
(b) MCLGs for the following contaminants are as indicated:
(a) [Reserved]
(b) MCLGs for the following contaminants are as indicated:
MCLGs for the following contaminants are as indicated:
MCLGs for the following disinfection byproducts are as indicated:
MRDLGs for disinfectants are as follows:
MCLGs for radionuclides are as indicated in the following table:
At 65 FR 76748, Dec. 7, 2000, § 141.55 was added, effective Dec. 8, 2003.
At 65 FR 76748, Dec. 7, 2000, the heading of subpart G was revised to read “National Primary Drinking Water Regulations: Maximum Contaminant Levels and Maximum Residual Disinfectant Levels”, effective Dec. 8, 2003.
(a) The effective dates for § 141.61 are as follows:
(1) The effective date for paragraphs (a)(1) through (a)(8) of § 141.61 is January 9, 1989.
(2) The effective date for paragraphs (a)(9) through (a)(18) and (c)(1) through (c)(18) of § 141.61 is July 30, 1992.
(3) The effective date for paragraphs (a)(19) through (a)(21), (c)(19) through (c)(25), and (c)(27) through (c)(33) of § 141.61 is January 17, 1994. The effective date of § 141.61(c)(26) is August 17, 1992.
(b) The effective dates for § 141.62 are as follows:
(1) The effective date of paragraph (b)(1) of § 141.62 is October 2, 1987.
(2) The effective date for paragraphs (b)(2) and (b)(4) through (b)(10) of § 141.62 is July 30, 1992.
(3) The effective date for paragraphs (b)(11) through (b)(15) of § 141.62 is January 17, 1994.
(4) The effective date for § 141.62(b)(16) is January 23, 2006.
(a) The following maximum contaminant levels for organic contaminants apply to community and non-transient, non-community water systems.
(b) The Administrator, pursuant to section 1412 of the Act, hereby identifies as indicated in the Table below granular activated carbon (GAC), packed tower aeration (PTA), or oxidation (OX) as the best technology treatment technique, or other means available for achieving compliance with the maximum contaminant level for organic contaminants identified in paragraphs (a) and (c) of this section:
(c) The following maximum contaminant levels for synthetic organic contaminants apply to community water systems and non-transient, non-community water systems:
(a) [Reserved]
(b) The maximum contaminant levels for inorganic contaminants specified in paragraphs (b) (2)-(6), (b)(10), and (b) (11)-(16) of this section apply to community water systems and non-transient, non-community water systems. The maximum contaminant level specified in paragraph (b)(1) of this section only applies to community water systems. The maximum contaminant levels specified in (b)(7), (b)(8), and (b)(9) of this section apply to community water systems; non-transient, non-community water systems; and transient non-community water systems.
(c) The Administrator, pursuant to section 1412 of the Act, hereby identifies the following as the best technology, treatment technique, or other means available for achieving compliance with the maximum contaminant levels for inorganic contaminants identified in paragraph (b) of this section, except fluoride:
(d) The Administrator, pursuant to section 1412 of the Act, hereby identifies in the following table the affordable technology, treatment technique, or other means available to systems serving 10,000 persons or fewer for achieving compliance with the maximum contaminant level for arsenic:
(a) The MCL is based on the presence or absence of total coliforms in a sample, rather than coliform density.
(1) For a system which collects at least 40 samples per month, if no more than 5.0 percent of the samples collected during a month are total coliform-positive, the system is in compliance with the MCL for total coliforms.
(2) For a system which collects fewer than 40 samples/month, if no more than one sample collected during a month is total coliform-positive, the system is in compliance with the MCL for total coliforms.
(b) Any fecal coliform-positive repeat sample or
(c) A public water system must determine compliance with the MCL for total coliforms in paragraphs (a) and
(d) The Administrator, pursuant to section 1412 of the Act, hereby identifies the following as the best technology, treatment techniques, or other means available for achieving compliance with the maximum contaminant level for total coliforms in paragraphs (a) and (b) of this section:
(1) Protection of wells from contamination by coliforms by appropriate placement and construction;
(2) Maintenance of a disinfectant residual throughout the distribution system;
(3) Proper maintenance of the distribution system including appropriate pipe replacement and repair procedures, main flushing programs, proper operation and maintenance of storage tanks and reservoirs, and continual maintenance of positive water pressure in all parts of the distribution system;
(4) Filtration and/or disinfection of surface water, as described in subpart H, or disinfection of ground water using strong oxidants such as chlorine, chlorine dioxide, or ozone; and
(5) For systems using ground water, compliance with the requirements of an EPA-approved State Wellhead Protection Program developed and implemented under section 1428 of the SDWA.
(a) The maximum contaminant levels (MCLs) for disinfection byproducts are as follows:
(b)
(2) A system that is installing GAC or membrane technology to comply with this section may apply to the State for an extension of up to 24 months past the dates in paragraphs (b)(1) of this section, but not beyond December 31, 2003. In granting the extension, States must set a schedule for compliance and may specify any interim measures that the system must take. Failure to meet the schedule or interim treatment requirements constitutes a violation of a National Primary Drinking Water Regulation.
(c) The Administrator, pursuant to Section 1412 of the Act, hereby identifies the following as the best technology, treatment techniques, or other means available for achieving compliance with the maximum contaminant levels for disinfection byproducts identified in paragraph (a) of this section:
(a) Maximum residual disinfectant levels (MRDLs) are as follows:
(b)
(2) Transient NCWSs. Subpart H systems serving 10,000 or more persons and using chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2002. Subpart H systems serving fewer than 10,000 persons and using chlorine dioxide as a disinfectant or oxidant and systems using only ground water not under the direct influence of surface water and using chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2004.
(c) The Administrator, pursuant to Section 1412 of the Act, hereby identifies the following as the best technology, treatment techniques, or other means available for achieving compliance with the maximum residual disinfectant levels identified in paragraph (a) of this section: control of treatment processes to reduce disinfectant demand and control of disinfection treatment processes to reduce disinfectant levels.
(a) [Reserved]
(b)
(c)
(d)
(2) Except for the radionuclides listed in table A, the concentration of man-made radionuclides causing 4 mrem total body or organ dose equivalents must be calculated on the basis of 2 liter per day drinking water intake using the 168 hour data list in “Maximum Permissible Body Burdens and Maximum Permissible Concentrations of Radionuclides in Air and in Water for Occupational Exposure,” NBS (National Bureau of Standards) Handbook 69 as amended August 1963, U.S. Department of Commerce. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies of this document are available from the National Technical Information Service, NTIS ADA 280 282, U.S. Department of Commerce, 5285 Port Royal Road, Springfield, Virginia 22161. The toll-free number is 800-553-6847. Copies may be inspected at EPA's Drinking Water Docket, 401 M Street, SW., Washington, DC 20460; or at the Office of the Federal Register, 800 North Capitol Street, NW., Suite 700, Washington, DC. If two or more radionuclides are present, the sum of their annual dose equivalent to the total body or to any organ shall not exceed 4 mrem/year.
(e)
(f)
(2) [Reserved]
(g)
(h)
At 65 FR 76748, Dec. 7, 2000, § 141.66 was added, effective Dec. 8, 2003.
(a) The requirements of this subpart H constitute national primary drinking water regulations. These regulations establish criteria under which filtration is required as a treatment technique for public water systems supplied by a surface water source and public water systems supplied by a ground water source under the direct influence of surface water. In addition, these regulations establish treatment technique requirements in lieu of maximum contaminant levels for the following contaminants:
(1) At least 99.9 percent (3-log) removal and/or inactivation of
(2) At least 99.99 percent (4-log) removal and/or inactivation of viruses between a point where the raw water is not subject to recontamination by surface water runoff and a point downstream before or at the first customer.
(b) A public water system using a surface water source or a ground water source under the direct influence of surface water is considered to be in compliance with the requirements of paragraph (a) of this section if:
(1) It meets the requirements for avoiding filtration in § 141.71 and the disinfection requirements in § 141.72(a); or
(2) It meets the filtration requirements in § 141.73 and the disinfection requirements in § 141.72(b).
(c) Each public water system using a surface water source or a ground water source under the direct influence of surface water must be operated by qualified personnel who meet the requirements specified by the State.
(d)
(e)
A public water system that uses a surface water source must meet all of the conditions of paragraphs (a) and (b) of this section, and is subject to paragraph (c) of this section, beginning December 30, 1991, unless the State has determined, in writing pursuant to § 1412(b)(7)(C)(iii), that filtration is required. A public water system that uses a ground water source under the direct influence of surface water must meet all of the conditions of paragraphs (a) and (b) of this section and is subject to paragraph (c) of this section, beginning 18 months after the State determines that it is under the direct influence of surface water, or December 30, 1991, whichever is later, unless the State has determined, in writing pursuant to § 1412(b)(7)(C)(iii), that filtration is required. If the State determines in writing pursuant to § 1412(b)(7)(C)(iii) before December 30, 1991, that filtration is required, the system must have installed filtration and meet the criteria for filtered systems specified in §§ 141.72(b) and 141.73 by June 29, 1993. Within 18 months of the failure of a system using surface water or a ground water source under the direct influence of surface water to meet any one of the requirements of paragraphs (a) and (b) of this section or after June 29, 1993, whichever is later, the system must have installed filtration and meet the criteria for filtered systems specified in §§ 141.72(b) and 141.73.
(a)
(2) The turbidity level cannot exceed 5 NTU (measured as specified in § 141.74 (a)(4) and (b)(2)) in representative samples of the source water immediately prior to the first or only point of disinfectant application unless: (i) the State determines that any such event was caused by circumstances that were unusual and unpredictable; and (ii) as a result of any such event, there have not been more than two events in the past 12 months the system served water to the public, or more than five events in the past 120 months the system served water to the public, in which the turbidity level exceeded 5 NTU. An “event” is a series of consecutive days during which at least one turbidity measurement each day exceeds 5 NTU.
(b)
(ii) The public water system must meet the requirements of § 141.72(a)(2) at all times the system serves water to the public.
(iii) The public water system must meet the requirements of § 141.72(a)(3) at all times the system serves water to the public unless the State determines that any such failure was caused by circumstances that were unusual and unpredictable.
(iv) The public water system must meet the requirements of § 141.72(a)(4) on an ongoing basis unless the State determines that failure to meet these requirements was not caused by a deficiency in treatment of the source water.
(2) The public water system must maintain a watershed control program which minimizes the potential for contamination by
(i) Characterize the watershed hydrology and land ownership;
(ii) Identify watershed characteristics and activities which may have an adverse effect on source water quality; and
(iii) Monitor the occurrence of activities which may have an adverse effect on source water quality.
The public water system must demonstrate through ownership and/or written agreements with landowners within the watershed that it can control all human activities which may have an adverse impact on the microbiological quality of the source water. The public water system must submit an annual report to the State that identifies any special concerns about the watershed and how they are being handled; describes activities in the watershed that affect water quality; and projects what adverse activities are expected to occur in the future and describes how the public water system expects to address them. For systems using a ground water source under the direct influence of surface water, an approved wellhead protection program developed under section 1428 of the Safe Drinking Water Act may be used, if the State deems it appropriate, to meet these requirements.
(3) The public water system must be subject to an annual on-site inspection to assess the watershed control program and disinfection treatment process. Either the State or a party approved by the State must conduct the on-site inspection. The inspection must be conducted by competent individuals such as sanitary and civil engineers, sanitarians, or technicians who have experience and knowledge about the operation and maintenance of a public water system, and who have a sound understanding of public health principles and waterborne diseases. A report of the on-site inspection summarizing all findings must be prepared every year. The on-site inspection must indicate to the State's satisfaction that the watershed control program and disinfection treatment process are adequately designed and maintained. The on-site inspection must include:
(i) A review of the effectiveness of the watershed control program;
(ii) A review of the physical condition of the source intake and how well it is protected;
(iii) A review of the system's equipment maintenance program to ensure there is low probability for failure of the disinfection process;
(iv) An inspection of the disinfection equipment for physical deterioration;
(v) A review of operating procedures;
(vi) A review of data records to ensure that all required tests are being conducted and recorded and disinfection is effectively practiced; and
(vii) Identification of any improvements which are needed in the equipment, system maintenance and operation, or data collection.
(4) The public water system must not have been identified as a source of a waterborne disease outbreak, or if it has been so identified, the system must have been modified sufficiently to prevent another such occurrence, as determined by the State.
(5) The public water system must comply with the maximum contaminant level (MCL) for total coliforms in § 141.63 at least 11 months of the 12 previous months that the system served water to the public, on an ongoing basis, unless the State determines that failure to meet this requirement was not caused by a deficiency in treatment of the source water.
(6) The public water system must comply with the requirements for trihalomethanes in §§ 141.12 and 141.30 until December 31, 2001. After December 31, 2001, the system must comply with the requirements for total trihalomethanes, haloacetic acids (five), bromate, chlorite, chlorine, chloramines, and chlorine dioxide in subpart L of this part.
(c)
(2) A system that has not installed filtration is in violation of a treatment technique requirement if:
(i) The turbidity level (measured as specified in § 141.74(a)(4) and (b)(2)) in a representative sample of the source water immediately prior to the first or only point of disinfection application exceeds 5 NTU; or
(ii) The system is identified as a source of a waterborne disease outbreak.
A public water system that uses a surface water source and does not provide filtration treatment must provide the disinfection treatment specified in paragraph (a) of this section beginning December 30, 1991, unless the State determines that filtration is required in writing pursuant to § 1412 (b)(7)(C)(iii). A public water system that uses a ground water source under the direct influence of surface water and does not provide filtration treatment must provide disinfection treatment specified in paragraph (a) of this section beginning December 30, 1991, or 18 months after the State determines that the ground water source is under the influence of surface water, whichever is later, unless the State has determined that filtration is required in writing pursuant to § 1412(b)(7)(C)(iii). If the State has determined that filtration is required, the system must comply with any interim disinfection requirements the State deems necessary before filtration is installed. A system that uses a surface water source that provides filtration treatment must provide the disinfection treatment specified in paragraph (b) of this section beginnng June 29, 1993, or beginning when filtration is installed, whichever is later. A system that uses a ground water source under the direct influence of surface water and provides filtration treatment must provide disinfection treatment as specified in paragraph (b) of this section by June 29, 1993, or beginning when filtration is installed, whichever is later. Failure to meet any requirement of this section after the applicable date specified in this introductory paragraph is a treatment technique violation.
(a)
(1) The disinfection treatment must be sufficient to ensure at least 99.9 percent (3-log) inactivation of
(2) The disinfection system must have either (i) redundant components, including an auxiliary power supply with automatic start-up and alarm to ensure that disinfectant application is maintained continuously while water is being delivered to the distribution system, or (ii) automatic shut-off of delivery of water to the distribution system whenever there is less than 0.2 mg/l of residual disinfectant concentration in the water. If the State determines that automatic shut-off would cause unreasonable risk to health or interfere with fire protection, the system
(3) The residual disinfectant concentration in the water entering the distribution system, measured as specified in § 141.74 (a)(5) and (b)(5), cannot be less than 0.2 mg/l for more than 4 hours.
(4)(i) The residual disinfectant concentration in the distribution system, measured as total chlorine, combined chlorine, or chlorine dioxide, as specified in § 141.74 (a)(5) and (b)(6), cannot be undetectable in more than 5 percent of the samples each month, for any two consecutive months that the system serves water to the public. Water in the distribution system with a heterotrophic bacteria concentration less than or equal to 500/ml, measured as heterotrophic plate count (HPC) as specified in § 141.74(a)(3), is deemed to have a detectable disinfectant residual for purposes of determining compliance with this requirement. Thus, the value “V” in the following formula cannot exceed 5 percent in one month, for any two consecutive months.
(ii) If the State determines, based on site-specific considerations, that a system has no means for having a sample transported and analyzed for HPC by a certified laboratory under the requisite time and temperature conditions specified by § 141.74(a)(3) and that the system is providing adequate disinfection in the distribution system, the requirements of paragraph (a)(4)(i) of this section do not apply to that system.
(b)
(1) The disinfection treatment must be sufficient to ensure that the total treatment processes of that system achieve at least 99.9 percent (3-log) inactivation and/or removal of
(2) The residual disinfectant concentration in the water entering the distribution system, measured as specified in § 141.74 (a)(5) and (c)(2), cannot be less than 0.2 mg/l for more than 4 hours.
(3)(i) The residual disinfectant concentration in the distribution system, measured as total chlorine, combined chlorine, or chlorine dioxide, as specified in § 141.74 (a)(5) and (c)(3), cannot be undetectable in more than 5 percent of the samples each month, for any two consecutive months that the system serves water to the public. Water in the distribution system with a heterotrophic bacteria concentration less than or equal to 500/ml, measured as heterotrophic plate count (HPC) as specified in § 141.74(a)(3), is deemed to have a detectable disinfectant residual for purposes of determining compliance with this requirement. Thus, the value “V” in the following formula cannot exceed 5 percent in one month, for any two consecutive months.
(ii) If the State determines, based on site-specific considerations, that a system has no means for having a sample transported and analyzed for HPC by a certified laboratory under the requisite time and temperature conditions specified in § 141.74(a)(3) and that the system is providing adequate disinfection in the distribution system, the requirements of paragraph (b)(3)(i) of this section do not apply.
A public water system that uses a surface water source or a ground water source under the direct influence of surface water, and does not meet all of the criteria in § 141.71 (a) and (b) for avoiding filtration, must provide treatment consisting of both disinfection, as specified in § 141.72(b), and filtration treatment which complies with the requirements of paragraph (a), (b), (c), (d), or (e) of this section by June 29, 1993, or within 18 months of the failure to meet any one of the criteria for avoiding filtration in § 141.71 (a) and (b), whichever is later. Failure to meet any requirement of this section after the date specified in this introductory paragraph is a treatment technique violation.
(a)
(2) The turbidity level of representative samples of a system's filtered water must at no time exceed 5 NTU, measured as specified in § 141.74 (a)(4) and (c)(1).
(3) Beginning January 1, 2002, systems serving at least 10,000 people must meet the turbidity requirements in § 141.173(a).
(4) Beginning January 14, 2005, systems serving fewer than 10,000 people must meet the turbidity requirements in §§ 141.550 through 141.553.
(b)
(2) The turbidity level of representative samples of a system's filtered water must at no time exceed 5 NTU, measured as specified in § 141.74 (a)(4) and (c)(1).
(c)
(2) The turbidity level of representative samples of a system's filtered water must at no time exceed 5 NTU, measured as specified in § 141.74 (a)(4) and (c)(1).
(d)
(a)
(1) Public water systems must conduct analysis of pH and temperature in accordance with one of the methods listed at § 141.23(k)(1). Public water systems must conduct analysis of total coliforms, fecal coliforms, heterotrophic bacteria, and turbidity in accordance with one of the following analytical methods and by using analytical test procedures contained in
(2) Public water systems must measure residual disinfectant concentrations with one of the analytical methods in the following table. Except for the method for ozone residuals, the disinfectant residual methods are contained in the 18th, 19th, and 20th editions of Standard Methods for the Examination of Water and Wastewater, 1992, 1995, and 1998; the cited methods published in any of these three editions may be used. The ozone method, 4500-O
(b)
(1) Fecal coliform or total coliform density measurements as required by § 141.71(a)(1) must be performed on representative source water samples immediately prior to the first or only point of disinfectant application. The system must sample for fecal or total
Also, one fecal or total coliform density measurement must be made every day the system serves water to the public and the turbidity of the source water exceeds 1 NTU (these samples count towards the weekly coliform sampling requirement) unless the State determines that the system, for logistical reasons outside the system's control, cannot have the sample analyzed within 30 hours of collection.
(2) Turbidity measurements as required by § 141.71(a)(2) must be performed on representative grab samples of source water immediately prior to the first or only point of disinfectant application every four hours (or more frequently) that the system serves water to the public. A public water system may substitute continuous turbidity monitoring for grab sample monitoring if it validates the continuous measurement for accuracy on a regular basis using a protocol approved by the State.
(3) The total inactivation ratio for each day that the system is in operation must be determined based on the CT
(i) The temperature of the disinfected water must be measured at least once per day at each residual disinfectant concentration sampling point.
(ii) If the system uses chlorine, the pH of the disinfected water must be measured at least once per day at each chlorine residual disinfectant concentration sampling point.
(iii) The disinfectant contact time(s) (“T”) must be determined for each day during peak hourly flow.
(iv) The residual disinfectant concentration(s) (“C”) of the water before or at the first customer must be measured each day during peak hourly flow.
(v) If a system uses a disinfectant other than chlorine, the system may demonstrate to the State, through the use of a State-approved protocol for on-site disinfection challenge studies or other information satisfactory to the State, that CT
(4) The total inactivation ratio must be calculated as follows:
(i) If the system uses only one point of disinfectant application, the system may determine the total inactivation ratio based on either of the following two methods:
(A) One inactivation ratio (CTcalc/CT
(B) Successive CTcalc/CT
(ii) If the system uses more than one point of disinfectant application before or at the first customer, the system must determine the CT value of each disinfection sequence immediately prior to the next point of disinfectant application during peak hourly flow. The CTcalc/CT
must be calculated using the method in paragraph (b)(4)(i)(B) of this section to determine if the system is in compliance with § 142.72(a).
(iii) Although not required, the total percent inactivation for a system with one or more points of residual disinfectant concentration monitoring may be calculated by solving the following equation:
(5) The residual disinfectant concentration of the water entering the distribution system must be monitored continuously, and the lowest value must be recorded each day, except that if there is a failure in the continuous monitoring equipment, grab sampling every 4 hours may be conducted in lieu of continuous monitoring, but for no more than 5 working days following the failure of the equipment, and systems serving 3,300 or fewer persons may take grab samples in lieu of providing continuous monitoring on an ongoing basis at the frequencies prescribed below:
(6)(i) The residual disinfectant concentration must be measured at least at the same points in the distribution system and at the same time as total coliforms are sampled, as specified in § 141.21, except that the State may allow a public water system which uses both a surface water source or a ground water source under direct influence of surface water, and a ground water source, to take disinfectant residual samples at points other than the total coliform sampling points if the State determines that such points are more representative of treated (disinfected) water quality within the distribution system. Heterotrophic bacteria, measured as heterotrophic plate count (HPC) as specified in paragraph (a)(3) of this section, may be measured in lieu of residual disinfectant concentration.
(ii) If the State determines, based on site-specific considerations, that a system has no means for having a sample transported and analyzed for HPC by a certified laboratory under the requisite time and temperature conditions specified by paragraph (a)(3) of this section and that the system is providing adequate disinfection in the distribution system, the requirements of paragraph (b)(6)(i) of this section do not apply to that system.
(c)
(1) Turbidity measurements as required by § 141.73 must be performed on representative samples of the system's filtered water every four hours (or more frequently) that the system serves water to the public. A public water system may substitute continuous turbidity monitoring for grab sample monitoring if it validates the continuous measurement for accuracy on a regular basis using a protocol approved by the State. For any systems
(2) The residual disinfectant concentration of the water entering the distribution system must be monitored continuously, and the lowest value must be recorded each day, except that if there is a failure in the continuous monitoring equipment, grab sampling every 4 hours may be conducted in lieu of continuous monitoring, but for no more than 5 working days following the failure of the equipment, and systems serving 3,300 or fewer persons may take grab samples in lieu of providing continuous monitoring on an ongoing basis at the frequencies each day prescribed below:
(3)(i) The residual disinfectant concentration must be measured at least at the same points in the distribution system and at the same time as total coliforms are sampled, as specified in § 141.21, except that the State may allow a public water system which uses both a surface water source or a ground water source under direct influence of surface water, and a ground water source to take disinfectant residual samples at points other than the total coliform sampling points if the State determines that such points are more representative of treated (disinfected) water quality within the distribution system. Heterotrophic bacteria, measured as heterotrophic plate count (HPC) as specified in paragraph (a)(3) of this section, may be measured in lieu of residual disinfectant concentration.
(ii) If the State determines, based on site-specific considerations, that a system has no means for having a sample transported and analyzed for HPC by a certified laboratory under the requisite time and temperature conditions specified by paragraph (a)(3) of this section and that the system is providing adequate disinfection in the distribution system, the requirements of paragraph (c)(3)(i) of this section do not apply to that system.
(a) A public water system that uses a surface water source and does not provide filtration treatment must report monthly to the State the information specified in this paragraph (a) beginning December 31, 1990, unless the State has determined that filtration is required in writing pursuant to section 1412(b)(7)(C)(iii), in which case the State may specify alternative reporting requirements, as appropriate, until filtration is in place. A public water system that uses a ground water source under the direct influence of surface water and does not provide filtration treatment must report monthly to the State the information specified in this paragraph (a) beginning December 31, 1990, or 6 months after the State determines that the ground water source is under the direct influence of surface water, whichever is later, unless the State has determined that filtration is required in writing pursuant to § 1412(b)(7)(C)(iii), in which case the State may specify alternative reporting requirements, as appropriate, until filtration is in place.
(1) Source water quality information must be reported to the State within 10
(i) The cumulative number of months for which results are reported.
(ii) The number of fecal and/or total coliform samples, whichever are analyzed during the month (if a system monitors for both, only fecal coliforms must be reported), the dates of sample collection, and the dates when the turbidity level exceeded 1 NTU.
(iii) The number of samples during the month that had equal to or less than 20/100 ml fecal coliforms and/or equal to or less than 100/100 ml total coliforms, whichever are analyzed.
(iv) The cumulative number of fecal or total coliform samples, whichever are analyzed, during the previous six months the system served water to the public.
(v) The cumulative number of samples that had equal to or less than 20/100 ml fecal coliforms or equal to or less than 100/100 ml total coliforms, whichever are analyzed, during the previous six months the system served water to the public.
(vi) The percentage of samples that had equal to or less than 20/100 ml fecal coliforms or equal to or less than 100/100 ml total coliforms, whichever are analyzed, during the previous six months the system served water to the public.
(vii) The maximum turbidity level measured during the month, the date(s) of occurrence for any measurement(s) which exceeded 5 NTU, and the date(s) the occurrence(s) was reported to the State.
(viii) For the first 12 months of recordkeeping, the dates and cumulative number of events during which the turbidity exceeded 5 NTU, and after one year of recordkeeping for turbidity measurements, the dates and cumulative number of events during which the turbidity exceeded 5 NTU in the previous 12 months the system served water to the public.
(ix) For the first 120 months of recordkeeping, the dates and cumulative number of events during which the turbidity exceeded 5 NTU, and after 10 years of recordkeeping for turbidity measurements, the dates and cumulative number of events during which the turbidity exceeded 5 NTU in the previous 120 months the system served water to the public.
(2) Disinfection information specified in § 141.74(b) must be reported to the State within 10 days after the end of each month the system serves water to the public. Information that must be reported includes:
(i) For each day, the lowest measurement of residual disinfectant concentration in mg/l in water entering the distribution system.
(ii) The date and duration of each period when the residual disinfectant concentration in water entering the distribution system fell below 0.2 mg/l and when the State was notified of the occurrence.
(iii) The daily residual disinfectant concentration(s) (in mg/l) and disinfectant contact time(s) (in minutes) used for calculating the CT value(s).
(iv) If chlorine is used, the daily measurement(s) of pH of disinfected water following each point of chlorine disinfection.
(v) The daily measurement(s) of water temperature in °C following each point of disinfection.
(vi) The daily CTcalc and CTcalc/CT
(vii) The daily determination of whether disinfection achieves adequate
(viii) The following information on the samples taken in the distribution system in conjunction with total coliform monitoring pursuant to § 141.72:
(A) Number of instances where the residual disinfectant concentration is measured;
(B) Number of instances where the residual disinfectant concentration is not measured but heterotrophic bacteria plate count (HPC) is measured;
(C) Number of instances where the residual disinfectant concentration is measured but not detected and no HPC is measured;
(D) Number of instances where the residual disinfectant concentration is detected and where HPC is >500/ml;
(E) Number of instances where the residual disinfectant concentration is not measured and HPC is >500/ml;
(F) For the current and previous month the system served water to the public, the value of “V” in the following formula:
(G) If the State determines, based on site-specific considerations, that a system has no means for having a sample transported and analyzed for HPC by a certified laboratory under the requisite time and temperature conditions specified by § 141.74(a)(3) and that the system is providing adequate disinfection in the distribution system, the requirements of paragraph (a)(2)(viii) (A)-(F) of this section do not apply to that system.
(ix) A system need not report the data listed in paragraphs (a)(2) (i), and (iii)-(vi) of this section if all data listed in paragraphs (a)(2) (i)-(viii) of this section remain on file at the system, and the State determines that:
(A) The system has submitted to the State all the information required by paragraphs (a)(2) (i)-(viii) of this section for at least 12 months; and
(B) The State has determined that the system is not required to provide filtration treatment.
(3) No later than ten days after the end of each Federal fiscal year (September 30), each system must provide to the State a report which summarizes its compliance with all watershed control program requirements specified in § 141.71(b)(2).
(4) No later than ten days after the end of each Federal fiscal year (September 30), each system must provide to the State a report on the on-site inspection conducted during that year pursuant to § 141.71(b)(3), unless the on-site inspection was conducted by the State. If the inspection was conducted by the State, the State must provide a copy of its report to the public water system.
(5)(i) Each system, upon discovering that a waterborne disease outbreak potentially attributable to that water system has occurred, must report that occurrence to the State as soon as possible, but no later than by the end of the next business day.
(ii) If at any time the turbidity exceeds 5 NTU, the system must consult with the primacy agency as soon as practical, but no later than 24 hours after the exceedance is known, in accordance with the public notification requirements under § 141.203(b)(3).
(iii) If at any time the residual falls below 0.2 mg/l in the water entering the distribution system, the system must notify the State as soon as possible, but no later than by the end of the next business day. The system also must notify the State by the end of the next business day whether or not the residual was restored to at least 0.2 mg/l within 4 hours.
(b) A public water system that uses a surface water source or a ground water source under the direct influence of surface water and provides filtration treatment must report monthly to the State the information specified in this paragraph (b) beginning June 29, 1993, or when filtration is installed, whichever is later.
(1) Turbidity measurements as required by § 141.74(c)(1) must be reported within 10 days after the end of each month the system serves water to the public. Information that must be reported includes:
(i) The total number of filtered water turbidity measurements taken during the month.
(ii) The number and percentage of filtered water turbidity measurements taken during the month which are less than or equal to the turbidity limits specified in § 141.73 for the filtration technology being used.
(iii) The date and value of any turbidity measurements taken during the month which exceed 5 NTU.
(2) Disinfection information specified in § 141.74(c) must be reported to the State within 10 days after the end of each month the system serves water to the public. Information that must be reported includes:
(i) For each day, the lowest measurement of residual disinfectant concentration in mg/l in water entering the distribution system.
(ii) The date and duration of each period when the residual disinfectant concentration in water entering the distribution system fell below 0.2 mg/l and when the State was notified of the occurrence.
(iii) The following information on the samples taken in the distribution system in conjunction with total coliform monitoring pursuant to § 141.72:
(A) Number of instances where the residual disinfectant concentration is measured;
(B) Number of instances where the residual disinfectant concentration is not measured but heterotrophic bacteria plate count (HPC) is measured;
(C) Number of instances where the residual disinfectant concentration is measured but not detected and no HPC is measured;
(D) Number of instances where no residual disinfectant concentration is detected and where HPC is >500/ml;
(E) Number of instances where the residual disinfectant concentration is not measured and HPC is >500/ml;
(F) For the current and previous month the system serves water to the public, the value of “V” in the following formula:
(G) If the State determines, based on site-specific considerations, that a system has no means for having a sample transported and analyzed for HPC by a certified laboratory within the requisite time and temperature conditions specified by § 141.74(a)(3) and that the system is providing adequate disinfection in the distribution system, the requirements of paragraph (b)(2)(iii) (A)-(F) of this section do not apply.
(iv) A system need not report the data listed in paragraph (b)(2)(i) of this section if all data listed in paragraphs (b)(2) (i)-(iii) of this section remain on file at the system and the State determines that the system has submitted all the information required by paragraphs (b)(2) (i)-(iii) of this section for at least 12 months.
(3)(i) Each system, upon discovering that a waterborne disease outbreak potentially attributable to that water system has occurred, must report that occurrence to the State as soon as possible, but no later than by the end of the next business day.
(ii) If at any time the turbidity exceeds 5 NTU, the system must consult with the primacy agency as soon as practical, but no later than 24 hours after the exceedance is known, in accordance with the public notification requirements under § 141.203(b)(3).
(iii) If at any time the residual falls below 0.2 mg/l in the water entering the distribution system, the system must notify the State as soon as possible, but no later than by the end of the next business day. The system also must notify the State by the end of the next business day whether or not the residual was restored to at least 0.2 mg/l within 4 hours.
(a)
(b)
(1) A plant schematic showing the origin of all flows which are recycled (including, but not limited to, spent filter backwash water, thickener supernatant, and liquids from dewatering processes), the hydraulic conveyance used to transport them, and the location where they are re-introduced back into the treatment plant.
(2) Typical recycle flow in gallons per minute (gpm), the highest observed plant flow experienced in the previous year (gpm), design flow for the treatment plant (gpm), and State-approved operating capacity for the plant where the State has made such determinations.
(c)
(d)
(1) Copy of the recycle notification and information submitted to the State under paragraph (b) of this section.
(2) List of all recycle flows and the frequency with which they are returned.
(3) Average and maximum backwash flow rate through the filters and the average and maximum duration of the filter backwash process in minutes.
(4) Typical filter run length and a written summary of how filter run length is determined.
(5) The type of treatment provided for the recycle flow.
(6) Data on the physical dimensions of the equalization and/or treatment units, typical and maximum hydraulic loading rates, type of treatment chemicals used and average dose and frequency of use, and frequency at which solids are removed, if applicable.
(a)
(2) The requirements set forth in §§ 141.86 to 141.91 shall take effect on July 7, 1991. The requirements set forth in §§ 141.80 to 141.85 shall take effect on December 7, 1992.
(b)
(c)
(2) The copper action level is exceeded if the concentration of copper in more than 10 percent of tap water samples collected during any monitoring period conducted in accordance with § 141.86 is greater than 1.3 mg/L (i.e., if the “90th percentile” copper level is greater than 1.3 mg/L).
(3) The 90th percentile lead and copper levels shall be computed as follows:
(i) The results of all lead or copper samples taken during a monitoring period shall be placed in ascending order
(ii) The number of samples taken during the monitoring period shall be multiplied by 0.9.
(iii) The contaminant concentration in the numbered sample yielded by the calculation in paragraph (c)(3)(ii) is the 90th percentile contaminant level.
(iv) For water systems serving fewer than 100 people that collect 5 samples per monitoring period, the 90th percentile is computed by taking the average of the highest and second highest concentrations.
(d)
(2) Any water system that complies with the applicable corrosion control treatment requirements specified by the State under §§ 141.81 and 141.82 shall be deemed in compliance with the treatment requirement contained in paragraph (d)(1) of this section.
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(a) Systems shall complete the applicable corrosion control treatment requirements described in § 141.82 by the deadlines established in this section.
(1) A large system (serving >50,000 persons) shall complete the corrosion control treatment steps specified in paragraph (d) of this section, unless it is deemed to have optimized corrosion control under paragraph (b)(2) or (b)(3) of this section.
(2) A small system (serving ≤3300 persons) and a medium-size system (serving >3,300 and ≤50,000 persons) shall complete the corrosion control treatment steps specified in paragraph (e) of this section, unless it is deemed to have optimized corrosion control under paragraph (b)(1), (b)(2), or (b)(3) of this section.
(b) A system is deemed to have optimized corrosion control and is not required to complete the applicable corrosion control treatment steps identified in this section if the system satisfies one of the criteria specified in paragraphs (b)(1) through (b)(3) of this section. Any such system deemed to have optimized corrosion control under this paragraph, and which has treatment in place, shall continue to operate and maintain optimal corrosion control treatment and meet any requirements that the State determines
(1) A small or medium-size water system is deemed to have optimized corrosion control if the system meets the lead and copper action levels during each of two consecutive six-month monitoring periods conducted in accordance with § 141.86.
(2) Any water system may be deemed by the State to have optimized corrosion control treatment if the system demonstrates to the satisfaction of the State that it has conducted activities equivalent to the corrosion control steps applicable to such system under this section. If the State makes this determination, it shall provide the system with written notice explaining the basis for its decision and shall specify the water quality control parameters representing optimal corrosion control in accordance with § 141.82(f). Water systems deemed to have optimized corrosion control under this paragraph shall operate in compliance with the State-designated optimal water quality control parameters in accordance with § 141.82(g) and continue to conduct lead and copper tap and water quality parameter sampling in accordance with § 141.86(d)(3) and § 141.87(d), respectively. A system shall provide the State with the following information in order to support a determination under this paragraph:
(i) The results of all test samples collected for each of the water quality parameters in § 141.82(c)(3).
(ii) A report explaining the test methods used by the water system to evaluate the corrosion control treatments listed in § 141.82(c)(1), the results of all tests conducted, and the basis for the system's selection of optimal corrosion control treatment;
(iii) A report explaining how corrosion control has been installed and how it is being maintained to insure minimal lead and copper concentrations at consumers’ taps; and
(iv) The results of tap water samples collected in accordance with § 141.86 at least once every six months for one year after corrosion control has been installed.
(3) Any water system is deemed to have optimized corrosion control if it submits results of tap water monitoring conducted in accordance with § 141.86 and source water monitoring conducted in accordance with § 141.88 that demonstrates for two consecutive 6-month monitoring periods that the difference between the 90th percentile tap water lead level computed under § 141.80(c)(3), and the highest source water lead concentration is less than the Practical Quantitation Level for lead specified in § 141.89(a)(1)(ii).
(i) Those systems whose highest source water lead level is below the Method Detection Limit may also be deemed to have optimized corrosion control under this paragraph if the 90th percentile tap water lead level is less than or equal to the Practical Quantitation Level for lead for two consecutive 6-month monitoring periods.
(ii) Any water system deemed to have optimized corrosion control in accordance with this paragraph shall continue monitoring for lead and copper at the tap no less frequently than once every three calendar years using the reduced number of sites specified in § 141.86(c) and collecting the samples at times and locations specified in § 141.86(d)(4)(iv). Any such system that has not conducted a round of monitoring pursuant to § 141.86(d) since September 30, 1997, shall complete a round of monitoring pursuant to this paragraph no later than September 30, 2000.
(iii) Any water system deemed to have optimized corrosion control pursuant to this paragraph shall notify the State in writing pursuant to § 141.90(a)(3) of any change in treatment or the addition of a new source. The State may require any such system to conduct additional monitoring or to take other action the State deems appropriate to ensure that such systems maintain minimal levels of corrosion in the distribution system.
(iv) As of July 12, 2001, a system is not deemed to have optimized corrosion control under this paragraph, and shall implement corrosion control treatment pursuant to paragraph (b)(3)(v) of this section unless it meets the copper action level.
(v) Any system triggered into corrosion control because it is no longer deemed to have optimized corrosion control under this paragraph shall implement corrosion control treatment in
(c) Any small or medium-size water system that is required to complete the corrosion control steps due to its exceedance of the lead or copper action level may cease completing the treatment steps whenever the system meets both action levels during each of two consecutive monitoring periods conducted pursuant to § 141.86 and submits the results to the State. If any such water system thereafter exceeds the lead or copper action level during any monitoring period, the system (or the State, as the case may be) shall recommence completion of the applicable treatment steps, beginning with the first treatment step which was not previously completed in its entirety. The State may require a system to repeat treatment steps previously completed by the system where the State determines that this is necessary to implement properly the treatment requirements of this section. The State shall notify the system in writing of such a determination and explain the basis for its decision. The requirement for any small- or medium-size system to implement corrosion control treatment steps in accordance with paragraph (e) of this section (including systems deemed to have optimized corrosion control under paragraph (b)(1) of this section) is triggered whenever any small- or medium-size system exceeds the lead or copper action level.
(d)
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(e)
(1)
(2)
(i) For medium-size systems, within 18 months after such system exceeds the lead or copper action level,
(ii) For small systems, within 24 months after such system exceeds the lead or copper action level.
(3)
(4)
(5)
(6)
(7)
(8)
Each system shall complete the corrosion control treatment requirements described below which are applicable to such system under § 141.81.
(a)
(b)
(c)
(i) Alkalinity and pH adjustment;
(ii) Calcium hardness adjustment; and
(iii) The addition of a phosphate or silicate based corrosion inhibitor at a concentration sufficient to maintain an effective residual concentration in all test tap samples.
(2) The water system shall evaluate each of the corrosion control treatments using either pipe rig/loop tests, metal coupon tests, partial-system tests, or analyses based on documented analogous treatments with other systems of similar size, water chemistry and distribution system configuration.
(3) The water system shall measure the following water quality parameters in any tests conducted under this paragraph before and after evaluating the corrosion control treatments listed above:
(i) Lead;
(ii) Copper;
(iii) pH;
(iv) Alkalinity;
(v) Calcium;
(vi) Conductivity;
(vii) Orthophosphate (when an inhibitor containing a phosphate compound is used);
(viii) Silicate (when an inhibitor containing a silicate compound is used);
(ix) Water temperature.
(4) The water system shall identify all chemical or physical constraints that limit or prohibit the use of a particular corrosion control treatment and document such constraints with at least one of the following:
(i) Data and documentation showing that a particular corrosion control treatment has adversely affected other water treatment processes when used by another water system with comparable water quality characteristics; and/or
(ii) Data and documentation demonstrating that the water system has previously attempted to evaluate a particular corrosion control treatment and has found that the treatment is ineffective or adversely affects other water quality treatment processes.
(5) The water system shall evaluate the effect of the chemicals used for corrosion control treatment on other water quality treatment processes.
(6) On the basis of an analysis of the data generated during each evaluation, the water system shall recommend to the State in writing the treatment option that the corrosion control studies indicate constitutes optimal corrosion control treatment for that system. The water system shall provide a rationale for its recommendation along with all supporting documentation specified in paragraphs (c) (1) through (5) of this section.
(d)
(2) The State shall notify the system of its decision on optimal corrosion control treatment in writing and explain the basis for this determination. If the State requests additional information to aid its review, the water system shall provide the information.
(e)
(f)
(1) A minimum value or a range of values for pH measured at each entry point to the distribution system;
(2) A minimum pH value, measured in all tap samples. Such value shall be equal to or greater than 7.0, unless the State determines that meeting a pH level of 7.0 is not technologically feasible or is not necessary for the system to optimize corrosion control;
(3) If a corrosion inhibitor is used, a minimum concentration or a range of concentrations for the inhibitor, measured at each entry point to the distribution system and in all tap samples, that the State determines is necessary to form a passivating film on the interior walls of the pipes of the distribution system;
(4) If alkalinity is adjusted as part of optimal corrosion control treatment, a minimum concentration or a range of concentrations for alkalinity, measured at each entry point to the distribution system and in all tap samples;
(5) If calcium carbonate stabilization is used as part of corrosion control, a minimum concentration or a range of concentrations for calcium, measured in all tap samples.
(g)
(1) On days when more than one measurement for the water quality parameter is collected at the sampling location, the daily value shall be the average of all results collected during the day regardless of whether they are collected through continuous monitoring, grab sampling, or a combination of both. If EPA has approved an alternative formula under § 142.16 of this chapter in the State's application for a program revision submitted pursuant to § 142.12 of this chapter, the State's formula shall be used to aggregate multiple measurements taken at a sampling point for the water quality parameter in lieu of the formula in this paragraph.
(2) On days when only one measurement for the water quality parameter is collected at the sampling location, the daily value shall be the result of that measurement.
(3) On days when no measurement is collected for the water quality parameter at the sampling location, the daily value shall be the daily value calculated on the most recent day on which the water quality parameter was measured at the sample site.
(h)
(i)
(1) A State has failed to issue a treatment determination by the applicable deadlines contained in § 141.81,
(2) A State has abused its discretion in a substantial number of cases or in cases affecting a substantial population, or
(3) The technical aspects of a State's determination would be indefensible in an expected Federal enforcement action taken against a system.
Systems shall complete the applicable source water monitoring and treatment requirements (described in the referenced portions of paragraph (b) of this section, and in §§ 141.86, and 141.88) by the following deadlines.
(a)
(2)
(3)
(4)
(5)
(6)
(b)
(2)
(3)
(4)
(5)
(6)
(7)
(i) A State has failed to issue a treatment determination by the applicable deadlines contained in § 141.83(a),
(ii) A state has abused its discretion in a substantial number of cases or in cases affecting a substantial population, or
(iii) The technical aspects of a State's determination would be indefensible in an expected Federal enforcement action taken against a system.
(a) Systems that fail to meet the lead action level in tap samples taken pursuant to § 141.86(d)(2), after installing corrosion control and/or source water treatment (whichever sampling occurs later), shall replace lead service lines in accordance with the requirements of this section. If a system is in violation of § 141.81 or § 141.83 for failure to install source water or corrosion control treatment, the State may require the system to commence lead service line replacement under this section after the date by which the system was required to conduct monitoring under § 141.86(d)(2) has passed.
(b) A water system shall replace annually at least 7 percent of the initial number of lead service lines in its distribution system. The initial number of lead service lines is the number of lead lines in place at the time the replacement program begins. The system shall identify the initial number of lead service lines in its distribution system, including an identification of the portion(s) owned by the system, based on a materials evaluation, including the evaluation required under § 141.86(a) and relevant legal authorities (
(c) A system is not required to replace an individual lead service line if the lead concentration in all service line samples from that line, taken pursuant to § 141.86(b)(3), is less than or equal to 0.015 mg/L.
(d) A water system shall replace that portion of the lead service line that it owns. In cases where the system does not own the entire lead service line, the system shall notify the owner of the line, or the owner's authorized agent, that the system will replace the portion of the service line that it owns and shall offer to replace the owner's portion of the line. A system is not required to bear the cost of replacing the privately-owned portion of the line, nor is it required to replace the privately-owned portion where the owner chooses not to pay the cost of replacing the privately-owned portion of the line, or where replacing the privately-owned portion would be precluded by State, local or common law. A water system that does not replace the entire length of the service line also shall complete the following tasks.
(1) At least 45 days prior to commencing with the partial replacement of a lead service line, the water system shall provide notice to the resident(s) of all buildings served by the line explaining that they may experience a temporary increase of lead levels in their drinking water, along with guidance on measures consumers can take to minimize their exposure to lead. The
(2) The water system shall provide the information required by paragraph (d)(1) of this section to the residents of individual dwellings by mail or by other methods approved by the State. In instances where multi-family dwellings are served by the line, the water system shall have the option to post the information at a conspicuous location.
(e) The State shall require a system to replace lead service lines on a shorter schedule than that required by this section, taking into account the number of lead service lines in the system, where such a shorter replacement schedule is feasible. The State shall make this determination in writing and notify the system of its finding within 6 months after the system is triggered into lead service line replacement based on monitoring referenced in paragraph (a) of this section.
(f) Any system may cease replacing lead service lines whenever first draw samples collected pursuant to § 141.86(b)(2) meet the lead action level during each of two consecutive monitoring periods and the system submits the results to the State. If first draw tap samples collected in any such system thereafter exceeds the lead action level, the system shall recommence replacing lead service lines pursuant to paragraph (b) of this section.
(g) To demonstrate compliance with paragraphs (a) through (d) of this section, a system shall report to the State the information specified in § 141.90(e).
A water system that exceeds the lead action level based on tap water samples collected in accordance with § 141.86 shall deliver the public education materials contained in paragraphs (a) and (b) of this section in accordance with the requirements in paragraph (c) of this section.
(a)
(i)
(ii)
(iii)
(B) Lead is unusual among drinking water contaminants in that it seldom occurs naturally in water supplies like rivers and lakes. Lead enters drinking water primarily as a result of the corrosion, or wearing away, of materials containing lead in the water distribution system and household plumbing. These materials include lead-based solder used to join copper pipe, brass and chrome plated brass faucets, and in some cases, pipes made of lead that connect your house to the water main (service lines). In 1986, Congress banned the use of lead solder containing greater than 0.2% lead, and restricted the lead content of faucets, pipes and other plumbing materials to 8.0%.
(C) When water stands in lead pipes or plumbing systems containing lead for several hours or more, the lead may dissolve into your drinking water. This means the first water drawn from the tap in the morning, or later in the afternoon after returning from work or school, can contain fairly high levels of lead.
(iv)
(B) If a water test indicates that the drinking water drawn from a tap in your home contains lead above 15 ppb, then you should take the following precautions:
(
(
(
(
(
(
(C) The steps described above will reduce the lead concentrations in your drinking water. However, if a water test indicates that the drinking water
(
(
(D) You can consult a variety of sources for additional information. Your family doctor or pediatrician can perform a blood test for lead and provide you with information about the health effects of lead. State and local government agencies that can be contacted include:
(
(
(
(E) The following is a list of some State approved laboratories in your area that you can call to have your water tested for lead. [Insert names and phone numbers of at least two laboratories].
(2)
(i)
(ii)
(iii)
(B) Lead is unusual among drinking water contaminants in that it seldom occurs naturally in water supplies like rivers and lakes. Lead enters drinking water primarily as a result of the corrosion, or wearing away, of materials containing lead in the water distribution system and household plumbing. These materials include lead-based solder used to join copper pipe, brass and chrome-plated brass faucets, and in some cases, pipes made of lead that connect houses and buildings to water mains (service lines). In 1986, Congress banned the use of lead solder containing greater than 0.2% lead, and restricted the lead content of faucets, pipes and other plumbing materials to 8.0%.
(C) When water stands in lead pipes or plumbing systems containing lead for several hours or more, the lead may dissolve into your drinking water. This means the first water drawn from the tap in the morning, or later in the afternoon if the water has not been used all day, can contain fairly high levels of lead.
(iv)
(B) Do not cook with, or drink water from the hot water tap. Hot water can dissolve more lead more quickly than cold water. If you need hot water, draw water from the cold tap and then heat it.
(C) The steps described above will reduce the lead concentrations in your drinking water. However, if you are still concerned, you may wish to use bottled water for drinking and cooking.
(D) You can consult a variety of sources for additional information. Your family doctor or pediatrician can perform a blood test for lead and provide you with information about the health effects of lead. State and local government agencies that can be contacted include:
(
(
(b)
(1) Why should everyone want to know the facts about lead and drinking water? Because unhealthy amounts of lead can enter drinking water through the plumbing in your home. That's why I urge you to do what I did. I had my water tested for [insert free or $ per sample]. You can contact the [insert the name of the city or water system] for information on testing and on simple ways to reduce your exposure to lead in drinking water.
(2) To have your water tested for lead, or to get more information about this public health concern, please call [insert the phone number of the city or water system].
(c)
(2) A community water system that exceeds the lead action level on the basis of tap water samples collected in accordance with § 141.86, and that is not already repeating public education tasks pursuant to paragraph (c)(3), (c)(7), or (c)(8), of this section, shall, within 60 days:
(i) Insert notices in each customer's water utility bill containing the information in paragraph (a)(1) of this section, along with the following alert on the water bill itself in large print: “SOME HOMES IN THIS COMMUNITY HAVE ELEVATED LEAD LEVELS IN THEIR DRINKING WATER. LEAD CAN POSE A SIGNIFICANT RISK TO YOUR HEALTH. PLEASE READ THE ENCLOSED NOTICE FOR FURTHER INFORMATION.” A community water system having a billing cycle that does not include a billing within 60 days of exceeding the action level, or that cannot insert information in the water utility bill without making major changes to its billing system, may use a separate mailing to deliver the information in paragraph (a)(1) of this section as long as the information is delivered to each customer within 60 days of exceeding the action level. Such water systems shall also include the “alert” language specified in this paragraph.
(ii) Submit the information in paragraph (a)(1) of this section to the editorial departments of the major daily and weekly newspapers circulated throughout the community.
(iii) Deliver pamphlets and/or brochures that contain the public education materials in paragraphs (a)(1)(ii) and (a)(1)(iv) of this section to facilities and organizations, including the following:
(iv) Submit the public service announcement in paragraph (b) of this section to at least five of the radio and television stations with the largest audiences that broadcast to the community served by the water system.
(3) A community water system shall repeat the tasks contained in paragraphs (c)(2) (i), (ii) and (iii) of this section every 12 months, and the tasks contained in paragraphs (c)(2)(iv) of this section every 6 months for as long as the system exceeds the lead action level.
(4) Within 60 days after it exceeds the lead action level (unless it already is repeating public education tasks pursuant to paragraph (c)(5) of this section), a non-transient non-community water system shall deliver the public education materials specified by paragraph (a)(1) of this section or the public education materials specified by paragraph (a)(2) of this section as follows:
(i) Post informational posters on lead in drinking water in a public place or common area in each of the buildings served by the system; and
(ii) Distribute informational pamphlets and/or brochures on lead in drinking water to each person served by the non-transient non-community water system. The State may allow the system to utilize electronic transmission in lieu of or combined with printed materials as long as it achieves at least the same coverage.
(5) A non-transient non-community water system shall repeat the tasks contained in paragraph (c)(4) of this section at least once during each calendar year in which the system exceeds the lead action level.
(6) A water system may discontinue delivery of public education materials if the system has met the lead action level during the most recent six-month monitoring period conducted pursuant to § 141.86. Such a system shall recommence public education in accordance with this section if it subsequently exceeds the lead action level during any monitoring period.
(7) A community water system may apply to the State, in writing, (unless the State has waived the requirement for prior State approval) to use the text specified in paragraph (a)(2) of this section in lieu of the text in paragraph (a)(1) of this section and to perform the tasks listed in paragraphs (c)(4) and (c)(5) of this section in lieu of the tasks
(i) The system is a facility, such as a prison or a hospital, where the population served is not capable of or is prevented from making improvements to plumbing or installing point of use treatment devices; and
(ii) The system provides water as part of the cost of services provided and does not separately charge for water consumption.
(8)(i) A community water system serving 3,300 or fewer people may omit the task contained in paragraph (c)(2)(iv) of this section. As long as it distributes notices containing the information contained in paragraph (a)(1) of this section to every household served by the system, such systems may further limit their public education programs as follows:
(A) Systems serving 500 or fewer people may forego the task contained in paragraph (c)(2)(ii) of this section. Such a system may limit the distribution of the public education materials required under paragraph (c)(2)(iii) of this section to facilities and organizations served by the system that are most likely to be visited regularly by pregnant women and children, unless it is notified by the State in writing that it must make a broader distribution.
(B) If approved by the State in writing, a system serving 501 to 3,300 people may omit the task in paragraph (c)(2)(ii) of this section and/or limit the distribution of the public education materials required under paragraph (c)(2)(iii) of this section to facilities and organizations served by the system that are most likely to be visited regularly by pregnant women and children.
(ii) A community water system serving 3,300 or fewer people that delivers public education in accordance with paragraph (c)(8)(i) of this section shall repeat the required public education tasks at least once during each calendar year in which the system exceeds the lead action level.
(d)
(a)
(2) A water system shall use the information on lead, copper, and galvanized steel that it is required to collect under § 141.42(d) of this part [special monitoring for corrosivity characteristics] when conducting a materials evaluation. When an evaluation of the information collected pursuant to § 141.42(d) is insufficient to locate the requisite number of lead and copper sampling sites that meet the targeting criteria in paragraph (a) of this section, the water system shall review the sources of information listed below in order to identify a sufficient number of sampling sites. In addition, the system shall seek to collect such information where possible in the course of its normal operations (e.g., checking service line materials when reading water meters or performing maintenance activities):
(i) All plumbing codes, permits, and records in the files of the building department(s) which indicate the plumbing materials that are installed within publicly and privately owned structures connected to the distribution system;
(ii) All inspections and records of the distribution system that indicate the
(iii) All existing water quality information, which includes the results of all prior analyses of the system or individual structures connected to the system, indicating locations that may be particularly susceptible to high lead or copper concentrations.
(3) The sampling sites selected for a community water system's sampling pool (“tier l sampling sites”) shall consist of single family structures that:
(i) Contain copper pipes with lead solder installed after 1982 or contain lead pipes; and/or
(ii) Are served by a lead service line. When multiple-family residences comprise at least 20 percent of the structures served by a water system, the system may include these types of structures in its sampling pool.
(4) Any community water system with insufficient tier 1 sampling sites shall complete its sampling pool with “tier 2 sampling sites”, consisting of buildings, including multiple-family residences that:
(i) Contain copper pipes with lead solder installed after 1982 or contain lead pipes; and/or
(ii) Are served by a lead service line.
(5) Any community water system with insufficient tier 1 and tier 2 sampling sites shall complete its sampling pool with “tier 3 sampling sites”, consisting of single family structures that contain copper pipes with lead solder installed before 1983. A community water system with insufficient tier 1, tier 2, and tier 3 sampling sites shall complete its sampling pool with representative sites throughout the distribution system. For the purpose of this paragraph, a representative site is a site in which the plumbing materials used at that site would be commonly found at other sites served by the water system.
(6) The sampling sites selected for a non-transient noncommunity water system (“tier l sampling sites”) shall consist of buildings that:
(i) Contain copper pipes with lead solder installed after 1982 or contain lead pipes; and/or
(ii) Are served by a lead service line.
(7) A non-transient non-community water system with insufficient tier 1 sites that meet the targeting criteria in paragraph (a)(6) of this section shall complete its sampling pool with sampling sites that contain copper pipes with lead solder installed before 1983. If additional sites are needed to complete the sampling pool, the non-transient non-community water system shall use representative sites throughout the distribution system. For the purpose of this paragraph, a representative site is a site in which the plumbing materials used at that site would be commonly found at other sites served by the water system.
(8) Any water system whose distribution system contains lead service lines shall draw 50 percent of the samples it collects during each monitoring period from sites that contain lead pipes, or copper pipes with lead solder, and 50 percent of the samples from sites served by a lead service line. A water system that cannot identify a sufficient number of sampling sites served by a lead service line shall collect first-draw samples from all of the sites identified as being served by such lines.
(b)
(2) Each first-draw tap sample for lead and copper shall be one liter in volume and have stood motionless in the plumbing system of each sampling site for at least six hours. First-draw samples from residential housing shall be collected from the cold water kitchen tap or bathroom sink tap. First-draw samples from a nonresidential building shall be one liter in volume and shall be collected at an interior tap from which water is typically drawn for consumption. Non-first-draw samples collected in lieu of first-draw samples pursuant to paragraph (b)(5) of this section shall be one liter in volume and shall be collected at an interior tap from which water is typically drawn for consumption. First-draw samples may be collected by the system or the system may allow residents
(3) Each service line sample shall be one liter in volume and have stood motionless in the lead service line for at least six hours. Lead service line samples shall be collected in one of the following three ways:
(i) At the tap after flushing the volume of water between the tap and the lead service line. The volume of water shall be calculated based on the interior diameter and length of the pipe between the tap and the lead service line;
(ii) Tapping directly into the lead service line; or
(iii) If the sampling site is a building constructed as a single-family residence, allowing the water to run until there is a significant change in temperature which would be indicative of water that has been standing in the lead service line.
(4) A water system shall collect each first draw tap sample from the same sampling site from which it collected a previous sample. If, for any reason, the water system cannot gain entry to a sampling site in order to collect a follow-up tap sample, the system may collect the follow-up tap sample from another sampling site in its sampling pool as long as the new site meets the same targeting criteria, and is within reasonable proximity of the original site.
(5) A non-transient non-community water system, or a community water system that meets the criteria of §§ 141.85(c)(7)(i) and (ii), that does not have enough taps that can supply first-draw samples, as defined in § 141.2, may apply to the State in writing to substitute non-first-draw samples. Such systems must collect as many first-draw samples from appropriate taps as possible and identify sampling times and locations that would likely result in the longest standing time for the remaining sites. The State has the discretion to waive the requirement for prior State approval of non-first-draw sample sites selected by the system, either through State regulation or written notification to the system.
(c)
(d)
The first six-month monitoring period for small, medium-size and large systems shall begin on the following dates:
(i) All large systems shall monitor during two consecutive six-month periods.
(ii) All small and medium-size systems shall monitor during each six-month monitoring period until:
(A) The system exceeds the lead or copper action level and is therefore required to implement the corrosion control treatment requirements under § 141.81, in which case the system shall continue monitoring in accordance with paragraph (d)(2) of this section, or
(B) The system meets the lead and copper action levels during two consecutive six-month monitoring periods, in which case the system may reduce monitoring in accordance with paragraph (d)(4) of this section.
(2)
(ii) Any small or medium-size system which installs optimal corrosion control treatment pursuant to § 141.81(e)(5) shall monitor during two consecutive six-month monitoring periods by the date specified in § 141.81(e)(6).
(iii) Any system which installs source water treatment pursuant to § 141.83(a)(3) shall monitor during two consecutive six-month monitoring periods by the date specified in § 141.83(a)(4).
(3)
(4)
(ii) Any water system that maintains the range of values for the water quality control parameters reflecting optimal corrosion control treatment specified by the State under § 141.82(f) during each of two consecutive six-month monitoring periods may reduce the frequency of monitoring to once per year and reduce the number of lead and copper samples in accordance with paragraph (c) of this section if it receives written approval from the State. The State shall review monitoring, treatment, and other relevant information submitted by the water system in accordance with § 141.90, and shall notify the system in writing when it determines the system is eligible to commence reduced monitoring pursuant to this paragraph. The State shall review, and where appropriate, revise its determination when the system submits new monitoring or treatment data, or when other data relevant to the number and frequency of tap sampling becomes available.
(iii) A small or medium-size water system that meets the lead and copper action levels during three consecutive years of monitoring may reduce the frequency of monitoring for lead and copper from annually to once every three years. Any water system that maintains the range of values for the water quality control parameters reflecting optimal corrosion control treatment specified by the State under § 141.82(f) during three consecutive years of monitoring may reduce the frequency of monitoring from annually to once every three years if it receives written approval from the State. The State shall review monitoring, treatment, and other relevant information submitted by the water system in accordance with § 141.90, and shall notify the system in writing when it determines the system is eligible to reduce the frequency of monitoring to once every three years. The State shall review, and where appropriate, revise its determination when the system submits new monitoring or treatment data, or when other data relevant to the number and frequency of tap sampling becomes available.
(iv) A water system that reduces the number and frequency of sampling shall collect these samples from representative sites included in the pool of targeted sampling sites identified in paragraph (a) of this section. Systems sampling annually or less frequently
(A) The State, at its discretion, may approve a different period for conducting the lead and copper tap sampling for systems collecting a reduced number of samples. Such a period shall be no longer than four consecutive months and must represent a time of normal operation where the highest levels of lead are most likely to occur. For a non-transient non-community water system that does not operate during the months of June through September, and for which the period of normal operation where the highest levels of lead are most likely to occur is not known, the State shall designate a period that represents a time of normal operation for the system.
(B) Systems monitoring annually, that have been collecting samples during the months of June through September and that receive State approval to alter their sample collection period under paragraph (d)(4)(iv)(A) of this section, must collect their next round of samples during a time period that ends no later than 21 months after the previous round of sampling. Systems monitoring triennially that have been collecting samples during the months of June through September, and receive State approval to alter the sampling collection period as per paragraph (d)(4)(iv)(A) of this section, must collect their next round of samples during a time period that ends no later than 45 months after the previous round of sampling. Subsequent rounds of sampling must be collected annually or triennially, as required by this section. Small systems with waivers, granted pursuant to paragraph (g) of this section, that have been collecting samples during the months of June through September and receive State approval to alter their sample collection period under paragraph (d)(4)(iv)(A) of this section must collect their next round of samples before the end of the 9-year period.
(v) Any water system that demonstrates for two consecutive 6-month monitoring periods that the tap water lead level computed under § 141.80(c)(3) is less than or equal to 0.005 mg/L and the tap water copper level computed under § 141.80(c)(3) is less than or equal to 0.65 mg/L may reduce the number of samples in accordance with paragraph (c) of this section and reduce the frequency of sampling to once every three calendar years.
(vi)(A) A small or medium-size water system subject to reduced monitoring that exceeds the lead or copper action level shall resume sampling in accordance with paragraph (d)(3) of this section and collect the number of samples specified for standard monitoring under paragraph (c) of this section. Such a system shall also conduct water quality parameter monitoring in accordance with § 141.87(b), (c) or (d) (as appropriate) during the monitoring period in which it exceeded the action level. Any such system may resume annual monitoring for lead and copper at the tap at the reduced number of sites specified in paragraph (c) of this section after it has completed two subsequent consecutive six-month rounds of monitoring that meet the criteria of paragraph (d)(4)(i) of this section and/or may resume triennial monitoring for lead and copper at the reduced number of sites after it demonstrates through subsequent rounds of monitoring that it meets the criteria of either paragraph (d)(4)(iii) or (d)(4)(v) of this section.
(B) Any water system subject to the reduced monitoring frequency that fails to operate at or above the minimum value or within the range of values for the water quality parameters specified by the State under § 141.82(f) for more than nine days in any six-month period specified in § 141.87(d) shall conduct tap water sampling for lead and copper at the frequency specified in paragraph (d)(3) of this section, collect the number of samples specified for standard monitoring under paragraph (c) of this section, and shall resume monitoring for water quality parameters within the distribution system in accordance with § 141.87(d). Such a system may resume reduced monitoring for lead and copper at the tap and for water quality parameters within the distribution system under the following conditions:
(
(
(
(vii) Any water system subject to a reduced monitoring frequency under paragraph (d)(4) of this section that either adds a new source of water or changes any water treatment shall inform the State in writing in accordance with § 141.90(a)(3). The State may require the system to resume sampling in accordance with paragraph (d)(3) of this section and collect the number of samples specified for standard monitoring under paragraph (c) of this section or take other appropriate steps such as increased water quality parameter monitoring or re-evaluation of its corrosion control treatment given the potentially different water quality considerations.
(e)
(f)
(1) The State may invalidate a lead or copper tap water sample at least if one of the following conditions is met.
(i) The laboratory establishes that improper sample analysis caused erroneous results.
(ii) The State determines that the sample was taken from a site that did not meet the site selection criteria of this section.
(iii) The sample container was damaged in transit.
(iv) There is substantial reason to believe that the sample was subject to tampering.
(2) The system must report the results of all samples to the State and all supporting documentation for samples the system believes should be invalidated.
(3) To invalidate a sample under paragraph (f)(1) of this section, the decision and the rationale for the decision must be documented in writing. States may not invalidate a sample solely on the grounds that a follow-up sample result is higher or lower than that of the original sample.
(4) The water system must collect replacement samples for any samples invalidated under this section if, after the invalidation of one or more samples, the system has too few samples to meet the minimum requirements of paragraph (c) of this section. Any such replacement samples must be taken as soon as possible, but no later than 20 days after the date the State invalidates the sample or by the end of the applicable monitoring period, whichever occurs later. Replacement samples taken after the end of the applicable monitoring period shall not also be used to meet the monitoring requirements of a subsequent monitoring period. The replacement samples shall be
(g)
(1)
(i)
(A) It contains no plastic pipes which contain lead plasticizers, or plastic service lines which contain lead plasticizers; and
(B) It is free of lead service lines, lead pipes, lead soldered pipe joints, and leaded brass or bronze alloy fittings and fixtures, unless such fittings and fixtures meet the specifications of any standard established pursuant to 42 U.S.C. 300g-6(e) (SDWA section 1417(e)).
(ii)
(2)
(i)
(ii)
(3)
(4)
(ii) A system with a partial waiver must conduct tap water monitoring for the waived contaminant in accordance with paragraph (d)(4)(iv) of this section at the reduced number of sampling sites specified in paragraph (c) of this section at least once every nine years and provide the materials certification specified in paragraph (g)(1) of this section pertaining to the waived contaminant along with the monitoring results. Such a system also must continue to monitor for the non-waived contaminant in accordance with requirements of paragraph (d)(1) through (d)(4) of this section, as appropriate.
(iii) If a system with a full or partial waiver adds a new source of water or changes any water treatment, the system must notify the State in writing in accordance with § 141.90(a)(3). The State has the authority to require the system to add or modify waiver conditions (
(iv) If a system with a full or partial waiver becomes aware that it is no longer free of lead-containing or copper-containing materials, as appropriate, (
(5)
(i) A system with a full waiver or a lead waiver no longer satisfies the materials criteria of paragraph (g)(1)(i) of this section or has a 90th percentile lead level greater than 0.005 mg/L.
(ii) A system with a full waiver or a copper waiver no longer satisfies the materials criteria of paragraph (g)(1)(ii) of this section or has a 90th percentile copper level greater than 0.65 mg/L.
(iii) The State notifies the system, in writing, that the waiver has been revoked, setting forth the basis of its decision.
(6)
(i) If the system exceeds the lead and/or copper action level, the system must implement corrosion control treatment in accordance with the deadlines specified in § 141.81(e), and any other applicable requirements of this subpart.
(ii) If the system meets both the lead and the copper action level, the system must monitor for lead and copper at the tap no less frequently than once every three years using the reduced number of sample sites specified in paragraph (c) of this section.
(7)
(i) If the system has demonstrated that it is both free of lead-containing and copper-containing materials, as required by paragraph (g)(1) of this section and that its 90th percentile lead levels and 90th percentile copper levels meet the criteria of paragraph (g)(2) of this section, the waiver remains in effect so long as the system continues to meet the waiver eligibility criteria of paragraph (g)(5) of this section. The first round of tap water monitoring conducted pursuant to paragraph (g)(4) of this section shall be completed no later than nine years after the last time the system has monitored for lead and copper at the tap.
(ii) If the system has met the materials criteria of paragraph (g)(1) of this section but has not met the monitoring criteria of paragraph (g)(2) of this section, the system shall conduct a round of monitoring for lead and copper at the tap demonstrating that it meets the criteria of paragraph (g)(2) of this section no later than September 30,
All large water systems, and all small- and medium-size systems that exceed the lead or copper action level shall monitor water quality parameters in addition to lead and copper in accordance with this section. The requirements of this section are summarized in the table at the end of this section.
(a)
(ii) Samples collected at the entry point(s) to the distribution system shall be from locations representative of each source after treatment. If a system draws water from more than one source and the sources are combined before distribution, the system must sample at an entry point to the distribution system during periods of normal operating conditions (i.e., when water is representative of all sources being used).
(2)
(ii) Except as provided in paragraph (c)(3) of this section, systems shall collect two samples for each applicable water quality parameter at each entry point to the distribution system during each monitoring period specified in paragraph (b) of this section. During each monitoring period specified in paragraphs (c)-(e) of this section, systems shall collect one sample for each applicable water quality parameter at each entry point to the distribution system.
(b)
(1) At taps:
(i) pH;
(ii) Alkalinity;
(iii) Orthophosphate, when an inhibitor containing a phosphate compound is used;
(iv) Silica, when an inhibitor containing a silicate compound is used;
(v) Calcium;
(vi) Conductivity; and
(vii) Water temperature.
(2) At each entry point to the distribution system: all of the applicable parameters listed in paragraph (b)(1) of this section.
(c)
(1) At taps, two samples for:
(i) pH;
(ii) Alkalinity;
(iii) Orthophosphate, when an inhibitor containing a phosphate compound is used;
(iv) Silica, when an inhibitor containing a silicate compound is used;
(v) Calcium, when calcium carbonate stabilization is used as part of corrosion control.
(2) Except as provided in paragraph (c)(3) of this section, at each entry point to the distribution system, at least one sample no less frequently than every two weeks (biweekly) for:
(i) pH;
(ii) When alkalinity is adjusted as part of optimal corrosion control, a reading of the dosage rate of the chemical used to adjust alkalinity, and the alkalinity concentration; and
(iii) When a corrosion inhibitor is used as part of optimal corrosion control, a reading of the dosage rate of the inhibitor used, and the concentration of orthophosphate or silica (whichever is applicable).
(3) Any ground water system can limit entry point sampling described in paragraph (c)(2) of this section to those entry points that are representative of water quality and treatment conditions throughout the system. If water from untreated ground water sources mixes with water from treated ground water sources, the system must monitor for water quality parameters both at representative entry points receiving treatment and representative entry points receiving no treatment. Prior to the start of any monitoring under this paragraph, the system shall provide to the State written information identifying the selected entry points and documentation, including information on seasonal variability, sufficient to demonstrate that the sites are representative of water quality and treatment conditions throughout the system.
(d)
(e)
(2)(i) Any water system that maintains the range of values for the water
(ii) A water system may reduce the frequency with which it collects tap samples for applicable water quality parameters specified in paragraph (e)(1) of this section to every three years if it demonstrates during two consecutive monitoring periods that its tap water lead level at the 90th percentile is less than or equal to the PQL for lead specified in § 141.89 (a)(1)(ii), that its tap water copper level at the 90th percentile is less than or equal to 0.65 mg/L for copper in § 141.80(c)(2), and that it also has maintained the range of values for the water quality parameters reflecting optimal corrosion control treatment specified by the State under § 141.82(f).
(3) A water system that conducts sampling annually shall collect these samples evenly throughout the year so as to reflect seasonal variability.
(4) Any water system subject to the reduced monitoring frequency that fails to operate at or above the minimum value or within the range of values for the water quality parameters specified by the State in § 141.82(f) for more than nine days in any six-month period specified in § 141.82(g) shall resume distribution system tap water sampling in accordance with the number and frequency requirements in paragraph (d) of this section. Such a system may resume annual monitoring for water quality parameters at the tap at the reduced number of sites specified in paragraph (e)(1) of this section after it has completed two subsequent consecutive six-month rounds of monitoring that meet the criteria of that paragraph and/or may resume triennial monitoring for water quality parameters at the tap at the reduced number of sites after it demonstrates through subsequent rounds of monitoring that it meets the criteria of either paragraph (e)(2)(i) or (e)(2)(ii) of this section.
(f)
(a)
(i) Groundwater systems shall take a minimum of one sample at every entry point to the distribution system which is representative of each well after treatment (hereafter called a sampling point). The system shall take one sample at the same sampling point unless conditions make another sampling point more representative of each source or treatment plant.
(ii) Surface water systems shall take a minimum of one sample at every entry point to the distribution system after any application of treatment or in the distribution system at a point which is representative of each source after treatment (hereafter called a sampling point). The system shall take each sample at the same sampling point unless conditions make another sampling point more representative of each source or treatment plant.
For the purposes of this paragraph, surface water systems include systems with a combination of surface and ground sources.
(iii) If a system draws water from more than one source and the sources are combined before distribution, the system must sample at an entry point to the distribution system during periods of normal operating conditions (
(iv) The State may reduce the total number of samples which must be analyzed by allowing the use of compositing. Compositing of samples must be done by certified laboratory personnel. Composite samples from a maximum of five samples are allowed, provided that if the lead concentration in the composite sample is greater than or equal to 0.001 mg/L or the copper concentration is greater than or equal to 0.160 mg/L, then either:
(A) A follow-up sample shall be taken and analyzed within 14 days at each sampling point included in the composite; or
(B) If duplicates of or sufficient quantities from the original samples from each sampling point used in the composite are available, the system may use these instead of resampling.
(2) Where the results of sampling indicate an exceedance of maximum permissible source water levels established under § 141.83(b)(4), the State may require that one additional sample
(b)
(c)
(d)
(i) A water system using only groundwater shall collect samples once during the three-year compliance period (as that term is defined in § 141.2) in effect when the applicable State determination under paragraph (d)(1) of this section is made. Such systems shall collect samples once during each subsequent compliance period.
(ii) A water system using surface water (or a combination of surface and groundwater) shall collect samples once during each year, the first annual monitoring period to begin on the date on which the applicable State determination is made under paragraph (d)(1) of this section.
(2) A system is not required to conduct source water sampling for lead and/or copper if the system meets the action level for the specific contaminant in tap water samples during the entire source water sampling period applicable to the system under paragraph (d)(1) (i) or (ii) of this section.
(e)
(i) The system demonstrates that finished drinking water entering the distribution system has been maintained below the maximum permissible lead and copper concentrations specified by the State in § 141.83(b)(4) during at least three consecutive compliance periods under paragraph (d)(1) of this section; or
(ii) The State has determined that source water treatment is not needed and the system demonstrates that, during at least three consecutive compliance periods in which sampling was conducted under paragraph (d)(1) of this section, the concentration of lead in source water was less than or equal to 0.005 mg/L and the concentration of copper in source water was less than or equal to 0.65 mg/L.
(2) A water system using surface water (or a combination of surface water and ground water) may reduce the monitoring frequency in paragraph (d)(1) of this section to once during each nine-year compliance cycle (as that term is defined in § 141.2) if the system meets one of the following criteria:
(i) The system demonstrates that finished drinking water entering the distribution system has been maintained below the maximum permissible lead and copper concentrations specified by the State in § 141.83(b)(4) for at least three consecutive years; or
(ii) The State has determined that source water treatment is not needed and the system demonstrates that, during at least three consecutive years, the concentration of lead in source
(3) A water system that uses a new source of water is not eligible for reduced monitoring for lead and/or copper until concentrations in samples collected from the new source during three consecutive monitoring periods are below the maximum permissible lead and copper concentrations specified by the State in § 141.83(a)(5).
(a) Analyses for lead, copper, pH, conductivity, calcium, alkalinity, orthophosphate, silica, and temperature shall be conducted with the methods in § 141.23(k)(1).
(1) Analyses for alkalinity, calcium, conductivity, orthophosphate, pH, silica, and temperature may be performed by any person acceptable to the State. Analyses under this section for lead and copper shall only be conducted by laboratories that have been certified by EPA or the State. To obtain certification to conduct analyses for lead and copper, laboratories must:
(i) Analyze Performance Evaluation samples, which include lead and copper, provided by or acceptable to EPA or the State at least once a year by each method for which the laboratory desires certification; and
(ii) Achieve quantitative acceptance limits as follows:
(A) For lead: ±30 percent of the actual amount in the Performance Evaluation sample when the actual amount is greater than or equal to 0.005 mg/L. The Practical Quantitation Level, or PQL for lead is 0.005 mg/L.
(B) For Copper: ±10 percent of the actual amount in the Performance Evaluation sample when the actual amount is greater than or equal to 0.050 mg/L. The Practical Quantitation Level, or PQL for copper is 0.050 mg/L.
(iii) Achieve the method detection limit for lead of 0.001 mg/L according to the procedures in appendix B of part 136 of this title. This need only be accomplished if the laboratory will be processing source water composite samples under § 141.88(a)(1)(iii).
(iv) Be currently certified by EPA or the State to perform analyses to the specifications described in paragraph (a)(2) of this section.
(2) States have the authority to allow the use of previously collected monitoring data for purposes of monitoring, if the data were collected and analyzed in accordance with the requirements of this subpart.
(3) All lead and copper levels measured between the PQL and MDL must be either reported as measured or they can be reported as one-half the PQL specified for lead and copper in paragraph (a)(1)(ii) of this section. All levels below the lead and copper MDLs must be reported as zero.
(4) All copper levels measured between the PQL and the MDL must be either reported as measured or they can be reported as one-half the PQL (0.025 mg/L). All levels below the copper MDL must be reported as zero.
(b) [Reserved]
All water systems shall report all of the following information to the State in accordance with this section.
(a)
(i) The results of all tap samples for lead and copper including the location of each site and the criteria under § 141.86(a) (3), (4), (5), (6), and/or (7) under which the site was selected for the system's sampling pool;
(ii) Documentation for each tap water lead or copper sample for which
(iii) [Reserved]
(iv) The 90th percentile lead and copper concentrations measured from among all lead and copper tap water samples collected during each monitoring period (calculated in accordance with § 141.80(c)(3)), unless the State calculates the system's 90th percentile lead and copper levels under paragraph (h) of this section;
(v) With the exception of initial tap sampling conducted pursuant to § 141.86(d)(1), the system shall designate any site which was not sampled during previous monitoring periods, and include an explanation of why sampling sites have changed;
(vi) The results of all tap samples for pH, and where applicable, alkalinity, calcium, conductivity, temperature, and orthophosphate or silica collected under § 141.87 (b)-(e);
(vii) The results of all samples collected at the entry point(s) to the distribution system for applicable water quality parameters under § 141.87 (b)-(e);
(viii) A water system shall report the results of all water quality parameter samples collected under § 141.87(c) through (f) during each six-month monitoring period specified in § 141.87(d) within the first 10 days following the end of the monitoring period unless the State has specified a more frequent reporting requirement.
(2) For a non-transient non-community water system, or a community water system meeting the criteria of §§ 141.85(c)(7)(i) and (ii), that does not have enough taps that can provide first-draw samples, the system must either:
(i) Provide written documentation to the State identifying standing times and locations for enough non-first-draw samples to make up its sampling pool under § 141.86(b)(5) by the start of the first applicable monitoring period under § 141.86(d) that commences after April 11, 2000, unless the State has waived prior State approval of non-first-draw sample sites selected by the system pursuant to § 141.86(b)(5); or
(ii) If the State has waived prior approval of non-first-draw sample sites selected by the system, identify, in writing, each site that did not meet the six-hour minimum standing time and the length of standing time for that particular substitute sample collected pursuant to § 141.86(b)(5) and include this information with the lead and copper tap sample results required to be submitted pursuant to paragraph (a)(1)(i) of this section.
(3) No later than 60 days after the addition of a new source or any change in water treatment, unless the State requires earlier notification, a water system deemed to have optimized corrosion control under § 141.81(b)(3), a water system subject to reduced monitoring pursuant to § 141.86(d)(4), or a water system subject to a monitoring waiver pursuant to § 141.86(g), shall send written documentation to the State describing the change. In those instances where prior State approval of the treatment change or new source is not required, water systems are encouraged to provide the notification to the State beforehand to minimize the risk the treatment change or new source will adversely affect optimal corrosion control.
(4) Any small system applying for a monitoring waiver under § 141.86(g), or subject to a waiver granted pursuant to § 141.86(g)(3), shall provide the following information to the State in writing by the specified deadline:
(i) By the start of the first applicable monitoring period in § 141.86(d), any small water system applying for a monitoring waiver shall provide the documentation required to demonstrate that it meets the waiver criteria of §§ 141.86(g)(1) and (2).
(ii) No later than nine years after the monitoring previously conducted pursuant to § 141.86(g)(2) or § 141.86(g)(4)(i), each small system desiring to maintain its monitoring waiver shall provide the information required by §§ 141.86(g)(4)(i) and (ii).
(iii) No later than 60 days after it becomes aware that it is no longer free of lead-containing and/or copper-containing material, as appropriate, each small system with a monitoring waiver shall provide written notification to the State, setting forth the circumstances resulting in the lead-containing and/or copper-containing materials being introduced into the system
(iv) By October 10, 2000, any small system with a waiver granted prior to April 11, 2000 and that has not previously met the requirements of § 141.86(g)(2) shall provide the information required by that paragraph.
(5) Each ground water system that limits water quality parameter monitoring to a subset of entry points under § 141.87(c)(3) shall provide, by the commencement of such monitoring, written correspondence to the State that identifies the selected entry points and includes information sufficient to demonstrate that the sites are representative of water quality and treatment conditions throughout the system.
(b)
(2) With the exception of the first round of source water sampling conducted pursuant to § 141.88(b), the system shall specify any site which was not sampled during previous monitoring periods, and include an explanation of why the sampling point has changed.
(c)
(1) For systems demonstrating that they have already optimized corrosion control, information required in § 141.81(b) (2) or (3).
(2) For systems required to optimize corrosion control, their recommendation regarding optimal corrosion control treatment under § 141.82(a).
(3) For systems required to evaluate the effectiveness of corrosion control treatments under §141.82(c), the information required by that paragraph.
(4) For systems required to install optimal corrosion control designated by the State under § 141.82(d), a letter certifying that the system has completed installing that treatment.
(d)
(1) If required under § 141.83(b)(1), their recommendation regarding source water treatment;
(2) For systems required to install source water treatment under § 141.83(b)(2), a letter certifying that the system has completed installing the treatment designated by the State within 24 months after the State designated the treatment.
(e)
(1) Within 12 months after a system exceeds the lead action level in sampling referred to in § 141.84(a), the system shall demonstrate in writing to the State that it has conducted a material evaluation, including the evaluation in § 141.86(a), to identify the initial number of lead service lines in its distribution system, and shall provide the State with the system's schedule for replacing annually at least 7 percent of the initial number of lead service lines in its distribution system.
(2) Within 12 months after a system exceeds the lead action level in sampling referred to in § 141.84(a), and every 12 months thereafter, the system shall demonstrate to the State in writing that the system has either:
(i) Replaced in the previous 12 months at least 7 percent of the initial lead service lines (or a greater number of lines specified by the State under § 141.84(e)) in its distribution system, or
(ii) Conducted sampling which demonstrates that the lead concentration in all service line samples from an individual line(s), taken pursuant to § 141.86(b)(3), is less than or equal to 0.015 mg/L. In such cases, the total number of lines replaced and/or which meet the criteria in § 141.84(c) shall equal at least 7 percent of the initial number of lead lines identified under paragraph (a) of this section (or the percentage specified by the State under § 141.84(e)).
(3) The annual letter submitted to the State under paragraph (e)(2) of this
(i) The number of lead service lines scheduled to be replaced during the previous year of the system's replacement schedule;
(ii) The number and location of each lead service line replaced during the previous year of the system's replacement schedule;
(iii) If measured, the water lead concentration and location of each lead service line sampled, the sampling method, and the date of sampling.
(4) Any system which collects lead service line samples following partial lead service line replacement required by § 141.84 shall report the results to the State within the first ten days of the month following the month in which the system receives the laboratory results, or as specified by the State. States, at their discretion may eliminate this requirement to report these monitoring results. Systems shall also report any additional information as specified by the State, and in a time and manner prescribed by the State, to verify that all partial lead service line replacement activities have taken place.
(f)
(i) A demonstration that the system has delivered the public education materials that meet the content requirements in § 141.85(a) and (b) and the delivery requirements in § 141.85(c); and
(ii) A list of all the newspapers, radio stations, television stations, and facilities and organizations to which the system delivered public education materials during the period in which the system was required to perform public education tasks.
(2) Unless required by the State, a system that previously has submitted the information required by paragraph (f)(1)(ii) of this section need not resubmit the information required by paragraph (f)(1)(ii) of this section, as long as there have been no changes in the distribution list and the system certifies that the public education materials were distributed to the same list submitted previously.
(g)
(h)
(1) The State has previously notified the water system that it will calculate the water system's 90th percentile lead and copper concentrations, based on the lead and copper tap results submitted pursuant to paragraph (h)(2)(i) of this section, and has specified a date before the end of the applicable monitoring period by which the system must provide the results of lead and copper tap water samples;
(2) The system has provided the following information to the State by the date specified in paragraph (h)(1) of this section:
(i) The results of all tap samples for lead and copper including the location of each site and the criteria under § 141.86(a)(3), (4), (5), (6), and/or (7) under which the site was selected for the system's sampling pool, pursuant to paragraph (a)(1)(i) of this section; and
(ii) An identification of sampling sites utilized during the current monitoring period that were not sampled during previous monitoring periods, and an explanation why sampling sites have changed; and
(3) The State has provided the results of the 90th percentile lead and copper calculations, in writing, to the water system before the end of the monitoring period.
Any system subject to the requirements of this subpart shall retain on its premises original records of all sampling data and analyses, reports, surveys, letters, evaluations, schedules, State determinations, and any other information required by §§ 141.81 through 141.88. Each water system shall retain the records required by this section for no fewer than 12 years.
(a) Public water systems may use point-of-entry devices to comply with maximum contaminant levels only -if they meet the requirements of this -section.
(b) It is the responsibility of the -public water system to operate and -maintain the point-of-entry treat-ment system.
(c) The public water system must develop and obtain State approval for a monitoring plan before point-of-entry devices are installed for compliance. Under the plan approved by the State, point-of-entry devices must provide health protection equivalent to central water treatment. “Equivalent” means that the water would meet all national primary drinking water regulations and would be of acceptable quality similar to water distributed by a well-operated central treatment plant. In addition to the VOCs, monitoring must include physical measurements and observations such as total flow treated and mechanical condition of the treatment equipment.
(d) Effective technology must be properly applied under a plan approved by the State and the micro-bi-o-logi-cal safety of the water must be maintained.
(1) The State must require adequate certification of performance, field testing, and, if not included in the certification process, a rigorous engineering design review of the point-of-entry devices.
(2) The design and application of the point-of-entry devices must consider the tendency for increase in heterotrophic bacteria concentrations in water treated with activated carbon. It may be necessary to use frequent backwashing, post-contactor disinfection, and Heterotrophic Plate Count monitoring to ensure that the microbiological safety of the water is not compromised.
(e)
Public water systems shall not use bottled water to achieve compliance with an MCL. Bottled water may be used on a temporary basis to avoid unreasonable risk to health.
The requirements of subpart K of this part constitute national primary drinking water regulations. These regulations establish treatment techniques in lieu of maximum contaminant levels for specified contaminants.
Each public water system must certify annually in writing to the State (using third party or manufacturer's certification) that when acrylamide and epichlorohydrin are used in drinking water systems, the combination (or product) of dose and monomer level does not exceed the levels specified as follows:
(a) The requirements of this subpart L constitute national primary drinking water regulations.
(1) The regulations in this subpart establish criteria under which community water systems (CWSs) and nontransient, noncommunity water systems (NTNCWSs) which add a chemical disinfectant to the water in any part of the drinking water treatment process must modify their practices to meet MCLs and MRDLs in §§ 141.64 and 141.65, respectively, and must meet the treatment technique requirements for disinfection byproduct precursors in § 141.135.
(2) The regulations in this subpart establish criteria under which transient NCWSs that use chlorine dioxide as a disinfectant or oxidant must modify their practices to meet the MRDL for chlorine dioxide in § 141.65.
(3) EPA has established MCLs for TTHM and HAA5 and treatment technique requirements for disinfection byproduct precursors to limit the levels of known and unknown disinfection byproducts which may have adverse health effects. These disinfection byproducts may include chloroform; bromodichloromethane; dibromochloromethane; bromoform; dichloroacetic acid; and trichloroacetic acid.
(b)
(2)
(c) Each CWS and NTNCWS regulated under paragraph (a) of this section must be operated by qualified personnel who meet the requirements specified by the State and are included in a State register of qualified operators.
(d)
(a)
(2) The following documents are incorporated by reference. The Director of the Federal Register approves this incorporation by reference in accordance with 5 U.S.C. 552(a) and 1 CFR part 51. Copies may be inspected at EPA's Drinking Water Docket, 401 M St., SW., Washington, DC 20460, or at
(b)
(2) Analysis under this section for disinfection byproducts must be conducted by laboratories that have received certification by EPA or the State, except as specified under paragraph (b)(3) of this section.To receive certification to conduct analyses for the contaminants in § 141.64(a), the laboratory must carry out annual analyses of performance evaluation (PE)
(3) A party approved by EPA or the State must measure daily chlorite samples at the entrance to the distribution system.
(c)
(2) If approved by the State, systems may also measure residual disinfectant concentrations for chlorine, chloramines, and chlorine dioxide by using DPD colorimetric test kits.
(3) A party approved by EPA or the State must measure residual disinfectant concentration.
(d)
(1)
(2)
(3)
(4)
(i) Dissolved Organic Carbon (DOC). Standard Method 5310 B (High-Temperature Combustion Method) or Standard Method 5310 C (Persulfate-Ultraviolet or Heated-Persulfate Oxidation Method) or Standard Method 5310 D (Wet-Oxidation Method). Prior to analysis, DOC samples must be filtered through a 0.45 μm pore-diameter filter. Water passed through the filter prior to filtration of the sample must serve as the filtered blank. This filtered blank must be analyzed using procedures identical to those used for analysis of the samples and must meet the following criteria: DOC < 0.5 mg/L. DOC samples must be filtered through the 0.45 μm pore-diameter filter prior to acidification. DOC samples must either be analyzed or must be acidified to achieve pH less than 2.0 by minimal addition of phosphoric or sulfuric acid as soon as practical after sampling, not to exceed 48 hours. Acidified DOC samples must be analyzed within 28 days.
(ii) Ultraviolet Absorption at 254 nm (UV
(5)
(a)
(2) Systems may consider multiple wells drawing water from a single aquifer as one treatment plant for determining the minimum number of TTHM and HAA5 samples required, with State approval in accordance with criteria developed under § 142.16(h)(5) of this chapter.
(3) Failure to monitor in accordance with the monitoring plan required under paragraph (f) of this section is a monitoring violation.
(4) Failure to monitor will be treated as a violation for the entire period covered by the annual average where compliance is based on a running annual average of monthly or quarterly samples or averages and the system's failure to monitor makes it impossible to determine compliance with MCLs or MRDLs.
(5) Systems may use only data collected under the provisions of this subpart or subpart M of this part to qualify for reduced monitoring.
(b)
(ii) Systems may reduce monitoring, except as otherwise provided, in accordance with the following table:
(iii) Systems that do not meet these levels must resume monitoring at the frequency identified in paragraph (b)(1)(i) of this section (minimum monitoring frequency column) in the quarter immediately following the monitoring period in which the system exceeds 0.060 mg/L or 0.045 mg/L for TTHM or HAA5 respectively. For systems using only ground water not under the direct influence of surface water and serving fewer than 10,000 persons, if either the TTHM annual average is >0.080 mg/L or the HAA5 annual average is >0.060 mg/L, the system must go to the increased monitoring identified in paragraph (b)(1)(i) of this section (sample location column) in
(iv) Systems on increased monitoring may return to routine monitoring if, after at least one year of monitoring their TTHM annual average is ≤0.060 mg/L and their HAA5 annual average is ≤0.045 mg/L.
(v) The State may return a system to routine monitoring at the State's discretion.
(2)
(i)
(B)
(ii)
(iii)
(B) Chlorite monitoring in the distribution system required by paragraph (b)(2)(i)(B) of this section may be reduced to one three-sample set per quarter after one year of monitoring where no individual chlorite sample taken in the distribution system under paragraph (b)(2)(i)(B) of this section has exceeded the chlorite MCL and the system has not been required to conduct monitoring under paragraph (b)(2)(ii) of this section. The system may remain on the reduced monitoring schedule until either any of the three individual chlorite samples taken quarterly in the distribution system under paragraph (b)(2)(i)(B) of this section exceeds the chlorite MCL or the system is required to conduct monitoring under paragraph (b)(2)(ii) of this section, at which time the system must revert to routine monitoring.
(3)
(ii)
(c)
(ii)
(2)
(ii)
(iii)
(d)
(2)
(e)
(f)
(1) Specific locations and schedules for collecting samples for any parameters included in this subpart.
(2) How the system will calculate compliance with MCLs, MRDLs, and treatment techniques.
(3) If approved for monitoring as a consecutive system, or if providing water to a consecutive system, under the provisions of § 141.29, the sampling plan must reflect the entire distribution system.
(a)
(2) All samples taken and analyzed under the provisions of this subpart must be included in determining compliance, even if that number is greater than the minimum required.
(3) If, during the first year of monitoring under § 141.132, any individual quarter's average will cause the running annual average of that system to exceed the MCL, the system is out of compliance at the end of that quarter.
(b)
(ii) For systems monitoring less frequently than quarterly, systems demonstrate MCL compliance if the average of samples taken that year under the provisions of § 141.132(b)(1) does not exceed the MCLs in § 141.64. If the average of these samples exceeds the MCL, the system must increase monitoring to once per quarter per treatment plant and such a system is not in violation of the MCL until it has completed one year of quarterly monitoring, unless the result of fewer than four quarters of monitoring will cause the running annual average to exceed the MCL, in which case the system is in violation at the end of that quarter. Systems required to increase monitoring frequency to quarterly monitoring must calculate compliance by including the sample which triggered the increased monitoring plus the following three quarters of monitoring.
(iii) If the running annual arithmetic average of quarterly averages covering any consecutive four-quarter period exceeds the MCL, the system is in violation of the MCL and must notify the public pursuant to § 141.32 or § 141.202, whichever is effective for your system, in addition to reporting to the State pursuant to § 141.134.
(iv) If a PWS fails to complete four consecutive quarters of monitoring, compliance with the MCL for the last four-quarter compliance period must be based on an average of the available data.
(2)
(3)
(c)
(ii) In cases where systems switch between the use of chlorine and chloramines for residual disinfection during the year, compliance must be determined by including together all monitoring results of both chlorine and chloramines in calculating compliance. Reports submitted pursuant to § 141.134 must clearly indicate which residual disinfectant was analyzed for each sample.
(2)
(ii)
(d)
(a) Systems required to sample quarterly or more frequently must report to the State within 10 days after the end of each quarter in which samples were collected, notwithstanding the provisions of § 141.31. Systems required to sample less frequently than quarterly must report to the State within 10 days after the end of each monitoring period in which samples were collected.
(b)
(c)
(d)
(a)
(2)
(i) The system's source water TOC level, measured according to § 141.131(d)(3), is less than 2.0 mg/L, calculated quarterly as a running annual average.
(ii) The system's treated water TOC level, measured according to § 141.131(d)(3), is less than 2.0 mg/L, calculated quarterly as a running annual average.
(iii) The system's source water TOC level, measured according to § 141.131(d)(3), is less than 4.0 mg/L, calculated quarterly as a running annual average; the source water alkalinity, measured according to § 141.131(d)(1), is greater than 60 mg/L (as CaCO
(iv) The TTHM and HAA5 running annual averages are no greater than 0.040 mg/L and 0.030 mg/L, respectively, and the system uses only chlorine for primary disinfection and maintenance of a residual in the distribution system.
(v) The system's source water SUVA, prior to any treatment and measured monthly according to § 141.131(d)(4), is less than or equal to 2.0 L/mg-m, calculated quarterly as a running annual average.
(vi) The system's finished water SUVA, measured monthly according to § 141.131(d)(4), is less than or equal to 2.0 L/mg-m, calculated quarterly as a running annual average.
(3)
(i) Softening that results in lowering the treated water alkalinity to less than 60 mg/L (as CaCO
(ii) Softening that results in removing at least 10 mg/L of magnesium hardness (as CaCO
(b)
(2) Required Step 1 TOC reductions, indicated in the following table, are based upon specified source water parameters measured in accordance with
(3) Subpart H conventional treatment systems that cannot achieve the Step 1 TOC removals required by paragraph (b)(2) of this section due to water quality parameters or operational constraints must apply to the State, within three months of failure to achieve the TOC removals required by paragraph (b)(2) of this section, for approval of alternative minimum TOC (Step 2) removal requirements submitted by the system. If the State approves the alternative minimum TOC removal (Step 2) requirements, the State may make those requirements retroactive for the purposes of determining compliance. Until the State approves the alternate minimum TOC removal (Step 2) requirements, the system must meet the Step 1 TOC removals contained in paragraph (b)(2) of this section.
(4)
(i)
(ii) Bench- or pilot-scale testing of enhanced coagulation must be conducted by using representative water samples and adding 10 mg/L increments of alum (or equivalent amounts of ferric salt) until the pH is reduced to a level less than or equal to the enhanced coagulation Step 2 target pH shown in the following table:
(iii) For waters with alkalinities of less than 60 mg/L for which addition of small amounts of alum or equivalent addition of iron coagulant drives the pH below 5.5 before significant TOC removal occurs, the system must add
(iv) The system may operate at any coagulant dose or pH necessary (consistent with other NPDWRs) to achieve the minimum TOC percent removal approved under paragraph (b)(3) of this section.
(v) If the TOC removal is consistently less than 0.3 mg/L of TOC per 10 mg/L of incremental alum dose at all dosages of alum (or equivalant addition of iron coagulant), the water is deemed to contain TOC not amenable to enhanced coagulation. The system may then apply to the State for a waiver of enhanced coagulation requirements.
(c)
(i) Determine actual monthly TOC percent removal, equal to:
(ii) Determine the required monthly TOC percent removal (from either the table in paragraph (b)(2) of this section or from paragraph (b)(3) of this section).
(iii) Divide the value in paragraph (c)(1)(i) of this section by the value in paragraph (c)(1)(ii) of this section.
(iv) Add together the results of paragraph (c)(1)(iii) of this section for the last 12 months and divide by 12.
(v) If the value calculated in paragraph (c)(1)(iv) of this section is less than 1.00, the system is not in compliance with the TOC percent removal requirements.
(2) Systems may use the provisions in paragraphs (c)(2)(i) through (v) of this section in lieu of the calculations in paragraph (c)(1)(i) through (v) of this section to determine compliance with TOC percent removal requirements.
(i) In any month that the system's treated or source water TOC level, measured according to § 141.131(d)(3), is less than 2.0 mg/L, the system may assign a monthly value of 1.0 (in lieu of the value calculated in paragraph (c)(1)(iii) of this section) when calculating compliance under the provisions of paragraph (c)(1) of this section.
(ii) In any month that a system practicing softening removes at least 10 mg/L of magnesium hardness (as CaCO
(iii) In any month that the system's source water SUVA, prior to any treatment and measured according to § 141.131(d)(4), is ≤2.0 L/mg-m, the system may assign a monthly value of 1.0 (in lieu of the value calculated in paragraph (c)(1)(iii) of this section) when calculating compliance under the provisions of paragraph (c)(1) of this section.
(iv) In any month that the system's finished water SUVA, measured according to § 141.131(d)(4), is ≤2.0 L/mg-m, the system may assign a monthly value of 1.0 (in lieu of the value calculated in paragraph (c)(1)(iii) of this section) when calculating compliance under the provisions of paragraph (c)(1) of this section.
(v) In any month that a system practicing enhanced softening lowers alkalinity below 60 mg/L (as CaCO
(3) Subpart H systems using conventional treatment may also comply with the requirements of this section by meeting the criteria in paragraph (a)(2) or (3) of this section.
(d)
(a) This subpart establishes the minimum requirements for the content of annual reports that community water systems must deliver to their customers. These reports must contain information on the quality of the water delivered by the systems and characterize the risks (if any) from exposure to contaminants detected in the drinking water in an accurate and understandable manner.
(b) Notwithstanding the provisions of § 141.3, this subpart applies only to community water systems.
(c) For the purpose of this subpart,
(d) For the purpose of this subpart,
(e) A State that has primary enforcement responsibility may adopt by rule, after notice and comment, alternative requirements for the form and content of the reports. The alternative requirements must provide the same type and amount of information as required by §§ 141.153 and 141.154, and must be designed to achieve an equivalent level of public information and education as would be achieved under this subpart.
(f) For purpose of §§ 141.154 and 141.155 of this subpart, the term “primacy agency” refers to the State or tribal government entity that has jurisdiction over, and primary enforcement responsibility for, public water systems, even if that government does not have interim or final primary enforcement responsibility for this rule. Where the State or tribe does not have primary enforcement responsibility for public water systems, the term “primacy agency” refers to the appropriate EPA regional office.
(a) The regulations in this subpart shall take effect on September 18, 1998.
(b) Each existing community water system must deliver its first report by October 19, 1999, its second report by July 1, 2000, and subsequent reports by July 1 annually thereafter. The first report must contain data collected during, or prior to, calendar year 1998 as prescribed in § 141.153(d)(3). Each report thereafter must contain data collected during, or prior to, the previous calendar year.
(c) A new community water system must deliver its first report by July 1 of the year after its first full calendar year in operation and annually thereafter.
(d) A community water system that sells water to another community water system must deliver the applicable information required in § 141.153 to the buyer system:
(1) No later than April 19, 1999, by April 1, 2000, and by April 1 annually thereafter or
(2) On a date mutually agreed upon by the seller and the purchaser, and specifically included in a contract between the parties.
(a) Each community water system must provide to its customers an annual report that contains the information specified in this section and § 141.154.
(b) Information on the source of the water delivered:
(1) Each report must identify the source(s) of the water delivered by the community water system by providing information on:
(i) The type of the water: e.g., surface water, ground water; and
(ii) The commonly used name (if any) and location of the body (or bodies) of water.
(2) If a source water assessment has been completed, the report must notify consumers of the availability of this information and the means to obtain it. In addition, systems are encouraged to highlight in the report significant sources of contamination in the source water area if they have readily available information. Where a system has received a source water assessment from the primacy agency, the report must include a brief summary of the system's susceptibility to potential sources of contamination, using language provided by the primacy agency or written by the operator.
(c)
(i)
(ii)
(2) A report for a community water system operating under a variance or an exemption issued under § 1415 or 1416 of SDWA must include the following definition:
(3) A report that contains data on contaminants that EPA regulates using any of the following terms must include the applicable definitions:
(i)
(ii)
(iii)
(iv)
(d) Information on detected contaminants.
(1) This sub-section specifies the requirements for information to be included in each report for contaminants subject to mandatory monitoring (except
(i) Contaminants subject to a MCL, action level, maximum residual disinfectant level, or treatment technique (regulated contaminants).
(ii) Contaminants for which monitoring is required by § 141.40 (unregulated contaminants); and
(iii) Disinfection by-products or microbial contaminants for which monitoring is required by §§ 141.142 and 141.143, except as provided under paragraph (e)(1) of this section, and which are detected in the finished water.
(2) The data relating to these contaminants must be displayed in one table or in several adjacent tables. Any additional monitoring results which a community water system chooses to include in its report must be displayed separately.
(3) The data must be derived from data collected to comply with EPA and State monitoring and analytical requirements during calendar year 1998 for the first report and subsequent calendar years thereafter except that:
(i) Where a system is allowed to monitor for regulated contaminants less often than once a year, the table(s) must include the date and results of the most recent sampling and the report must include a brief statement indicating that the data presented in the report are from the most recent testing done in accordance with the regulations. No data older than 5 years need be included.
(ii) Results of monitoring in compliance with §§ 141.142 and 141.143 need only be included for 5 years from the date of last sample or until any of the detected contaminants becomes regulated and subject to routine monitoring requirements, whichever comes first.
(4) For detected regulated contaminants (listed in appendix A to this subpart), the table(s) must contain:
(i) The MCL for that contaminant expressed as a number equal to or greater than 1.0 (as provided in appendix A to this subpart);
(ii) The MCLG for that contaminant expressed in the same units as the MCL;
(iii) If there is no MCL for a detected contaminant, the table must indicate that there is a treatment technique, or specify the action level, applicable to that contaminant, and the report must include the definitions for treatment technique and/or action level, as appropriate, specified in paragraph(c)(3) of this section;
(iv) For contaminants subject to an MCL, except turbidity and total coliforms, the highest contaminant level used to determine compliance with an NPDWR and the range of detected levels, as follows:
(A) When compliance with the MCL is determined annually or less frequently: The highest detected level at any sampling point and the range of detected levels expressed in the same units as the MCL.
(B) When compliance with the MCL is determined by calculating a running annual average of all samples taken at a sampling point: the highest average of any of the sampling points and the range of all sampling points expressed in the same units as the MCL.
(C) When compliance with the MCL is determined on a system-wide basis by calculating a running annual average of all samples at all sampling points: the average and range of detection expressed in the same units as the MCL.
(d)(4)(iv): When rounding of results to determine compliance with the MCL is allowed by the regulations, rounding should be done prior to multiplying the results by the factor listed in appendix A of this subpart.
(v) For turbidity.
(A) When it is reported pursuant to § 141.13: The highest average monthly value.
(B) When it is reported pursuant to the requirements of § 141.71: the highest monthly value. The report should include an explanation of the reasons for measuring turbidity.
(C) When it is reported pursuant to § 141.73 or § 141.173 or § 141.551: the highest single measurement and the lowest monthly percentage of samples meeting the turbidity limits specified in § 141.73 or § 141.173, or § 141.551 for the filtration technology being used. The report should include an explanation of the reasons for measuring turbidity;
(vi) For lead and copper: the 90th percentile value of the most recent round of sampling and the number of sampling sites exceeding the action level;
(vii) For total coliform:
(A) The highest monthly number of positive samples for systems collecting fewer than 40 samples per month; or
(B) The highest monthly percentage of positive samples for systems collecting at least 40 samples per month;
(viii) For fecal coliform: The total number of positive samples; and
(ix) The likely source(s) of detected contaminants to the best of the operator's knowledge. Specific information regarding contaminants may be available in sanitary surveys and source water assessments, and should be used when available to the operator. If the operator lacks specific information on the likely source, the report must include one or more of the typical sources for that contaminant listed in appendix A to this subpart that is most applicable to the system.
(5) If a community water system distributes water to its customers from multiple hydraulically independent distribution systems that are fed by different raw water sources, the table should contain a separate column for each service area and the report should identify each separate distribution system. Alternatively, systems could produce separate reports tailored to include data for each service area.
(6) The table(s) must clearly identify any data indicating violations of MCLs, MRDLs, or treatment techniques, and the report must contain a clear and readily understandable explanation of the violation including: the length of the violation, the potential adverse health effects, and actions taken by the system to address the violation. To describe the potential health effects, the system must use the relevant language of appendix A to this subpart.
(7) For detected unregulated contaminants for which monitoring is required (except Cryptosporidium), the table(s) must contain the average and range at which the contaminant was detected. The report may include a brief explanation of the reasons for monitoring for unregulated contaminants.
(e) Information on Cryptosporidium, radon, and other contaminants:
(1) If the system has performed any monitoring for Cryptosporidium, including monitoring performed to satisfy the requirements of § 141.143, which indicates that Cryptosporidium may be present in the source water or the finished water, the report must include:
(i) A summary of the results of the monitoring; and
(ii) An explanation of the significance of the results.
(2) If the system has performed any monitoring for radon which indicates that radon may be present in the finished water, the report must include:
(i) The results of the monitoring; and
(ii) An explanation of the significance of the results.
(3) If the system has performed additional monitoring which indicates the presence of other contaminants in the finished water, EPA strongly encourages systems to report any results which may indicate a health concern. To determine if results may indicate a health concern, EPA recommends that systems find out if EPA has proposed an NPDWR or issued a health advisory for that contaminant by calling the Safe Drinking Water Hotline (800-426-4791). EPA considers detects above a proposed MCL or health advisory level to indicate possible health concerns. For such contaminants, EPA recommends that the report include:
(i) The results of the monitoring; and
(ii) An explanation of the significance of the results noting the existence of a health advisory or a proposed regulation.
(f) Compliance with NPDWR. In addition to the requirements of § 141.153(d)(6), the report must note any violation that occurred during the year covered by the report of a requirement listed below, and include a clear and readily understandable explanation of the violation, any potential adverse health effects, and the steps the system has taken to correct the violation.
(1) Monitoring and reporting of compliance data;
(2) Filtration and disinfection prescribed by subpart H of this part. For systems which have failed to install adequate filtration or disinfection equipment or processes, or have had a failure of such equipment or processes which constitutes a violation, the report must include the following language as part of the explanation of potential adverse health effects: Inadequately treated water may contain disease-causing organisms. These organisms include bacteria, viruses, and parasites which can cause symptoms such as nausea, cramps, diarrhea, and associated headaches.
(3) Lead and copper control requirements prescribed by subpart I of this part. For systems that fail to take one or more actions prescribed by §§ 141.80(d), 141.81, 141.82, 141.83 or 141.84, the report must include the applicable language of appendix A to this subpart for lead, copper, or both.
(4) Treatment techniques for Acrylamide and Epichlorohydrin prescribed by subpart K of this part. For systems that violate the requirements of subpart K of this part, the report must include the relevant language from appendix A to this subpart.
(5) Recordkeeping of compliance data.
(6) Special monitoring requirements prescribed by §§ 141.40 and 141.41; and
(7) Violation of the terms of a variance, an exemption, or an administrative or judicial order.
(g) Variances and Exemptions. If a system is operating under the terms of a variance or an exemption issued under § 1415 or 1416 of SDWA, the report must contain:
(1) An explanation of the reasons for the variance or exemption;
(2) The date on which the variance or exemption was issued;
(3) A brief status report on the steps the system is taking to install treatment, find alternative sources of water, or otherwise comply with the terms and schedules of the variance or exemption; and
(4) A notice of any opportunity for public input in the review, or renewal, of the variance or exemption.
(h) Additional information:
(1) The report must contain a brief explanation regarding contaminants which may reasonably be expected to be found in drinking water including bottled water. This explanation may include the language of paragraphs (h)(1) (i) through (iii) or systems may use their own comparable language. The report also must include the language of paragraph (h)(1)(iv) of this section.
(i) The sources of drinking water (both tap water and bottled water) include rivers, lakes, streams, ponds, reservoirs, springs, and wells. As water travels over the surface of the land or through the ground, it dissolves naturally-occurring minerals and, in some cases, radioactive material, and can pick up substances resulting from the presence of animals or from human activity.
(ii) Contaminants that may be present in source water include:
(A)
(B)
(C)
(D)
(E)
(iii) In order to ensure that tap water is safe to drink, EPA prescribes regulations which limit the amount of certain contaminants in water provided by public water systems. FDA regulations establish limits for contaminants in bottled water which must provide the same protection for public health.
(iv) Drinking water, including bottled water, may reasonably be expected to contain at least small amounts of some contaminants. The presence of contaminants does not necessarily indicate that water poses a health risk. More information about contaminants and potential health effects can be obtained by calling the Environmental Protection Agency's Safe Drinking Water Hotline (800-426-4791).
(2) The report must include the telephone number of the owner, operator, or designee of the community water system as a source of additional information concerning the report.
(3) In communities with a large proportion of non-English speaking residents, as determined by the Primacy Agency, the report must contain information in the appropriate language(s) regarding the importance of the report or contain a telephone number or address where such residents may contact the system to obtain a translated copy of the report or assistance in the appropriate language.
(4) The report must include information (e.g., time and place of regularly scheduled board meetings) about opportunities for public participation in decisions that may affect the quality of the water.
(5) The systems may include such additional information as they deem necessary for public education consistent with, and not detracting from, the purpose of the report.
(a) All reports must prominently display the following language: Some people may be more vulnerable to contaminants in drinking water than the general population. Immuno-compromised persons such as persons with cancer undergoing chemotherapy, persons who have undergone organ transplants, people with HIV/AIDS or other immune system disorders, some elderly, and infants can be particularly at
(b) Ending in the report due by July 1, 2001, a system which detects arsenic at levels above 0.025 mg/L, but below the 0.05 mg/L, and beginning in the report due by July 1, 2002, a system that detects arsenic above 0.005 mg/L and up to and including 0.010 mg/L:
(1) Must include in its report a short informational statement about arsenic, using language such as: While your drinking water meets EPA's standard for arsenic, it does contain low levels of arsenic. EPA's standard balances the current understanding of arsenic's possible health effects against the costs of removing arsenic from drinking water. EPA continues to research the health effects of low levels of arsenic, which is a mineral known to cause cancer in humans at high concentrations and is linked to other health effects such as skin damage and circulatory problems.
(2) May write its own educational statement, but only in consultation with the Primacy Agency.
(c) A system which detects nitrate at levels above 5 mg/l, but below the MCL:
(1) Must include a short informational statement about the impacts of nitrate on children using language such as: Nitrate in drinking water at levels above 10 ppm is a health risk for infants of less than six months of age. High nitrate levels in drinking water can cause blue baby syndrome. Nitrate levels may rise quickly for short periods of time because of rainfall or agricultural activity. If you are caring for an infant you should ask advice from your health care provider.
(2) May write its own educational statement, but only in consultation with the Primacy Agency.
(d) Systems which detect lead above the action level in more than 5%, and up to and including 10%, of homes sampled:
(1) Must include a short informational statement about the special impact of lead on children using language such as: Infants and young children are typically more vulnerable to lead in drinking water than the general population. It is possible that lead levels at your home may be higher than at other homes in the community as a result of materials used in your home's plumbing. If you are concerned about elevated lead levels in your home's water, you may wish to have your water tested and flush your tap for 30 seconds to 2 minutes before using tap water. Additional information is available from the Safe Drinking Water Hotline (800-426-4791).
(2) May write its own educational statement, but only in consultation with the Primacy Agency.
(e) Community water systems that detect TTHM above 0.080 mg/l, but below the MCL in § 141.12, as an annual average, monitored and calculated under the provisions of § 141.30, must include health effects language for TTHMs prescribed by appendix A.
(f) Beginning in the report due by July 1, 2002, and ending January 22, 2006, a community water system that detects arsenic above 0.010 mg/L and up to and including 0.05 mg/L must include the arsenic health effects language prescribed by Appendix A to Subpart O of this part.
(a) Except as provided in paragraph (g) of this section, each community water system must mail or otherwise directly deliver one copy of the report to each customer.
(b) The system must make a good faith effort to reach consumers who do not get water bills, using means recommended by the primacy agency. EPA expects that an adequate good faith effort will be tailored to the consumers who are served by the system but are not bill-paying customers, such as renters or workers. A good faith effort to reach consumers would include a mix of methods appropriate to the particular system such as: Posting the reports on the Internet; mailing to postal patrons in metropolitan areas;
(c) No later than the date the system is required to distribute the report to its customers, each community water system must mail a copy of the report to the primacy agency, followed within 3 months by a certification that the report has been distributed to customers, and that the information is correct and consistent with the compliance monitoring data previously submitted to the primacy agency.
(d) No later than the date the system is required to distribute the report to its customers, each community water system must deliver the report to any other agency or clearinghouse identified by the primacy agency.
(e) Each community water system must make its reports available to the public upon request.
(f) Each community water system serving 100,000 or more persons must post its current year's report to a publicly-accessible site on the Internet.
(g) The Governor of a State or his designee, or the Tribal Leader where the tribe has met the eligibility requirements contained in§ 142.72 for the purposes of waiving the mailing requirement, can waive the requirement of paragraph (a) of this section for community water systems serving fewer than 10,000 persons. In consultation with the tribal government, the Regional Administrator may waive the requirement of§ 141.155(a) in areas in Indian country where no tribe has been deemed eligible.
(1) Such systems must:
(i) Publish the reports in one or more local newspapers serving the area in which the system is located;
(ii) Inform the customers that the reports will not be mailed, either in the newspapers in which the reports are published or by other means approved by the State; and
(iii) Make the reports available to the public upon request.
(2) Systems serving 500 or fewer persons may forego the requirements of paragraphs (g)(1)(i) and (ii) of this section if they provide notice at least once per year to their customers by mail, door-to-door delivery or by posting in an appropriate location that the report is available upon request.
(h) Any system subject to this subpart must retain copies of its Consumer Confidence Report for no less than 3 years.
At 65 FR 76749, Dec. 7, 2000, the table in appendix A to subpart O was amended under the heading “Radioactive contaminants” by revising the entries for “Beta/photon emitters (mrem/yr)”, “Alpha emitters (pCi/l)”, and “Combined radium (pCi/l)” and adding a new entry for “Uranium (pCi/L)”, effective Dec. 8, 2003. For the convenience of the user, the revised and added entries are set forth as follows:
(a) The requirements of this subpart P constitute national primary drinking water regulations. These regulations establish requirements for filtration and disinfection that are in addition to criteria under which filtration and disinfection are required under subpart H of this part. The requirements of this subpart are applicable to subpart H systems serving at least 10,000 people, beginning January 1, 2002 unless otherwise specified in this subpart. The regulations in this subpart establish or extend treatment technique requirements in lieu of maximum contaminant levels for the following contaminants:
(1) At least 99 percent (2-log) removal of
(2) Compliance with the profiling and benchmark requirements under the provisions of § 141.172.
(b) A public water system subject to the requirements of this subpart is considered to be in compliance with the requirements of paragraph (a) of this section if:
(1) It meets the requirements for avoiding filtration in §§ 141.71 and 141.171 and the disinfection requirements in §§ 141.72 and 141.172; or
(2) It meets the applicable filtration requirements in either § 141.73 or § 141.173 and the disinfection requirements in §§ 141.72 and 141.172.
(c) Systems are not permitted to begin construction of uncovered finished water storage facilities beginning February 16, 1999.
(d) Subpart H systems that did not conduct optional monitoring under § 141.172 because they served fewer than 10,000 persons when such monitoring was required, but serve more than 10,000 persons prior to January 14, 2005 must comply with §§ 141.170, 141.171, 141.173, 141.174, and 141.175. These systems must also consult with the State to establish a disinfection benchmark. A system that decides to make a significant change to its disinfection practice, as described in § 141.172(c)(1)(i) through (iv) must consult with the State prior to making such change.
In addition to the requirements of § 141.71, a public water system subject to the requirements of this subpart that does not provide filtration must meet all of the conditions of paragraphs (a) and (b) of this section.
(a)
(1) Identify watershed characteristics and activities which may have an adverse effect on source water quality; and
(2) Monitor the occurrence of activities which may have an adverse effect on source water quality.
(b) During the onsite inspection conducted under the provisions of § 141.71(b)(3), the State must determine whether the watershed control program established under § 141.71(b)(2) is adequate to limit potential contamination by
(a)
(1) The TTHM annual average must be the annual average during the same period as is used for the HAA5 annual average.
(i) Those systems that collected data under the provisions of subpart M (Information Collection Rule) must use the results of the samples collected during the last four quarters of required monitoring under § 141.142.
(ii) Those systems that use “grandfathered” HAA5 occurrence data that meet the provisions of paragraph (a)(2)(ii) of this section must use TTHM data collected at the same time under the provisions of §§ 141.12 and 141.30.
(iii) Those systems that use HAA5 occurrence data that meet the provisions of paragraph (a)(2)(iii)(A) of this section must use TTHM data collected at the same time under the provisions of §§ 141.12 and 141.30.
(2) The HAA5 annual average must be the annual average during the same period as is used for the TTHM annual average.
(i) Those systems that collected data under the provisions of subpart M (Information Collection Rule) must use the results of the samples collected during the last four quarters of required monitoring under § 141.142.
(ii) Those systems that have collected four quarters of HAA5 occurrence data that meets the routine monitoring sample number and location requirements for TTHM in §§ 141.12 and 141.30 and handling and analytical method requirements of § 141.142(b)(1) may use those data to determine whether the requirements of this section apply.
(iii) Those systems that have not collected four quarters of HAA5 occurrence data that meets the provisions of either paragraph (a)(2)(i) or (ii) of this section by March 16, 1999 must either:
(A) Conduct monitoring for HAA5 that meets the routine monitoring sample number and location requirements for TTHM in §§ 141.12 and 141.30 and handling and analytical method requirements of § 141.142(b)(1) to determine the HAA5 annual average and whether the requirements of paragraph (b) of this section apply. This monitoring must be completed so that the applicability determination can be made no later than March 31, 2000, or
(B) Comply with all other provisions of this section as if the HAA5 monitoring had been conducted and the results required compliance with paragraph (b) of this section.
(3) The system may request that the State approve a more representative annual data set than the data set determined under paragraph (a)(1) or (2) of this section for the purpose of determining applicability of the requirements of this section.
(4) The State may require that a system use a more representative annual data set than the data set determined under paragraph (a)(1) or (2) of this section for the purpose of determining applicability of the requirements of this section.
(5) The system must submit data to the State on the schedule in paragraphs (a)(5)(i) through (v) of this section.
(i) Those systems that collected TTHM and HAA5 data under the provisions of subpart M (Information Collection Rule), as required by paragraphs (a)(1)(i) and (a)(2)(i) of this section, must submit the results of the samples collected during the last 12 months of required monitoring under § 141.142 not later than December 31, 1999.
(ii) Those systems that have collected four consecutive quarters of HAA5 occurrence data that meets the routine monitoring sample number and location for TTHM in §§ 141.12 and 141.30 and handling and analytical method requirements of § 141.142(b)(1), as allowed
(iii) Those systems that conduct monitoring for HAA5 using the monitoring requirements specified by paragraphs (a)(1)(iii) and (a)(2)(iii)(A) of this section, must submit TTHM and HAA5 data not later than March 31, 2000.
(iv) Those systems that elect to comply with all other provisions of this section as if the HAA5 monitoring had been conducted and the results required compliance with this section, as allowed under paragraphs (a)(2)(iii)(B) of this section, must notify the State in writing of their election not later than December 31, 1999.
(v) If the system elects to request that the State approve a more representative annual data set than the data set determined under paragraph (a)(2)(i) of this section, the system must submit this request in writing not later than December 31, 1999.
(6) Any system having either a TTHM annual average ≥0.064 mg/L or an HAA5 annual average ≥0.048 mg/L during the period identified in paragraphs (a)(1) and (2) of this section must comply with paragraph (b) of this section.
(b)
(2) The system must monitor daily for a period of 12 consecutive calendar months to determine the total logs of inactivation for each day of operation, based on the CT99.9 values in Tables 1.1-1.6, 2.1, and 3.1 of § 141.74(b), as appropriate, through the entire treatment plant. This system must begin this monitoring not later than April 1, 2000. As a minimum, the system with a single point of disinfectant application prior to entrance to the distribution system must conduct the monitoring in paragraphs (b)(2)(i) through (iv) of this section. A system with more than one point of disinfectant application must conduct the monitoring in paragraphs (b)(2)(i) through (iv) of this section for each disinfection segment. The system must monitor the parameters necessary to determine the total inactivation ratio, using analytical methods in § 141.74(a), as follows:
(i) The temperature of the disinfected water must be measured once per day at each residual disinfectant concentration sampling point during peak hourly flow.
(ii) If the system uses chlorine, the pH of the disinfected water must be measured once per day at each chlorine residual disinfectant concentration sampling point during peak hourly flow.
(iii) The disinfectant contact time(s) (“T”) must be determined for each day during peak hourly flow.
(iv) The residual disinfectant concentration(s) (“C”) of the water before or at the first customer and prior to each additional point of disinfection must be measured each day during peak hourly flow.
(3) In lieu of the monitoring conducted under the provisions of paragraph (b)(2) of this section to develop the disinfection profile, the system may elect to meet the requirements of paragraph (b)(3)(i) of this section. In addition to the monitoring conducted under the provisions of paragraph (b)(2) of this section to develop the disinfection profile, the system may elect to meet the requirements of paragraph (b)(3)(ii) of this section.
(i) A PWS that has three years of existing operational data may submit those data, a profile generated using those data, and a request that the State approve use of those data in lieu of monitoring under the provisions of paragraph (b)(2) of this section not later than March 31, 2000. The State must determine whether these operational data are substantially equivalent to data collected under the provisions of paragraph (b)(2) of this section. These data must also be representative of
(ii) In addition to the disinfection profile generated under paragraph (b)(2) of this section, a PWS that has existing operational data may use those data to develop a disinfection profile for additional years. Such systems may use these additional yearly disinfection profiles to develop a benchmark under the provisions of paragraph (c) of this section. The State must determine whether these operational data are substantially equivalent to data collected under the provisions of paragraph (b)(2) of this section. These data must also be representative of inactivation through the entire treatment plant and not just of certain treatment segments.
(4) The system must calculate the total inactivation ratio as follows:
(i) If the system uses only one point of disinfectant application, the system may determine the total inactivation ratio for the disinfection segment based on either of the methods in paragraph (b)(4)(i)(A) or (b)(4)(i)(B) of this section.
(A) Determine one inactivation ratio (CTcalc/CT
(B) Determine successive CTcalc/CT
(ii) If the system uses more than one point of disinfectant application before the first customer, the system must determine the CT value of each disinfection segment immediately prior to the next point of disinfectant application, or for the final segment, before or at the first customer, during peak hourly flow. The (CTcalc/CT
(iii) The system must determine the total logs of inactivation by multiplying the value calculated in paragraph (b)(4)(i) or (ii) of this section by 3.0.
(5) A system that uses either chloramines or ozone for primary disinfection must also calculate the logs of inactivation for viruses using a method approved by the State.
(6) The system must retain disinfection profile data in graphic form, as a spreadsheet, or in some other format acceptable to the State for review as part of sanitary surveys conducted by the State.
(c)
(i) Changes to the point of disinfection;
(ii) Changes to the disinfectant(s) used in the treatment plant;
(iii) Changes to the disinfection process; and
(iv) Any other modification identified by the State.
(2) Any system that is modifying its disinfection practice must calculate its disinfection benchmark using the procedure specified in paragraphs (c)(2)(i) through (ii) of this section.
(i) For each year of profiling data collected and calculated under paragraph (b) of this section, the system must determine the lowest average monthly
(ii) The disinfection benchmark is the lowest monthly average value (for systems with one year of profiling data) or average of lowest monthly average values (for systems with more than one year of profiling data) of the monthly logs of
(3) A system that uses either chloramines or ozone for primary disinfection must also calculate the disinfection benchmark for viruses using a method approved by the State.
(4) The system must submit information in paragraphs (c)(4)(i) through (iii) of this section to the State as part of its consultation process.
(i) A description of the proposed change;
(ii) The disinfection profile for
(iii) An analysis of how the proposed change will affect the current levels of disinfection.
A public water system subject to the requirements of this subpart that does not meet all of the criteria in this subpart and subpart H of this part for avoiding filtration must provide treatment consisting of both disinfection, as specified in § 141.72(b), and filtration treatment which complies with the requirements of paragraph (a) or (b) of this section or § 141.73 (b) or (c) by December 31, 2001.
(a)
(2) The turbidity level of representative samples of a system's filtered water must at no time exceed 1 NTU, measured as specified in § 141.74(a) and (c).
(3) A system that uses lime softening may acidify representative samples prior to analysis using a protocol approved by the State.
(b)
(a) Monitoring requirements for systems using filtration treatment. In addition to monitoring required by § 141.74, a public water system subject to the requirements of this subpart that provides conventional filtration treatment or direct filtration must conduct continuous monitoring of turbidity for each individual filter using an approved method in § 141.74(a) and must calibrate turbidimeters using the procedure specified by the manufacturer. Systems must record the results of individual filter monitoring every 15 minutes.
(b) If there is a failure in the continuous turbidity monitoring equipment, the system must conduct grab sampling every four hours in lieu of continuous monitoring, but for no more than five working days following the failure of the equipment.
In addition to the reporting and recordkeeping requirements in § 141.75, a public water system subject to the requirements of this subpart that provides conventional filtration treatment or direct filtration must report monthly to the State the information specified in paragraphs (a) and (b) of this section beginning January 1, 2002. In
(a) Turbidity measurements as required by § 141.173 must be reported within 10 days after the end of each month the system serves water to the public. Information that must be reported includes:
(1) The total number of filtered water turbidity measurements taken during the month.
(2) The number and percentage of filtered water turbidity measurements taken during the month which are less than or equal to the turbidity limits specified in § 141.173(a) or (b).
(3) The date and value of any turbidity measurements taken during the month which exceed 1 NTU for systems using conventional filtration treatment or direct filtration, or which exceed the maximum level set by the State under § 141.173(b).
(b) Systems must maintain the results of individual filter monitoring taken under § 141.174 for at least three years. Systems must report that they have conducted individual filter turbidity monitoring under § 141.174 within 10 days after the end of each month the system serves water to the public. Systems must report individual filter turbidity measurement results taken under § 141.174 within 10 days after the end of each month the system serves water to the public only if measurements demonstrate one or more of the conditions in paragraphs (b)(1) through (4) of this section. Systems that use lime softening may apply to the State for alternative exceedance levels for the levels specified in paragraphs (b)(1) through (4) of this section if they can demonstrate that higher turbidity levels in individual filters are due to lime carryover only and not due to degraded filter performance.
(1) For any individual filter that has a measured turbidity level of greater than 1.0 NTU in two consecutive measurements taken 15 minutes apart, the system must report the filter number, the turbidity measurement, and the date(s) on which the exceedance occurred. In addition, the system must either produce a filter profile for the filter within 7 days of the exceedance (if the system is not able to identify an obvious reason for the abnormal filter performance) and report that the profile has been produced or report the obvious reason for the exceedance.
(2) For any individual filter that has a measured turbidity level of greater than 0.5 NTU in two consecutive measurements taken 15 minutes apart at the end of the first four hours of continuous filter operation after the filter has been backwashed or otherwise taken offline, the system must report the filter number, the turbidity, and the date(s) on which the exceedance occurred. In addition, the system must either produce a filter profile for the filter within 7 days of the exceedance (if the system is not able to identify an obvious reason for the abnormal filter performance) and report that the profile has been produced or report the obvious reason for the exceedance.
(3) For any individual filter that has a measured turbidity level of greater than 1.0 NTU in two consecutive measurements taken 15 minutes apart at any time in each of three consecutive months, the system must report the filter number, the turbidity measurement, and the date(s) on which the exceedance occurred. In addition, the system must conduct a self-assessment of the filter within 14 days of the exceedance and report that the self-assessment was conducted. The self assessment must consist of at least the following components: assessment of filter performance; development of a filter profile; identification and prioritization of factors limiting filter performance; assessment of the applicability of corrections; and preparation of a filter self-assessment report.
(4) For any individual filter that has a measured turbidity level of greater than 2.0 NTU in two consecutive measurements taken 15 minutes apart at any time in each of two consecutive months, the system must report the
(c)
(2) If at any time the turbidity in representative samples of filtered water exceeds the maximum level set by the State under § 141.173(b) for filtration technologies other than conventional filtration treatment, direct filtration, slow sand filtration, or diatomaceous earth filtration, the system must inform the State as soon as possible, but no later than the end of the next business day.
Public water systems in States with primacy for the public water system supervision (PWSS) program must comply with the requirements in this subpart no later than May 6, 2002 or on the date the State-adopted rule becomes effective, whichever comes first. Public water systems in jurisdictions where EPA directly implements the PWSS program must comply with the requirements in this subpart on October 31, 2000. Prior to these dates, public water systems must continue to comply with the public notice requirements in § 141.32 of this part. The term “primacy agency” is used in this subpart to refer to either EPA or the State or the Tribe in cases where EPA, the State, or the Tribe exercises primary enforcement responsibility for this subpart.
(a)
(b)
(c)
(1) Each public water system must provide public notice to persons served by the water system, in accordance with this subpart. Public water systems that sell or otherwise provide drinking water to other public water systems (i.e., to consecutive systems) are required to give public notice to the owner or operator of the consecutive system; the consecutive system is responsible for providing public notice to the persons it serves.
(2) If a public water system has a violation in a portion of the distribution system that is physically or hydraulically isolated from other parts of the distribution system, the primacy agency may allow the system to limit distribution of the public notice to only persons served by that portion of the system which is out of compliance. Permission by the primacy agency for limiting distribution of the notice must be granted in writing.
(3) A copy of the notice must also be sent to the primacy agency, in accordance with the requirements under § 141.31(d).
(a)
(b)
(1) Provide a public notice as soon as practical but no later than 24 hours after the system learns of the violation;
(2) Initiate consultation with the primacy agency as soon as practical, but no later than 24 hours after the public water system learns of the violation or situation, to determine additional public notice requirements; and
(3) Comply with any additional public notification requirements (including any repeat notices or direction on the duration of the posted notices) that are established as a result of the consultation with the primacy agency. Such requirements may include the timing, form, manner, frequency, and content of repeat notices (if any) and other actions designed to reach all persons served.
(c)
(1) Appropriate broadcast media (such as radio and television);
(2) Posting of the notice in conspicuous locations throughout the area served by the water system;
(3) Hand delivery of the notice to persons served by the water system; or
(4) Another delivery method approved in writing by the primacy agency.
(a)
(b)
(1) Public water systems must provide the public notice as soon as practical, but no later than 30 days after the system learns of the violation. If the public notice is posted, the notice must remain in place for as long as the violation or situation persists, but in no case for less than seven days, even if the violation or situation is resolved. The primacy agency may, in appropriate circumstances, allow additional time for the initial notice of up to three months from the date the system learns of the violation. It is not appropriate for the primacy agency to grant an extension to the 30-day deadline for any unresolved violation or to allow across-the-board extensions by rule or policy for other violations or situations requiring a Tier 2 public notice. Extensions granted by the primacy agency must be in writing.
(2) The public water system must repeat the notice every three months as long as the violation or situation persists, unless the primacy agency determines that appropriate circumstances warrant a different repeat notice frequency. In no circumstance may the repeat notice be given less frequently than once per year. It is not appropriate for the primacy agency to allow less frequent repeat notice for an MCL violation under the Total Coliform Rule or a treatment technique violation under the Surface Water Treatment Rule or Interim Enhanced Surface Water Treatment Rule. It is also not appropriate for the primacy agency to allow through its rules or policies across-the-board reductions in the repeat notice frequency for other ongoing violations requiring a Tier 2 repeat notice. Primacy agency determinations allowing repeat notices to be given less frequently than once every three months must be in writing.
(3) For the turbidity violations specified in this paragraph, public water systems must consult with the primacy agency as soon as practical but no later than 24 hours after the public water system learns of the violation, to determine whether a Tier 1 public notice under § 141.202(a) is required to protect public health. When consultation does not take place within the 24-hour period, the water system must distribute a Tier 1 notice of the violation within the next 24 hours (
(i) Violation of the turbidity MCL under § 141.13(b); or
(ii) Violation of the SWTR, IESWTR or LT1ESWTR treatment technique requirement resulting from a single exceedance of the maximum allowable turbidity limit.
(c)
(1) Unless directed otherwise by the primacy agency in writing, community water systems must provide notice by:
(i) Mail or other direct delivery to each customer receiving a bill and to other service connections to which water is delivered by the public water system; and
(ii) Any other method reasonably calculated to reach other persons regularly served by the system, if they would not normally be reached by the notice required in paragraph (c)(1)(i) of
(2) Unless directed otherwise by the primacy agency in writing, non-community water systems must provide notice by:
(i) Posting the notice in conspicuous locations throughout the distribution system frequented by persons served by the system, or by mail or direct delivery to each customer and service connection (where known); and
(ii) Any other method reasonably calculated to reach other persons served by the system if they would not normally be reached by the notice required in paragraph (c)(2)(i) of this section. Such persons may include those served who may not see a posted notice because the posted notice is not in a location they routinely pass by. Other methods may include: Publication in a local newspaper or newsletter distributed to customers; use of E-mail to notify employees or students; or, delivery of multiple copies in central locations (
(a)
(b)
(1) Public water systems must provide the public notice not later than one year after the public water system learns of the violation or situation or begins operating under a variance or exemption. Following the initial notice, the public water system must repeat the notice annually for as long as the violation, variance, exemption, or other situation persists. If the public notice is posted, the notice must remain in place for as long as the violation, variance, exemption, or other situation persists, but in no case less than seven days (even if the violation or situation is resolved).
(2) Instead of individual Tier 3 public notices, a public water system may use an annual report detailing all violations and situations that occurred during the previous twelve months, as long as the timing requirements of paragraph (b)(1) of this section are met.
(c)
(1) Unless directed otherwise by the primacy agency in writing, community water systems must provide notice by:
(i) Mail or other direct delivery to each customer receiving a bill and to other service connections to which water is delivered by the public water system; and
(ii) Any other method reasonably calculated to reach other persons regularly served by the system, if they would not normally be reached by the notice required in paragraph (c)(1)(i) of this section. Such persons may include those who do not pay water bills or do not have service connection addresses (
(2) Unless directed otherwise by the primacy agency in writing, non-community water systems must provide notice by:
(i) Posting the notice in conspicuous locations throughout the distribution system frequented by persons served by the system, or by mail or direct delivery to each customer and service connection (where known); and
(ii) Any other method reasonably calculated to reach other persons served by the system, if they would not normally be reached by the notice required in paragraph (c)(2)(i) of this section. Such persons may include those who may not see a posted notice because the notice is not in a location they routinely pass by. Other methods may include: Publication in a local newspaper or newsletter distributed to customers; use of E-mail to notify employees or students; or, delivery of multiple copies in central locations (
(d)
(1) The CCR is provided to persons served no later than 12 months after the system learns of the violation or situation as required under § 141.204(b);
(2) The Tier 3 notice contained in the CCR follows the content requirements under § 141.205; and
(3) The CCR is distributed following the delivery requirements under § 141.204(c).
(a)
(1) A description of the violation or situation, including the contaminant(s) of concern, and (as applicable) the contaminant level(s);
(2) When the violation or situation occurred;
(3) Any potential adverse health effects from the violation or situation, including the standard language under paragraph (d)(1) or (d)(2) of this section, whichever is applicable;
(4) The population at risk, including subpopulations particularly vulnerable if exposed to the contaminant in their drinking water;
(5) Whether alternative water supplies should be used;
(6) What actions consumers should take, including when they should seek medical help, if known;
(7) What the system is doing to correct the violation or situation;
(8) When the water system expects to return to compliance or resolve the situation;
(9) The name, business address, and phone number of the water system
(10) A statement to encourage the notice recipient to distribute the public notice to other persons served, using the standard language under paragraph (d)(3) of this section, where applicable.
(b)
(1) If a public water system has been granted a variance or an exemption, the public notice must contain:
(i) An explanation of the reasons for the variance or exemption;
(ii) The date on which the variance or exemption was issued;
(iii) A brief status report on the steps the system is taking to install treatment, find alternative sources of water, or otherwise comply with the terms and schedules of the variance or exemption; and
(iv) A notice of any opportunity for public input in the review of the variance or exemption.
(2) If a public water system violates the conditions of a variance or exemption, the public notice must contain the ten elements listed in paragraph (a) of this section.
(c)
(1) Each public notice required by this section:
(i) Must be displayed in a conspicuous way when printed or posted;
(ii) Must not contain overly technical language or very small print;
(iii) Must not be formatted in a way that defeats the purpose of the notice;
(iv) Must not contain language which nullifies the purpose of the notice.
(2) Each public notice required by this section must comply with multilingual requirements, as follows:
(i) For public water systems serving a large proportion of non-English speaking consumers, as determined by the primacy agency, the public notice must contain information in the appropriate language(s) regarding the importance of the notice or contain a telephone number or address where persons served may contact the water system to obtain a translated copy of the notice or to request assistance in the appropriate language.
(ii) In cases where the primacy agency has not determined what constitutes a large proportion of non-English speaking consumers, the public water system must include in the public notice the same information as in paragraph (c)(2)(i) of this section, where appropriate to reach a large proportion of non-English speaking persons served by the water system.
(d)
(1) Standard health effects language for MCL or MRDL violations, treatment technique violations, and violations of the condition of a variance or exemption. Public water systems must include in each public notice the health effects language specified in Appendix B to this subpart corresponding to each MCL, MRDL, and treatment technique violation listed in Appendix A to this subpart, and for each violation of a condition of a variance or exemption.
(2) Standard language for monitoring and testing procedure violations. Public water systems must include the following language in their notice, including the language necessary to fill in the blanks, for all monitoring and testing procedure violations listed in Appendix A to this subpart:
We are required to monitor your drinking water for specific contaminants on a regular basis. Results of regular monitoring are an indicator of whether or not your drinking water meets health standards. During [compliance period], we “did not monitor or test” or “did not complete all monitoring or testing” for [contaminant(s)], and therefore cannot be sure of the quality of your drinking water during that time.
(3) Standard language to encourage the distribution of the public notice to all persons served. Public water systems must include in their notice the following language (where applicable):
Please share this information with all the other people who drink this water, especially those who may not have received this notice directly (for example, people in apartments, nursing homes, schools, and businesses). You can do this by posting this notice in a public place or distributing copies by hand or mail.
(a)
(b)
(a)
(b)
(a)
(b)
(c)
This is an alert about your drinking water and a cosmetic dental problem that might affect children under nine years of age. At low levels, fluoride can help prevent cavities, but children drinking water containing more than 2 milligrams per liter (mg/l) of fluoride may develop cosmetic discoloration of their permanent teeth (dental fluorosis). The drinking water provided by your community water system [
Dental fluorosis, in its moderate or severe forms, may result in a brown staining and/or pitting of the permanent teeth. This problem occurs only in developing teeth, before they erupt from the gums. Children under nine should be provided with alternative sources of drinking water or water that has been treated to remove the fluoride to avoid the possibility of staining and pitting of their permanent teeth. You may also want to contact your dentist about proper use by young children of fluoride-containing products. Older children and adults may safely drink the water.
Drinking water containing more than 4 mg/L of fluoride (the U.S. Environmental Protection Agency's drinking water standard) can increase your risk of developing bone disease. Your drinking water does not contain more than 4 mg/l of fluoride, but we're required to notify you when we discover that the fluoride levels in your drinking water exceed 2 mg/l because of this cosmetic dental problem.
For more information, please call [name of water system contact] of [name of community water system] at [phone number]. Some home water treatment units are also available to remove fluoride from drinking water. To learn more about available home water treatment units, you may call NSF International at 1-877-8-NSF-HELP.”
(a)
(b)
(a)
(b)
1. Violations and other situations not listed in this table (e.g., reporting violations and failure to prepare Consumer Confidence Reports), do not require notice, unless otherwise determined by the primary agency. Primacy agencies may, at their option, also require a more stringent public notice tier (e.g., Tier 1 instead of Tier 2 or Tier 2 instead of Tier 3) for specific violations and situations listed in this Appendix, as authorized under § 141.202(a) and § 141.203(a).
2. MCL—Maximum contaminant level, MRDL—Maximum residual disinfectant level, TT—Treatment technique
3. The term Violations of National Primary Drinking Water Regulations (NPDWR) is used here to include violations of MCL, MRDL, treatment technique, monitoring, and testing procedure requirements.
4. Failure to test for fecal coliform or E. coli is a Tier 1 violation if testing is not done after any repeat sample tests positive for coliform. All other total coliform monitoring and testing procedure violations are Tier 3.
5. Systems that violate the turbidity MCL of 5 NTU based on an average of measurements over two consecutive days must consult with the primacy agency within 24 hours after learning of the violation. Based on this consultation, the primacy agency may subsequently decide to elevate the violation to Tier 1. If a system is unable to make contact with the primacy agency in the 24-hour period, the violation is automatically elevated to Tier 1.
6. Systems with treatment technique violations involving a single exceedance of a maximum turbidity limit under the Surface Water Treatment Rule (SWTR), the Interim Enhanced Surface Water Treatment Rule (IESWTR), or the Long Term 1 Enhanced Surface Water Treatment Rule (LT1ESWTR) are required to consult with the primacy agency within 24 hours after learning of the violation. Based on this consultation, the primacy agency may subsequently decide to elevate the violation to Tier 1. If a system is unable to make contact with the primacy agency in the 24-hour period, the violation is automatically elevated to Tier 1.
7. Most of the requirements of the Interim Enhanced Surface Water Treatment Rule (63
8. The arsenic MCL citations are effective January 23, 2006. Until then, the citations are § 141.11(b) and § 141.23(n).
9. The arsenic Tier 3 violation MCL citations are effective January 23, 2006. Until then, the citations are § 141.23(a), (l).
10. Failure to take a confirmation sample within 24 hours for nitrate or nitrite after an initial sample exceeds the MCL is a Tier 1 violation. Other monitoring violations for nitrate are Tier 3.
11. Subpart H community and non-transient non-community systems serving ≥10,000 must comply with new DBP MCLs, disinfectant MRDLs, and related monitoring requirements beginning January 1, 2002. All other community and non-transient non-community systems must meet the MCLs and MRDLs beginning January 1, 2004. Subpart H transient non-community systems serving 10,000 or more persons and using chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2002. Subpart H transient non-community systems serving fewer than 10,000 persons and using only ground water not under the direct influence of surface water and using chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2004.
12. § 141.12 will no longer apply after January 1, 2004.
13. Failure to monitor for chlorine dioxide at the entrance to the distribution system the day after exceeding the MRDL at the entrance to the distribution system is a Tier 2 violation.
14. If any daily sample taken at the entrance to the distribution system exceeds the MRDL for chlorine dioxide and one or more samples taken in the distribution system the next day exceed the MRDL, Tier 1 notification is required. Failure to take the required samples in the distribution system after the MRDL is exceeded at the entry point also triggers Tier 1 notification.
15. Some water systems must monitor for certain unregulated contaminants listed in § 141.40.
16. This citation refers to §§ 1415 and 1416 of the Safe Drinking Water Act. §§ 1415 and 1416 require that “a schedule prescribed. . . for a public water system granted a variance [or exemption] shall require compliance by the system. . .”
17. In addition to §§ 1415 and 1416 of the Safe Drinking Water Act, 40 CFR 142.307 specifies the items and schedule milestones that must be included in a variance for small systems.
18. Other waterborne emergencies require a Tier 1 public notice under § 141.202(a) for situations that do not meet the definition of a waterborne disease outbreak given in 40 CFR 141.2 but that still have the potential to have
19. Primacy agencies may place other situations in any tier they believe appropriate, based on threat to public health.
At 65 FR 76750, Dec. 7, 2000, the table in appendix A to subpart Q was amended under I.F. “Radioactive contaminants” by revising entries 1, 2, and 3, and by adding entry 4; by redesignating table endnotes 9 through 17 as 11 through 19; and by adding new endnotes 9 and 10, effective Dec. 8, 2003. For the convenience of the user, the revised and added text is set forth as follows:
1. Violations and other situations not listed in this table (
2. MCL—Maximum contaminant level, MRDL—Maximum residual disinfectant level, TT—Treatment technique.
3. The term Violations of National Primary Drinking Water Regulations (NPDWR) is used here to include violations of MCL, MRDL, treatment technique, monitoring, and testing procedure requirements.
9. The uranium MCL Tier 2 violation citations are effective December 8, 2003 for all community water systems.
10. The uranium Tier 3 violation citations are effective December 8, 2000 for all community water systems.
1. MCLG—Maximum contaminant level goal
2. MCL—Maximum contaminant level
3. For water systems analyzing at least 40 samples per month, no more than 5.0 percent of the monthly samples may be positive for total coliforms. For systems analyzing fewer than 40 samples per month, no more than one sample per month may be positive for total coliforms.
4. There are various regulations that set turbidity standards for different types of systems, including 40 CFR 141.13, and the 1989 Surface Water Treatment Rule, the 1998 Interim Enhanced Surface Water Treatment Rule and the 2001 Long Term 1 Enhanced Surface Water Treatment Rule. The MCL for the montly turbidity average is 1 NTU; the MCL for the 2-day average is 5 NTU for systems that are required to filter but have not yet installed filtration (40 CFR 141.13).
5. NTU—Nephelometric turbidity unit
6. There are various regulations that set turbidity standards for different types of systems, including 40 CFR 141.13, and the 1989 Surface Water Treatment Rule, the 1998 Interim Enhanced Surface Water Treatment Rule and the 2001 Long Term 1 Enhanced Surface Water Treatment Rule. Systems subject to the Surface Water Treatment Rule (both filtered and unfiltered) may not exceed 5 NTU. In addition, in filtered systems, 95 percent of samples each month must not exceed 0.5 NTU in systems using conventional or direct filtration and must not exceed 1 NTU in systems using slow sand or diatomaceous earth filtration or other filtration technologies approved by the primacy agency.
7. TT—Treatment technique
8. There are various regulations that set turbidity standards for different types of systems, including 40 CFR 141.13, the 1989 Surface Water Treatment Rule (SWTR), the 1998 Interim Enhanced Surface Water Treatment Rule (IESWTR) and the 2001 Long Term 1 Enhanced Surface Water Treatment Rule (LT1ESWTR). For systems subject to the IESWTR (systems serving at least 10,000 people, using surface water or ground water under the direct influence of surface water), that use conventional filtration or direct filtration, after January 1, 2002, the turbidity level of a system's combined filter effluent may not exceed 0.3 NTU in at least 95 percent of monthly measurements, and the turbidity level of a system's combined filter effluent must not exceed 1 NTU at any time. Systems subject to the IESWTR using technologies other than conventional, direct, slow sand, or diatomaceous earth filtration must meet turbidity limits set by the primacy agency. For systems subject to the LT1ESWTR (systems serving fewer than 10,000 people, using surface water or ground water under the direct influence of surface water) that use conventional filtration or direct filtration, after January 14, 2005 the turbidity level of a system's combined filter effluent may not exceed 0.3 NTU in at least 95 percent of monthly measurements, and the turbidity level of a system's combined filter effluent must not exceed 1 NTU at any time. Systems subject to the LT1ESWTR using technologies other than conventional, direct, slow sand, or diatomaceous earth filtration must meet turbidity limits set by the primacy agency.
9. The bacteria detected by heterotrophic plate count (HPC) are notnecessarily harmful. HPC is simply an alternative method of determining disinfectant residual levels. The number of such bacteria is an indicator of whether there is enough disinfectant in the distribution system.
10. SWTR, IESWTR, and LT1ESWTR treatment technique violations that involve turbidity exceedances may use the health effects language for turbidity instead.
11. These arsenic values are effective January 23, 2006. Until then, the MCL is 0.05 mg/L and there is no MCLG.
12. Millions fibers per liter.
13. Action Level = 0.015 mg/L
14. Action Level = 1.3 mg/L
15. Millirems per years
16. Picocuries per liter
17. Surface water systems and ground water systems under the direct influence of surface water are regulated under Subpart H of 40 CFR 141. Subpart H community and non-transient non-community systems serving ≥ 10,000 must comply with DBP MCLs and disinfectant maximum residual disinfectant levels (MRDLs) beginning January 1, 2002. All other community and non-transient noncommunity systems must meet the MCLs and MRDLs beginning January 1, 2004. Subpart H transient non-community systems serving 10,000 or more persons and using chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2002. Subpart H transient non-community systems serving fewer than 10,000 persons and systems using only ground water not under the direct influence of surface water and using chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2004.
18. The MCL of 0.10 mg/l for TTHMs is in effect until January 1, 2002 for Subpart H community water systems serving 10,000 or more. This MCL is in effect until January 1, 2004 for community water systems with a population of 10,000 or more using only ground water not under the direct influence of surface water. After these deadlines, the MCL will be 0.080 mg/l. On January 1, 2004, all systems serving less than 10,000 will have to comply with the new MCL as well.
19. The MCL for total trihalomethanes is the sum of the concentrations of the individual trihalomethanes.
20. The MCL for haloacetic acids is the sum of the concentrations of the individual haloacetic acids.
21. MRDLG—Maximum residual disinfectant level goal.
22. MRDL—Maximum residual disinfectant level.
At 65 FR 76751, Dec. 7, 2000, appendix B to subpart Q of part 141 was amended by redesignating table entries 79 through 84 and 86 through 88 as 80 through 85 and 87 through 89, respectively, and entries 85a and 85b as 86a and 86b, respectively; by adding a new entry 79 for uranium under “G. Radioactive contaminants”; by redesignating table endnote entries 16 through 21 as 17 through 22; and by adding a new endnote 16, effective Dec. 8, 2003. For the convenience of the user, the added text is set forth as follows:
1. MCLG-Maximum contaminant level goal.
2. MCL-Maximum contaminant level.
16. The uranium MCL is effective December 8, 2003 for all community water systems.
The requirements of this subpart constitute national primary drinking water regulations. These regulations establish requirements for filtration and disinfection that are in addition to criteria under which filtration and disinfection are required under subpart H of this part. The regulations in this subpart establish or extend treatment technique requirements in lieu of maximum contaminant levels for the following contaminants:
(a) At least 99 percent (2 log) removal of Cryptosporidium between a point where the raw water is not subject to recontamination by surface water runoff and a point downstream before or at the first customer for filtered systems, or
(b) Compliance with the profiling and benchmark requirements in §§ 141.530 through 141.544.
You are subject to these requirements if your system:
(a) Is a public water system;
(b) Uses surface water or GWUDI as a source; and
(c) Serves fewer than 10,000 persons.
You must comply with these requirements in this subpart beginning January 14, 2005 except where otherwise noted.
There are seven requirements of this subpart, and you must comply with all requirements that are applicable to your system. These requirements are:
(a) You must cover any finished water reservoir that you began to construct on or after March 15, 2002 as described in §§ 141.510 and 141.511;
(b) If your system is an unfiltered system, you must comply with the updated watershed control requirements described in §§ 141.520-141.522;
(c) If your system is a community or non-transient non-community water systems you must develop a disinfection profile as described in §§ 141.530-141.536;
(d) If your system is considering making a significant change to its disinfection practices, you must develop a disinfection benchmark and consult with the State for approval of the change as described in §§ 141.540-141.544;
(e) If your system is a filtered system, you must comply with the combined filter effluent requirements as described in §§ 141.550-141.553;
(f) If your system is a filtered system that uses conventional or direct filtration, you must comply with the individual filter turbidity requirements as described in §§ 141.560-141.564; and
(g) You must comply with the applicable reporting and recordkeeping requirements as described in §§ 141.570 and 141.571.
All subpart H systems which serve fewer than 10,000 are subject to this requirement.
If your system begins construction of a finished water reservoir on or after March 15, 2002 the reservoir must be covered. Finished water reservoirs for which your system began construction prior to March 15, 2002 are not subject to this requirement.
If you are a subpart H system serving fewer than 10,000 persons which does not provide filtration, you must continue to comply with all of the filtration avoidance criteria in § 141.71, as well as the additional watershed control requirements in § 141.521.
Your system must take any additional steps necessary to minimize the potential for contamination by
(a) Identify watershed characteristics and activities which may have an adverse effect on source water quality; and
(b) Monitor the occurrence of activities which may have an adverse effect on source water quality.
During an onsite inspection conducted under the provisions of § 141.71(b)(3), the State must determine whether your watershed control program is adequate to limit potential contamination by
A disinfection profile is a graphical representation of your system's level of
States may only determine that a system's profile is unnecessary if a system's TTHM and HAA5 levels are below 0.064 mg/L and 0.048 mg/L, respectively. To determine these levels, TTHM and HAA5 samples must be collected after January 1, 1998, during the month with the warmest water temperature, and at the point of maximum residence time in your distribution system.
A disinfection profile consists of three steps:
(a) First, your system must collect data for several parameters from the plant as discussed in § 141.533 over the course of 12 months. If your system serves between 500 and 9,999 persons you must begin to collect data no later than July 1, 2003. If your system serves fewer than 500 persons you must begin to collect data no later than January 1, 2004.
(b) Second, your system must use this data to calculate weekly log inactivation as discussed in §§ 141.534 and 141.535; and
(c) Third, your system must use these weekly log inactivations to develop a disinfection profile as specified in § 141.536.
Your system must monitor the following parameters to determine the total log inactivation using the analytical methods in § 141.74 (a), once per week on the same calendar day, over 12 consecutive months:
(a) The temperature of the disinfected water at each residual disinfectant concentration sampling point during peak hourly flow;
(b) If your system uses chlorine, the pH of the disinfected water at each residual disinfectant concentration sampling point during peak hourly flow;
(c) The disinfectant contact time(s) (“T”) during peak hourly flow; and
(d) The residual disinfectant concentration(s) (“C”) of the water before or at the first customer and prior to each additional point of disinfection during peak hourly flow.
Calculate the total inactivation ratio as follows, and multiply the value by 3.0 to determine log inactivation of
If your system uses chloramines, ozone, or chlorine dioxide for primary disinfection, you must also calculate the logs of inactivation for viruses and develop an additional disinfection profile for viruses using methods approved by the State.
Each log inactivation serves as a data point in your disinfection profile. Your system will have obtained 52 measurements (one for every week of the year). This will allow your system and the State the opportunity to evaluate how microbial inactivation varied over the course of the year by looking at all 52 measurements (your Disinfection Profile). Your system must retain the Disinfection Profile data in graphic form, such as a spreadsheet, which must be available for review by the State as part of a sanitary survey. Your system must use this data to calculate a benchmark if you are considering changes to disinfection practices.
If you are a subpart H system required to develop a disinfection profile under §§ 141.530 through 141.536, your system must develop a Disinfection Benchmark if you decide to make a significant change to your disinfection practice. Your system must consult with the State for approval before you can implement a significant disinfection practice change.
Significant changes to disinfection practice include:
(a) Changes to the point of disinfection;
(b) Changes to the disinfectant(s) used in the treatment plant;
(c) Changes to the disinfection process; or
(d) Any other modification identified by the State.
If your system is considering a significant change to its disinfection practice, your system must calculate a disinfection benchmark(s) as described
(a) A description of the proposed change;
(b) The disinfection profile for
(c) An analysis of how the proposed change will affect the current levels of disinfection; and
(d) Any additional information requested by the State.
If your system is making a significant change to its disinfection practice, it must calculate a disinfection benchmark using the procedure specified in the following table.
If your system uses chloramines, ozone or chlorine dioxide for primary disinfection your system must calculate the disinfection benchmark from the data your system collected for viruses to develop the disinfection profile in addition to the
All subpart H systems which serve populations fewer than 10,000, are required to filter, and utilize filtration other than slow sand filtration or diatomaceous earth filtration must meet the combined filter effluent turbidity requirements of §§ 141.551-141.553 . If your system uses slow sand or diatomaceous earth filtration you are not required to meet the combined filter effluent turbidity limits of subpart T, but you must continue to meet the combined filter effluent turbidity limits in § 141.73.
Your system must meet two strengthened combined filter effluent turbidity limits.
(a) The first combined filter effluent turbidity limit is a “95th percentile” turbidity limit that your system must meet in at least 95 percent of the turbidity measurements taken each month. Measurements must continue to be taken as described in § 141.74(a) and (c). Monthly reporting must be completed according to § 141.570. The following table describes the required limits for specific filtration technologies.
(b) The second combined filter effluent turbidity limit is a “maximum” turbidity limit which your system may at no time exceed during the month. Measurements must continue to be taken as described in § 141.74(a) and (c). Monthly reporting must be completed
(a) If your system consists of alternative filtration(filtration other than slow sand filtration, diatomaceous earth filtration, conventional filtration, or direct filtration) you are required to conduct a demonstration (see tables in § 141.551). Your system must demonstrate to the State, using pilot plant studies or other means, that your system's filtration, in combination with disinfection treatment, consistently achieves:
(1) 99 percent removal of
(2) 99.9 percent removal and/or inactivation of
(3) 99.99 percent removal and/or inactivation of viruses.
(b) [Reserved]
If your system practices lime softening, you may acidify representative combined filter effluent turbidity samples prior to analysis using a protocol approved by the State.
If your system is a subpart H system serving fewer than 10,000 people and utilizing conventional filtration or direct filtration, you must conduct continuous monitoring of turbidity for each individual filter at your system. The following requirements apply to continuous turbidity monitoring:
(a) Monitoring must be conducted using an approved method in § 141.74(a);
(b) Calibration of turbidimeters must be conducted using procedures specified by the manufacturer;
(c) Results of turbidity monitoring must be recorded at least every 15 minutes;
(d) Monthly reporting must be completed according to § 141.570; and
(e) Records must be maintained according to § 141.571.
If there is a failure in the continuous turbidity monitoring equipment, your system must conduct grab sampling every four hours in lieu of continuous monitoring until the turbidimeter is back on-line. Your system has 14 days to resume continuous monitoring before a violation is incurred.
Yes, if your system only consists of two or fewer filters, you may conduct continuous monitoring of combined filter effluent turbidity in lieu of individual filter effluent turbidity monitoring. Continuous monitoring must meet the same requirements set forth in § 141.560(a) through (d) and § 141.561.
Follow-up action is required according to the following tables:
If your system utilizes lime softening, you may apply to the State for alternative turbidity exceedance levels for the levels specified in the table in § 141.563. You must be able to demonstrate to the State that higher turbidity levels are due to lime carryover only, and not due to degraded filter performance.
This subpart T requires your system to report several items to the State. The following table describes the items which must be reported and the frequency of reporting. Your system is required to report the information described in the following table, if it is subject to the specific requirement shown in the first column.
Your system must keep several types of records based on the requirements of subpart T, in addition to recordkeeping requirements under § 141.75. The following table describes the necessary records, the length of time these records must be kept, and for which requirement the records pertain. Your system is required to maintain records described in this table, if it is subject to the specific requirement shown in the first column.
42 U.S.C. 300f, 300g-1, 300g-2, 300g-3, 300g-4, 300g-5, 300g-6, 300j-4, 300j-9, and 300j-11.
This part sets forth, pursuant to sections 1413 through 1416, 1445, and 1450 of
As used in this part, and except as otherwise specifically provided:
Any collection, treatment, storage, and distribution facilities under control of the operator of such system and used primarily in connection with such system; and any collection or pretreatment storage facilities not under such control which are used primarily in connection with such system. Such term does not include any “special irrigation district.” A public water system is either a “community water system” or a “noncommunity water system” as defined in § 141.2.
(1) The water is used exclusively for purposes other than residential uses (consisting of drinking, bathing, and cooking, or other similar uses);
(2) The Administrator or the State exercising primary enforcement responsibility for public water systems, determines that alternative water to achieve the equivalent level of public health protection provided by the applicable national primary drinking water regulation is provided for residential or similar uses for drinking and cooking; or
(3) The Administrator or the State exercising primary enforcement responsibility for public water systems, determines that the water provided for residential or similar uses for drinking, cooking, and bathing is centrally treated or treated at the point of entry by the provider, a pass-through entity, or the user to achieve the equivalent level of protection provided by the applicable national primary drinking water regulations.
(a) Except where otherwise provided, this part applies to each public water system in each State; except that this part shall not apply to a public water system which meets all of the following conditions:
(1) Which consists only of distribution and storage facilities (and does not have any collection and treatment facilities);
(2) Which obtains all of its water from, but is not owned or operated by, a public water system to which such regulations apply;
(3) Which does not sell water to any person; and
(4) Which is not a carrier which conveys passengers in interstate commerce.
(b) In order to qualify for primary enforcement responsibility, a State's program for enforcement of primary drinking water regulations must apply to all other public water systems in the State, except for:
(1) Public water systems on carriers which convey passengers in interstate commerce;
(2) Public water systems on Indian land with respect to which the State does not have the necessary jurisdiction or its jurisdiction is in question; or
(c) Section 1451 of the SDWA authorizes the Administrator to delegate primary enforcement responsibility for public water systems to Indian Tribes. An Indian Tribe must meet the statutory criteria at 42 U.S.C. 300j-11(b)(1) before it is eligible to apply for Public Water System Supervision grants and primary enforcement responsibility. All primary enforcement responsibility requirements of parts 141 and 142 apply to Indian Tribes except where specifically noted.
Nothing in this part shall diminish any authority of a State or political subdivision to adopt or enforce any law or regulation respecting drinking water regulations or public water systems, but no such law or regulation shall relieve any person of any requirements otherwise applicable under this part.
A State has primary enforcement responsibility for public water systems in the State during any period for which the Administrator determines, based upon a submission made pursuant to § 142.11, and submission under § 142.12, that such State, pursuant to appropriate State legal authority:
(a) Has adopted drinking water regulations which are no less stringent than the national primary drinking water regulations (NPDWRs) in effect under part 141 of this chapter;
(b) Has adopted and is implementing adequate procedures for the enforcement of such State regulations, such procedures to include:
(1) Maintenance of an inventory of public water systems.
(2) A systematic program for conducting sanitary surveys of public water systems in the State, with priority given to sanitary surveys of public water systems not in compliance with State primary drinking water regulations.
(3)(i) The establishment and maintenance of a State program for the certification of laboratories conducting analytical measurements of drinking water contaminants pursuant to the requirements of the State primary drinking water regulations including the designation by the State of a laboratory officer, or officers, certified by the Administrator, as the official(s) responsible for the State's certification program. The requirements of this paragraph may be waived by the Administrator for any State where all analytical measurements required by the State's primary drinking water regulations are conducted at laboratories operated by the State and certified by the Agency. Until such time as the Agency establishes a National quality assurance program for laboratory certification the State shall maintain an interim program for the purpose of approving those laboratories from which the required analytical measurements will be acceptable.
(ii) Upon a showing by an Indian Tribe of an intergovernmental or other agreement to have all analytical tests performed by a certified laboratory, the Administrator may waive this requirement.
(4) Assurance of the availability to the State of laboratory facilities certified by the Administrator and capable of performing analytical measurements of all contaminants specified in the State primary drinking water regulations. Until such time as the Agency establishes a National quality assurance program for laboratory certification the Administrator will approve such State laboratories on an interim basis.
(5) The establishment and maintenance of an activity to assure that the design and construction of new or substantially modified public water system facilities will be capable of compliance with the State primary drinking water regulations.
(6) Statutory or regulatory enforcement authority adequate to compel compliance with the State primary drinking water regulations in appropriate cases, such authority to include:
(i) Authority to apply State primary drinking water regulations to all public water systems in the State covered by the national primary drinking water regulations, except for interstate carrier conveyances and systems on Indian land with respect to which the State does not have the necessary jurisdiction or its jurisdiction is in question.
(ii) Authority to sue in courts of competent jurisdiction to enjoin any threatened or continuing violation of the State primary drinking water regulations.
(iii) Right of entry and inspection of public water systems, including the right to take water samples, whether or not the State has evidence that the
(iv) Authority to require suppliers of water to keep appropriate records and make appropriate reports to the State.
(v) Authority to require public water systems to give public notice that is no less stringent than the EPA requirements in Subpart Q of Part 141 of this chapter and § 142.16(a).
(vi) Authority to assess civil or criminal penalties for violation of the State's primary drinking water regulations and public notification requirements, including the authority to assess daily penalties or multiple penalties when a violation continues;
(vii) Authority to require community water systems to provide consumer confidence reports as required under 40 CFR part 141, subpart O.
(c) Has established and will maintain record keeping and reporting of its activities under paragraphs (a), (b) and (d) in compliance with §§ 142.14 and 142.15;
(d)
(2) If it permits variances (other than small system variances) or exemptions, or both, from the requirements of the State primary drinking water regulations, it shall do so under conditions and in a manner no less stringent than the requirements of Sections 1415 and 1416 of the Act. In granting these variances, the State must adopt the Administrator's findings of best available technology, treatment techniques, or other means available as specified in Subpart G of this part. (States with primary enforcement responsibility may adopt procedures different from those set forth in Subparts E and F of this part, which apply to the issuance of variances (other than small system variances) and exemptions by the Administrator in States that do not have primary enforcement responsibility, provided that the State procedures meet the requirements of this paragraph); and
(e) Has adopted and can implement an adequate plan for the provision of safe drinking water under emergency circumstances including, but not limited to, earthquakes, floods, hurricanes, and other natural disasters.
(f)(1) Has adopted authority for assessing administrative penalties unless the constitution of the State prohibits the adoption of such authority. For public water systems serving a population of more than 10,000 individuals, States must have the authority to impose a penalty of at least $1,000 per day per violation. For public water systems serving a population of 10,000 or fewer individuals, States must have penalties that are adequate to ensure compliance with the State regulations as determined by the State.
(2) As long as criteria in paragraph (f)(1) of this section are met, States may establish a maximum administrative penalty per violation that may be assessed on a public water system.
(g) An Indian Tribe shall not be required to exercise criminal enforcement jurisdiction to meet the requirements for primary enforcement responsibility.
(a) A State may apply to the Administrator for a determination that the State has primary enforcement responsibility for public water systems in the State pursuant to section 1413 of the Act. The application shall be as concise as possible and include a side-by-side comparison of the Federal requirements and the corresponding State authorities, including citations to the specific statutes and administrative regulations or ordinances and, wherever appropriate, judicial decisions which demonstrate adequate authority to meet the requirements of § 142.10. The following information is to be included with the State application.
(1) The text of the State's primary drinking water regulations, with references to those State regulations that vary from comparable regulations set forth in part 141 of this chapter, and a
(2) A description, accompanied by appropriate documentation, of the State's procedures for the enforcement of the State primary drinking water regulations. The submission shall include:
(i) A brief description of the State's program to maintain a current inventory of public water systems.
(ii) A brief description of the State's program for conducting sanitary surveys, including an explanation of the priorities given to various classes of public water systems.
(iii) A brief description of the State's laboratory approval or certification program, including the name(s) of the responsible State laboratory officer(s) certified by the Administrator.
(iv) Identification of laboratory facilities, available to the State, certified or approved by the Administrator and capable of performing analytical measurements of all contaminants specified in the State's primary drinking water regulations.
(v) A brief description of the State's program activity to assure that the design and construction of new or substantially modified public water system facilities will be capable of compliance with the requirements of the State primary drinking water regulations.
(vi) Copies of State statutory and regulatory provisions authorizing the adoption and enforcement of State primary drinking water regulations, and a brief description of State procedures for administrative or judicial action with respect to public water systems not in compliance with such regulations.
(3) A statement that the State will make such reports and will keep such records as may be required pursuant to §§ 142.14 and 142.15.
(4) If the State permits variances or exemptions from its primary drinking water regulations, the text of the State's statutory and regulatory provisions concerning variances and exemptions.
(5) A brief description of the State's plan for the provision of safe drinking water under emergency conditions.
In satisfaction of this requirement, for public water supplies from groundwater sources, EPA will accept the contingency plan for providing alternate drinking water supplies that is part of a State's Wellhead Protection Program, where such program has been approved by EPA pursuant to section 1428 of the SDWA.
(6)(i) A copy of the State statutory and regulatory provisions authorizing the executive branch of the State government to impose an administrative penalty on all public water systems, and a brief description of the State's authority for administrative penalties that will ensure adequate compliance of systems serving a population of 10,000 or fewer individuals.
(ii) In instances where the State constitution prohibits the executive branch of the State government from assessing any penalty, the State shall submit a copy of the applicable part of its constitution and a statement from its Attorney General confirming this interpretation.
(7)(i) A statement by the State Attorney General (or the attorney for the State primacy agency if it has independent legal counsel) or the attorney representing the Indian tribe that certifies that the laws and regulations adopted by the State or tribal ordinances to carry out the program were duly adopted and are enforceable. State statutes and regulations cited by the State Attorney General and tribal ordinances cited by the attorney representing the Indian tribe shall be in the form of lawfully adopted State statutes and regulations or tribal ordinances at the time the certification is made and shall be fully effective by the time the program is approved by EPA. To qualify as “independent legal counsel,” the attorney signing the statement required by this section shall have full authority to independently represent the State primacy agency or Indian tribe in court on all matters pertaining to the State or tribal program.
(ii) After EPA has received the documents required under paragraph (a) of this section, EPA may selectively require supplemental statements by the
(b)(1) The administrator shall act on an application submitted pursuant to § 142.11 within 90 days after receiving such application, and shall promptly inform the State in writing of this action. If he denies the application, his written notification to the State shall include a statement of reasons for the denial.
(2) A final determination by the Administrator that a State has met or has not met the requirements for primary enforcement responsibility shall take effect in accordance with the public notice requirements and related procedures under § 142.13.
(3) When the Administrator's determination becomes effective pursuant to § 142.13, it shall continue in effect unless terminated pursuant to § 142.17.
(a)
(1) Whenever a State revises its approved primacy program to adopt new or revised Federal regulations, the State must submit a request to the Administrator for approval of the program revision, using the procedures described in paragraphs (b), (c), and (d) of this section. The Administrator shall approve or disapprove each State request for approval of a program revision based on the requirements of the Safe Drinking Water Act and of this part.
(2) For all State program revisions not covered under § 142.12(a)(1), the review procedures outlined in § 142.17(a) shall apply.
(b)
(2) The final date for submission of a complete and final State request for a program revision may be extended by EPA for up to a two-year period upon a written application by the State to the Administrator. In the extension application the State must demonstrate it is requesting the extension because it cannot meet the original deadline for reasons beyond its control despite a good faith effort to do so. The application must include a schedule for the submission of a final request by a certain time and provide sufficient information to demonstrate that the State:
(i)(A) Currently lacks the legislative or regulatory authority to enforce the new or revised requirements, or
(B) Currently lacks the program capability adequate to implement the new or revised requirements; or
(C) Is requesting the extension to group two or more program revisions in a single legislative or regulatory action; and
(ii) Is implementing the EPA requirements to be adopted by the State in its program revision pursuant to paragraph (b)(3) of this section within the scope of its current authority and capabilities.
(3) To be granted an extension, the State must agree with EPA to meet
(i) Informing public water systems of the new EPA (and upcoming State) requirements and that EPA will be overseeing implementation of the requirements until the State, if eligible for interim primacy, submits a complete and final primacy revision request to EPA, or in all other cases, until EPA approves the State program revision;
(ii) Collecting, storing and managing laboratory results, public notices, and other compliance and operation data required by the EPA regulations;
(iii) Assisting EPA in the development of the technical aspects of enforcement actions and conducting informal follow-up on violations (telephone calls, letters, etc.);
(iv) Providing technical assistance to public water systems;
(v) Providing EPA with all information prescribed by § 142.15 of this part on State reporting; and
(vi) For States whose request for an extension is based on a current lack of program capability adequate to implement the new requirements, taking steps agreed to by EPA and the State during the extension period to remedy the deficiency.
(c)
(i) The documentation necessary (pursuant to § 142.11(a)) to update the approved State primacy program, and identification of those elements of the approved State primacy program that have not changed because of the program revision. The documentation shall include a side-by-side comparison of the Federal requirements and the corresponding State authorities, including citations to the specific statutes and administrative regulations or ordinances and, wherever appropriate, judicial decisions which demonstrate adequate authority to meet the requirements of § 142.10 as they apply to the program revision.
(ii) Any additional materials that are listed in § 142.16 of this part for a specific EPA regulation, as appropriate; and
(iii) For a complete and final State request only, unless one of the conditions listed in paragraph (c)(2) of this section are met, a statement by the State Attorney General (or the attorney for the State primacy agency if it has independent legal counsel) or the attorney representing the Indian tribe that certifies that the laws and regulations adopted by the State or tribal ordinances to carry out the program revision were duly adopted and are enforceable. State statutes and regulations cited by the State Attorney General and tribal ordinances cited by the attorney for the Indian tribe shall be in the form of lawfully adopted State statutes and regulations or tribal ordinances at the time the certification is made and shall be fully effective by the time the request for program revision is approved by EPA. To qualify as “independent legal counsel,” the attorney signing the statement required by this section shall have full authority to independently represent the State primacy agency or tribe in court on all matters pertaining to the State or tribal program.
(2) An Attorney General's statement will be required as part of the State request for EPA approval of a program revision unless EPA specifically waives this requirement for a specific regulation at the time EPA promulgates the regulation, or by later written notice from the Administrator to the State.
(3) After EPA has received the documents required under paragraph (c)(1) of this section, EPA may selectively require supplemental statements by the State Attorney General (or the attorney for the State primacy agency if it has independent legal counsel) or the attorney representing the Indian tribe. Each supplemental statement shall address all issues concerning the adequacy of State authorities to meet the requirements of § 142.10 that have been identified by EPA after thorough examination as unresolved by the documents submitted under paragraph (c)(1) of this section.
(d)
(ii) The Administrator will review the preliminary request submitted in accordance with paragraph (d)(1)(i) of this section and make a tentative determination on the request. The Administrator will send the tentative determination and other comments or suggestions to the State for its use in developing the State's final request under paragraph (d)(2) of this section.
(2)
(3)
(ii) If the Administrator disapproves a final request for approval of a program revision, the Administrator will notify the State in writing. Such notification will include a statement of the reasons for disapproval.
(iii) A final determination by the Administrator on a State's request for approval of a program revision shall take effect in accordance with the public notice requirements and related procedures under § 142.13.
(e)
(a) The Administrator shall provide an opportunity for a public hearing before a final determination pursuant to § 142.11 that the State meets or does not meet the requirements for obtaining primary enforcement responsibility, or a final determination pursuant to § 142.12(d)(3) to approve or disapprove a State request for approval of a program revision, or a final determination pursuant to § 142.17 that a State no longer meets the requirements for primary enforcement responsibility.
(b) The Administrator shall publish notice of any determination specified in paragraph (a) of this section in the
(c) Requests for hearing submitted pursuant to paragraph (b) of this section shall be submitted to the Administrator within 30 days after publication of notice of opportunity for hearing in the
(1) The name, address and telephone number of the individual, organization or other entity requesting a hearing.
(2) A brief statement of the requesting person's interest in the Administrator's determination and of information that the requesting person intends to submit at such hearing.
(3) The signature of the individual making the request; or, if the request is made on behalf of an organization or other entity, the signature of a responsible official of the organization or other entity.
(d) The Administrator shall give notice in the
(e) Hearings convened pursuant to paragraph (d) of this section shall be conducted before a hearing officer to be designated by the Administrator. The hearing shall be conducted by the hearing officer in an informal, orderly and expeditious manner. The hearing officer shall have authority to call witnesses, receive oral and written testimony and take such other action as may be necessary to assure the fair and efficient conduct of the hearing. Following the conclusion of the hearing, the hearing officer shall forward the record of the hearing to the Administrator.
(f) After reviewing the record of the hearing, the Administrator shall issue an order affirming the determination referred to in paragraph (a) of this section or rescinding such determination. If the determination is affirmed, it shall become effective as of the date of the Administrator's order.
(g) If no timely request for hearing is received and the Administrator does not determine to hold a hearing on his own motion, the Administrator's determination shall become effective 30 days after notice is issued pursuant to paragraph (b) of this section.
(h) If a determination of the Administrator that a State no longer meets the requirements for primary enforcement responsibility becomes effective, the State may subsequently apply for a determination that it meets such requirements by submitting to the Administrator information demonstrating that it has remedied the deficiencies found by the Administrator without adversely sacrificing other aspects of its program required for primary enforcement responsibility.
(a) Each State which has primary enforcement responsibility shall maintain records of tests, measurements, analyses, decisions, and determinations performed on each public water system to determine compliance with applicable provisions of State primary drinking water regulations.
(1) Records of microbiological analyses shall be retained for not less than 1 year. Actual laboratory reports may be kept or data may be transferred to tabular summaries, provided that the information retained includes:
(i) The analytical method used;
(ii) The number of samples analyzed each month;
(iii) The analytical results, set forth in a form which makes possible comparison with the limits specified in §§ 141.63, 141.71, and 141.72 of this chapter.
(2) Records of microbiological analyses of repeat or special samples shall
(3) Records of turbidity measurements must be kept for not less than one year. The information retained must be set forth in a form which makes possible comparison with the limits specified in §§ 141.71, 141.73, 141.173 and 141.175, 141.550-141.553 and 141.560-141.564 of this chapter. Until June 29, 1993, for any public water system which is providing filtration treatment and until December 30, 1991, for any public water system not providing filtration treatment and not required by the State to provide filtration treatment, records kept must be set forth in a form which makes possible comparison with the limits contained in § 141.13 of this chapter.
(4)(i) Records of disinfectant residual measurements and other parameters necessary to document disinfection effectiveness in accordance with §§ 141.72 and 141.74 of this chapter and the reporting requirements of §§ 141.75, 141.175, and 141.570, of this chapter must be kept for not less than one year.
(ii) Records of decisions made on a system-by-system and case-by-case basis under provisions of part 141, subpart H, subpart P, or subpart T of this chapter, must be made in writing and kept by the State.
(A) Records of decisions made under the following provisions shall be kept for 40 years (or until one year after the decision is reversed or revised) and a copy of the decision must be provided to the system:
(
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(
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(B) Records of decisions made under the following provisions shall be kept for one year after the decision is made:
(
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(C) Records of decisions made under the following provisions shall be kept
(
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(iii) Records of any determination that a public water system supplied by a surface water source or a ground water source under the direct influence of surface water is not required to provide filtration treatment shall be kept for 40 years or until withdrawn, whichever is earlier. A copy of the determination must be provided to the system.
(5) Records of each of the following decisions made pursuant to the total coliform provisions of part 141 shall be made in writing and retained by the State.
(i) Records of the following decisions must be retained for 5 years.
(A) Section 141.21(b)(1)—Any decision to waive the 24-hour time limit for collecting repeat samples after a total coliform-positive routine sample if the public water system has a logistical problem in collecting the repeat sample that is beyond the system's control, and what alternative time limit the system must meet.
(B) Section 141.21(b)(5)—Any decision to allow a system to waive the requirement for five routine samples the month following a total coliform-positive sample. If the waiver decision is made as provided in § 141.21(b)(5), the record of the decision must contain all the items listed in that paragraph.
(C) Section 141.21(c)—Any decision to invalidate a total coliform-positive sample. If the decision to invalidate a total coliform-positive sample as provided in § 141.21(c)(1)(iii) is made, the record of the decision must contain all the items listed in that paragraph.
(ii) Records of each of the following decisions must be retained in such a manner so that each system's current status may be determined.
(A) Section 141.21(a)(2)—Any decision to reduce the total coliform monitoring frequency for a community water system serving 1,000 persons or fewer, that has no history of total coliform contamination in its current configuration and had a sanitary survey conducted within the past five years showing that the system is supplied solely by a protected groundwater source and is free of sanitary defects, to less than once per month, as provided in § 141.21(a)(2); and what the reduced monitoring frequency is. A copy of the reduced monitoring frequency must be provided to the system.
(B) Section 141.21(a)(3)(i)—Any decision to reduce the total coliform monitoring frequency for a non-community water system using only ground water and serving 1,000 persons or fewer to less than once per quarter, as provided in § 141.21(a)(3)(i), and what the reduced monitoring frequency is. A copy of the reduced monitoring frequency must be provided to the system.
(C) Section 141.21(a)(3)(ii)—Any decision to reduce the total coliform monitoring frequency for a non-community water system using only ground water and serving more than 1,000 persons during any month the system serves 1,000 persons or fewer, as provided in § 141.21(a)(3)(ii). A copy of the reduced monitoring frequency must be provided to the system.
(D) Section 141.21(a)(5)—Any decision to waive the 24-hour limit for taking a total coliform sample for a public water system which uses surface water, or ground water under the direct influence of surface water, and which does not practice filtration in accordance with part 141, subpart H, and which measures a source water turbidity level
(E) Section 141.21(d)(1)—Any decision that a non-community water system is using only protected and disinfected ground water and therefore may reduce the frequency of its sanitary survey to less than once every five years, as provided in § 141.21(d), and what that frequency is. A copy of the reduced frequency must be provided to the system.
(F) Section 141.21(d)(2)—A list of agents other than the State, if any, approved by the State to conduct sanitary surveys.
(G) Section 141.21(e)(2)—Any decision to allow a public water system to forgo fecal coliform or
(6) Records of analysis for other than microbiological contaminants (including total coliform, fecal coliform, and heterotrophic plate count), residual disinfectant concentration, other parameters necessary to determine disinfection effectiveness (including temperature and pH measurements), and turbidity shall be retained for not less than 12 years and shall include at least the following information:
(i) Date and place of sampling.
(ii) Date and results of analyses.
(7) Any decisions made pursuant to the provisions of part 141, subpart P or subpart T of this chapter.
(i) Records of systems consulting with the State concerning a modification to disinfection practice under §§ 141.170(d), 141.172(c), and 141.542 of this chapter, including the status of the consultation.
(ii) Records of decisions that a system using alternative filtration technologies, as allowed under §§ 141.173(b) and § 141.552 of this chapter, can consistently achieve a 99.9 percent removal and/or inactivation of
(iii) Records of systems required to do filter self-assessment, CPE, or CCP under the requirements of §§ 141.175 and 141.563 of this chapter.
(b) Records required to be kept pursuant to paragraph (a) of this section must be in a form admissible -as evidence in State enforcement proceedings.
(c) Each State which has primary enforcement responsibility shall maintain current inventory information for every public water system in the State and shall retain inventory records of public water systems for not less than 12 years.
(d) Each State which has primary enforcement responsibility shall retain, for not less than 12 years, files which shall include for each such public water system in the State:
(1) Reports of sanitary surveys;
(2) Records of any State approvals;
(3) Records of any enforcement actions.
(4) A record of the most recent vulnerability determination, including the monitoring results and other data supporting the determination, the State's findings based on the supporting data and any additional bases for such determination; except that it shall be kept in perpetuity or until a more current vulnerability determination has been issued.
(5) A record of all current monitoring requirements and the most recent monitoring frequency decision pertaining to each contaminant, including the monitoring results and other data supporting the decision, the State's findings based on the supporting data and any additional bases for such decision; except that the record shall be kept in perpetuity or until a more recent monitoring frequency decision has been issued.
(6) A record of the most recent asbestos repeat monitoring determination, including the monitoring results and other data supporting the determination, the State's findings based on the supporting data and any additional bases for the determination and the repeat monitoring frequency; except that these records shall be maintained in
(7) Records of annual certifications received from systems pursuant to part 141, subpart K demonstrating the system's compliance with the treatment techniques for acrylamide and/or epichlorohydrin in § 14.111.
(8) Records of the currently applicable or most recent State determinations, including all supporting information and an explanation of the technical basis for each decision, made under the following provisions of 40 CFR, part 141, subpart I for the control of lead and copper:
(i) Section 141.81(b)—for any water system deemed to be optimized under § 141.81(b)(1) or (b)(3) of this chapter, any conditions imposed by the State on specific water systems to ensure the continued operation and maintenance of corrosion control treatment in place;
(ii) Section 141.82(b)—decisions to require a water system to conduct corrosion control treatment studies;
(iii) Section 141.82(d)—designations of optimal corrosion control treatment;
(iv) Section 141.82(f)—designations of optimal water quality parameters;
(v) Section 141.82(h)—decisions to modify a public water system's optimal corrosion control treatment or water quality parameters;
(vi) Section 141.83(b)(2)—determinations of source water treatment;
(vii) Section 141.83(b)(4)—designations of maximum permissible concentrations of lead and copper in source water;
(viii) Section 141.84(e)—determinations establishing shorter lead service line service line replacement schedules under § 141.84;
(ix) Sections 141.81(b)(3)(iii), 141.86(d)(4)(vii), and 141.86(g)(4)(iii)—determinations of additional monitoring requirements and/or other actions required to maintain optimal corrosion control by systems monitoring for lead and copper at the tap less frequently than once every six months that change treatment or add a new source of water;
(x) Section 141.85—system-specific decisions regarding the content of written public education materials and/or the distribution of these materials;
(xi) Section 141.86(b)(5)—system-specific determinations regarding use of non-first-draw samples at non-transient non-community water systems, and community water systems meeting the criteria of §§ 141.85(c)(7)(i) and (ii) of this chapter, that operate 24 hours a day;
(xii) Section 141.86(c)—system-specific designations of sampling locations for systems subject to reduced monitoring;
(xiii) Section 141.86(d)(iv)(A)—system-specific determinations pertaining to alternative sample collection periods for systems subject to reduced monitoring;
(xiv) Section 141.86(g)—determinations of small system monitoring waivers, waiver recertifications, and waiver revocations;
(xv) Section 141.87(c)(3)—determinations regarding representative entry point locations at ground water systems;
(xvi) Section 141.90(e)(4)—system-specific determinations regarding the submission of information to demonstrate compliance with partial lead service line replacement requirements; and
(xvii) Section 141.90(f)—system-specific decisions regarding the resubmission of detailed documentation demonstrating completion of public education requirements.
(9) Records of reports and any other information submitted by PWSs under § 141.90 of this chapter, including records of any 90th percentile values calculated by the State under § 141.90(h) of this chapter.
(10) Records of State activities, and the results thereof, to:
(i) Verify compliance with State determinations issued under §§ 141.82(f) of this chapter, 141.82(h) of this chapter, 141.83(b)(2) of this chapter, and 141.83(b)(4) of this chapter;
(ii) Verify compliance with the requirements related to partial lead service line replacement under § 141.84(d) of this chapter and compliance with lead service line replacement schedules under § 141.84(e) of this chapter; and
(iii) Invalidate tap water lead and copper samples under § 141.86(f) of this chapter.
(11) Records of each system's currently applicable or most recently designated monitoring requirements. If, for the records identified in paragraphs (d)(8)(i) through (d)(8)(xvii) of this section, no change is made to State determinations during a 12-year retention period, the State shall retain the record until a new decision, determination, or designation has been issued.
(12) Records of the currently applicable or most recent State determinations, including all supporting information and an explanation of the technical basis for each decision, made under the following provisions of 40 CFR part 141, subpart L for the control of disinfectants and disinfection byproducts. These records must also include interim measures toward installation.
(i) States must keep records of systems that are installing GAC or membrane technology in accordance with § 141.64(b)(2) of this chapter. These records must include the date by which the system is required to have completed installation.
(ii) States must keep records of systems that are required, by the State, to meet alternative minimum TOC removal requirements or for whom the State has determined that the source water is not amenable to enhanced coagulation in accordance with § 141.135(b)(3) and (4) of this chapter, respectively. These records must include the alternative limits and rationale for establishing the alternative limits.
(iii) States must keep records of subpart H systems using conventional treatment meeting any of the alternative compliance criteria in § 141.135(a)(2) or (3) of this chapter.
(iv) States must keep a register of qualified operators that have met the State requirements developed under § 142.16(f)(2).
(13) Records of systems with multiple wells considered to be one treatment plant in accordance with § 141.132(a)(2) of this chapter and § 142.16(f)(5).
(14) Monitoring plans for subpart H systems serving more than 3,300 persons in accordance with § 141.132(f) of this chapter.
(15) List of laboratories approved for analyses in accordance with § 141.131(b) of this chapter.
(16) List of systems required to monitor for disinfectants and disinfection byproducts in accordance with part 141, subpart L of this chapter. The list must indicate what disinfectants and DBPs, other than chlorine, TTHM, and HAA5, if any, are measured.
(e) Each State which has primary enforcement responsibility shall retain records pertaining to each variance and exemption granted by it for a period of not less than 5 years following the expiration of such variance or exemption.
(f) Public notification records under Subpart Q of Part 141 of this chapter received from public water systems (including certifications of compliance and copies of public notices) and any state determinations establishing alternative public notification requirements for the water systems must be retained for three years.
(g) Records required to be kept under this section shall be available to the Regional Administrator upon request. The records required to be kept under this section shall be maintained and made available for public inspection by the State, or, the State at its option may require suppliers of water to make available for public inspection those records maintained in accordance with § 141.33.
Each State which has primary enforcement responsibility shall submit to the Administrator the following information:
(a) Each State which has primary enforcement responsibility shall submit quarterly reports to the Administrator on a schedule and in a format prescribed by the Administrator, consisting of the following information:
(1) New violations by public water systems in the State during the previous quarter of State regulations adopted to incorporate the requirements of national primary drinking water regulations, including violations of the public notification requirements
(2) New enforcement actions taken by the State during the previous quarter against public water systems with respect to State regulations adopted to incorporate the requirements of national primary drinking water regulations;
(3) Notification of any new variance or exemption granted during the previous quarter. The notice shall include a statement of reasons for the granting of the variance or exemption, including documentation of the need for the variance or exemption and the finding that the granting of the variance or exemption will not result in an unreasonable risk to health. The State may use a single notification statement to report two or more similar variances or exemptions.
(b) Each State which has primary enforcement responsibility shall submit annual reports to the Administrator on a schedule and in a format prescribed by the Administrator, consisting of the following information:
(1) All additions or corrections to the State's inventory of public water systems;
(2) A summary of the status of each variance and exemption currently in effect.
(c)
(B) A list identifying the name and PWS identification number of each public water system supplied by a surface water source or ground water source under the direct influence of surface water, which the State has determined, based on an evaluation of site-specific considerations, has no means of having a sample transported and analyzed for HPC by a certified laboratory under the requisite time and temperature conditions specified in § 141.74(a)(3) and is providing adequate disinfection in the distribution system, regardless of whether the system is in compliance with the criteria of § 141.72 (a)(4)(i) or (b)(3)(i) of this chapter, as allowed by § 141.72 (a)(4)(ii) and (b)(3)(ii). The list must include the effective date of each determination.
(ii) Notification within 60 days of the end of the calendar quarter of any determination that a public water system using a surface water source or a ground water source under the direct influence of surface water is not required to provide filtration treatment. The notification must include a statement describing the system's compliance with each requirement of the State's regulations that implement § 141.71 and a summary of comments, if any, received from the public on the determination. A single notification may be used to report two or more such determinations.
(2)
(3) [Reserved]
(4) States shall report quarterly, in a format and on a schedule prescribed by the Administrator, the following information related to each system's compliance with the treatment techniques for lead and copper under 40 CFR part 141, subpart I during the preceding calendar quarter. Specifically, States shall report as follows:
(i) For any reports provided prior to May 15, 2000, States shall report the name and PWS identification number:
(A) Each public water system which exceeded the lead and copper action levels and the date upon which the exceedance occurred;
(B) Each public water system required to complete the corrosion control evaluation specified in § 141.82(c) and the date the State received the results of the evaluations from each system;
(C) Each public water system for which the State has designated optimal corrosion control treatment under § 141.82(d), the date of the determination, and each system that completed
(D) Each public water system for which the State has designated optimal water quality parameters under § 141.82(f) and the date of the determination;
(E) Each public water system which the State has required to install source water treatment under § 141.83(b)(2), -the date of the determination, and -each system that completed in-stal-la-tion of treatment as certified under § 141.90(d)(2);
(F) Each public water system for which the State has specified maximum permissible source water levels under § 141.83(b)(4); and
(G) Each public water system required to begin replacing lead service lines as specified in § 141.84, each public water system for which the State has established a replacement schedule under § 141.84(f), and each system reporting compliance with its replacement schedule under § 141.90(e)(2).
(ii) For any reports provided after May 14, 2000 and before January 14, 2002, States may report in accordance with either paragraph (c)(4)(i) or (c)(4)(iii) of this section.
(iii) For all reports submitted on or after January 14, 2002, States shall report the PWS identification number of each public water system identified in paragraphs (c)(4)(iii)(A) through (F) of this section.
(A) For each large and medium-size public water system, all 90th percentile lead levels calculated during each monitoring period specified in § 141.86 of this chapter, and the first and last day of the monitoring period for which the 90th percentile lead level was calculated;
(B) For each small public water system, the 90th percentile lead level calculated during each monitoring period in which the system exceeds the lead action level, and the first and last day of each monitoring period in which an exceedance occurred;
(C) For each public water system (regardless of size), the 90th percentile copper level calculated during each monitoring period in which the system exceeds the copper action level, and the first and last day of each monitoring period in which an exceedance occurred;
(D) For each public water system for which the State has designated optimal water quality parameters under § 141.82(f) of this chapter, or which the State has deemed to have optimized corrosion control under § 141.81(b)(1) or (b)(3) of this chapter, the date of the determination and the paragraph(s) under which the State made its determination;
(E) For each public water system required to begin replacing lead service lines as specified in § 141.84 of this chapter and the date each system must begin replacement; and
(F) For each public water system that has implemented optimal corrosion control, completed applicable source water treatment requirements pursuant to § 141.83 of this chapter and/or completed lead service line replacement requirements pursuant to § 141.84 of this chapter, and the date of the State's determination that these requirements have been met. The date reported shall be the latest of the following events:
(
(
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(5)
(d) The reports submitted pursuant to this section shall be made available
(a)
(1) Each State that has primary enforcement authority under this part must submit complete and final requests for approval of program revisions to adopt the requirements of Subpart Q of Part 141 of this chapter, using the procedures in § 142.12(b) through (d). At its option, a State may, by rule, and after notice and comment, establish alternative public notification requirements with respect to the form and content of the public notice required under Subpart Q of Part 141 of this chapter. The alternative requirements must provide the same type and amount of information required under Subpart Q and must meet the primacy requirements under § 142.10.
(2) As part of the revised primacy program, a State must also establish enforceable requirements and procedures when the State adds to or changes the requirements under:
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(vii)
(viii)
(ix)
(x)
(b)
(1)
(ii) States must have the appropriate rules or other authority to assure that PWSs respond in writing to significant deficiencies outlined in sanitary survey reports required under paragraph (b)(3) of this section no later than 45 days after receipt of the report, indicating how and on what schedule the system will address significant deficiencies noted in the survey.
(iii) States must have the appropriate rules or other authority to assure that PWSs take necessary steps to address significant deficiencies identified in sanitary survey reports required under paragraph (b)(3) of this section, if such deficiencies are within the control of the PWS and its governing body.
(2)
(A) Section 141.70(c) (qualification of operators)—Qualify operators of systems using a surface water source or a ground water source under the direct influence of surface water.
(B) Determine which systems using a ground water source are under the direct influence of surface water by June 29, 1994 for community water systems and by June 29, 1999 for non-community water systems.
(C) Section 141.72(b)(1) (achieving required
(D) Section 141.74(a) (State approval of parties to conduct analyses)—approve parties to conduct pH, temperature, turbidity, and residual disinfectant concentration measurements.
(E) Determine appropriate filtration treatment technology for source waters of various qualities.
(ii) For a State which does not require all public water systems using a surface water source or ground water source under the direct influence of surface water to provide filtration treatment, a State application for program revision approval must include a description of how the State will accomplish the following:
(A) Section 141.71(b)(2) (watershed control program)—Judge the adequacy of watershed control programs.
(B) Section 141.71(b)(3) (approval of on-site inspectors)—Approve on-site inspectors other than State personnel and evaluate the results of on-site inspections.
(iii) For a State which adopts any of the following discretionary elements of part 141 of this chapter, the application must describe how the State will:
(A) Section 141.72 (interim disinfection requirements)—Determine interim disinfection requirements for un-fil-tered systems which the State has de-ter-mined must filter which will be in effect until fil-tra-tion is installed.
(B) Section 141.72 (a)(4)(ii) and (b)(3)(ii) (de-ter-mi-na-tion of adequate disinfection in system without disinfectant residual)—Determine that a system is unable to measure HPC but is still providing adequate disinfection in the distribution system, as allowed by § 141.72(a)(4)(ii) for systems which do not provide filtration treatment and § 141.72(b)(3)(ii) for systems which do provide filtration treatment.
(C) Section 141.73 (a)(1) and (b)(1) (alternative turbidity limit)—Determine whether an alternative turbidity limit is appropriate and what the level should be as allowed by § 141.73(a)(1) for a system using conventiona1 filtration treatment or direct filtration and by
(D) Section 141.73(d) (alternative filtration technologies)—Determine that a public water system has demonstrated that an alternate filtration technology, in combination with disinfection treatment, achieves adequate removal and/or disinfection of
(E) Section 141.74(a)(5) (alternate analytical method for chlorine)—Approve DPD colorimetric test kits for free and combined chlorine measurement or approve calibration of automated methods by the Indigo Method for ozone determination.
(F) Section 141.74 (b)(2) and (c)(1) (approval of continuous turbidity monitoring)—Approve continuous turbidity monitoring, as allowed by § 141.74(b)(2) for a public water system which does not provide filtration treatment and § 141.74(c)(1) for a system which does provide filtration treatment.
(G) Section 141.74 (b)(6)(i) and (c)(3)(i) (approval of alternate disinfectant residual concentration sampling plans)—Approve alternate disinfectant residual concentration sampling plans for systems which have a combined ground water and surface water or ground water and ground water under the direct influence of a surface water distribution system, as allowed by § 141.74(b)(6)(i) for a public water system which does not provide filtration treatment and § 141.74(c)(3)(i) for a public water system which does provide filtration treatment.
(H) Section 141.74(c)(1) (reduction of turbidity monitoring)—Decide whether to allow reduction of turbidity monitoring for systems using slow sand filtration, an approved alternate filtration technology or serving 500 people or fewer.
(I) Section 141.75 (a)(2)(ix) and (b)(2)(iv) (reduced reporting)—Determine whether reduced reporting is appropriate, as allowed by § 141.75(a)(2)(ix) for a public water system which does not provide filtration treatment and § 141.75(b)(2)(iv) for a public water system which does provide filtration treatment.
(iv) For a State which does not require all public water systems using a surface water source or ground water source under the direct influence of surface water to provide filtration treatment and which uses any of the following discretionary provisions, the application must describe how the State will:
(A) Section 141.71(a)(2)(i) (source water turbidity requirements)—Determine that an exceedance of turbidity limits in source water was caused by circumstances that were unusual and unpredictable.
(B) Section 141.71(b)(1)(i) (monthly CT compliance requirements)—Determine whether failure to meet the requirements for monthly CT compliance in § 141.72(a)(1) was caused by circumstances that were unusual and unpredictable.
(C) Section 141.71(b)(1)(iii) (residual disinfectant concentration requirements)—Determine whether failure to meet the requirements for residual disinfectant concentration entering the distribution system in § 141.72(a)(3)(i) was caused by circumstances that were unusual and unpredictable.
(D) Section 141.71(b)(1)(iv) (distribution system disinfectant residual concentration requirements)—Determine whether failure to meet the requirements for distribution system residual disinfectant concentration in § 141.72(a)(4) was related to a deficiency in treatment.
(E) Section 141.71(b)(4) (system modification to prevent waterborne disease outbreak)—Determine that a system, after having been identified as the source of a waterborne disease outbreak, has been modified sufficiently to prevent another such occurrence.
(F) Section 141.71(b)(5) (total coliform MCL)—Determine whether a total coliform MCL violation was caused by a deficiency in treatment.
(G) Section 141.72(a)(1) (disinfection requirements)—Determine that different ozone, chloramine, or chlorine dioxide CT
(H) Section 141.72(a)(2)(ii) (shut-off of water to distribution system)—Determine whether a shut-off of water to the distribution system when the disinfectant residual concentration entering the distribution system is less than 0.2 mg/
(I) Section 141.74(b)(1) (coliform monitoring)—Determine that coliform monitoring which otherwise might be required is not feasible for a system.
(J) Section 141.74(b), table 3.1 (disinfection with chloramines)—Determine the conditions to be met to insure 99.99 percent removal and/or inactivation of viruses in systems which use either preformed chloramines or chloramines for which ammonia is added to the water before chlorine, as allowed by table 3.1.
(3)
(i) The State must conduct sanitary surveys for all surface water systems (including groundwater under the influence) that address the eight sanitary survey components listed in paragraphs (b)(3)(i)(A) through (H) of this section no less frequently than every three years for community systems and no less frequently than every five years for noncommunity systems. The State may allow sanitary surveys conducted after December 1995 to serve as the first set of required sanitary surveys if the surveys address the eight sanitary survey components listed in paragraphs (b)(3)(i)(A) through (H) of this section.
(A) Source.
(B) Treatment.
(C) Distribution system.
(D) Finished water storage.
(E) Pumps, pump facilities, and controls.
(F) Monitoring and reporting and data verification.
(G) System management and operation.
(H) Operator compliance with State requirements.
(ii) For community systems determined by the State to have outstanding performance based on prior sanitary surveys, subsequent sanitary surveys may be conducted no less than every five years. In its primacy application, the State must describe how it will decide whether a system has outstanding performance and is thus eligible for sanitary surveys at a reduced frequency.
(iii) Components of a sanitary survey may be completed as part of a staged or phased state review process within the established frequency.
(iv) When conducting sanitary surveys for systems required to comply with the disinfection profiling requirements in § 141.172 of this chapter, the State must also review the disinfection profile as part of the sanitary survey.
(v) In its primacy application, the State must describe how it will decide whether a deficiency identified during a sanitary survey is significant for the purposes of paragraph (b)(1)(ii) of this section.
(c)
(1) The application must describe the State's plan for determining whether sample siting plans are acceptable (including periodic reviews), as required by § 141.21(a)(1).
(2) The national primary drinking water regulation for total coliforms -in part 141 gives States the option to -impose lesser requirements in certain -circumstances, which are listed below. -If a State chooses to exercise any of -these options, its application for ap-pro-val of a program revision must include the in-for-ma-tion listed below (the State need only provide the information listed for those options it has chosen to use).
(i) Section 141.21(a)(2) (Reduced monitoring requirements for community water systems serving 1,000 or fewer
(ii) Section 141.21(a)(3)(i) (Reduced monitoring requirements for non-community water systems using ground water and serving 1,000 persons or fewer)—A description of how the State will determine whether it is appropriate to reduce the total coliform monitoring frequency for such systems using the criteria in § 141.21(a)(3)(i) and how it will determine the revised frequency.
(iii) Section 141.21(a)(3)(ii) (Reduced monitoring for non-community water systems using ground water and serving more than 1,000 persons)—A description of how the State will determine whether it is appropriate to reduce the total coliform monitoring frequency for non-community water systems using only ground water and serving more than 1,000 persons during any month the system serves 1,000 persons or fewer and how it will determine the revised frequency.
(iv) Section 141.21(a)(5) (Waiver of time limit for sampling after a turbidity sampling result exceeds 1 NTU)—A description of how the State will determine whether it is appropriate to waive the 24-hour time limit.
(v) Section 141.21(b)(1) (Waiver of time limit for repeat samples)—A description of how the State will determine whether it is appropriate to waive the 24-hour time limit and how it will determine what the revised time limit will be.
(vi) Section 141.21(b)(3) (Alternative repeat monitoring requirements for systems with a single service connection)—A description of how the State will determine whether it is appropriate to allow a system with a single service connection to use an alternative repeat monitoring scheme, as provided in § 141.21(b)(3), and what the alternative requirements will be.
(vii) Section 141.21(b)(5) (Waiver of requirement to take five routine samples the month after a system has a total coliform-positive sample)—A description of how the State will determine whether it is appropriate to waive the requirement for certain systems to collect five routine samples during the next month it serves water to the public, using the criteria in § 141.21(b)(5).
(viii) Section 141.21(c) (Invalidation of total coliform-positive samples)—A description of how the State will determine whether it is appropriate to invalidate a total coliform-positive sample, using the criteria in § 141.21(c).
(ix) Section 141.21(d) (Sanitary surveys)—A description of the State's criteria and procedures for approving agents other than State personnel to conduct sanitary surveys.
(x) Section 141.21(e)(2) (Waiver of fecal coliform or
(d) Requirements for States to adopt 40 CFR part 141, subpart I—Control of Lead and Copper. An application for approval of a State program revision which adopts the requirements specified in 40 CFR part 141, subpart I, must contain (in addition to the general primacy requirements enumerated elsewhere in this part, including the requirement that State regulations be at least as stringent as the federal requirements) a description of how the State will accomplish the following program requirements:
(1) Section 141.82—State designation of optimal corrosion control.
(i) Sections 141.82(d), 141.82(f), and 141.82(h)—Designating optimal corrosion control treatment methods, optimal water quality parameters, and modifications thereto.
(ii) Section 141.82(g)—Designating an alternative approach for aggregating multiple measurements collected during the same day for a water quality parameter at a sampling location, if the State elects to adopt a formula other than the one specified in § 141.82(g)(1) of this chapter.
(2) Sections 141.83(b)(2) and 141.83(b)(4)—Designating source water treatment methods, maximum permissible source water levels for lead and copper and modifications thereto.
(3) Section 141.90(e)—Verifying compliance with lead service line replacement schedules and completion of all partial lead service line replacement activities.
(4) Section 141.86(d)(4)(iv)(A)—Designating an alternative period for sample collection for community water systems subject to reduced monitoring.
(e) An application for approval of a State program revision which adopts the requirements specified in §§ 141.11, 141.23, 141.24, 141.61 and 141.62 must contain the following (in addition to the general primacy requirements enumerated elsewhere in this part, including the requirement that State regulations be at least as stringent as the federal requirements):
(1) If a State chooses to issue waivers from the monitoring requirements in §§ 141.23 and 141.24, the State shall describe the procedures and criteria which it will use to review waiver applications and issue waiver determinations.
(i) The procedures for each contaminant or class of contaminants shall include a description of:
(A) The waiver application requirements;
(B) The State review process for “use” waivers and for “susceptibility” waivers; and
(C) The State decision criteria, including the factors that will be considered in deciding to grant or deny waivers. The decision criteria must include the factors specified in §§ 141.24(f)(8) and 141.24(h)(6).
(ii) The State must specify the monitoring data and other documentation required to demonstrate that the contaminant is eligible for a “use” and/or “susceptibility” waiver.
(2) A monitoring plan for the initial monitoring period by which the State will assure all systems complete the required initial monitoring within the regulatory deadlines.
States may update their monitoring plan submitted under the Phase II Rule or simply note in their application that they will use the same monitoring plan for the Phase V Rule.
(i) The initial monitoring plan must describe how systems will be scheduled during the initial monitoring period and demonstrate that the analytical workload on certified laboratories for each of the three years has been taken into account, to assure that the State's plan will result in a high degree of monitoring compliance and that as a result there is a high probability of compliance and will be updated as necessary.
(ii) The State must demonstrate that the initial monitoring plan is enforceable under State law.
(f)
(2) Each State that has primary enforcement responsibility must make reports submitted to the States in compliance with 40 CFR 141.155(c) available to the public upon request.
(3) Each State that has primary enforcement responsibility must maintain a copy of the reports for a period of one year and the certifications obtained pursuant to 40 CFR 141.155(c) for a period of 5 years.
(4) Each State that has primary enforcement responsibility must report violations of this subpart in accordance with the requirements of § 142.15(a)(1).
(g)
(1)
(2)
(ii) Section 141.172(b)(5) of this chapter—How the State will approve a method to calculate the logs of inactivation for viruses for a system that uses either chloramines or ozone for primary disinfection.
(iii) Section 141.172(c) of this chapter—How the State will consult with PWSs to evaluate modifications to disinfection practice.
(iv) Section 141.173(b) of this chapter—For filtration technologies other than conventional filtration treatment, direct filtration, slow sand filtration, or diatomaceous earth filtration, how the State will determine that a public water system may use a filtration technology if the PWS demonstrates to the State, using pilot plant studies or other means, that the alternative filtration technology, in combination with disinfection treatment that meets the requirements of § 141.172(b) of this chapter, consistently achieves 99.9 percent removal and/or inactivation of
(h)
(1) Section 141.64(b)(2) of this chapter (interim treatment requirements). Determine any interim treatment requirements for those systems electing to install GAC or membrane filtration and granted additional time to comply with § 141.64 of this chapter.
(2) Section 141.130(c) of this chapter (qualification of operators). Qualify operators of public water systems subject to 40 CFR part 141, subpart L. Qualification requirements established for operators of systems subject to 40 CFR part 141, subpart H—Filtration and Disinfection may be used in whole or in part to establish operator qualification requirements for meeting 40 CFR part 141, subpart L requirements if the State determines that the 40 CFR part 141, subpart H requirements are appropriate and applicable for meeting subpart L requirements.
(3) Section 141.131(c)(2) of this chapter (DPD colorimetric test kits). Approve DPD colorimetric test kits for free and total chlorine measurements. State approval granted under § 141.74(a)(2) of this chapter for the use of DPD colorimetric test kits for free chlorine testing is acceptable for the use of DPD test kits in measuring free chlorine residuals as required in 40 CFR part 141, subpart L.
(4) Sections 141.131(c)(3) and (d) of this chapter (State approval of parties
(5) Section 141.132(a)(2) of this chapter (multiple wells as a single source). Define the criteria to use to determine if multiple wells are being drawn from a single aquifer and therefore be considered a single source for compliance with monitoring requirements.
(6) Approve alternate minimum TOC removal (Step 2) requirements, as allowed under the provisions of § 141.135(b) of this chapter.
(i)
(1)
(ii) [Reserved]
(2) [Reserved]
(j)
(1)
(2)
(ii) Section 141.536 of this chapter—How the State will approve a method to calculate the logs of inactivation for viruses for a system that uses either chloramines, ozone, or chlorine dioxide for primary disinfection.
(iii) Section 141.542 of this chapter—How the State will consult with the system and approve significant changes to disinfection practices.
(iv) Section 141.552 of this chapter—For filtration technologies other than conventional filtration treatment, direct filtration, slow sand filtration, or diatomaceous earth filtration, how the State will determine that a public water system may use a filtration technology if the PWS demonstrates to the State, using pilot plant studies or
1: At 65 FR 76751, Dec. 7, 2000, § 142.16 was amended by adding and reserving paragraphs (i), (j), and (k) and by adding a new paragraph (l), effective Dec. 8, 2003. For the convenience of the user, the added text is set forth as follows:
(l) An application for approval of a State program revision for radionuclides which adopts the requirements specified in § 141.26(a)(2)(ii)(C) of this chapter must contain the following (in addition to the general primacy requirements enumerated in this part, including that State regulations be at least as stringent as the Federal requirements):
(1) If a State chooses to use grandfathered data in the manner described in § 141.26(a)(2)(ii)(C) of this chapter, then the State must describe the procedures and criteria which it will use to make these determinations (whether distribution system or entry point sampling points are used).
(i) The decision criteria that the State will use to determine that data collected in the distribution system are representative of the drinking water supplied from each entry point to the distribution system. These determinations must consider:
(A) All previous monitoring data.
(B) The variation in reported activity levels.
(C) Other factors affecting the representativeness of the data (
(ii) [Reserved]
(2) A monitoring plan by which the State will assure all systems complete the required monitoring within the regulatory deadlines. States may update their existing monitoring plan or use the same monitoring plan submitted for the requirements in § 142.16(e)(5) under the national primary drinking water regulations for the inorganic and organic contaminants (
2: At 66 FR 7066, Jan. 22, 2001, § 142.16 was amended by revising paragraph (e) introductory text and adding paragraphs (j) and (k), effective Jan. 22, 2004. For the convenience of the user, the revised and added text is set forth as follows:
(e) An application for approval of a State program revision which adopts the requirements specified in §§ 141.11, 141.23, 141.24, 141.32, 141.40, 141.61 and 141.62 for a newly regulated contaminant must contain the following (in addition to the general primacy requirements enumerated elsewhere in this part, including the requirement that State regulations be at least as stringent as the federal requirements):
(j) An application for approval of a State program revision which adopts the requirements specified in §§ 141.11, 141.23, 141.24, 141.32, 141.40, 141.61 and 141.62 for an existing regulated contaminant must contain the following (in addition to the general primacy requirements enumerated elsewhere in this part, including the requirement that State regulations be at least as stringent as the federal requirements):
(1) If a State chooses to issue waivers from the monitoring requirements in §§ 141.23, 141.24, and 141.40, the State shall describe the procedures and criteria which it will use to review waiver applications and issue wavier determinations. The State shall provide the same information required in paragraph (e)(1)(i) and (ii) of this section. States may update their existing waiver criteria or use the requirements submitted under the National Primary Drinking Water Regulations
(2) A monitoring plan by which the State will ensure all systems complete the required monitoring by the regulatory deadlines. States may update their existing monitoring plan or use the same monitoring plan submitted under the National Primary Drinking Water Regulations for the inorganic and organic contaminants (i.e. Phase II/V rule) in 16(e) of this section. States may simply note in their application any revisions to an existing monitoring plan or note that the same monitoring plan will be used. The State must demonstrate that the monitoring plan is enforceable under State law.
(k) States establish the initial monitoring requirements for new systems and new sources. States must explain their initial monitoring schedules and how these monitoring schedules ensure that public water systems and sources comply with MCL's and monitoring requirements. States must also specify the time frame in which new systems will demonstrate compliance with the MCLs.
(a)(1) At least annually the Administrator shall review, with respect to each State determined to have primary enforcement responsibility, the compliance of the State with the requirements set forth in 40 CFR part 142, subpart B, and the approved State primacy program. At the time of this review, the State shall notify the Administrator of any State-initiated program changes (i.e., changes other than those to adopt new or revised EPA regulations), and of any transfer of all or part of its program from the approved State agency to any other State agency.
(2) When, on the basis of the Administrator's review or other available information, the Administrator determines that a State no longer meets the requirements set forth in 40 CFR part 142, subpart B, the Administrator shall initiate proceedings to withdraw primacy approval. Among the factors the Administrator intends to consider as relevant to this determination are the following, where appropriate: whether the State has requested and has been granted, or is awaiting EPA's decision on, an extension under § 142.12(b)(2) of the deadlines for meeting those requirements; and whether the State is taking corrective actions that may have been required by the Administrator. The Administrator shall notify the State in writing that EPA is initiating primacy withdrawal proceedings and shall summarize in the notice the information available that indicates that the State no longer meets such requirements.
(3) The State notified pursuant to paragraph (a)(2) of this section may, within 30 days of receiving the Administrator's notice, submit to the Administrator evidence demonstrating that the State continues to meet the requirements for primary enforcement responsibility.
(4) After reviewing the submission of the State, if any, made pursuant to paragraph (a)(3) of this section, the Administrator shall make a final determination either that the State no longer meets the requirements of 40 CFR part 142, subpart B, or that the State continues to meet those requirements, and shall notify the State of his or her determination. Any final determination that the State no longer meets the requirements of 40 CFR part 142, subpart B, shall not become effective except as provided in § 142.13.
(b) If a State which has primary enforcement responsibility decides to relinquish that authority, it may do so by notifying the Administrator in writing of the State's decision at least 90 days before the effective date of the decision.
(a) A Regional Administrator may annul a State monitoring determination for the types of determinations identified in §§ 141.23(b), 141.23(c), 141.24(f), 141.24(h), and 141.40(n) in accordance with the procedures in paragraph (b) of this section.
(b) When information available to a Regional Administrator, such as the results of an annual review, indicate a State determination fails to apply the standards of the approved State program, he may propose to annul the State monitoring determination by sending the State and the affected PWS
(1) Identify the PWS, the State determination, and the provisions at issue;
(2) Explain why the State determination is not in compliance with the State program and must be changed; and
(3) Describe the actions and terms of operation the PWS will be required to implement.
(c) The State and PWS shall have 60 days to comment on the draft Rescission Order.
(d) The Regional Administrator may not issue a Rescission Order to impose conditions less stringent than those imposed by the State.
(e) The Regional Administrator shall also provide an opportunity for comment upon the draft Rescission Order, by
(1) Publishing a notice in a newspaper in general circulation in communities served by the affected system; and
(2) Providing 30 days for public comment on the draft order.
(f) The State shall demonstrate that the determination is reasonable, based on its approved State program.
(g) The Regional Administrator shall decide within 120 days after issuance of the draft Rescission Order to:
(1) Issue the Rescission Order as drafted;
(2) Issue a modified Rescission Order; or
(3) Cancel the Rescission Order.
(h) The Regional Administrator shall set forth the reasons for his decision, including a responsiveness summary addressing significant comments from the State, the PWS and the public.
(i) The Regional Administrator shall send a notice of his final decision to the State, the PWS and all parties who commented upon the draft Rescission Order.
(j) The Rescission Order shall remain in effect until cancelled by the Regional Administrator. The Regional Administrator may cancel a Rescission Order at any time, so long as he notifies those who commented on the draft order.
(k) The Regional Administrator may not delegate the signature authority for a final Rescission Order or the cancellation of an order.
(l) Violation of the actions, or terms of operation, required by a Rescission Order is a violation of the Safe Drinking Water Act.
(a) Pursuant to the procedures in this section, the Regional Administrator may review state determinations establishing corrosion control or source water treatment requirements for lead or copper and may issue an order establishing federal treatment requirements for a public water system pursuant to § 141.82 (d) and (f) and § 141.83(b) (2) and (4) where the Regional Administrator finds that:
(1) A State has failed to issue a treatment determination by the applicable deadline;
(2) A State has abused its discretion in making corrosion control or source water treatment determinations in a substantial number of cases or in cases affecting a substantial population, or
(3) The technical aspects of State's determination would be indefensible in an expected federal enforcement action taken against a system.
(b) If the Regional Administrator determines that review of state de-ter-mi-na-tion(s) under this section may be appropriate, he shall request the State to forward to EPA the state determination and all information that was considered by the State in making its determination, including public comments, if any, within 60 days of the Regional Adminstrator's request.
(c) Proposed review of state determinations:
(1) Where the Regional Administrator finds that review of a state determination under paragraph (a) of this section is appropriate, he shall issue a proposed review order which shall:
(i) Identify the public water system(s) affected, the State determination being reviewed and the provisions of state and/or federal law at issue;
(ii) Identify the determination that the State failed to carry out by the applicable deadline, or identify the particular provisions of the State determination which, in the Regional Administrator's judgment, fail to carry out properly applicable treatment requirements, and explain the basis for the Regional Administrator's conclusion;
(iii) Identify the treatment requirements which the Regional Administrator proposes to apply to the affected system(s), and explain the basis for the proposed requirements;
(iv) Request public comment on the proposed order and the supporting record.
(2) The Regional Administrator shall provide notice of the proposed review order by:
(i) Mailing the proposed order to the affected public water system(s), the state agency whose order is being -reviewed, and any other parties of -interest known to the Regional Administrator; and
(ii) Publishing a copy of the proposed order in a newspaper of general circulation in the affected communities.
(3) The Regional Administrator shall make available for public inspection during the comment period the record supporting the proposed order, which shall include all of the information submitted by the State to EPA under paragraph (b) of this section, all other studies, monitoring data and other information considered by the Agency in developing the proposed order.
(d) Final review order:
(1) Based upon review of all information obtained regarding the proposed review order, including public comments, the Regional Administrator shall issue a final review order within 120 days after issuance of the proposed order which affirms, modifies, or withdraws the proposed order. The Regional Administrator may extend the time period for issuing the final order for good cause. If the final order modifies or withdraws the proposed order, the final order shall explain the reasons supporting the change.
(2) The record of the final order shall consist of the record supporting the proposed order, all public comments, all other information considered by the Regional Administrator in issuing the final order and a document responding to all significant public comments submitted on the proposed order. If new points are raised or new material supplied during the public comment period, the Regional Administrator may support the responses on those matters by adding new materials to the record. The record shall be complete when the final order is issued.
(3) Notice of the final order shall be provided by mailing the final order to the affected system(s), the State, and all parties who commented on the proposed order.
(4) Upon issuance of the final order, its terms constitute requirements of the national primary drinking water regulation for lead and/or copper until such time as the Regional Administrator issues a new order (which may include recision of the previous order) pursuant to the procedures in this section. Such requirements shall supersede any inconsistent treatment requirements established by the State pursuant to the national primary drinking water regulations for lead and copper.
(5) The Regional Administrator may not issue a final order to impose conditions less stringent than those imposed by the State.
(e) The Regional Administrator may not delegate authority to sign the final order under this section.
(f) Final action of the Regional Administrator under paragraph (d) of this section shall constitute action of the Administrator for purposes of 42 U.S.C. § 300j-7(a)(2).
(a) States with primary enforcement responsibility may issue variances to public water systems (other than small system variances) from the requirements of primary drinking water regulations under conditions and in a manner which are not less stringent than the requirements under Section 1415(a) of the Act. In States that do not have
(1) A State must document all findings that are required under Section 1415(a) of the Act.
(2) If a State prescribes a schedule pursuant to section 1415(a) of the Act requiring compliance with a contaminant level for which the variance is granted later than five years from the date of issuance of the variance the State must—
(i) Document its rationale for the extended compliance schedule;
(ii) Discuss the rationale for the extended compliance schedule in the required public notice and opportunity for public hearing; and
(iii) Provide the shortest practicable time schedule feasible under the circumstances.
(b) States with primary enforcement responsibility may issue exemptions from the requirements of primary drinking water regulations under conditions and in a manner which are not less stringent than the requirements under Section 1416 of the Act. In States that do not have primary enforcement responsibility, exemptions may be granted by the Administrator pursuant to Subpart F of this part.
(1) A State must document all findings that are required under Section 1416 of the Act:
(i) Before finding that management and restructuring changes cannot be made, a State must consider the following measures, and the availability of State Revolving Loan Fund assistance, or any other Federal or State program, that is reasonably likely to be available within the period of the exemption to implement these measures:
(A) Consideration of rate increases, accounting changes, the appointment of a State-certified operator under the State's Operator Certification program, contractual agreements for joint operation with one or more public water systems;
(B) Activities consistent with the State's Capacity Development Strategy to help the public water system acquire and maintain technical, financial, and managerial capacity to come into compliance with the Act; and
(C) Ownership changes, physical consolidation with another public water system, or other feasible and appropriate means of consolidation which would result in compliance with the Act;
(ii) The State must consider the availability of an alternative source of water, including the feasibility of partnerships with neighboring public water systems, as identified by the public water system or by the State consistent with the Capacity Development Strategy.
(2) In the case of a public water system serving a population of not more than 3,300 persons and which needs financial assistance for the necessary improvements under the initial compliance schedule, an exemption granted by the State under section 1416(b)(2)(B)(i) or (ii) of the Act may be renewed for one or more additional 2-year periods, but not to exceed a total of 6 additional years, only if the State establishes that the public water system is taking all practicable steps to meet the requirements of Section 1416(b)(2)(B) of the Act and the established compliance schedule to achieve full compliance with the contaminant level or treatment technique for which the exemption was granted. A State must document its findings in granting an extension under this paragraph.
A State with primary enforcement responsibility shall act on any variance or exemption request submitted to it, within 90 days of receipt of the request.
(a) Not later than 18 months after the effective date of the interim national primary drinking water regulations the Administrator shall complete a comprehensive review of the variances and exemptions granted (and schedules prescribed pursuant thereto) by the States
(b) Notice of a proposed review shall be published in the
(a) If the Administrator finds that a State has, in a substantial number of instances, abused its discretion in granting variances or exemptions under section 1415(a) or section 1416(a) of the Act or failed to prescribe schedules in accordance with section 1415(a) or section 1416(b) of the Act, he shall notify the State of his findings. Such notice shall:
(1) Identify each public water system for which the finding was made;
(2) Specify the reasons for the finding; and
(3) As appropriate, propose revocation of specific variances or exemptions, or propose revised schedules for specific public water systems.
(b) The Administrator shall also notify the State of a public hearing to be held on the provisions of the notice required by paragraph (a) of this section. Such notice shall specify the time and location for the hearing. If, upon notification of a finding by the Administrator, the State takes adequate corrective action, the Administrator shall rescind his notice to the State of a public hearing, provided that the Administrator is notified of the corrective action prior to the hearing.
(c) The Administrator shall publish notice of the public hearing in the
(d) Hearings convened pursuant to paragraphs (b) and (c) of this section shall be conducted before a hearing officer to be designated by the Administrator. The hearing shall be conducted by the hearing officer in an informal, orderly and expeditious manner. The hearing officer shall have authority to call witnesses, receive oral and written testimony and take such other action as may be necessary to assure the fair and efficient conduct of the hearing. Following the conclusion of the hearing, the hearing officer shall forward the record of the hearing to the Administrator.
(e) Within 180 days after the date notice is given pursuant to paragraph (b) of this section, the Administrator shall:
(1) Rescind the finding for which the notice was given and promptly notify the State of such rescission, or
(2) Promulgate with any modifications as appropriate such revocation and revised schedules proposed in such notice and promptly notify the State of such action.
(f) A revocation or revised schedule shall take effect 90 days after the State is notified under paragraph (e)(2) of this section.
If, upon notification of a finding by the Administrator under § 142.23, the State takes adequate corrective action before the effective date of the revocation or revised schedule, the Administrator shall rescind the application of his finding to that variance, exemption or schedule.
(a) The Administrator shall notify a State and the appropriate supplier of water whenever he finds during a period in which the State has primary enforcement responsibility for public water systems that a public water system within such State is not in compliance with any primary drinking water regulation contained in part 141 of this chapter or with any schedule or other requirements imposed pursuant to a variance or exemption granted under section 1415 or 1416 of the Act:
(b) The Administrator shall provide advice and technical assistance to such State and public water system as may be appropriate to bring the system into compliance by the earliest feasible time.
(a) If the Administrator makes a finding of noncompliance pursuant to § 142.30 with respect to a public water system in a State which has primary enforcement responsibility, the Administrator may, for the purpose of assisting that State in carrying out such responsibility and upon the petition of such State or public water system or persons served by such system, hold, after appropriate notice, public hearings for the purpose of gathering information as described in § 142.33.
(b) A petition for a public hearing pursuant to paragraph (a) of this section shall be filed with the Administrator and shall include the following information:
(1) The name, address and telephone number of the individual or other entity requesting a hearing.
(2) If the petition is filed by a person other than the State or public water system, a statement that the person is served by the system.
(3) A brief statement of information that the requesting person intends to submit at the requested hearing.
(4) The signature of the individual submitting the petition; or, if the petition is filed on behalf of a State, public water system or other entity, the signature of a responsible official of the State or other entity.
(a) If the Administrator grants the petition for public hearing, he shall give appropriate public notice of such hearing. Such notice shall be by publication in the
(b) A hearing officer designated by the Administrator shall gather during the public hearing information from technical or other experts, Federal, State, or other public officials, representatives of the public water system, persons served by the system, and other interested persons on:
(1) The ways in which the system can within the earliest feasible time be brought into compliance, and
(2) The means for the maximum feasible protection of the public health during any period in which such system is not in compliance.
(c) On the basis of the hearing and other available information the Administrator shall issue recommendations which shall be sent to the State and public water system and shall be made available to the public and communications media.
(a) Any supplier of water or other person subject to a national primary drinking water regulation shall, at any time, allow the Administrator, or a designated representative of the Administrator, upon presenting appropriate credentials and a written notice of inspection, to enter any establishment, facility or other property of such supplier or other person to determine whether such supplier or other person has acted or is acting in compliance with the requirements of the Act or
(b) Prior to entry into any establishment, facility or other property within a State which has primary enforcement responsibility, the Administrator shall notify, in writing, the State agency charged with responsibility for safe drinking water of his intention to make such entry and shall include in his notification a statement of reasons for such entry. The Administrator shall, upon a showing by the State agency that such an entry will be detrimental to the administration of the State's program of primary enforcement responsibility, take such showing into consideration in determining whether to make such entry. The Administrator shall in any event offer the State agency the opportunity of having a representative accompany the Administrator or his representative on such entry.
(c) No State agency which receives notice under paragraph (b) of this section may use the information contained in the notice to inform the person whose property is proposed to be entered of the proposed entry; if a State so uses such information, notice to the agency under paragraph (b) of this section is not required for subsequent inspections of public water systems until such time as the Administrator determines that the agency has provided him satisfactory assurances that it will no longer so use information contained in a notice received under paragraph (b) of this section.
(a) The Administrator may grant one or more variances to any public water system within a State that does not have primary enforcement responsibility from any requirement respecting a maximum contaminant level of an applicable national primary drinking water regulation upon a finding that:
(1) Because of characteristics of the raw water sources which are reasonably available to the system, the system cannot meet the requirements respecting the maximum contaminant levels of such drinking water regulations despite application of the best technology, treatment techniques, or other means, which the Administrator finds are generally available (taking costs into consideration); and
(2) The granting of a variance will not result in an unreasonable risk to the health of persons served by the system.
(b) The Administrator may grant one or more variances to any public water system within a State that does not have primary enforcement responsibility from any requirement of a specified treatment technique of an applicable national primary drinking water regulation upon a finding that the public water system applying for the variance has demonstrated that such treatment technique is not necessary to protect the health of persons because of the nature of the raw water source of such system.
A supplier of water may request the granting of a variance pursuant to this subpart for a public water system within a State that does not have primary enforcement responsibility by submitting a request for a variance in writing to the Administrator. Suppliers of water may submit a joint request for variances when they seek similar variances under similar circumstances. Any written request for a variance or variances shall include the following information:
(a) The nature and duration of variance requested.
(b) Relevant analytical results of water quality sampling of the system, including results of relevant tests conducted pursuant to the requirements of the national primary drinking water regulations.
(c) For any request made under § 142.40(a):
(1) Explanation in full and evidence of the best available treatment technology and techniques.
(2) Economic and legal factors relevant to ability to comply.
(3) Analytical results of raw water quality relevant to the variance request.
(4) A proposed compliance schedule, including the date each step toward compliance will be achieved. Such schedule shall include as a minimum the following dates:
(i) Date by which arrangement for alternative raw water source or improvement of existing raw water source will be completed.
(ii) Date of initiation of the connection of the alternative raw water source or improvement of existing raw water source.
(iii) Date by which final compliance is to be achieved.
(5) A plan for the provision of safe drinking water in the case of an excessive rise in the contaminant level for which the variance is requested.
(6) A plan for additional interim control measures during the effective period of variance.
(d) For any request made under § 142.40(b), a statement that the system will perform monitoring and other reasonable requirements prescribed by the Administrator as a condition to the variance.
(e) Other information, if any, believed to be pertinent by the applicant.
(f) Such other information as the Administrator may require.
(a) The Administrator shall act on any variance request submitted pursuant to § 142.41 within 90 days of receipt of the request.
(b) In his consideration of whether the public water system is unable to comply with a contaminant level required by the national primary drinking water regulations because of the nature of the raw water source, the Administrator shall consider such factors as the following:
(1) The availability and effectiveness of treatment methods for the contaminant for which the variance is requested.
(2) Cost and other economic considerations such as implementing treatment, improving the quality of the source water or using an alternate source.
(c) A variance may be issued to a public water system on the condition that the public water system install the best technology, treatment techniques, or other means, which the Administrator finds are available (taking costs into consideration) and based upon an evaluation satisfactory to the Administrator that indicates that alternative sources of water are not reasonably available to the public water system.
(d) In his consideration of whether a public water system should be granted a variance to a required treatment technique because such treatment is unnecessary to protect the public health, the Administrator shall consider such factors as the following:
(1) Quality of the water source including water quality data and pertinent sources of pollution.
(2) Source protection measures employed by the public water system.
(a) If the Administrator decides to deny the application for a variance, he shall notify the applicant of his intention to issue a denial. Such notice shall include a statement of reasons for the proposed denial, and shall offer the applicant an opportunity to present, within 30 days of receipt of the notice, additional information or argument to the Administrator. The Administrator shall make a final determination on the request within 30 days after receiving any such additional information or argument. If no additional information or argument is submitted by the applicant the application shall be denied.
(b) If the Administrator proposes to grant a variance request submitted pursuant to § 142.41, he shall notify the applicant of his decision in writing. Such notice shall identify the variance, the facility covered, and shall specify the period of time for which the variance will be effective.
(1) For the type of variance specified in § 142.40(a) such notice shall provide that the variance will be terminated
(2) For the type of variance specified in § 142.40(b) such notice shall provide that the variance may be terminated at any time upon a finding that the nature of the raw water source is such that the specified treatment technique for which the variance was granted is necessary to protect the health of persons or upon a finding that the public water system has failed to comply with monitoring and other requirements prescribed by the Administrator as a condition to the granting of the variance.
(c) For a variance specified in § 142.40(a)(1) the Administrator shall propose a schedule for:
(1) Compliance (including increments of progress) by the public water system with each contaminant level requirement covered by the variance; and,
(2) Implementation by the public water system of such additional control measures as the Administrator may require for each contaminant covered by the variance.
(d) The proposed schedule for compliance shall specify dates by which steps towards compliance are to be taken, including at the minimum, where applicable:
(1) Date by which arrangement for an alternative raw water source or improvement of existing raw water source will be completed.
(2) Date of initiation of the connection for the alternative raw water source or improvement of the existing raw water source.
(3) Date by which final compliance is to be achieved.
(e) The proposed schedule may, if the public water system has no access to an alternative raw water source, and can effect or anticipate no adequate improvement of the existing raw water source, specify an indefinite time period for compliance until a new and effective treatment technology is developed at which time a new compliance schedule shall be prescribed by the Administrator.
(f) The proposed schedule for implementation of additional interim control measures during the period of variance shall specify interim treatment techniques, methods and equipment, and dates by which steps toward meeting the additional interim control measures are to be met.
(g) The schedule shall be prescribed by the Administrator at the time of granting of the variance, subsequent to provision of opportunity for hearing pursuant to § 142.44.
(a) Before a variance and schedule proposed by the Administrator pursuant to § 142.43 may take effect, the Administrator shall provide notice and opportunity for public hearing on the variance and schedule. A notice given pursuant to the preceding sentence may cover the granting of more than one variance and a hearing held pursuant to such notice shall include each of the variances covered by the notice.
(b) Public notice of an opportunity for hearing on a variance and schedule shall be circulated in a manner designed to inform interested and potentially interested persons of the proposed variance and schedule, and shall include at least the following:
(1) Posting of a notice in the principal post office of each municipality or area served by the public water system, and publishing of a notice in a newspaper or newspapers of general circulation in the area served by the public water system; and
(2) Mailing of a notice to the agency of the State in which the system is located which is responsible for the State's water supply program, and to other appropriate State or local agencies at the Administrator's discretion.
(3) Such notice shall include a summary of the proposed variance and schedule and shall inform interested persons that they may request a public hearing on the proposed variance and schedule.
(c) Requests for hearing may be submitted by any interested person other
(1) The name, address and telephone number of the individual, organization or other entity requesting a hearing;
(2) A brief statement of the interest of the person making the request in the proposed variance and schedule, and of information that the requester intends to submit at such hearing;
(3) The signature of the individual making the request, or, if the request is made on behalf of an organization or other entity, the signature of a responsible official of the organization or other entity.
(d) The Administrator shall give notice in the manner set forth in paragraph (b) of this section of any hearing to be held pursuant to a request submitted by an interested person or on his own motion. Notice of the hearing shall also be sent to the persons requesting the hearing, if any. Notice of the hearing shall include a statement of the purpose of the hearing, information regarding the time and location for the hearing, and the address and telephone number of an office at which interested persons may obtain further information concerning the hearing. At least one hearing location specified in the public notice shall be within the involved State. Notice of hearing shall be given not less than 15 days prior to the time scheduled for the hearing.
(e) A hearing convened pursuant to paragraph (d) of this section shall be conducted before a hearing officer to be designated by the Administrator. The hearing shall be conducted by the hearing officer in an informal, orderly and expeditious manner. The hearing officer shall have authority to call witnesses, receive oral and written testimony and take such other action as may be necessary to assure the fair and efficient conduct of the hearing. Following the conclusion of the hearing, the hearing officer shall forward the record of the hearing to the Administrator.
(f) The variance and schedule shall become effective 30 days after notice of opportunity for hearing is given pursuant to paragraph (b) of this section if no timely request for hearing is submitted and the Administrator does not determine to hold a public hearing on his own motion.
Within 30 days after the termination of the public hearing held pursuant to § 142.44, the Administrator shall, taking into consideration information obtained during such hearing and relevant information, confirm, revise or rescind the proposed variance and schedule.
The Administrator may grant a variance from any treatment technique requirement of a national primary drinking water regulation to a supplier of water, whether or not the public water system for which the variance is requested is located in a State which has primary enforcement responsibility, upon a showing from any person that an alternative treatment technique not included in such requirement is at least as efficient in lowering the level of the contaminant with respect to which such requirements was prescribed. A variance under this paragraph shall be conditioned on the use of the alternative treatment technique which is the basis of the variance.
(a) The Administrator may exempt any public water system within a State that does not have primary enforcement responsibility from any requirement regarding a maximum contaminant level or any treatment technique requirement, or from both, of an applicable national primary drinking water regulation upon a finding that—
(1) Due to compelling factors (which may include economic factors, including qualification of the public water system as a system serving a disadvantaged community pursuant to section 1452(d) of the Act), the public water system is unable to comply with such contaminant level or treatment technique requirement or to implement measures to develop an alternative source of water supply;
(2) The public water system was in operation on the effective date of such contaminant level or treatment technique requirement, or for a public water system that was not in operation by that date, no reasonable alternative source of drinking water is available to such new public water system;
(3) The granting of the exemption will not result in an unreasonable risk to health; and
(4) Management or restructuring changes (or both), as provided in § 142.20(b)(1)(i), cannot reasonably be made that will result in compliance with the applicable national primary drinking water regulation or, if compliance cannot be achieved, improve the quality of the drinking water.
(b) No exemption shall be granted unless the public water system establishes that the public water system is taking all practicable steps to meet the standard; and
(1) The public water system cannot meet the standard without capital improvements which cannot be completed prior to the date established pursuant to Section 1412(b)(10) of the Act;
(2) In the case of a public water system which needs financial assistance for the necessary improvements, the public water system has entered into an agreement to obtain such financial assistance or assistance pursuant to Section 1452 of the Act, or any other Federal or State program that is reasonably likely to be available within the period of the exemption; or
(3) The public water system has entered into an enforceable agreement to become a part of a regional public water system.
(c) A public water system may not receive an exemption under this subpart if the public water system was granted a variance under Section 1415(e) of the Act.
A supplier of water may request the granting of an exemption pursuant to this subpart for a public water system within a State that does not have primary enforcement responsibility by submitting a request for exemption in writing to the Administrator. Suppliers of water may submit a joint request for exemptions when they seek similar exemptions under similar circumstances. Any written request for an exemption or exemptions shall include the following information:
(a) The nature and duration of exemption requested.
(b) Relevant analytical results of water quality sampling of the system, including results of relevant tests conducted pursuant to the requirements of the national primary drinking water regulations.
(c) Explanation of the compelling factors such as time or economic factors which prevent such system from achieving compliance.
(d) Other information, if any, believed by the applicant to be pertinent to the application.
(e) A proposed compliance schedule, including the date when each step toward compliance will be achieved.
(f) Such other information as the Administrator may require.
(a) The Administrator shall act on any exemption request submitted pursuant to § 142.51 within 90 days of receipt of the request.
(b) In his consideration of whether the public water system is unable to comply due to compelling factors, the Administrator shall consider such factors as the following:
(1) Construction, installation, or modification of the treatment equipment or systems.
(2) The time needed to put into operation a new treatment facility to replace an existing system which is not in compliance.
(3) Economic feasibility of compliance.
(a) If the Administrator decides to deny the application for an exemption, he shall notify the applicant of his intention to issue a denial. Such notice shall include a statement of reasons for the proposed denial, and shall offer the applicant an opportunity to present, within 30 days of receipt of the notice, additional information or argument to the Administrator. The Administrator shall make a final determination on the request within 30 days after receiving any such additional information or argument. If no additional information or argument is submitted by the applicant, the application shall be denied.
(b) If the Administrator grants an exemption request submitted pursuant to § 142.51, he shall notify the applicant of his decision in writing. Such notice shall identify the facility covered, and shall specify the termination date of the exemption. Such notice shall provide that the exemption will be terminated when the system comes into compliance with the applicable regulation, and may be terminated upon a finding by the Administrator that the system has failed to comply with any requirements of a final schedule issued pursuant to § 142.55.
(c) The Administrator shall propose a schedule for:
(1) Compliance (including increments of progress or measures to develop an alternative source of water supply) by the public water system with each contaminant level requirement or treatment technique requirement with respect to which the exemption was granted; and
(2) Implementation by the public water system of such control measures as the Administrator may require for each contaminant covered by the exemption.
(d) The schedule shall be prescribed by the Administrator at the time the exemption is granted, subsequent to provision of opportunity for hearing pursuant to § 142.54.
(a) Before a schedule proposed by the Administrator pursuant to § 142.53 may take effect, the Administrator shall provide notice and opportunity for public hearing on the schedule. A notice given pursuant to the preceding sentence may cover the proposal of more than one such schedule and a hearing held pursuant to such notice shall include each of the schedules covered by the notice.
(b) Public notice of an opportunity for hearing on an exemption schedule shall be circulated in a manner designed to inform interested and potentially interested persons of the proposed schedule, and shall include at least the following:
(1) Posting of a notice in the principal post office of each municipality or area served by the public water system, and publishing of a notice in a newspaper or newspapers of general circulation in the area served by the public water system.
(2) Mailing of a notice to the agency of the State in which the system is located which is responsible for the State's water supply program and to other appropriate State or local agencies at the Administrator's discretion.
(3) Such notices shall include a summary of the proposed schedule and shall inform interested persons that they may request a public hearing on the proposed schedule.
(c) Requests for hearing may be submitted by any interested person other than a Federal agency. Frivolous or insubstantial requests for hearing may be denied by the Administrator. Requests must be submitted to the Administrator within 30 days after issuance of the public notices provided for in paragraph (b) of this section. Such requests shall include the following information:
(1) The name, address and telephone number of the individual, organization or other entity requesting a hearing;
(2) A brief statement of the interest of the person making the request in the proposed schedule and of information that the requesting person intends to submit at such hearing; and
(3) The signature of the individual making the request, or, if the request
(d) The Administrator shall give notice in the manner set forth in paragraph (b) of this section of any hearing to be held pursuant to a request submitted by an interested person or on his own motion. Notice of the hearing shall also be sent to the person requesting the hearing, if any. Notice of the hearing shall include a statement of the purpose of the hearing, information regarding the time and location of the hearing, and the address and telephone number of an office at which interested persons may obtain further information concerning the hearing. At least one hearing location specified in the public notice shall be within the involved State. Notice of the hearing shall be given not less than 15 days prior to the time scheduled for the hearing.
(e) A hearing convened pursuant to paragraph (d) of this section shall be conducted before a hearing officer to be designated by the Administrator. The hearing shall be conducted by the hearing officer in an informal, orderly and expeditious manner. The hearing officer shall have authority to call witnesses, receive oral and written testimony and take such action as may be necessary to assure the fair and efficient conduct of the hearing. Following the conclusion of the hearing, the hearing officer shall forward the record of the hearing to the Administrator.
(a) Within 30 days after the termination of the public hearing pursuant to § 142.54, the Administrator shall, taking into consideration information obtained during such hearing, revise the proposed schedule as necessary and prescribe the final schedule for compliance and interim measures for the public water system granted an exemption under § 142.52.
(b) Such schedule must require compliance with each contaminant level and treatment technique requirement with respect to which the exemption was granted as expeditiously as practicable but not later than 3 years after the otherwise applicable compliance date established in section 1412(b)(10) of the Act.
(c) [Reserved]
In the case of a public water system which serves a population of not more than 3,300 persons and which needs financial assistance for the necessary improvements, an exemption granted under § 142.50(b) (1) or (2) may be renewed for one or more additional 2-year periods, but not to exceed a total of 6 additional years, if the public water system establishes that the public water system is taking all practicable steps to meet the requirements of section 1416(b)(2)(B) of the Act and the established compliance schedule.
(a) A State may require a public water system to use bottled water, point-of-use devices, or point-of-entry devices as a condition of granting an exemption from the requirements of §§ 141.61 (a) and (c), and 141.62 of this chapter.
(b) Public water systems using bottled water as a condition of obtaining an exemption from the requirements of §§ 141.61 (a) and (c) and 141.62(b) must meet the requirements in § 142.62(g).
(c) Public water systems that use point-of-use or point-of-entry devices as a condition for receiving an exemption must meet the requirements in § 141.62(h).
(a) The Administrator, pursuant to section 1415(a)(1)(A) of the Act, hereby identifies the following as the best technology, treatment techiques or other means generally available for achieving compliance with the maximum contaminant level for total trihalomethanes (§ 141.12(c)):
(1) Use of chloramines as an alternate or supplemental disinfectant or oxidant.
(2) Use of chlorine dioxide as an alternate or supplemental disinfectant or oxidant.
(3) Improved existing clarification for THM precursor reduction.
(4) Moving the point of chlorination to reduce TTHM formation and, where necessary, substituting for the use of chlorine as a pre-oxidant chloramines, chlorine dioxide or potassium permanganate.
(5) Use of powdered activated carbon for THM precursor or TTHM reduction seasonally or intermittently at dosages not to exceed 10 mg/L on an annual average basis.
(b) The Administrator in a state that does not have primary enforcement responsibility or a state with primary enforcement responsibility (primacy state) that issues variances shall require a community water system to install and/or use any treatment method identified in § 142.60(a) as a condition for granting a variance unless the Administrator or primacy state determines that such treatment method identified in § 142.60(a) is not available and effective for TTHM control for the system. A treatment method shall not be considered to be “available and effective” for an individual system if the treatment method would not be technically appropriate and technically feasible for that system or would only result in a marginal reduction in TTHM for the system. If, upon application by a system for a variance, the Administrator or primacy state that issues variances determines that none of the treatment methods identified in § 142.60(a) is available and effective for the system, that system shall be entitled to a variance under the provisions of section 1415(a)(1)(A) of the Act. The Administrator's or primacy state's determination as to the availability and effectiveness of such treatment methods shall be based upon studies by the system and other relevant information. If a system submits information intending to demonstrate that a treatment method is not available and effective for TTHM control for that system, the Administrator or primacy state shall make a finding whether this information supports a decision that such treatment method is not available and effective for that system before requiring installation and/or use of such treatment method.
(c) Pursuant to § 142.43 (c) through (g) or corresponding state regulations, the Administrator or primacy state that issues variances shall issue a schedule of compliance that may require the system being granted the variance to examine the following treatment methods (1) to determine the probability that any of these methods will significantly reduce the level of TTHM for that system, and (2) if such probability exists, to determine whether any of these methods are technically feasible and economically reasonable, and that the TTHM reductions obtained will be commensurate with the costs incurred with the installation and use of such treatment methods for that system:
Introduction of off-line water storage for THM precursor reduction.
Aeration for TTHM reduction, where geographically and environmentally appropriate.
Introduction of clarification where not currently practiced.
Consideration of alternative sources of raw water.
Use of ozone as an alternate or supplemental disinfectant or oxidant.
(d) If the Administrator or primacy state that issues variances determines that a treatment method identified in § 142.60(c) is technically feasible, economically reasonable and will achieve TTHM reductions commensurate with the costs incurred with the installation and/or use of such treatment method for the system, the Administrator or
(a) The Administrator, pursuant to section 1415(a)(1)(A) of the Act, hereby identifies the following as the best technology, treatment techniques or other means generally available for achieving compliance with the Maximum Contaminant Level for fluoride.
(1) Activated alumina absorption, centrally applied
(2) Reverse osmosis, centrally applied
(b) The Administrator in a state that does not have primary enforcement responsibility or a state with primary enforcement responsibility (primacy state) that issues variances shall require a community water system to install and/or use any treatment method identified in § 142.61(a) as a condition for granting a variance unless the Administrator or the primacy state determines that such treatment method identified in § 142.61(a) as a condition for granting a variance is not available and effective for fluoride control for the system. A treatment method shall not be considered to be “available and effective” for an individual system if the treatment method would not be technically appropriate and technically feasible for that system. If, upon application by a system for a variance, the Administrator or primacy state that issues variances determines that none of the treatment methods identified in § 142.61(a) are available and effective for the system, that system shall be entitled to a variance under the provisions of section 1415(a)(1)(A) of the Act. The Administrator's or primacy state's determination as to the availability and effectiveness of such treatment methods shall be based upon studies by the system and other relevant information. If a system submits information to demonstrate that a treatment method is not available and effective for fluoride control for that system, the Administrator or primacy state shall make a finding whether this information supports a decision that such treatment method is not available and effective for that system before requiring installation and/or use of such treatment method.
(c) Pursuant to § 142.43 (c)-(g) or corresponding state regulations, the Administrator or primacy state that issues variances shall issue a schedule of compliance that may require the system being granted the variance to examine the following treatment methods (1) to determine the probability that any of these methods will significantly reduce the level of fluoride for that system, and (2) if such probability exists, to determine whether any of these methods are technically feasible and economically reasonable, and that the fluoride reductions obtained will be commensurate with the costs incurred with the installation and use of such treatment methods for that system:
(1) Modification of lime softening;
(2) Alum coagulation;
(3) Electrodialysis;
(4) Anion exchange resins;
(5) Well field management;
(6) Alternate source;
(7) Regionalization.
(d) If the Administrator or primary state that issues variances determines that a treatment method identified in § 142.61(c) or other treatment method is technically feasible, economically reasonable, and will achieve fluoride reductions commensurate with the costs incurred with the installation and/or use of such treatment method for the system, the Administrator or primacy state shall require the system to install and/or use that treatment method in connection with a compliance schedule issued under the provisions of section 1415(a)(1)(A) of the Act. The Administrator's or primacy state's determination shall be based upon studies
(a) The Administrator, pursuant to section 1415(a)(1)(A) of the Act hereby identifies the technologies listed in paragraphs (a)(1) through (a)(54) of this section as the best technology, treatment techniques, or other means available for achieving compliance with the maximum contaminant levels for organic chemicals listed in § 141.61 (a) and (c):
(b) The Administrator, pursuant to section 1415(a)(1)(A) of the Act, hereby identifies the following as the best technology, treatment techniques, or other means available for achieving compliance with the maximum contaminant levels for the inorganic chemicals listed in § 141.62:
(c) A State shall require community water systems and non-transient, non-community water systems to install and/or use any treatment method identified in § 142.62 (a) and (b) as a condition for granting a variance except as provided in paragraph (d) of this section. If, after the system's installation of the treatment method, the system cannot meet the MCL, that system shall be eligible for a variance under the provisions of section 1415(a)(1)(A) of the Act.
(d) If a system can demonstrate through comprehensive engineering assessments, which may include pilot plant studies, that the treament methods identified in § 142.62 (a) and (b) would only achieve a
(e) If the State determines that a treatment method identified in paragraph (d) of this section is technically feasible, the Administrator or primacy State may require the system to install and/or use that treatment method in connection with a compliance schedule issued under the provisions of section 1415(a)(1)(A) of the Act. The State's determination shall be based upon studies by the system and other relevant information.
(f) The State may require a public water system to use bottled water, point-of-use devices, point-of-entry devices or other means as a condition of granting a variance or an exemption from the requirements of §§ 141.61 (a) and (c) and 141.62, to avoid an unreasonable risk to health. The State may require a public water system to use bottled water and point-of-use devices or other means,
(g) Public water systems that use bottled water as a condition for receiving a variance or an exemption from the requirements of §§ 141.61 (a) and (c) and 141.62, or an exemption from the requirements of §§ 141.81-141.84 must meet the requirements specified in either paragraph (g)(1) or (g)(2) and paragraph (g)(3) of this section:
(1) The Administrator or primacy State must require and approve a monitoring program for bottled water. The
(2) The public water system must receive a certification from the bottled water company that the bottled water supplied has been taken from an “approved source” as defined in 21 CFR 129.3(a); the bottled water company has conducted monitoring in accordance with 21 CFR 129.80(g) (1) through (3); and the bottled water does not exceed any MCLs or quality limits as set out in 21 CFR 103.35, part 110, and part 129. The public water system shall provide the certification to the State the first quarter after it supplies bottled water and annually thereafter. At the State's option a public water system may satisfy the requirements of this subsection if an approved monitoring program is already in place in another State.
(3) The public water system is fully responsible for the provision of sufficient quantities of bottled water to every person supplied by the public water system via door-to-door bottled water delivery.
(h) Public water systems that use point-of-use or point-of-entry devices as a condition for obtaining a variance or an exemption from NPDWRs must meet the following requirements:
(1) It is the responsibility of the public water system to operate and maintain the point-of-use and/or point-of-entry treatment system.
(2) Before point-of-use or point-of-entry devices are installed, the public water system must obtain the approval of a monitoring plan which ensures that the devices provide health protection equivalent to that provided by central water treatment.
(3) The public water system must apply effective technology under a State-approved plan. The micro-biological safety of the water must be maintained at all times.
(4) The State must require adequate certification of performance, field testing, and, if not included in the certification process, a rigorous engineering design review of the point-of-use and/or point-of-entry devices.
(5) The design and application of the point-of-use and/or point-of-entry devices must consider the potential for increasing concentrations of het-er-o-trophic bacteria in water treated with activated carbon. It may be necessary to use frequent backwashing, post-contactor disinfection, and Heterotrophic Plate Count monitoring to ensure that the microbiological safety of the water is not compromised.
(6) The State must be assured that buildings connected to the system have sufficient point-of-use or point-of-entry devices that are properly installed, maintained, and monitored such that all consumers will be protected.
(7) In requiring the use of a point-of-entry device as a condition for granting an exemption from the treatment requirements for lead and copper under §§ 141.83 or 141.84, the State must be assured that use of the device will not cause increased corrosion of lead and copper bearing materials located between the device and the tap that could increase contaminant levels at the tap.
(a) No variances or exemptions from the maximum contaminant level in § 141.63 of this chapter are permitted.
(b) EPA has stayed the effective date of this section relating to the total coliform MCL of § 141.63(a) of this chapter for systems that demonstrate to the State that the violation of the total coliform MCL is due to a persistent growth of total coliforms in the distribution system rather than fecal or pathogenic contamination, a treatment lapse or deficiency, or a problem
(a) No variances from the requirements in part 141, subpart H are permitted.
(b) No exemptions from the requirements in § 141.72 (a)(3) and (b)(2) to provide disinfection are permitted.
(a)(1) Variances and exemptions from the maximum contaminant levels for combined radium-226 and radium-228, uranium, gross alpha particle activity (excluding Radon and Uranium), and beta particle and photon radioactivity.
(i) The Administrator, pursuant to section 1415(a)(1)(A) of the Act, hereby identifies the following as the best available technology, treatment techniques, or other means available for achieving compliance with the maximum contaminant levels for the radionuclides listed in § 141.66(b), (c), (d), and (e) of this chapter, for the purposes of issuing variances and exemptions, as shown in Table A to this paragraph.
(ii) In addition, the Administrator hereby identifies the following as the best available technology, treatment techniques, or other means available for achieving compliance with the maximum contaminant levels for the radionuclides listed in § 141.66(b), (c), (d), and (e) of this chapter, for the purposes of issuing variances and exemptions to small drinking water systems, defined here as those serving 10,000 persons or fewer, as shown in Table C to this paragraph.
(2) A State shall require community water systems to install and/or use any treatment technology identified in Table A to this section, or in the case of small water systems (those serving 10,000 persons or fewer), Table B and Table C of this section, as a condition for granting a variance except as provided in paragraph (a)(3) of this section. If, after the system's installation of the treatment technology, the system cannot meet the MCL, that system shall be eligible for a variance under the provisions of section 1415(a)(1)(A) of the Act.
(3) If a community water system can demonstrate through comprehensive engineering assessments, which may include pilot plant studies, that the treatment technologies identified in this section would only achieve a de minimus reduction in the contaminant level, the State may issue a schedule of compliance that requires the system being granted the variance to examine other treatment technologies as a condition of obtaining the variance.
(4) If the State determines that a treatment technology identified under paragraph (a)(3) of this section is technically feasible, the Administrator or primacy State may require the system to install and/or use that treatment technology in connection with a compliance schedule issued under the provisions of section 1415(a)(1)(A) of the Act. The State's determination shall be based upon studies by the system and other relevant information.
(5) The State may require a community water system to use bottled water, point-of-use devices, point-of-entry devices or other means as a condition of granting a variance or an exemption from the requirements of § 141.66 of this chapter, to avoid an unreasonable risk to health.
(6) Community water systems that use bottled water as a condition for receiving a variance or an exemption from the requirements of § 141.66 of this chapter must meet the requirements specified in either § 142.62(g)(1) or § 142.62(g)(2) and (g)(3).
(7) Community water systems that use point-of-use or point-of-entry devices as a condition for obtaining a variance or an exemption from the radionuclides NPDWRs must meet the conditions in § 142.62(h)(1) through (h)(6).
At 65 FR 76751, Dec. 7, 2000, § 142.65 was added, effective Dec. 8, 2003.
The Administrator is authorized to treat an Indian tribe as eligible to apply for primary enforcement for the Public Water System Program and the authority to waive the mailing requirements of § 141.155(a) if it meets the following criteria:
(a) The Indian Tribe is recognized by the Secretary of the Interior.
(b) The Indian Tribe has a tribal governing body which is currently “carrying out substantial governmental duties and powers” over a defined area, (
(c) The Indian Tribe demonstrates that the functions to be performed in regulating the public water systems that the applicant intends to regulate are within the area of the Indian Tribal government's jurisdiction.
(d) The Indian Tribe is reasonably expected to be capable, in the Administrator's judgment, of administering (in a manner consistent with the terms and purposes of the Act and all applicable regulations) an effective Public Water System program.
An Indian Tribe may apply to the Administrator for a determination that it meets the criteria of section 1451 of the Act. The application shall be concise and describe how the Indian Tribe will meet each of the requirements of § 142.72. The application shall consist of the following information:
(a) A statement that the Tribe is recognized by the Secretary of the Interior.
(b) A descriptive statement demonstrating that the Tribal governing body is currently carrying out substantial governmental duties and powers over a defined area. The statement should:
(1) Describe the form of the Tribal government;
(2) Describe the types of governmental functions currently performed by the Tribal governing body such as, but not limited to, the exercise of police powers affecting (or relating to) the health, safety, and welfare of the affected population; taxation; and the exercise of the power of eminent domain; and
(3) Identify the sources of the Tribal government's authority to carry out the governmental functions currently being performed.
(c) A map or legal description of the area over which the Indian Tribe asserts jurisdiction; a statement by the Tribal Attorney General (or equivalent official) which describes the basis for the Tribe's jurisdictional assertion (including the nature or subject matter of the asserted jurisdiction); a copy of those documents such as Tribal constitutions, by-laws, charters, executive orders, codes, ordinances, and/or resolutions which the Tribe believes are relevant to its assertions regarding jurisdiction; and a description of the locations of the public water systems the Tribe proposes to regulate.
(d) A narrative statement describing the capability of the Indian Tribe to administer an effective Public Water System program. The narrative statement should include:
(1) A description of the Indian Tribe's previous management experience which may include, the administration of programs and services authorized by the Indian Self-Determination and Education Assistance Act (25 U.S.C. 450
(2) A list of existing environmental or public health programs administered by the Tribal governing body and a copy of related Tribal laws, regulations and policies.
(3) A description of the Indian Tribe's accounting and procurement systems.
(4) A description of the entity (or entities) which exercise the executive, legislative, and judicial functions of the Tribal government.
(5) A description of the existing, or proposed, agency of the Indian Tribe
(6) A description of the technical and administrative capabilities of the staff to administer and manage an effective Public Water System Program or a plan which proposes how the Tribe will acquire additional administrative and/or technical expertise. The plan must address how the Tribe will obtain the funds to acquire the additional administrative and technical expertise.
(e) The Administrator may, in his discretion, request further documentation necessary to support a Tribe's eligibility.
(f) If the Administrator has previously determined that a Tribe has met the prerequisites that make it eligible to assume a role similar to that of a state as provided by statute under the Safe Drinking Water Act, the Clean Water Act, or the Clean Air Act, then that Tribe need provide only that information unique to the Public Water System program (paragraphs (c), (d)(5) and (6) of this section).
(a) The Administrator shall process a completed application of an Indian Tribe in a timely manner. He shall promptly notify the Indian Tribe of receipt of the application.
(b) A tribe that meets the requirements of § 141.72 of this chapter is eligible to apply for development grants and primacy enforcement responsibility for a Public Water System Program and associated funding under section 1443(a) of the Act and for primary enforcement responsibility for public water systems under section 1413 of the Act and for the authority to waive the mailing requirement of § 141.155(a) of this chapter.
(a) The Administrator may initiate a comprehensive review of the decisions made by States with primary enforcement responsibility to determine, in accordance with § 141.71 of this chapter, if public water systems using surface water sources must provide filtration treatment. The Administrator shall complete this review within one year of its initiation and shall schedule subsequent reviews as (s)he deems necessary.
(b) EPA shall publish notice of a proposed review in the
(1) Provide information regarding the location of data and other information pertaining to the review to be conducted and other information including new scientific matter bearing on the application of the criteria for avoiding filtration; and
(2) Advise the public of the opportunity to submit comments.
(c) Upon completion of any such review, the Administrator shall notify each State affected by the results of the review and shall make the results available to the public.
(a) If the Administrator finds through periodic review or other available information that a State (1) has abused its discretion in applying the criteria for avoiding filtration under § 141.71 of this chapter in determining that a system does not have to provide filtration treatment, or (2) has failed to prescribe compliance schedules for those systems which must provide filtration in accordance with section 1412(b)(7)(C)(ii) of the Act, (s)he shall notify the State of these findings. Such notice shall:
(1) Identify each public water system for which the Administrator finds the State has abused its discretion;
(2) Specify the reasons for the finding;
(3) As appropriate, propose that the criteria of § 141.71 of this chapter be applied properly to determine the need for a public water system to provide filtration treatment or propose a revised schedule for compliance by the public water system with the filtration treatment requirements;
(b) The Administrator shall also notify the State that a public hearing is to be held on the provisions of the notice required by paragraph (a) of this section. Such notice shall specify the time and location of the hearing. If, upon notification of a finding by the Administrator that the State has abused its discretion under § 141.71 of this chapter, the State takes corrective action satisfactory to the Administrator, the Administrator may rescind the notice to the State of a public hearing.
(c) The Administrator shall publish notice of the public hearing in the
(d) Hearings convened pursuant to paragraphs (b) and (c) of this section shall be conducted before a hearing officer to be designated by the Administrator. The hearing shall be conducted by the hearing officer in an informal, orderly, and expeditious manner. The hearing officer shall have the authority to call witnesses, receive oral and written testimony, and take such other action as may be necessary to ensure the fair and efficient conduct of the hearing. Following the conclusion of the hearing, the hearing officer may make a recommendation to the Administrator based on the testimony presented at the hearing and shall forward any such recommendation and the record of the hearing to the Administrator.
(e) Within 180 days after the date notice is given pursuant to paragraph (b) of this section, the Administrator shall:
(1) Rescind the notice to the State of a public hearing if the State takes corrective action satisfactory to the Administrator; or
(2) Rescind the finding for which the notice was given and promptly notify the State of such rescission; or
(3) Uphold the finding for which the notice was given. In this event, the Administrator shall revoke the State's decision that filtration was not required or revoke the compliance schedule approved by the State, and promulgate, as appropriate, with any appropriate modifications, a revised filtration decision or compliance schedule and promptly notify the State of such action.
(f) Revocation of a State's filtration decision or compliance schedule and/or promulgation of a revised filtration decision or compliance schedule shall take effect 90 days after the State is notified under paragraph (e)(3) of this section.
Section 1415(e) of the Act authorizes the issuance of variances from the requirement to comply with a maximum contaminant level or treatment technique to systems serving fewer than 10,000 persons. The purpose of this subpart is to provide the procedures and criteria for obtaining these variances. The regulations in this subpart shall take effect on September 14, 1998.
A small system variance under this subpart may only be issued by either:
(a) A State that is exercising primary enforcement responsibility under Subpart B for public water systems under the State's jurisdiction; or
(b) The Administrator, for a public water system in a State which does not
(a) A State exercising primary enforcement responsibility for public water systems (or the Administrator for other systems) may grant a small system variance to public water systems serving 3,300 or fewer persons.
(b) With the approval of the Administrator pursuant to § 142.312, a State exercising primary enforcement responsibility for public water systems may grant a small system variance to public water systems serving more than 3,300 persons but fewer than 10,000 persons.
(c) In determining the number of persons served by the public water system, the State or Administrator must include persons served by consecutive systems. A small system variance granted to a public water system would also apply to any consecutive system served by it.
(a) A small system variance is not available under this subpart for a national primary drinking water regulation for a microbial contaminant (including a bacterium, virus, or other organism) or an indicator or treatment technique for a microbial contaminant.
(b) A small system variance under this subpart is otherwise only available for compliance with a requirement specifying a maximum contaminant level or treatment technique for a contaminant with respect to which;
(1) a national primary drinking water regulation was promulgated on or after January 1, 1986; and
(2) the Administrator has published a small system variance technology pursuant to Section 1412(b)(15) of the Act.
Small system variances are not available for public water systems above the pre-1986 maximum contaminant level even if subsequently revised. If the Agency revises a pre-1986 maximum contaminant level and makes it more stringent, then a variance would be available for that contaminant, but only up to the pre-1986 maximum contaminant level.
No small system variance can be granted by a State until the later of the following:
(a) 90 days after the State proposes to grant the small system variance;
(b) If a State is proposing to grant a small system variance to a public water system serving 3,300 or fewer persons and the Administrator objects to the small system variance, the date on which the State makes the recommended modifications or responds in writing to each objection; or
(c) If a State is proposing to grant a small system variance to a public water system serving a population more than 3,300 and fewer than 10,000 persons, the date the Administrator approves the small system variance. The Administrator must approve or disapprove the variance within 90 days after it is submitted to the Administrator for review.
(a) A public water system requesting a small system variance must provide accurate and correct information to the State or the Administrator to issue a small system variance in accordance with this subpart. A State may assist a public water system in compiling information required for the State or the Administrator to issue a small system variance in accordance with this subpart.
(b) Based upon an application for a small system variance and other information, and before a small system variance may be proposed under this subpart, the State or the Administrator must find and document the following:
(1) The public water system is eligible for a small system variance pursuant to §§ 142.303 (i.e., the system serves a population of fewer than 10,000 persons) and 142.304 (i.e., the contaminant for which the small system variance is
(2) The public water system cannot afford to comply, in accordance with the affordability criteria established by the State (or by the Administrator in States which do not have primary enforcement responsibility), with the national primary drinking water regulation for which a small system variance is sought, including by:
(i) Treatment;
(ii) Alternative sources of water supply;
(iii) Restructuring or consolidation changes, including ownership change and/or physical consolidation with another public water system; or
(iv) Obtaining financial assistance pursuant to Section 1452 of the Act or any other Federal or State program;
(3) The public water system meets the source water quality requirements for installing the small system variance technology developed pursuant to guidance published under section 1412(b)(15) of the Act;
(4) The public water system is financially and technically capable of installing, operating and maintaining the applicable small system variance technology; and
(5) The terms and conditions of the small system variance, as developed through compliance with § 142.307, ensure adequate protection of human health, considering the following:
(i) The quality of the source water for the public water system; and
(ii) Removal efficiencies and expected useful life of the small system variance technology.
(a) A State or the Administrator must clearly specify enforceable terms and conditions of a small system variance.
(b) The terms and conditions of a small system variance issued under this subpart must include, at a minimum, the following requirements:
(1) Proper and effective installation, operation and maintenance of the applicable small system variance technology in accordance with guidance published by the Administrator pursuant to section 1412(b)(15) of the Act, taking into consideration any relevant source water characteristics and any other site-specific conditions that may affect proper and effective operation and maintenance of the technology;
(2) Monitoring requirements, for the contaminant for which a small system variance is sought, as specified in 40 CFR part 141; and
(3) Any other terms or conditions that are necessary to ensure adequate protection of public health, which may include:
(i) Public education requirements; and
(ii) Source water protection requirements.
(c) The State or the Administrator must establish a schedule for the public water system to comply with the terms and conditions of the small system variance which must include, at a minimum, the following requirements:
(1) Increments of progress, such as milestone dates for the public water system to apply for financial assistance and begin capital improvements;
(2) Quarterly reporting to the State or Administrator of the public water system's compliance with the terms and conditions of the small system variance;
(3) Schedule for the State or the Administrator to review the small system variance under paragraph (d) of this section; and
(4) Compliance with the terms and conditions of the small system variance as soon as practicable but not later than 3 years after the date on which the small system variance is granted. The Administrator or State may allow up to 2 additional years if the Administrator or State determines that additional time is necessary for the public water system to:
(i) Complete necessary capital improvements to comply with the small system variance technology, secure an alternative source of water, or restructure or consolidate; or
(ii) Obtain financial assistance provided pursuant to section 1452 of the Act or any other Federal or State program.
(d) The State or the Administrator must review each small system variance granted not less often than every
(a) At least fifteen (15) days before the date of proposal, and at least thirty (30) days prior to a public meeting to discuss the proposed small system variance, the State, Administrator, or public water system as directed by the State or Administrator, must provide notice to all persons served by the public water system. For billed customers, identified in paragraph (a)(1) of this section, this notice must include the information listed in paragraph (c) of this section. For other persons regularly served by the system, identified in paragraph (a)(2) of this section, the notice shall include the information identified in paragraph (d) of this section. Notice must be provided to all persons served by:
(1) Direct mail or other home delivery to billed customers or other service connections, and
(2) Any other method reasonably calculated to notify, in a brief and concise manner, other persons regularly served by the system. Such methods may include publication in a local newspaper, posting in public places or delivery to community organizations.
(b) At the time of proposal, the State must publish a notice in the State equivalent to the
(c) The notice in paragraphs (a)(1) and (b) of this section must include, at a minimum, the following:
(1) Identification of the contaminant[s] for which a small system variance is sought;
(2) A brief statement of the health effects associated with the contaminant[s] for which a small system variance is sought using language in Appendix C of Part 141 Subpart O of this chapter;
(3) The address and telephone number at which interested persons may obtain further information concerning the contaminant and the small system variance;
(4) A brief summary, in easily understandable terms, of the terms and conditions of the small system variance;
(5) A description of the consumer petition process under § 142.310 and information on contacting the EPA Regional Office;
(6) a brief statement announcing the public meeting required under § 142.309(a), including a statement of the purpose of the meeting, information regarding the time and location for the meeting, and the address and telephone number at which interested persons may obtain further information concerning the meeting; and
(7) In communities with a large proportion of non-English-speaking residents, as determined by the primacy agency, information in the appropriate language regarding the content and importance of the notice.
(d) The notice in paragraph (a)(2) of this section must provide sufficient information to alert readers to the proposed variance and direct them where to receive additional information.
(e) At its option, the State or the Administrator may choose to issue separate notices or additional notices related to the proposed small system variance, provided that the requirements in paragraphs (a) through (d) of this section are satisfied.
(f) Prior to promulgating the final variance, the State or the Administrator must respond in writing to all significant public comments received relating to the small system variance. Response to public comment and any
(a) A State or the Administrator must provide for at least one (1) public meeting on the small system variance no later than 15 days after the small system variance is proposed.
(b) At the time of the public meeting, the State or Administrator must prepare and make publicly available, in addition to the information listed in § 142.308(c), either:
(1) The proposed small system variance, if the public meeting occurs after proposal of the small system variance; or
(2) A draft of the proposed small system variance, if the public meeting occurs prior to proposal of the proposed small system variance.
(c) Notice of the public meeting must be provided in the manner required under § 142.308 at least 30 days in advance of the public meeting. This notice must be provided by the State, the Administrator, or the public water system as directed by the State or Administrator.
(a) Any person served by the public water system may petition the Administrator to object to the granting of a small system variance within 30 days after a State proposes to grant a small system variance for a public water system.
(b) The Administrator must respond to a petition filed by any person served by the public water system and determine whether to object to the small system variance under § 142.311, no later than 60 days after the receipt of the petition.
(a) At the time a State proposes to grant a small system variance under this subpart, the State must submit to the Administrator the proposed small system variance and all supporting information, including any written public comments received prior to proposal.
(b) The Administrator may review and object to any proposed small system variance within 90 days of receipt of the proposed small system variance. The Administrator must notify the State in writing of each basis for the objection and propose a modification to the small system variance to resolve the concerns of the Administrator. The State must make the recommended modification, respond in writing to each objection, or withdraw the proposal to grant the small system variance.
(c) If the State issues the small system variance without resolving the concerns of the Administrator, the Administrator may overturn the State decision to grant the variance if the Administrator determines that the State decision does not comply with the Act or this rule.
(a) At the time a State proposes to grant a small system variance to a public water system serving a population of more than 3,300 and fewer than 10,000 persons, the State must submit the proposed small system variance and all supporting information, including public comments received prior to proposal, to the Administrator.
(b) The Administrator must approve or disapprove the small system variance within 90 days of receipt of the proposed small system variance and supporting information. The Administrator must approve the small system variance if it meets each requirement within the Act and this rule.
(c) If the Administrator disapproves the small system variance, the Administrator must notify the State in writing of the reasons for disapproval and the small system variance does not become effective. The State may resubmit the small system variance for review and approval with modifications to address the objections stated by the Administrator.
(a) The Administrator must periodically review each State program under this subpart to determine whether small system variances granted by the State comply with the requirements of the Act, this rule and the affordability criteria developed by the State.
(b) If the Administrator determines that small system variances granted by a State are not in compliance with the requirements of the Act, this rule or the affordability criteria developed by the State, the Administrator shall notify the State in writing of the deficiencies and make public the determinations.
(c) The Administrator's review will be based in part on quarterly reports prepared by the States pursuant to § 142.15(a)(1) relating to violations of increments of progress or other violated terms or conditions of small system variances.
42 U.S.C. 300f
This part establishes National Secondary Drinking Water Regulations pursuant to section 1412 of the Safe Drinking Water Act, as amended (42 U.S.C. 300g-1). These regulations control contaminants in drinking water that primarily affect the aesthetic qualities relating to the public acceptance of drinking water. At considerably higher concentrations of these contaminants, health implications may also exist as well as aesthetic degradation. The regulations are not Federally enforceable but are intended as guidelines for the States.
(a)
(b)
(c)
(d)
(e)
(f)
The secondary maximum contaminant levels for public water systems are as follows:
(a) It is recommended that the parameters in these regulations should be monitored at intervals no less frequent than the monitoring performed for inorganic chemical contaminants listed in the National Interim Primary Drinking Water Regulations as applicable to community water systems. More frequent monitoring would be appropriate for specific parameters such as pH, color, odor or others under certain circumstances as directed by the State.
(b) Measurement of pH, copper and fluoride to determine compliance under § 143.3 may be conducted with one of the methods in § 141.23(k)(1). Analyses of aluminum, chloride, foaming agents, iron, manganese, odor, silver, sulfate, total dissolved solids (TDS) and zinc to determine compliance under § 143.3 may be conducted with the methods in the following table. Criteria for analyzing aluminum, copper, iron, manganese, silver and zinc samples with digestion or directly without digestion, and other analytical test procedures are contained in
Safe Drinking Water Act, 42 U.S.C. 300f
(a)
(b)
(2) In addition to serving as minimum requirements for UIC programs, the regulations in this part constitute a part of the UIC program for States listed in part 147 to be administered directly by EPA.
(c) The information requirements located in the following sections have been cleared by the Office of Management and Budget: Sections 144.11, 144.28(c)(d)(i), 144.31, 14.33, 144.51(j)(m) (n), 144.52(a), 144.54, 144.55, 144.15, 144.23, 144.26, 144.27, 144.28(i)(k), 144.51(o), 146.52. The OMB clearance number is 2040-0042.
(d)
(2) Section 1422 of SDWA requires the Administrator to list in the
(3) Section 1423 of SDWA provides procedures for EPA enforcement of UIC requirements.
(4) Section 1431 authorizes the Administrator to take action to protect the health of persons when a contaminant which is present in or may enter a public water system or underground source of drinking water may present an imminent and substantial en-dan-ger-ment to the health of persons.
(5) Section 1445 of SDWA authorizes the promulgation of regulations for such recordkeeping, reporting, and monitoring requirements “as the Administrator may reasonably require
(6) Section 1450 of SDWA authorizes the Administrator “to prescribe such regulations as are necessary or appropriate to carry out his functions” under SDWA.
(e)
(f)
(i) Subpart A describes general elements of the program, including definitions and classifications.
(ii) Subpart B sets forth the general program requirements, including the performance standards applicable to all injection activities, basic elements that all UIC programs must contain, and provisions for waiving permit of rule requirements under certain circumstances.
(iii) Subpart C sets forth requirements for wells authorized by rule.
(iv) Subpart D sets forth permitting procedures.
(v) Subpart E sets forth specific conditions, or types of conditions, that must at a minimum be included in all permits.
(vi) Subpart F sets forth the financial responsibility requirements for owners and operators of all existing and new Class I hazardous waste injection wells.
(vii) Subpart G of this part sets forth requirements for owners and operators of Class V injection wells.
(2)
(3)
(4)
(g)
(1)
(i) Any injection well located on a drilling platform inside the State's territorial waters.
(ii) Any dug hole or well that is -deeper than its largest surface di-men-sion, where the principal function of the hole is emplacement of fluids.
(iii) Any well used by generators of hazardous waste, or by owners or operators of hazardous waste management facilities, to dispose of fluids containing hazardous waste. This includes the disposal of hazardous waste into what would otherwise be septic systems and cesspools, regardless of their capacity.
(iv) Any septic tank, cesspool, or other well used by a multiple dwelling, community, or Regional system for the injection of wastes.
(2)
(i) Injection wells located on a drilling platform or other site that is beyond the State's territorial waters.
(ii) Individual or single family residential waste disposal systems such as domestic cesspools or septic systems.
(iii) Non-residential cesspools, septic systems or similar waste disposal systems if such systems (A) Are used solely for the disposal of sanitary waste, and (B) have the capacity to serve fewer than 20 persons a day.
(iv) Injection wells used for injection of hydrocarbons which are of pipeline quality and are gases at standard temperature and pressure for the purpose of storage.
(v) Any dug hole, drilled hole, or bored shaft which is not used for the subsurface emplacement of fluids.
(3) The prohibition applicable to Class IV wells under § 144.13 does not apply to injections of hazardous wastes into aquifers or portions thereof which have been exempted pursuant to § 146.04.
(h)
Notwithstanding the requirements of this part or parts 124 and 146 of this chapter, the Administrator may promulgate an alternate UIC Program for Class II wells on any Indian reservation or Indian lands. In promulgating such a program the Administrator shall consider the following factors:
(a) The interest and preferences of the tribal government having responsibility for the given reservation or Indian lands;
(b) The consistency between the alternate program and any program in effect in an adjoining jurisdiction; and
(c) Such other factors as are necessary and appropriate to carry out the Safe Drinking Water Act.
Terms not defined in this section have the meaning given by the appropriate Act. When a defined term appears in a definition, the defined term is sometimes placed within quotation marks as an aid to readers.
(a) All land within the limits of any Indian reservation under the jurisdiction of the United States government, notwithstanding the issuance of any patent, and, including rights-of-way running through the reservation;
(b) All dependent Indian communities within the borders of the United States whether within the original or subsequently acquired territory thereof, and whether within or without the limits of a State; and
(c) All Indian allotments, the Indian titles to which have not been extinguished, including rights-of-way running through the same.
(a)(1) Which supplies any public water system; or
(2) Which contains a sufficient quantity of ground water to supply a public water system; and
(i) Currently supplies drinking water for human consumption; or
(ii) Contains fewer than 10,000 mg/l total dissolved solids; and
(b) Which is not an exempted aquifer.
The following is a list of Federal laws that may apply to the issuance of permits under these rules. When any of these laws is applicable, its procedures must be followed. When the applicable law requires consideration or adoption of particular permit conditions or requires the denial of a permit, those requirements also must be followed.
(a) The
(b)
(c) The
(d)
(e) The
(f)
(a) In accordance with 40 CFR part 2, any information submitted to EPA pursuant to these regulations may be claimed as confidential by the submitter. Any such claim must be asserted at the time of submission in the manner prescribed on the application form or instructions or, in the case of other submissions, by stamping the words “confidential business information” on each page containing such information. If no claim is made at the time of submission, EPA may make the information available to the public without further notice. If a claim is asserted, the information will be treated in accordance with the procedures in 40 CFR part 2 (Public Information).
(b) Claims of confidentiality for the following information will be denied:
(1) The name and address of any permit applicant or permittee;
(2) Information which deals with the existence, absence, or level of contaminants in drinking water.
Injection wells are classified as follows:
(a)
(2) Other industrial and municipal disposal wells which inject fluids beneath the lowermost formation containing, within one quarter mile of the well bore, an underground source of drinking water.
(3) Radioactive waste disposal wells which inject fluids below the lowermost formation containing an underground source of drinking water within one quarter mile of the well bore.
(b)
(1) Which are brought to the surface in connection with natural gas storage operations, or conventional oil or natural gas production and may be commingled with waste waters from gas plants which are an intergral part of production operations, unless those waters are classified as a hazardous waste at the time of injection.
(2) For enhanced recovery of oil or natural gas; and
(3) For storage of hydrocarbons which are liquid at standard temperature and pressure.
(c)
(1) Mining of sulfur by the Frasch process;
(2) In situ production of uranium or other metals; this category includes only in-situ production from ore bodies which have not been conventionally mined. Solution mining of conventional mines such as stopes leaching is included in Class V.
(3) Solution mining of salts or potash.
(d)
(2) Wells used by generators of hazardous waste or of radioactive waste, by owners or operators of hazardous waste management facilities, or by owners or operators of radioactive waste disposal sites to dispose of hazardous waste or radioactive waste above a formation which within one-quarter (
(3) Wells used by generators of hazardous waste or owners or operators of hazardous waste management facilities to dispose of hazardous waste, which cannot be classified under paragraph (a)(1) or (d) (1) and (2) of this section (e.g., wells used to dispose of hazardous waste into or above a formation which contains an aquifer which has been exempted pursuant to § 146.04).
(e) Class V. Injection wells not included in Class I, II, III, or IV. Specific types of Class V injection wells are described in § 144.81.
(a) The Director may identify (by narrative description, illustrations, maps, or other means) and shall protect, except where exempted under paragraph (b) of this section, as an underground source of drinking water, all aquifers or parts of aquifers which meet the definition of an “underground source of drinking water” in § 144.3. Even if an aquifer has not been specifically identified by the Director, it is an underground source of drinking water if it meets the definition in § 144.3.
(b)(1) The Director may identify (by narrative description, illustrations, maps, or other means) and describe in geographic and/or geometric terms (such as vertical and lateral limits and gradient) which are clear and definite, all aquifers or parts thereof which the Director proposes to designate as exempted aquifers using the criteria in 40 CFR 146.04.
(2) No designation of an exempted aquifer submitted as part of a UIC Program shall be final until approved by the Administrator as part of a UIC program.
(3) Subsequent to program approval or promulgation, the Director may, after notice and opportunity for a public hearing, identify additional exempted aquifers. For approved State programs exemption of aquifers identifed (i) under § 146.04(b) shall be treated as a program revision under § 145.32; (ii) under § 146.04(c) shall become final if the State Director submits the exemption in writing to the Administrator and the Administrator has not disapproved the designation within 45 days. Any disapproval by the Administrator shall state the reasons and shall constitute final Agency action for purposes of judicial review.
(c)(1) For Class III wells, the Director shall require an applicant for a permit which necessitates an aquifer exemption under § 146.04(b)(1) to furnish the data necessary to demonstrate that the aquifer is expected to be mineral or hydrocarbon producing. Information contained in the mining plan for the proposed project, such as a map and general description of the mining zone, general information on the mineralogy and geochemistry of the mining zone, analysis of the amenability of the mining zone to the proposed mining method, and a time-table of planned development of the mining zone shall be considered by the Director in addition to the information required by § 144.31(g).
(2) For Class II wells, a demonstration of commercial producibility shall be made as follows:
(i) For a Class II well to be used for enhanced oil recovery processes in a field or project containing aquifers from which hydrocarbons were previously produced, commercial producibility shall be presumed by the Director upon a demonstration by the applicant of historical production having occurred in the project area or field.
(ii) For Class II wells not located in a field or project containing aquifers from which hydrocarbons were previously produced, information such as logs, core data, formation description, formation depth, formation thickness
The Director shall prepare quarterly and annual reports as detailed below. When the State is the permit-issuing authority, the State Director shall submit any reports required under this section to the Regional Administrator. When EPA is the permit-issuing authority, the Regional Administrator shall submit any report required under this section to EPA Headquarters.
(a)
(1)
(i) Provide an alphabetized list of permittees. When two or more permittees have the same name, the lowest permit number shall be entered first.
(ii) For each entry on the list, include the following information in the following order:
(A) Name, location, and permit number of the noncomplying permittees.
(B) A brief description and date of each instance of noncompliance for that permittee. Instances of noncompliance may include one or more the kinds set forth in paragraph (a)(2) of this section. When a permittee has noncompliance of more than one kind, combine the information into a single entry for each such permittee.
(C) The date(s) and a brief description of the action(s) taken by the Director to ensure compliance.
(D) Status of the instance(s) of noncompliance with the date of the review of the status or the date of resolution.
(E) Any details which tend to explain or mitigate the instance(s) of noncompliance.
(2)
(i)
(ii)
(iii)
(iv)
(v)
(A) Whenever the permittee has violated a permit requirement (other than reported under paragraph (a)(2) (i) or (ii) of this section), and has not returned to compliance within 45 days from the date reporting of noncompliance was due under the permit; or
(B) When the Director determines that a pattern of noncompliance exists for a major facility permittee over the most recent four consecutive reporting periods. This pattern includes any violation of the same requirement in two consecutive reporting periods, and any violation of one or more requirements in each of four consecutive reporting periods; or
(C) When the Director determines significant permit noncompliance or other significant event has occurred,
(vi)
(b)
(2)
(i) Submit each year a program report to the Administrator (in a manner and form prescribed by the Administrator) consisting of:
(A) A detailed description of the State's implementation of its program;
(B) Suggested changes, if any to the program description (see § 145.23(f)) which are necessary to reflect more accurately the State's progress in issuing permits;
(C) An updated inventory of active underground injection operations in the State.
(ii) In addition to complying with the requirements of paragraph (b)(2)(i) of this section, the Director shall provide the Administrator, on February 28th and August 31st of each of the first two years of program operation, the information required in 40 CFR 146.15, 146.25, and 146.35.
(c)
(2)
Any underground injection, except into a well authorized by rule or except as authorized by permit issued under the UIC program, is prohibited. The construction of any well required to have a permit is prohibited until the permit has been issued.
(a) No owner or operator shall construct, operate, maintain, convert, plug, abandon, or conduct any other injection activity in a manner that allows the movement of fluid containing any contaminant into underground sources of drinking water, if the presence of that contaminant may cause a violation of any primary drinking water regulation under 40 CFR part 142 or may otherwise adversely affect the health of persons. The applicant for a permit shall have the burden of showing that the requirements of this paragraph are met.
(b) For Class I, II and III wells, if any water quality monitoring of an underground source of drinking water indicates the movement of any contaminant into the underground source of drinking water, except as authorized under part 146, the Director shall prescribe such additional requirements for
(c) For Class V wells, if at any time the Director learns that a Class V well may cause a violation of primary drinking water regulations under 40 CFR part 142, he or she shall:
(1) Require the injector to obtain an individual permit;
(2) Order the injector to take such actions (including, where required, closure of the injection well) as may be necessary to prevent the violation. For EPA administered programs, such orders shall be issued in accordance with the appropriate provisions of the SDWA; or
(3) Take enforcement action.
(d) Whenever the Director learns that a Class V well may be otherwise adversely affecting the health of persons, he or she may prescribe such actions as may be necessary to prevent the adverse effect, including any action authorized under paragraph (c) of this section.
(e) Notwithstanding any other provision of this section, the Director may take emergency action upon receipt of information that a contaminant which is present in or likely to enter a public water system or underground source of drinking water may present an imminent and substantial endangerment to the health of persons. If the Director is an EPA official, he must first determine that the appropriate State and local authorities have not taken appropriate action to protect the health of such persons, before taking emergency action.
(a) The following are prohibited, except as provided in paragraph (c) of this section:
(1) The construction of any Class IV well.
(2) The operation or maintenance of any Class IV well not in operation prior to July 18, 1980.
(3) The operation or maintenance of any Class IV well that was in operation prior to July 18, 1980, after six months following the effective date of a UIC program approved or promulgated for the state.
(4) Any increase in the amount of hazardous waste or change in the type of hazardous waste injected into a Class IV well.
(b) The owner or operator of a Class IV well shall comply with the requirements of § 144.14, and with the requirements of § 144.23 regarding closure of Class IV wells.
(c) Wells used to inject contaminated ground water that has been treated and is being reinjected into the same formation from which it was drawn are not prohibited by this section if such injection is approved by EPA, or a State, pursuant to provisions for cleanup of releases under the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA), 42 U.S.C. 9601-9657, or pursuant to requirements and provisions under the Resource Conservation and Recovery Act (RCRA), 42 U.S.C. 6901 through 6987.
(d)
(1) Wells used to inject hazardous waste into aquifers or portions thereof that have been exempted pursuant to § 146.4, if the exempted aquifer into which waste is injected underlies the lowermost formation containing a USDW. Such wells are Class I wells as specified in § 144.6(a)(1), and the owner or operator must comply with the requirements applicable to Class I wells.
(2) Wells used to inject hazardous waste where no USDW exists within one quarter mile of the well bore in any underground formation, provided that the Director determines that such injection is into a formation sufficiently isolated to ensure that injected
(a)
(b)
(c)
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(d)
(a)
(b) When injection occurs through or above an underground source of drinking water, but the radius of endangering influence when computed under § 146.06(a) is smaller or equal to the radius of the well, the Director may authorize a well or project with less stringent requirements for operation, monitoring, and reporting than required in 40 CFR part 146 or § 144.52 to the extent that the reduction in requirements will not result in an increased risk of movement of fluids into an underground source of drinking water.
(c) When reducing requirements under paragraph (a) or (b) of this section, the Director shall prepare a fact sheet under § 124.8 explaining the reasons for the action.
The Director or the Administrator may require, by written notice on a selective well-by-well basis, an owner or operator of an injection well to establish and maintain records, make reports, conduct monitoring, and provide
(a) An existing Class I, II (except enhanced recovery and hydrocarbon storage) and III injection well is authorized by rule if the owner or operator injects into the existing well within one year after the date at which a UIC program authorized under the SDWA becomes effective for the first time or inventories the well pursuant to the requirements of § 144.26. An owner or operator of a well which is authorized by rule pursuant to this section shall rework, operate, maintain, convert, plug, abandon or inject into the well in compliance with applicable regulations.
(b)
(c)
(1) Upon the effective date of an applicable permit denial;
(2) Upon failure to submit a permit application in a timely manner pursuant to §§ 144.25 or 144.31;
(3) Upon failure to submit inventory information in a timely manner pursuant to § 144.26;
(4) Upon failure to comply with a request for information in a timely manner pursuant to § 144.27;
(5) Upon failure to provide alternative financial assurance pursuant to § 144.28(d)(7);
(6) Forty-eight hours after receipt of a determination by the Director pursuant to § 144.28(f)(3) that the well lacks mechanical integrity, unless the Director requires immediate cessation;
(7) Upon receipt of notification from the Director pursuant to § 144.28(l) that the transferee has not demonstrated financial responsibility pursuant to § 144.28(d);
(8) For Class I and III wells:
(i) In States with approved programs, five years after the effective date of the UIC program unless a timely and complete permit application is pending the Director's decision; or
(ii) In States with programs administered by EPA, one year after the effective date of the UIC program unless a timely and complete permit application is pending the Director's decision; or
(9) For Class II wells (except enhanced recovery and hydrocarbon storage), five years after the effective date of the UIC program unless a timely and complete permit application is pending the Director's decision.
(d)
(e)
(a) An existing Class II enhanced recovery or hydrocarbon storage injection well is authorized by rule for the life of the well or project, if the owner or operator injects into the existing well within one year after the date
(b)
(c)
(1) Upon the effective date of an applicable permit denial;
(2) Upon failure to submit a permit application in a timely manner pursuant to §§ 144.25 or 144.31;
(3) Upon failure to submit inventory information in a timely manner pursuant to § 144.26;
(4) Upon failure to comply with a request for information in a timely manner pursuant to § 144.27;
(5) Upon failure to provide alternative financial assurance pursuant to § 144.28(d)(7);
(6) Forty-eight hours after receipt of a determination by the Director pursuant to § 144.28(f)(3) that the well lacks mechanical integrity, unless the Director requires immediate cessation; or
(7) Upon receipt of notification from the Director pursuant to § 144.28(l) that the transferee has not demonstrated financial responsibility pursuant to § 144.28(d).
(d)
(a) Injection into existing Class IV wells is authorized for up to six months after approval or promulgation of the UIC Program. Such wells are subject to the requirements of §§ 144.13 and 144.14(c).
(b)
(1) Prior to abandoning any Class IV well, the owner or operator shall plug or otherwise close the well in a manner acceptable to the Regional Administrator.
(2) [Reserved]
(3) The owner or operator of a Class IV well must notify the Regional Administrator of intent to abandon the well at least thirty days prior to abandonment.
(c) Notwithstanding the requirements of paragraphs (a) and (b) of this section, injection wells used to inject contaminated ground water that has been treated and is being injected into the same formation from which it was drawn are authorized by rule for the life of the well if such subsurface emplacement of fluids is approved by EPA, or a State, pursuant to provisions for cleanup of releases under the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA), 42 U.S.C. 9601-9675, or pursuant to requirements and provisions under the Resource Conservation and Recovery Act (RCRA), 42 U.S.C. 6901-6992k.
(a) A Class V injection well is authorized by rule, subject to the conditions in § 144.84
(b)
(c)
(1) Upon the effective date of an applicable permit denial;
(2) Upon failure to submit a permit application in a timely manner pursuant to §§ 144.25 or 144.31;
(3) Upon failure to submit inventory information in a timely manner pursuant to § 144.26; or
(4) Upon failure to comply with a request for information in a timely manner pursuant to § 144.27.
(a) The Director may require the owner or operator of any Class I, II, III or V injection well which is authorized by rule under this subpart to apply for and obtain an individual or area UIC permit. Cases where individual or area UIC permits may be required include:
(1) The injection well is not in compliance with any requirement of the rule;
Any underground injection which violates any authorization by rule is subject to appropriate enforcement action.
(2) The injection well is not or no longer is within the category of wells and types of well operations authorized in the rule;
(3) The protection of USDWs requires that the injection operation be regulated by requirements, such as for corrective action, monitoring and reporting, or operation, which are not contained in the rule.
(4) When the injection well is a Class I, II (except existing enhanced recovery and hydrocarbon storage) or III well, in accordance with a schedule established by the Director pursuant to § 144.31(c).
(b) For EPA-administered programs, the Regional Administrator may require an owner or operator of any well which is authorized by rule under this subpart to apply for an individual or area UIC permit under this paragraph only if the owner or operator has been notified in writing that a permit application is required. The owner or operator of a well which is authorized by rule under this subpart is prohibited from injecting into the well upon the effective date of permit denial, or upon failure by the owner or operator to submit an application in a timely manner as specified in the notice. The notice shall include: a brief statement of the reasons for requiring a permit; an application form; a statement setting a time for the owner or operator to file the application; and a statement of the consequences of denial or issuance of the permit, or failure to submit an application, as described in this paragraph.
(c) An owner or operator of a well authorized by rule may request to be excluded from the coverage of this subpart by applying for an individual or area UIC permit. The owner or operator shall submit an application under § 144.31 with reasons supporting the request, to the Director. The Director may grant any such requests.
The owner or operator of an injection well which is authorized by rule under this subpart shall submit inventory information to the Director. Such an owner or operator is prohibited from injecting into the well upon failure to submit inventory information for the well within the time frame specified in paragraph (d) of this section.
(a)
(1) Facility name and location;
(2) Name and address of legal contact;
(3) Ownership of facility;
(4) Nature and type of injection wells; and
(5) Operating status of injection wells.
This information is requested on national form “Inventory of Injection Wells,” OMB No. 158-R0170.
(b)
(1) This section applies to the following wells:
(i) Class II enhanced recovery wells;
(ii) Class IV wells;
(iii) The following Class V wells:
(A) Sand or other backfill wells [§ 146.5(e)(8)];
(B) Radioactive waste disposal wells that are not Class I wells (40 CFR 146.5 (e)(11))
(C) Geothermal energy recovery wells [§ 146.5(e)(12)];
(D) Brine return flow wells [§ 146.5(e)(14)];
(E) Wells used in experimental technologies [§ 146.5(e)(15)];
(F) Municipal and industrial disposal wells other than Class I; and
(G) Any other Class V wells at the discretion of the Regional Administrator.
(2) The owner or operator of a well listed in paragraph (b)(1) shall provide a listing of all wells owned or operated setting forth the following information for each well. (A single description of wells at a single facility with substantially the same characteristics is acceptable).
(i) For Class II only, the field name(s);
(ii) Location of each well or project given by Township, Range, Section, and Quarter-Section, or by latitude and longitude to the nearest second, according to the conventional practice in the State;
(iii) Date of completion of each well;
(iv) Identification and depth of the formation(s) into which each well is injecting;
(v) Total depth of each well;
(vi) Casing and cementing record, tubing size, and depth of packer;
(vii) Nature of the injected fluids;
(viii) Average and maximum injection pressure at the wellhead;
(ix) Average and maximum injection rate; and
(x) Date of the last mechanical integrity test, if any.
(c)
(d)
(2) For EPA administered programs the information need not be submitted if a complete permit application is submitted within one year of the effective data of the UIC program. The owner or operator of Class IV well shall submit inventory information no later than 60 days after the effective date of the program.
(a) For EPA administered programs only, in addition to the inventory requirements of § 144.26, the Regional Administrator may require the owner or operator of any well authorized by rule under this subpart to submit information as deemed necessary by the Regional Administrator to determine whether a well may be endangering an underground source of drinking water in violation of § 144.12 of this part.
(b) Such information requirements may include, but are not limited to:
(1) Performance of ground-water monitoring and the periodic submission of reports of such monitoring;
(2) An analysis of injected fluids, including periodic submission of such analyses; and
(3) A description of the geologic strata through and into which injection is taking place.
(c) Any request for information under this section shall be made in writing, and include a brief statement of the reasons for requiring the information. An owner or operator shall submit the information within the time period(s) provided in the notice.
(d) An owner or operator of an injection well authorized by rule under this subpart is prohibited from injecting into the well upon failure of the owner or operator to comply with a request
The following requirements apply to the owner or operator of a Class I, II or III well authorized by rule under this subpart, as provided by §§ 144.21(e) and 144.22(d).
(a) The owner or operator shall comply with all applicable requirements of this subpart and subpart B of this part. Any noncompliance with these requirements constitutes a violation of the Safe Drinking Water Act and is grounds for enforcement action, except that the owner or operator need not comply with these requirements to the extent and for the duration such noncompliance is authorized by an emergency permit under § 144.34.
(b)
(1) Any monitoring or other information which indicates that any contaminant may cause an endangerment to a USDW; or
(2) Any noncompliance or malfunction of the injection system which may cause fluid migration into or between USDWs.
(c)
(2) For EPA administered programs:
(i) The owner or operator shall submit the plan, on a form provided by the Regional Administrator, no later than one year after the effective date of the UIC program in the state.
(ii) The owner or operator shall submit any proposed significant revision to the method of plugging reflected in the plan no later than the notice of plugging required by § 144.28(j)(2) (i.e., 45 days prior to plugging unless shorter notice is approved).
(iii) The plan shall include the following information:
(A) The nature and quantity and material to be used in plugging;
(B) The location and extent (by depth) of the plugs;
(C) Any proposed test or measurement to be made;
(D) The amount, size, and location (by depth) of casing to be left in the well;
(E) The method and location where casing is to be parted; and
(F) [Reserved]
(G) The estimated cost of plugging the well.
(iv) After a cessation of operations of two years the owner or operator shall plug and abandon the well in accordance with the plan unless he:
(A) Provides notice to the Regional Administrator;
(B) Describe actions or procedures, satisfactory to the Regional Administrator, that the owner or operator will take to ensure that the well will not endanger USDWs during the period of temporary abandonment. These actions and procedures shall include compliance with the technical requirements applicable to active injection wells unless waived by the Regional Administrator.
(v) The owner or operator of any well that has been temporarily abandoned [ceased operations for more than two
(d)
(i) The well has been plugged and abandoned in accordance with an approved plugging and abandonment plan pursuant to §§ 144.28(c) and 146.10 and submission of a plugging and abandonment report has been made pursuant to § 144.28(k);
(ii) The well has been converted in compliance with the requirements of § 144.28(j); or
(iii) For EPA-administered programs, the transferor has received notice from the Director that the transferee has demonstrated financial responsibility for the well. The owner or operator shall show evidence of such financial responsibility to the Director by the submission of a surety bond, or other adequate assurance, such as a financial statement.
(2) For EPA-administered programs, the owner or operator shall submit such evidence no later than one year after the effective date of the UIC program in the State. Where the ownership or operational control of the well is transferred more than one year after the effective date of the UIC program, the transferee shall submit such evidence no later than the date specified in the notice required pursuant to § 144.28(l)(2).
(3) For EPA administered programs the Regional Administrator may require the owner or operator to submit a revised demonstration of financial responsibility if the Regional Administrator has reason to believe that the original demonstration is no longer adequate to cover the cost of closing, plugging and abandoning the well.
(4) For EPA administered programs the owner or operator of a well injecting hazardous waste must comply with the financial responsibility requirements of subpart F of this part.
(5) For EPA-administered programs, an owner or operator must notify the Regional Administrator by certified mail of the commencement of any voluntary or involuntary proceeding under Title 11 (Bankruptcy) of the United States Code which names the owner or operator as debtor, within 10 business days after the commencement of the proceeding. Any party acting as guarantor for the owner or operator for the purpose of financial responsibility must so notify the Regional Administrator, if the guarantor is named as debtor in any such proceeding.
(6) In the event of commencement of a proceeding specified in paragraph (d)(5) of this section, an owner or operator who has furnished a financial statement for the purpose of demonstrating financial responsibility under this section shall be deemed to be in violation of this paragraph until an alternative financial assurance demonstration acceptable to the Regional Administrator is provided either by the owner or operator or by its trustee in bankruptcy, receiver, or other authorized party. All parties shall be prohibited from injecting into the well until such alternate financial assurance is provided.
(e)
(1) The owner or operator shall case and cement the well to prevent movement of fluids into or between underground sources of drinking water. In determining and specifying casing and cementing requirements, the following factors shall be considered:
(i) Depth to the injection zone;
(ii) Depth to the bottom of all USDWs; and
(iii) Estimated maximum and average injection pressures.
(2) In addition, in determining and specifying casing and cementing requirements the Director may consider information on:
(i) Nature of formation fluids;
(ii) Lithology of injection and confining zones;
(iii) External pressure, internal pressure, and axial loading;
(iv) Hole size;
(v) Size and grade of all casing strings; and
(vi) Class of cement.
(3) The requirements in paragraphs (e) (1) and (2) of this section need not apply if:
(i) Regulatory controls for casing and cementing existed at the time of drilling of the well and the well is in compliance with those controls; and
(ii) Well injection will not result in the movement of fluids into an underground source of drinking water so as to create a significant risk to the health of persons.
(4) When a State did not have regulatory controls for casing and cementing prior to the time of the submission of the State program to the Administrator, the Director need not apply the casing and cementing requirements in paragraph (e)(1) of this section if he submits as a part of his application for primacy, an appropriate plan for casing and cementing of existing, newly converted, and newly drilled wells in existing fields, and the Administrator approves the plan.
(f)
(2) The owner or operator of a Class I, II or III injection well authorized by rule shall establish and maintain mechanical integrity as defined in § 146.8 of this chapter until the well is properly plugged in accordance with an approved plugging and abandonment plan pursuant to §§ 144.28(c) and 146.10, and a plugging and abandonment report pursuant to § 144.28(k) is submitted, or until the well is converted in compliance with § 144.28(j). For EPA-administered programs, the Regional Administrator may require by written notice that the owner or operator comply with a schedule describing when mechanical integrity demonstrations shall be made.
(3) When the Director determines that a Class I (non-hazardous), II or III injection well lacks mechanical integrity pursuant to § 146.8 of this chapter, the Director shall give written notice of his determination to the owner or operator. Unless the Director requires immediate cessation, the owner or operator shall cease injection into the well within 48 hours of receipt of the Director's determination. The Director may allow plugging of the well in accordance with the requirements of § 146.10 of this chapter, or require the owner or operator to perform such additional construction, operation, monitoring, reporting and corrective action as is necessary to prevent the movement of fluid into or between USDWs caused by the lack of mechanical integrity. The owner or operator may resume injection upon receipt of written notification from the Director that the owner or operator has demonstrated mechanical integrity pursuant to § 146.8 of this chapter.
(4) The Director may allow the owner or operator of a well which lacks mechanical integrity pursuant to § 146.8(a)(1) of this chapter to continue or resume injection if the owner or operator has made a satisfactory demonstration that there is no movement of fluid into or between USDWs.
(5) For Class I wells, unless an alternative to a packer has been approved under § 146.12(c) of this chapter, the owner or operator shall fill the annulus between the tubing and the long string of casings with a fluid approved by the Director and maintain a pressure, also approved by the Director, on the annulus. For EPA administered programs, the owner or operator of a Class I well completed with tubing and packer shall fill the annulus between tubing and casing with a noncorrosive fluid and maintain a positive pressure on the annulus. For other Class I wells, the owner or operator shall insure that the alternative completion method will reliably provide a comparable level of protection to underground sources of drinking water.
(6) Injection pressure.
(i) For Class I and III wells:
(A) Except during stimulation, the owner or operator shall not exceed an injection pressure at the wellhead which shall be calculated so as to assure that the pressure during injection does not initiate new fractures or propagate existing fractures in the injection zone; and
(B) The owner or operator shall not inject at a pressure which will initiate fractures in the confining zone or -cause
(ii) For Class II wells:
(A) The owner or operator shall not exceed a maximum injection pressure at the wellhead which shall be calculated so as to assure that the pressure during injection does not initiate new fractures of propagate existing fractures in the confining zone adjacent to the USDWs; and
(B) The owner or operator shall not inject at a pressure which will cause the movement of injection or formation fluids into an underground source of drinking water.
(g)
(1) The owner or operator of a Class I well shall:
(i) Analyze the nature of the injected fluids with sufficient frequency to yield data representative of their characteristics;
(ii) Install and use continuous recording devices to monitor injection pressure, flow rate and volume, and the pressure on the annulus between the tubing and the long string of casing;
(iii) Install and use monitoring wells within the area of review if required by the Director, to monitor any migration of fluids into and pressure in the underground sources of drinking water. The type, number and location of the wells, the parameters to be measured, and the frequency of monitoring must be approved by the Director.
(2) For Class II wells:
(i) The owner or operator shall monitor the nature of the injected fluids with sufficient frequency to yield data representative of their characteristics. For EPA administered programs, this frequency shall be at least once within the first year of the authorization and thereafter when changes are made to the fluid.
(ii) The owner or operator shall observe the injection pressure, flow rate, and cumulative volume at least with the following frequencies:
(A) Weekly for produced fluid disposal operations;
(B) Monthly for enhanced recovery operations;
(C) Daily during the injection of liquid hydrocarbons and injection for withdrawal of stored hydrocarbons; and
(D) Daily during the injection phase of cyclic steam operations.
(iii) The owner or operator shall record one observation of injection pressure, flow rate and cumulative volume at reasonable intervals no greater than thirty days.
(iv) For enhanced recovery and hydrocarbon storage wells:
(A) The owner or operator shall demonstrate mechanical integrity pursuant to § 146.8 of this chapter at least once every five years during the life of the injection well.
(B) For EPA administered programs, the Regional Administrator by written notice may require the owner or operator to comply with a schedule describing when such demonstrations shall be made.
(C) For EPA administered programs, the owner or operator of any well required to be tested for mechanical integrity shall notify the Regional Administrator at least 30 days prior to any required mechanical integrity test. The Regional Administrator may allow a shorter notification period if it would be sufficient to enable EPA to witness the mechanical integrity testing if it chose. Notification may be in the form of a yearly or quarterly schedule of planned mechanical integrity tests, or it may be on an individual basis.
(v) The owner or operator of a hydrocarbon storage or enhanced recovery wells may monitor them by manifold monitoring on a field or project basis rather than on an individual well basis if such facilities consist of more than one injection well, operate with a common manifold, and provided the owner or operator demonstrates to the Director that manifold monitoring is comparable to individual well monitoring.
(3)(i) For Class III wells the owner or operator shall provide to the Director a
(ii) Monitor injection pressure and either flow rate or volume semi-monthly, or meter and record daily injected and produced fluid volumes as appropriate;
(iii) Monitor the fluid level in the injection zone semi-monthly, where appropriate;
(iv) All Class III wells may be monitored on a field or project basis rather than an individual well basis by manifold monitoring. Manifold monitoring may be used in cases of facilities consisting of more than one injection well, operating with a common manifold. Separate monitoring systems for each well are not required provided the owner or operator demonstrates to the Director that manifold monitoring is comparable to individual well monitoring.
(h)
(1) For Class I wells, quarterly reports on:
(i) The physical, chemical, and other relevant characteristics of the injection fluids;
(ii) Monthly average, maximum, and minimum values for injection pressure, flow rate and volume, and annular pressure;
(iii) The results from ground-water monitoring wells prescribed in paragraph (g)(1)(iii) of this section;
(iv) The results of any test of the injection well conducted by the owner or operator during the reported quarter if required by the Director; and
(v) Any well work over performed during the reported quarter.
(2) For Class II wells:
(i) An annual report to the Director summarizing the results of all monitoring, as required in paragraph (g)(2) of this section. Such summary shall include monthly records of injected fluids, and any major changes in characteristics or sources of injected fluids. Previously submitted information may be included by reference.
(ii) The owner or operator of hydrocarbon storage and enhanced recovery projects may report on a field or project basis rather than on an individual well basis where manifold monitoring is used.
(3) For Class III wells:
(i) Quarterly reporting on all monitoring, as required in paragraph (g)(3) of this section;
(ii) Quarterly reporting of the results of any periodic tests required by the Director that are performed during the reported quarter;
(iii) Monitoring may be reported on a project or field basis rather than an individual well basis where manifold monitoring is used.
(i)
(1) Calibration and maintenance records and all original strip chart recordings for continuous monitoring instrumentation, and copies of all reports required by this section, for a period of at least three years from the date of the sample, measurement, or report. This period may be extended by request of the Director at any time; and
(2) The nature and composition of all injected fluids until three years after the completion of any plugging and abandonment procedures specified under § 144.52(l)(6). The Director may require the owner or operator to deliver the records to the Director at the conclusion of the retention period. For EPA administered programs, the owner or operator shall continue to retain the records after the three year retention period unless he delivers the records to the Regional Administrator or obtains written approval from the Regional Administrator to discard the records.
(j)
(2) For EPA-administered programs, the owner or operator shall notify the Regional Administrator at least 45 days before plugging and abandonment. The Regional Administrator, at his discretion, may allow a shorter notice period.
(k)
(1) A statement that the well was plugged in accordance with the plan previously submitted to the Regional Administrator; or
(2) Where actual plugging differed from the plan previously submitted, an updated version of the plan, on the form supplied by the Regional Administrator, specifying the different procedures used.
(l)
(1) The transferor of a Class I, II or III well authorized by rule shall notify the Regional Administrator of a transfer of ownership or operational control of the well at least 30 days in advance of the proposed transfer.
(2) The notice shall include a written agreement between the transferor and the transferee containing a specific date for transfer of ownership or operational control of the well; and a specific date when the financial responsibility demonstration of § 144.28(d) will be met by the transferee.
(3) The transferee is authorized to inject unless he receives notification from the Director that the transferee has not demonstrated financial responsibility pursuant to § 144.28(d).
(m)
(a)
(b)
(c)
(1) For existing wells, as expeditiously as practicable and in accordance with the schedule in any program description under § 145.23(f) or (for EPA administered programs) on a schedule established by the Regional Administrator, but no later than 4 years from
(2) For new injection wells, except new wells in projects authorized under § 144.21(d) or authorized by an existing area permit under § 144.33(c), a reasonable time before construction is expected to begin.
(d)
(e)
(1) The activities conducted by the applicant which require it to obtain permits under RCRA, UIC, the National Pollution Discharge Elimination system (NPDES) program under the Clean Water Act, or the Prevention of Significant Deterioration (PSD) program under the Clean Air Act.
(2) Name, mailing address, and location of the facility for which the application is submitted.
(3) Up to four SIC codes which best reflect the principal products or services provided by the facility.
(4) The operator's name, address, telephone number, ownership status, and status as Federal, State, private, public, or other entity.
(5) Whether the facility is located on Indian lands.
(6) A listing of all permits or construction approvals received or applied for under any of the following programs:
(i) Hazardous Waste Management program under RCRA.
(ii) UIC program under SDWA.
(iii) NPDES program under CWA.
(iv) Prevention of Significant Deterioration (PSD) program under the Clean Air Act.
(v) Nonattainment program under the Clean Air Act.
(vi) National Emission Standards for Hazardous Pollutants (NESHAPS) preconstruction approval under the Clean Air Act.
(vii) Ocean dumping permits under the Marine Protection Research and Sanctuaries Act.
(viii) Dredge and fill permits under section 404 of CWA.
(ix) Other relevant environmental permits, including State permits.
(7) A topographic map (or other map if a topographic map is unavailable) extending one mile beyond the property boundaries of the source depicting the facility and each of its intake and discharge structures; each of its hazardous waste treatment, storage, or disposal facilities; each well where fluids from the facility are injected underground; and those wells, springs, and other surface water bodies, and drinking water wells listed in public records or otherwise known to the applicant within a quarter mile of the facility property boundary.
(8) A brief description of the nature of the business.
(9) For EPA-administered programs, the applicant shall identify and submit on a list with the permit application the names and addresses of all owners of record of land within one-quarter mile of the facility boundary. This -requirement may be waived by the -Regional Administrator where the -site is located in a populous area and -the Regional Administrator determines -that the requirement would be impracticable.
(10) A plugging and abandonment plan that meets the requirements of § 146.10 of this chapter and is acceptable to the Director.
(f)
(g)
(i) Dates well was operated.
(ii) Specification of all wastes which have been injected in the well, if available.
(2) The owner or operator of any facility containing one or more active hazardous waste injection wells must submit all available information pertaining to any release of hazardous waste or constituents from any active hazardous waste injection well at the facility.
(3) The owner or operator of any facility containing one or more active Class I hazardous waste injection wells must conduct such preliminary site investigations as are necessary to determine whether a release is occurring, has occurred, or is likely to have occurred.
(a)
(1)
EPA does not require specific assignments or delegations of authority to responsible corporate officers identified in § 144.32(a)(1)(i). The Agency will presume that these responsible corporate officers have the requisite authority to sign permit applications unless the corporation has notified the Director to the contrary. Corporate procedures governing authority to sign permit applications may provide for assignment or delegation to applicable corporate positions under § 144.32(a)(1)(ii) rather than to specific individuals.
(2)
(3)
(b)
(1) The authorization is made in writing by a person described in paragraph (a) of this section;
(2) The authorization specifies either an individual or a position having responsibility for the overall operation of the regulated facility or activity, such as the position of plant manager, operator of a well or a well field, superintendent, or position of equivalent responsibility. (A duly authorized representative may thus be either a named individual or any individual occupying a named position); and
(3) The written authorization is submitted to the Director.
(c)
(d)
I certify under penalty of law that this document and all attachments were prepared under my direction or supervision in accordance with a system designed to assure that qualified personnel properly gather and evaluate the information submitted. Based on my inquiry of the person or persons who manage the system, or those persons directly responsible for gathering the information, the information submitted is, to the best of my knowledge and belief, true, accurate, and complete. I am aware that there are significant penalties for submitting false information, including the possibility of fine and imprisonment for knowing violations.
(a) The Director may issue a permit on an area basis, rather than for each well individually, provided that the permit is for injection wells:
(1) Described and identified by location in permit application(s) if they are existing wells, except that the Director may accept a single description of wells with substantially the same characteristics;
(2) Within the same well field, facility site, reservoir, project, or similar unit in the same State;
(3) Operated by a single owner or operator; and
(4) Used to inject other than hazardous waste.
(b) Area permits shall specify:
(1) The area within which underground injections are authorized, and
(2) The requirements for construction, monitoring, reporting, operation, and abandonment, for all wells authorized by the permit.
(c) The area permit may authorize the permittee to construct and operate, convert, or plug and abandon wells within the permit area provided:
(1) The permittee notifies the Director at such time as the permit requires;
(2) The additional well satisfies the criteria in paragraph (a) of this section and meets the requirements specified in the permit under paragraph (b) of this section; and
(3) The cumulative effects of drilling and operation of additional injection wells are considered by the Director during evaluation of the area permit application and are acceptable to the Director.
(d) If the Director determines that any well constructed pursuant to paragraph (c) of this section does not satisfy any of the requirements of paragraphs (c) (1) and (2) of this section the Director may modify the permit under § 144.39, terminate under § 144.40, or take enforcement action. If the Director determines that cumulative effects are unacceptable, the permit may be modified under § 144.39.
(a)
(1) An imminent and substantial endangerment to the health of persons will result unless a temporary emergency permit is granted; or
(2) A substantial and irretrievable loss of oil or gas resources will occur unless a temporary emergency permit is granted to a Class II well; and
(i) Timely application for a permit could not practicably have been made; and
(ii) The injection will not result in the movement of fluids into underground sources of drinking water; or
(3) A substantial delay in production of oil or gas resources will occur unless a temporary emergency permit is granted to a new Class II well and the temporary authorization will not result in the movement of fluids into an underground source of drinking water.
(b)
(2) Any temporary permit under paragraph (a)(2) of this section shall be for no longer than 90 days, except that
(3) Any temporary permit under paragraph (a)(3) of this section shall be issued only after a complete permit application has been submitted and shall be effective until final action on the application.
(4) Notice of any temporary permit under this paragraph shall be published in accordance with § 124.11 within 10 days of the issuance of the permit.
(5) The temporary permit under this section may be either oral or written. If oral, it must be followed within 5 calendar days by a written temporary emergency permit.
(6) The Director shall condition the temporary permit in any manner he or she determines is necessary to ensure that the injection will not result in the movement of fluids into an underground source of drinking water.
(a) Except for Class II and III wells, compliance with a permit during its term constitutes compliance, for purposes of enforcement, with Part C of the SDWA. However, a permit may be modified, revoked and reissued, or terminated during its term for cause as set forth in §§ 144.39 and 144.40.
(b) The issuance of a permit does not convey any property rights of any sort, or any exclusive privilege.
(c) The issuance of a permit does not authorize any injury to persons or property or invasion of other private rights, or any infringement of State or local law or regulations.
(a) Permits for Class I and Class V wells shall be effective for a fixed term not to exceed 10 years. UIC permits for Class II and III wells shall be issued for a period up to the operating life of the facility. The Director shall review each issued Class II or III well UIC permit at least once every 5 years to determine whether it should be modified, revoked and reissued, terminated, or a minor modification made as provided in §§ 144.39, 144.40, and 144.41.
(b) Except as provided in § 144.37, the term of a permit shall not be extended by modification beyond the maximum duration specified in this section.
(c) The Director may issue any permit for a duration that is less than the full allowable term under this section.
(a)
(1) The permittee has submitted a timely application which is a complete application for a new permit; and
(2) The Regional Administrator, through no fault of the permittee does not issue a new permit with an effective date on or before the expiration date of the previous permit (for example, when issuance is impracticable due to time or resource constraints).
(b)
(c)
(1) Initiate enforcement action based upon the permit which has been continued;
(2) Issue a notice of intent to deny the new permit. If the permit is denied, the owner or operator would then be required to cease the activities authorized by the continued permit or be subject to enforcement action for operating without a permit;
(3) Issue a new permit under part 124 with appropriate conditions; or
(4) Take other actions authorized by these regulations.
(d)
(a)
(b)
(1) The current permittee notifies the Director at least 30 days in advance of the proposed transfer date referred to in paragraph (b)(2) of this section;
(2) The notice includes a written agreement between the existing and new permittees containing a specific date for transfer or permit responsibility, coverage, and liability between them, and the notice demonstrates that the financial responsibility requirements of § 144.52(a)(7) will be met by the new permittee; and
(3) The Director does not notify the existing permittee and the proposed new permittee of his or her intent to modify or revoke and reissue the permit. A modification under this paragraph may also be a minor modification under § 144.41. If this notice is not received, the transfer is effective on the date specified in the agreement mentioned in paragraph (b)(2) of this section.
When the Director receives any information (for example, inspects the facility, receives information submitted by the permittee as required in the permit (see § 144.51 of this chapter), receives a request for modification or revocation and reissuance under § 124.5, or conducts a review of the permit file) he or she may determine whether or not one or more of the causes listed in paragraphs (a) and (b) of this section for modification or revocation and reissuance or both exist. If cause exists, the Director may modify or revoke and reissue the permit accordingly, subject to the limitations of paragraph (c) of this section, and may request an updated application if necessary. When a permit is modified, only the conditions subject to modification are reopened. If a permit is revoked and reissued, the entire permit is reopened and subject to revision and the permit is reissued for a new term. See § 124.5(c)(2) of this chapter. If cause does not exist under this section or § 144.41 of this chapter, the Director shall not modify or revoke and reissue the permit. If a permit modification satisfies the criteria in § 144.41 for “minor modifications” the permit may be modified without a draft permit or public review. Otherwise, a draft permit must be prepared and other procedures in part 124 must be followed.
(a)
(1)
(2)
(3)
(i) For promulgation of amended standards or regulations, when:
(A) The permit condition requested to be modified was based on a promulgated part 146 regulation; and
(B) EPA has revised, withdrawn, or modified that portion of the regulation on which the permit condition was based, and
(C) A permittee requests modification in accordance with § 124.5 within ninety (90) days after
(ii) For judicial decisions, a court of competent jurisdiction has remanded and stayed EPA promulgated regulations if the remand and stay concern that portion of the regulations on which the permit condition was based and a request is filed by the permittee in accordance with § 124.5 within ninety (90) days of judicial remand.
(4)
(b)
(1) Cause exists for termination under § 144.40, and the Director determines that modification or revocation and reissuance is appropriate.
(2) The Director has received notification (as required in the permit, see § 144.41(d)) of a proposed transfer of the permit. A permit also may be modified to reflect a transfer after the effective date of an automatic transfer (§ 144.38(b)) but will not be revoked and reissued after the effective date of the transfer except upon the request of the new permittee.
(3) A determination that the waste being injected is a hazardous waste as defined in § 261.3 either because the definition has been revised, or because a previous determination has been changed.
(c)
(a) The Director may terminate a permit during its term, or deny a permit renewal application for the following causes:
(1) Noncompliance by the permittee with any condition of the permit;
(2) The permittee's failure in the application or during the permit issuance process to disclose fully all relevant facts, or the permittee's misrepresentation of any relevant facts at any time; or
(3) A determination that the permitted activity endangers human health or the environment and can only be regulated to acceptable levels by permit modification or termination;
(b) The Director shall follow the -applicable procedures in part 124 in -terminating any permit under this section.
Upon the consent of the permittee, the Director may modify a permit to make the corrections or allowances for changes in the permitted activity listed in this section, without following the procedures of part 124. Any permit modification not processed as a minor modification under this section must be made for cause and with part 124 draft permit and public notice as required in § 144.39. Minor modifications may only:
(a) Correct typographical errors;
(b) Require more frequent monitoring or reporting by the permittee;
(c) Change an interim compliance date in a schedule of compliance, provided the new date is not more than 120 days after the date specified in the existing permit and does not interfere with attainment of the final compliance date requirement; or
(d) Allow for a change in ownership or operational control of a facility where the Director determines that no other change in the permit is necessary, provided that a written agreement containing a specific date for transfer of permit responsibility, coverage, and liability between the current and new permittees has been submitted to the Director.
(e) Change quantities or types of fluids injected which are within the capacity of the facility as permitted and, in the judgment of the Director, would not interfere with the operation of the facility or its ability to meet conditions described in the permit and would not change its classification.
(f) Change construction requirements approved by the Director pursuant to § 144.52(a)(1) (establishing UIC permit conditions), provided that any such alteration shall comply with the requirements of this part and part 146.
(g) Amend a plugging and abandonment plan which has been updated under § 144.52(a)(6).
The following conditions apply to all UIC permits. All conditions applicable to all permits shall be incorporated into the permits either expressly or -by reference. If incorporated by ref-er-ence, a specific citation to these reg-u-la-tions (or the cor-re-spond-ing approved State reg-u-la-tions) must be given in the permit.
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(1) Enter upon the permittee's premises where a regulated facility or activity is located or conducted, or where records must be kept under the conditions of this permit;
(2) Have access to and copy, at reasonable times, any records that must be kept under the conditions of this permit;
(3) Inspect at reasonable times any facilities, equipment (including monitoring and control equipment), practices, or operations regulated or required under this permit; and
(4) Sample or monitor at reasonable times, for the purposes of assuring permit compliance or as otherwise authorized by the SDWA, any substances or parameters at any location.
(j)
(2) The permittee shall retain records of all monitoring information, including the following:
(i) Calibration and maintenance records and all original strip chart recordings for continuous monitoring instrumentation, copies of all reports required by this permit, and records of all data used to complete the application for this permit, for a period of at least 3 years from the date of the sample, measurement, report, or application. This period may be extended by request of the Director at any time; and
(ii) The nature and composition of all injected fluids until three years after the completion of any plugging and abandonment procedures specified under § 144.52(a)(6), or under part 146 subpart G as appropriate. The Director may require the owner or operator to deliver the records to the Director at the conclusion of the retention period. For EPA administered programs, the owner or operator shall continue to retain the records after the three year retention period unless he delivers the records to the Regional Administrator or obtains written approval from the Regional Administrator to discard the records.
(3) Records of monitoring information shall include:
(i) The date, exact place, and time of sampling or measurements;
(ii) The individual(s) who performed the sampling or measurements;
(iii) The date(s) analyses were performed;
(iv) The individual(s) who performed the analyses;
(v) The analytical techniques or methods used; and
(vi) The results of such analyses.
(k)
(l)
(2)
(3)
(4)
(5)
(6)
(i) Any monitoring or other information which indicates that any contaminant may cause an endangerment to a USDW; or
(ii) Any noncompliance with a permit condition or malfunction of the injection system which may cause fluid migration into or between USDWs.
(7)
(8)
(m)
(1) The permittee has submitted notice of completion of construction to the Director; and
(2)(i) The Director has inspected or otherwise reviewed the new injection well and finds it is in compliance with the conditions of the permit; or
(ii) The permittee has not received notice form the Director of his or her intent to inspect or otherwise review the new injection well within 13 days of the date of the notice in paragraph (m)(1) of this section, in which case prior inspection or review is waived and the permittee may commence injection. The Director shall include in his notice a reasonable time period in which he shall inspect the well.
(n) The permittee shall notify the Director at such times as the permit requires before conversion or abandonment of the well or in the case of area permits before closure of the project.
(o) A Class I, II or III permit shall include and a Class V permit may include, conditions which meet the applicable requirements of § 146.10 of this chapter to insure that plugging and abandonment of the well will not allow the movement of fluids into or between USDWs. Where the plan meets the requirements of § 146.10 of this chapter, the Director shall incorporate it into the permit as a permit condition. Where the Director's review of an application indicates that the permittee's plan is inadequate, the Director may require the applicant to revise the plan, prescribe conditions meeting the requirements of this paragraph, or deny the permit. For purposes of this paragraph, temporary or intermittent cessation of injection operations is not abandonment.
(p)
(1) A statement that the well was plugged in accordance with the plan previously submitted to the Regional Administrator; or
(2) Where actual plugging differed from the plan previously submitted, and updated version of the plan on the form supplied by the regional administrator, specifying the differences.
(q)
(2) When the Director determines that a Class I, II, or III well lacks mechanical integrity pursuant to § 146.8 of this chapter, he shall give written notice of his determination to the owner or operator. Unless the Director requires immediate cessation, the owner or operator shall cease injection into the well within 48 hours of receipt of the Director's determination. The Director may allow plugging of the well pursuant to the requirements of § 146.10 of this chapter or require the permittee to perform such additional construction, operation, monitoring, reporting and corrective action as is necessary to prevent the movement of fluid into or between USDWs caused by the lack of mechanical integrity. The owner or operator may resume injection upon written notification from the Director that the owner or operator has demonstrated mechanical integrity pursuant to § 146.8 of this chapter.
(3) The Director may allow the owner or operator of a well which lacks mechanical integrity pursuant to § 146.8(a)(1) of this chapter to continue or resume injection, if the owner or operator has made a satisfactory demonstration that there is no movement of fluid into or between USDWs.
(a) In addition to conditions required in § 144.51, the Director shall establish conditions, as required on a case-by-case basis under § 144.36 (duration of permits), § 144.53(a) (schedules of compliance), §144.54 (monitoring), and for EPA permits only § 144.53(b) (alternate schedules of compliance), and § 144.4 (considerations under Federal law). Permits for owners or operators of hazardous waste injection wells shall include conditions meeting the requirements of § 144.14 (requirements for wells injecting hazardous waste), § 144.52 (a)(7) and (a)(9), and subpart G of part 146. Permits for other wells shall contain the following requirements, when applicable.
(1)
(2)
(3)
(4)
(5) Monitoring and reporting requirements as set forth in 40 CFR part 146. The permittee shall be required to identify types of tests and methods used to generate the monitoring data. For EPA administered programs, monitoring of the nature of injected fluids shall comply with applicable analytical methods cited and described in table I
(6) After a cessation of operations of two years the owner or operator shall plug and abandon the well in accordance with the plan unless he:
(i) Provides notice to the Regional Administrator;
(ii) Describes actions or procedures, satisfactory to the Regional Administrator, that the owner or operator will take to ensure that the well will not endanger USDWs during the period of temporary abandonment. These actions and procedures shall include compliance with the technical requirements applicable to active injection wells unless waived by the Regional Administrator.
(7)
(A) The well has been plugged and abandoned in accordance with an approved plugging and abandonment plan pursuant to §§ 144.51(o) and 146.10 of this chapter, and submitted a plugging and abandonment report pursuant to § 144.51(p); or
(B) The well has been converted in compliance with the requirements of § 144.51(n); or
(C) The transferor of a permit has received notice from the Director that the owner or operator receiving transfer of the permit, the new permittee, has demonstrated financial responsibility for the well.
(ii) The permittee shall show evidence of such financial responsibility to the Director by the submission of a surety bond, or other adequate assurance, such as a financial statement or other materials acceptable to the Director. For EPA administered programs, the Regional Administrator may on a periodic basis require the holder of a lifetime permit to submit an estimate of the resources needed to plug and abandon the well revised to reflect inflation of such costs, and a revised demonstration of financial responsibility, if necessary. The owner or operator of a well injecting hazardous waste must comply with the financial responsibility requirements of subpart F of this part.
(8)
(9)
(b)(1) In addition to conditions required in all permits the Director shall establish conditions in permits as required on a case-by-case basis, to provide for and assure compliance with all applicable requirements of the SDWA and parts 144, 145, 146 and 124.
(2) For a State issued permit, an applicable requirement is a State statutory or regulatory requirement which takes effect prior to final administrative disposition of the permit. For a permit issued by EPA, an applicable requirement is a statutory or regulatory requirement (including any interim final regulation) which takes effect prior to the issuance of the permit. Section 124.14 (reopening of comment period) provides a means for reopening EPA permit proceedings at the discretion of the Director where new requirements become effective during the permitting process and are of sufficient magnitude to make additional proceedings desirable. For State and EPA administered programs, an applicable requirement is also any requirement which takes effect prior to the modification or revocation and reissuance of a permit, to the extent allowed in § 144.39.
(3) New or reissued permits, and to the extent allowed under § 144.39 modified or revoked and reissued permits, shall incorporate each of the applicable requirements referenced in § 144.52.
(c)
(a)
(1)
(2)
(i) The time between interim dates shall not exceed 1 year.
(ii) If the time necessary for completion of any interim requirement is more than 1 year and is not readily divisible into stages for completion, the permit shall specify interim dates for the submission of reports of progress toward completion of the interim requirements and indicate a projected completion date.
(3)
(b)
(1) If the permittee decides to cease conducting regulated activities at a given time within the term of a permit which has already been issued:
(i) The permit may be modified to contain a new or additional schedule leading to timely cessation of activities; or
(ii) The permittee shall cease conducting permitted activities before noncompliance with any interim or final compliance schedule requirement already specified in the permit.
(2) If the decision to cease conducting regulated activities is made before issuance of a permit whose term will include the termination date, the permit shall contain a schedule leading to termination which will ensure timely compliance with applicable requirements.
(3) If the permittee is undecided whether to cease conducting regulated activities, the Director may issue or modify a permit to contain two schedules as follows:
(i) Both schedules shall contain an identical interim deadline requiring a final decision on whether to cease conducting regulated activities no later than a date which ensures sufficient time to comply with applicable requirements in a timely manner if the decision is to continue conducting regulated activities;
(ii) One schedule shall lead to timely compliance with applicable requirements;
(iii) The second schedule shall lead to cessation of regulated activities by a date which will ensure timely compliance with applicable requirements;
(iv) Each permit containing two schedules shall include a requirement that after the permittee has made a final decision under paragraph (b)(3)(i) of this section it shall follow the schedule leading to compliance if the decision is to continue conducting regulated activities, and follow the schedule leading to termination if the decision is to cease conducting regulated activities.
(4) The applicant's or permittee's decision to cease conducting regulated activities shall be evidenced by a firm public commitment satisfactory to the Director, such as a resolution of the board of directors of a corporation.
All permits shall specify:
(a) Requirements concerning the proper use, maintenance, and installation, when appropriate, of monitoring
(b) Required monitoring including type, intervals, and frequency sufficient to yield data which are representative of the monitored activity including when appropriate, continuous monitoring;
(c) Applicable reporting requirements based upon the impact of the regulated activity and as specified in part 146. Reporting shall be no less frequent than specified in the above regulations.
(a)
(b)
(2)
(3)
(4)
(a) The requirements of §§ 144.62, 144.63, and 144.70 apply to owners and operators of all existing and new Class I Hazardous waste injection wells, except as provided otherwise in this section.
(a)
(b)
(c)
(d) The following terms are used in the specifications for the financial test for plugging and abandonment. The definitions are intended to represent the common meanings of the terms as they are generally used by the business community.
(a) The owner or operator must prepare a written estimate, in current dollars, of the cost of plugging the injection well in accordance with the plugging and abandonment plan as specified in §§ 144.28 and 144.51. The plugging and abandonment cost estimate must equal the cost of plugging and abandonment at the point in the facility's operating life when the extent and manner of its operation would making plugging and abandonment the most expensive, as indicated by its plugging and abandonment plan.
(b) The owner or operator must adjust the plugging and abandonment cost estimate for inflation within 30 days after each anniversary of the date on which the first plugging and abandonment cost estimate was prepared. The adjustment must be made as specified in paragraphs (b) (1) and (2) of this section, using an inflation factor derived from the annual Oil and Gas Field Equipment Cost Index. The inflation factor is the result of dividing the latest published annual Index by the Index for the previous year.
(1) The first adjustment is made by multiplying the plugging and abandonment cost estimate by the inflation factor. The result is the adjusted plugging and abandonment cost estimate.
(2) Subsequent adjustments are made by multiplying the latest adjusted plugging and abandonment cost estimate by the latest inflation factor.
(c) The owner or operator must revise the plugging and abandonment cost estimate whenever a change in the plugging and abandonment plan increases the cost of plugging and abandonment. The revised plugging and abandonment cost estimate must be adjusted for inflation as specified in § 144.62(b).
(d) The owner or operator must keep the following at the facility during the operating life of the facility: the latest plugging and abandonment cost estimate prepared in accordance with § 144.62 (a) and (c) and, when this -estimate has been adjusted in ac-cord-ance with § 144.62(b), the latest -adjusted plugging and abandonment cost estimate.
An owner or operator of each facility must establish financial assurance for the plugging and abandonment of each existing and new Class I hazardous waste injection well. He must choose
(a)
(2) The wording of the trust agreement must be identical to the wording specified in § 144.70(a)(1), and the trust agreement must be accompanied by a formal certification of acknowledgment (for example, see § 144.70(a)(2)). Schedule A of the trust agreement must be updated within 60 days after a change in the amount of the current plugging and abandonment cost estimate covered by the agreement.
(3) Payments into the trust fund must be made annually by the owner or operator over the term of the initial permit or over the remaining operating life of the injection well as estimated in the plugging and abandonment plan, whichever period is shorter; this period is hereafter referred to as the “pay-in period.” The payments into the plugging and abandonment trust fund must be made as follows:
(i) For a new well, the first payment must be made before the initial injection of hazardous waste. A receipt from the trustee for this payment must be submitted by the owner or operator to the Regional Administrator before this initial injection of hazardous waste. The first payment must be at least equal to the current plugging and abandonment cost estimate, except as provided in § 144.70(g), divided by the number of years in the pay-in period. Subsequent payments must be made no later than 30 days after each anniversary date of the first payment. The amount of each subsequent payment must be determined by this formula:
(ii) If an owner or operator establishes a trust fund as specified in § 144.63(a) of this chapter, and the value of that trust fund is less than the current plugging and abandonment cost estimate when a permit is awarded for the injection well, the amount of the current plugging and abandonment cost estimate still to be paid into the trust fund must be paid in over the pay-in period as defined in paragraph (a)(3) of this section. Payments must continue to be made no later than 30 days after each anniversary date of the first payment made pursuant to part 144 of this chapter. The amount of each payment must be determined by this formula:
(4) The owner or operator may accelerate payments into the trust fund or he may deposit the full amount of the current plugging and abandonment cost estimate at the time the fund is established. However, he must maintain the value of the fund at no less than the value that the fund would have if annual payments were made as specified in paragraph (a)(3) of this section.
(5) If the owner or operator establishes a plugging and abandonment trust fund after having used one or more alternate mechanisms specified in this section or in § 144.63 of this chapter, his first payment must be in at least the amount that the fund would contain if the trust fund were established initially and annual payments made according to specifications of this paragraph.
(6) After the pay-in period is completed, whenever the current plugging
(7) If the value of the trust fund is greater than the total amount of the current plugging and abandonment cost estimate, the owner or operator may submit a written request to the Regional Administrator for release of the amount in excess of the current plugging and abandonment cost estimate.
(8) If an owner or operator substitutes other financial assurance as specified in this section for all or part of the trust fund, he may submit a written request to the Regional Administrator for release of the amount in excess of the current plugging and abandonment cost estimate covered by the trust fund.
(9) Within 60 days after receiving a request from the owner or operator for release of funds as specified in paragraph (a) (7) or (8) of this section, the Regional Administrator will instruct the trustee to release to the owner or operator such funds as the Regional Administrator specifies in writing.
(10) After beginning final plugging and abandonment, an owner or operator or any other person authorized to perform plugging and abandonment may request reimbursement for plugging and abandonment expenditures by submitting itemized bills to the Regional Administrator. Within 60 days after receiving bills for plugging and abandonment activities, the Regional Administrator will determine whether the plugging and abandonment expenditures are in accordance with the plugging and abandonment plan or otherwise justified, and if so, he will instruct the trustee to make reimbursement in such amounts as the Regional Administrator specifies in writing. If the Regional Administrator has reason to believe that the cost of plugging and abandonment will be significantly greater than the value of the trust fund, he may withhold reimbursement of such amounts as he deems prudent until he determines, in accordance with § 144.63(i), that the owner or operator is no longer required to maintain financial assurance for plugging and abandonment.
(11) The Regional Administrator will agree to termination of the trust when:
(i) An owner or operator substitutes alternate financial assurance as specified in this section; or
(ii) The Regional Administrator releases the owner or operator from the requirements of this section in accordance with § 144.63(i).
(b)
(2) The wording of the surety bond must be identical to the wording in § 144.70(b).
(3) The owner or operator who uses a surety bond to satisfy the requirements of this section must also establish a standby trust fund. Under the terms of the bond, all payments made thereunder will be deposited by the surety directly into the standby trust fund in accordance with instructions from the Regional Administrator. This standby trust fund must meet the requirements specified in § 144.63(a), except that:
(i) An originally signed duplicate of the trust agreement must be submitted to the Regional Administrator with the surety bond; and
(ii) Until the standby trust fund is funded pursuant to the requirements of
(A) Payments into the trust fund as specified in § 144.63(a);
(B) Updating of Schedule A of the trust agreement [see § 144.70(a)] to show current plugging and abandonment cost estimates;
(C) Annual valuations as required by the trust agreement; and
(D) Notices of nonpayment as required by the trust agreement.
(4) The bond must guarantee that the owner or operator will:
(i) Fund the standby trust fund in an amount equal to the penal sum of the bond before beginning of plugging and abandonment of the injection well; or
(ii) Fund the standby trust fund in an amount equal to the penal sum within 15 days after an order to begin plugging and abandonment is issued by the Regional Administrator or a U.S. district court or other court of competent jurisdiction; or
(iii) Provide alternate financial assurance as specified in this section, and obtain the Regional Administrator's written approval of the assurance provided, within 90 days after receipt by both the owner or operator and the Regional Administrator of a notice of cancellation of the bond from the surety.
(5) Under the terms of the bond, the surety will become liable on the bond obligation when the owner or operator fails to perform as guaranteed by the bond.
(6) The penal sum of the bond must be in amount at least equal to the current plugging and abandonment cost estimate, except as provided in § 144.63(g).
(7) Whenever the current plugging and abandonment cost estimate increases to an amount greater than the penal sum, the owner or operator, within 60 days after the increase, must either cause the penal sum to be increased to an amount at least equal to the current plugging and abandonment cost estimate and submit evidence of such increase to the Regional Administrator, or obtain other financial assurance as specified in this section to cover the increase. Whenever the current plugging and abandonment cost estimate decreases, the penal sum may be reduced to the amount of the current plugging and abandonment cost estimate following written approval by the Regional Administrator.
(8) Under the terms of the bond, the surety may cancel the bond by sending notice of cancellation by certified mail to the owner or operator and to the Regional Administrator. Cancellation may not occur, however, during 120 days beginning on the date of the receipt of the notice of cancellation by both owner or operator and the Regional Administrator as evidenced by the returned receipts.
(9) The owner or operator may cancel the bond if the Regional Administrator has given prior written consent based on his receipt of evidence of alternate financial assurance as specified in this section.
(c)
(2) The wording of the surety bond must be identical to the wording specified in § 144.70(c).
(3) The owner or operator who uses a surety bond to satisfy the requirements of this section must also establish a standby trust fund. Under the terms of the bond, all payments made thereunder will be deposited by the surety directly into the standby trust fund in accordance with instructions from the Regional Administrator. The standby trust must meet the requirements specified in § 144.63(a), except that:
(i) An original signed duplicate of the trust agreement must be submitted to the Regional Administrator with the surety bond; and
(ii) Unless the standby trust fund is funded pursuant to the requirements of this section, the following are not required by these regulations:
(A) Payments into the trust fund as specified in § 144.63(a);
(B) Updating of Schedule A of the trust agreement [see § 144.70(a)] to show current plugging and abandonment cost estimates;
(C) Annual valuations as required by the trust agreement; and
(D) Notices of nonpayment as required by the trust agreement.
(4) The bond must guarantee that the owner or operator will:
(i) Perform plugging and abandonment in accordance with the plugging and abandonment plan and other requirements of the permit for the injection well whenever required to do so; or
(ii) Provide alternate financial assurance as specified in this section, and obtain the Regional Administrator's written approval of the assurance provided, within 90 days after receipt by both the owner or operator and the Regional Administrator of a notice of cancellation of the bond from the surety.
(5) Under the terms of the bond, the surety will become liable on the bond obligation when the owner or operator fails to perform as guaranteed by the bond. Following a determination that the owner or operator has failed to perform plugging and abandonment in accordance with the plugging and abandonment plan and other permit requirements when required to do so, under terms of the bond the surety will perform plugging and abandonment as guaranteed by the bond or will deposit the amount of the penal sum into the standby trust fund.
(6) The penal sum of the bond must be in an amount at least equal to the current plugging and abandonment cost estimate.
(7) Whenever the current plugging and abandonment cost estimate increases to an amount greater than the penal sum, the owner or operator, within 60 days after the increase, must either cause the penal sum to be increased to an amount at least equal to the current plugging and abandonment cost estimate and submit evidence of such increase to the Regional Administrator, or obtain other financial assurance as specified in this section. Whenever the plugging and abandonment cost estimate decreases, the penal sum may be reduced to the amount of the current plugging and abandonment cost estimate following written approval by the Regional Administrator.
(8) Under the terms of the bond, the surety may cancel the bond by sending notice of cancellation by certified mail to the owner or operator and to the Regional Administrator. Cancellation may not occur, however, during the 120 days beginning on the date of receipt of the notice of cancellation by both the owner or operator and the Regional Administrator, as evidenced by the return receipts.
(9) The owner or operator may cancel the bond if the Regional Administrator has given prior written consent. The Regional Administrator will provide such written consent when:
(i) An owner or operator substitute alternate financial assurance as specified in this section; or
(ii) The Regional Administrator releases the owner or operator from the requirements of this section in accordance with § 144.63(i).
(10) The surety will not be liable for deficiencies in the performance of plugging and abandonment by the owner or operator after the Regional Administrator releases the owner or operator from the requirements of this section in accordance with § 144.63(i).
(d)
(2) The wording of the letter of credit must be identical to the wording specified in § 144.70(d).
(3) An owner or operator who uses a letter of credit to satisfy the requirements of this section must also establish a standby trust fund. Under the terms of the letter of credit, all amounts paid pursuant to a draft by the Regional Administrator will be deposited by the issuing institution directly into the standby trust fund in accordance with instructions from the Regional Administrator. This standby trust fund must meet the requirements of the trust fund specified in § 144.63(a), except that:
(i) An originally signed duplicate of the trust agreement must be submitted to the Regional Administrator with the letter of credit; and
(ii) Unless the standby trust fund is funded pursuant to the requirements of this section, the following are not required by these regulations:
(A) Payments into the trust fund as specified in § 144.63(a);
(B) Updating of Schedule A of the trust agreement (see § 144.70(a)) to show current plugging and abandonment cost estimates;
(C) Annual valuations as required by the trust agreement; and
(D) Notices of nonpayment as required by the trust agreement.
(4) The letter of credit must be accompanied by a letter from the owner or operator referring to the letter of credit by number, issuing institution, and date, and providing the following information: the EPA Identification Number, name, and address of the facility, and the amount of funds assured for plugging and abandonment of the well by the letter of credit.
(5) The letter of credit must be irrevocable and issued for a period of at least 1 year. The letter of credit must provide that the expiration date will be automatically extended for a period of at least 1 year unless, at least 120 days before the current expiration date, the issuing institution notifies both the owner or operator and the Regional Administrator by certified mail of a decision not to extend the expiration date. Under the terms of the letter of credit, the 120 days will begin on the date when both the owner or operator and the Regional Administrator have received the notice, as evidenced by the return receipts.
(6) The letter of credit must be issued in an amount at least equal to the current plugging and abandonment cost estimate, except as provided in § 144.63(g).
(7) Whenever the current plugging and abandonment cost estimate increases to an amount greater than the amount of the credit, the owner or operator, within 60 days after the increase, must either cause the amount of the credit to be increased so that it at least equals the current plugging and abandonment cost estimate and submit evidence of such increase to the Regional Administrator, or obtain other financial assurance as specified in this section to cover the increase. Whenever the current plugging and abandonment cost estimate decreases, the amount of the credit may be reduced to the amount of the current plugging and abandonment cost estimate following written approval by the Regional Administrator.
(8) Following a determination that the owner or operator has failed to perform final plugging and abandonment in accordance with the plugging and abandonment plan and other permit requirements when required to do so, the Regional Administrator may draw on the letter of credit.
(9) If the owner or operator does not establish alternate financial assurance as specified in this section and obtain written approval of such alternate assurance from the Regional Administrator within 90 days after receipt by both the owner or operator and the Regional Administrator of a notice from the issuing institution that it has decided not to extend the letter of credit beyond the current expiration date, the Regional Administrator will draw on the letter of credit. The Regional Administrator may delay the drawing if the issuing institution grants an extension of the term of the credit. During the last 30 days of any such extension the Regional Administrator will draw on the letter of credit if the owner or operator has failed to provide alternate financial assurance as specified in this section and obtain written approval of
(10) The Regional Administrator will return the letter of credit to the issuing institution for termination when:
(i) An owner or operator substitutes alternate financial assurance as specified in this section; or
(ii) The Regional Administrator releases the owner or operator from the requirements of this section in accordance with § 144.63(i).
(e)
(2) The wording of the certificate of insurance must be identical to the wording specified in § 144.70(e).
(3) The plugging and abandonment insurance policy must be issued for a face amount at least equal to the current plugging and abandonment estimate, except as provided in § 144.63(g). The term “face amount” means the total amount the insurer is obligated to pay under the policy. Actual payments by the insurer will not change the face amount, although the insurers future liability will be lowered by the amount of the payments.
(4) The plugging and abandonment insurance policy must guarantee that funds will be available whenever final plugging and abandonment occurs. The policy must also guarantee that once plugging and abandonment begins, the issurer will be responsible for paying out funds, up to an amount equal to the face amount of the policy, upon the direction of the Regional Administrator, to such party or parties as the Regional Administrator specifies.
(5) After beginning plugging and abandonment, an owner or operator or any other person authorized to perform plugging and abandonment may request reimbursement for plugging and abandonment expenditures by submitting itemized bills to the Regional Administrator. Within 60 days after receiving bills for plugging and abandonment activities, the Regional Administrator will determine whether the plugging and abandonment expenditures are in accordance with the plugging and abandonment plan or otherwise justified, and if so, he will instruct the insurer to make reimbursement in such amounts as the Regional Administrator specifies in writing. If the Regional Administrator has reason to believe that the cost of plugging and abandonment will be significantly greater than the face amount of the policy, he may withhold reimbursement of such amounts as he deems prudent until he determines, in accordance with § 144.63(i), that the owner or operator is no longer required to maintain financial assurance for plugging and abandonment of the injection well.
(6) The owner or operator must maintain the policy in full force and effect until the Regional Administrator consents to termination of the policy by the owner or operator as specified in paragraph (e)(10) of this section. Failure to pay the premium, without substitution of alternate financial assurance as specified in this section, will constitute a significant violation of these regulations, warranting such remedy as the Regional Administrator deems necessary. Such violation will be deemed to begin upon receipt by the Regional Administrator of a notice of future cancellation, termination, or failure to renew due to nonpayment of the premium, rather than upon the date of expiration.
(7) Each policy must contain provisions allowing assignment to a successor owner or operator. Such assignment may be conditional upon consent of the insurer, provided such consent is not unreasonably refused.
(8) The policy must provide that the insurer may not cancel, terminate, or fail to renew the policy except for failure to pay the premium. The automatic renewal of the policy must, at a
(i) The Regional Administrator deems the injection well abandoned; or
(ii) The permit is terminated or revoked or a new permit is denied; or
(iii) Plugging and abandonment is ordered by the Regional Administrator or a U.S. district court or other court of competent jurisdiction; or
(iv) The owner or operator is named as debtor in a voluntary or involuntary proceeding under title 11 (Bankruptcy), U.S. Code; or
(v) The premium due is paid.
(9) Whenever the current plugging and abandonment cost estimate increases to an amount greater than the face amount of the policy, the owner or operator, within 60 days after the increase, must either cause the face amount to be increased to an amount at least equal to the current plugging and abandonment estimate and submit evidence of such increase to the Regional Administrator, or obtain other financial assurance as specified in this section to cover the increase. Whenever the current plugging and abandonment cost estimate decreases, the face amount may be reduced to the amount of the current plugging and abandonment cost estimate following written approval by the Regional Administrator.
(10) The Regional Administrator will give written consent to the owner or operator that he may terminate the insurance policy when:
(i) An owner or operator substitutes alternate financial assurance as specified in this section; or
(ii) The Regional Administrator releases the owner or operator from the requirements of this section in accordance with § 144.63(i).
(f)
(i) The owner or operator must have:
(A) Two of the following three ratios: A ratio of total liabilities to net worth less than 2.0; a ratio of the sum of net income plus depreciation, depletion, and amortization to total liabilities greater than 0.1; and a ratio of current assets to current liabilities greater than 1.5; and
(B) Net working capital and tangible net worth each at least six times the sum of the current plugging and abandonment cost estimate; and
(C) Tangible net worth of at least $10 million; and
(D) Assets in the United States amounting to at least 90 percent of his total assets or at least six times the sum of the current plugging and abandonment cost estimate.
(ii) The owner or operator must have:
(A) A current rating for his most recent bond issuance of AAA, AA, A or BBB as issued by Standard and Poor's or Aaa, Aa, A, or Baa as issued by Moody's; and
(B) Tangible net worth at least six times the sum of the current plugging and abandonment cost estimate; and
(C) Tangible net worth of at least $10 million; and
(D) Assets located in the United States amounting to at least 90 percent of his total assets or at least six times the sum of the current plugging and abandonment cost estimates.
(2) The phrase “current plugging and abandonment cost estimate” as used in paragraph (f)(1) of this section refers to the cost estimate required to be shown in paragraphs 1 through 4 of the letter from the owner's or operator's chief financial officer § 144.70(f).
(3) To demonstrate that he meets this test, the owner or operator must
(i) A letter signed by the owner's or operator's chief financial officer and worded as specified in § 144.70(f); and
(ii) A copy of the independent certified public accountant's report on examination of the owner's or operator's financial statements for the latest completed fiscal year; and
(iii) A special report from the owner's or operator's independent certified public accountant to the owner or operator stating that:
(A) He has compared the data which the letter from the chief financial officer specifies as having been derived from the independently audited, year-end financial statements for the latest fiscal year with the amounts in such financial statements; and
(B) In connection with that procedure, no matters came to his attention which caused him to believe that the specified data should be adjusted.
(4) An owner or operator of a new injection well must submit the items specified in paragraph (f)(3) of this section to the Regional Administrator within 90 days after the close of each succeeding fiscal year. This information must consist of all three items specified in paragraph (f)(3) of this section.
(5) After the initial submission of items specified in paragraph (f)(3) of this section, the owner or operator must send updated information to the Regional Administrator within 90 days after the close of each succeeding fiscal year. This information must consist of all three items specified in paragraph (f)(3) of this section.
(6) If the owner or operator no longer meets the requirements of paragraph (f)(1) of this section, he must send notice to the Regional Administrator of intent to establish alternate financial assurance as specified in this section. The notice must be sent by certified mail within 90 days after the end of the fiscal year for which the year-end financial data show that the owner or operator no longer meets the requirements. The owner or operator must provide the alternate financial assurance within 120 days after the end of such fiscal year.
(7) The Regional Administrator may, based on a reasonable belief that the owner or operator may no longer meet the requirements of paragraph (f)(1) of this section, require reports of financial condition at any time from the owner or operator in addition to those specified in paragraph (f)(3) of this section. If the Regional Administrator finds, on the basis of such reports or other information, that the owner or operator no longer meets the requirements of paragraph (f)(1) of this section, the owner or operator must provide alternate financial assurance as specified in this section within 30 days after notification of such a finding.
(8) The Regional Administrator may disallow use of this test on the basis of qualifications in the opinion expressed by the independent certified public accountant in his report on examination of the owner's or operator's financial statements [see paragraph (f)(3)(ii) of this section]. An adverse opinion or disclaimer of opinion will be cause for disallowance. The Regional Administrator will evaluate other qualifications on an individual basis. The owner or operator must provide alternate financial assurance as specified in this section within 30 days after notification of the disallowance.
(9) The owner or operator is no longer required to submit the items specified in paragraph (f)(3) of this section when:
(i) An owner or operator substitutes alternate financial assurance as specified in this section; or
(ii) The Regional Administrator releases the owner or operator from the requirements of this section in accordance with § 144.63(i).
(10) An owner or operator may meet the requirements of this section by obtaining a written guarantee, hereafter referred to as “corporate guarantee.” The guarantee must be the parent corporation of the owner or operator. The guarantee must meet the requirements for owners or operators in paragraphs (f)(1) through (f)(8) of this section and must comply with the terms of the corporate guarantee. The wording of the corporate guarantee must be identical to the wording specified in § 144.70(h). The corporate guarantee must accompany the items sent to the Regional
(i) If the owner or operator fails to perform plugging and abandonment of the injection well covered by the corporate guarantee in accordance with the plugging and abandonment plan and other permit requirements whenever required to do so, the guarantee will do so or establish a trust fund as specified in § 144.63(a) in the name of the owner or operator.
(ii) The corporate guarantee will remain in force unless the guarantor sends notice of cancellation by certified mail to the owner or operator and the Regional Administrator, as evidenced by the return receipts. Cancellation may not occur, however, during the 120 days beginning on the date of receipt of the notice of cancellation by both the owner or operator and the Regional Administrator, as evidenced by the return receipts.
(iii) If the owner or operator fails to provide alternate financial assurance as specified in this section and obtain the written approval of such alternate assurance from the Regional Administrator within 90 days after receipt by both the owner or operator and the Regional Administrator of a notice of cancellation of the corporate guarantee from the guarantor, the guarantor will provide such alternative financial assurance in the name of the owner or operator.
(g)
(h)
(i)
(a) An owner or operator must notify the Regional Administrator by certified mail of the commencement of a voluntary or involuntary proceeding under title 11 (Bankruptcy), U.S. Code, naming the owner or operator as debtor, within 10 business days after the commencement of the proceeding. A guarantor of a corporate guarantee as specified in § 144.63(f) must make such a notification if he is named as debtor, as required under the terms of the guarantee (§ 144.70(f)).
(b) An owner or operator who fulfills the requirements of § 144.63 by obtaining a letter of credit, surety bond, or insurance policy will be deemed to be without the required financial assurance or liability coverage in the event of bankruptcy, insolvency, or a suspension or revocation of the license or charter of the issuing institution. The owner or operator must establish other financial assurance or liability coverage within 60 days after such an event.
(a) For a facility located in a State where EPA is administering the requirements of this subpart but where the State has plugging and abandonment regulations that include requirements for financial assurance of plugging and abandonment, an owner or operator may use State-required financial mechanisms to meet the requirements of this subpart if the Regional Administrator determines that the State mechanisms are at least equivalent to the mechanisms specified in this subpart. The Regional Administrator will evaluate the equivalency of the mechanisms mainly in terms of (1) certainty of the availability of funds for the required plugging and abandonment activities and (2) the amount of funds that will be made available. The Regional Administrator may also consider other factors. The owner or operator must submit to the Regional Administrator evidence of the establishment of the mechanism together with a letter requesting that the State-required mechanism be considered acceptable for meeting the requirements of this subpart. The submittal must include the following information: The facility's EPA Identification Number, name and address, and the amounts of funds for plugging and abandonment coverage assured by the mechanism. The Regional Administrator will notify the owner or operator of his determination regarding the mechanism's acceptability. The Regional Administrator may require the owner or operator to submit additional information as is deemed necessary for making this determination.
(b) If a State-required mechanism is found acceptable as specified in paragraph (a) of this section except for the amount of funds available, the owner or operator may satisfy the requirements of this subpart by increasing the funds available through the State-required mechanism or using additional mechanisms as specified in this subpart. The amounts of funds available through the State and Federal mechanisms must at least equal the amounts required by this subpart.
(a) If a State either assumes legal responsibility for an owner's or operator's compliance with the plugging and abandonment requirements of these regulations or assures that funds will be available from State sources to cover these requirements, the owner or operator will be in compliance with the requirements of this subpart if the Regional Administrator determines that the State's assumption of responsibility is at least equivalent to the mechanisms specified in this subpart. The Regional Administrator will evaluate the equivalency of State guarantees mainly in terms of (1) certainty of the availability of funds for the required plugging and abandonment coverage and (2) the amount of funds that will be made available. The Regional Administrator may also consider other factors. The owner or operator must submit to the Regional Administrator a letter from the State describing the nature of the State's assumption of responsibility together with a letter from the owner or operator requesting that the State's asumption of responsibility
(b) If a State's assumption of responsibility is found acceptable as specified in paragraph (a) of this section except for the amount of funds available, the owner or operator may satisfy the requirements of this subpart by use of both the State's assurance and additional financial mechanisms as specified in this subpart. The amount of funds available through the State and Federal mechanisms must at least equal the amount required by this subpart.
(a)(1) A trust agreement for a trust fund, as specified in § 144.63(a) of this chapter, must be worded as follows, except that instructions in brackets are to be replaced with the relevant information and the brackets deleted:
TRUST AGREEMENT, the “Agreement,” entered into as of [date] by and between [name of the owner or operator], a [name of State] [insert “corporation,” “partnership,” “association,” or “proprietorship”], the “Grantor,” and [name of corporate trustee], [insert “incorporated in the State of ___” or “a national bank”], the “Trustee.”
Whereas, the United States Environmental Protection Agency, “EPA,” an agency of the United States Government, has established certain regulations applicable to the Grantor, requiring that an owner or operator of an injection well shall provide assurance that funds will be available when needed for plugging and abandonment of the injection well,
Whereas, the Grantor has elected to establish a trust to provide all or part of such financial assurance for the facility(ies) identified herein,
Whereas, the Grantor, acting through its duly authorized officers, has selected the Trustee to be the trustee under this agreement, and the Trustee is willing to act as trustee,
Now, therefore, the Grantor and the Trustee agree as follows:
(a) The term “Grantor” means the owner or operator who enters into this Agreement and any successors or assigns of the Grantor.
(b) The term “Trustee” means the Trustee who enters into this Agreement and any successor Trustee.
(c) Facility or activity means any “underground injection well” or any other facility or activity that is subject to regulation under the Underground Injection Control Program.
(i) Securities or other obligations of the Grantor, or any other owner or operator of the facilities, or any of their affiliates as defined in the Investment Company Act of 1940, as amended, 15 U.S.C. 80a-2.(a), shall not be acquired or held, unless they are securities or other obligations of the Federal or a State government;
(ii) The Trustee is authorized to invest the Fund in time or demand deposits of the Trustee, to the extent insured by an agency of the Federal or State government; and
(iii) The Trustee is authorized to hold cash awaiting investment or distribution uninvested for a reasonable time and without liability for the payment of interest thereon.
(a) To transfer from time to time any or all of the assets of the Fund to any common, commingled, or collective trust fund created by the Trustee in which the Fund is eligible to participate, subject to all of the provisions thereof, to be commingled with the assets of other trusts participating therein; and
(b) To purchase shares in any investment company registered under the Investment Company Act of 1940, 15 U.S.C. 80a-1
(a) To sell, exchange, convey, transfer, or otherwise dispose of any property held by it, by public or private sale. No person dealing with the Trustee shall be bound to see to the application of the purchase money or to inquire into the validity or expediency of any such sale or other disposition;
(b) To make, execute, acknowledge, and deliver any and all documents of transfer and conveyance and any and all other instruments that may be necessary or appropriate to carry out the powers herein granted;
(c) To register any securities held in the Fund in its own name or in the name of a nominee and to hold any security in bearer form or in book entry, or to combine certificates representing such securities with certificates of the same issue held by the Trustee in other fiduciary capacities, or to deposit or arrange for the deposit of such securities in a qualified central depository even though, when so deposited, such securities may be merged and held in bulk in the name of the nominee of such depositary with other securities deposited therein by another person, or to deposit or arrange for the deposit of any securities issued by the United States Government, or any agency or instrumentality thereof, with a Federal Reserve bank, but the books and records of the Trustee shall at all times show that all such securities are part of the Fund;
(d) To deposit any cash in the Fund in interest-bearing accounts maintained or savings certificates issued by the Trustee, in its separate corporate capacity, or in any other banking institution affiliated with the Trustee, to the extent insured by an agency of the Federal or State government; and
(e) To compromise or otherwise adjust all claims in favor of or against the Fund.
In Witness Whereof the parties have caused this Agreement to be executed by their respective officers duly authorized and their corporate seals to be hereunto affixed and attested as of the date first above written. The parties below certify that the wording of this Agreement is identical to the wording specified in 40 CFR 144.70(a)(1) as such regulations were constituted on the date first above written.
By[Title]
By
(2) The following is an example of the certification of acknowledgment which must accompany the trust agreement for a trust fund as specified in § 144.63(a). State requirements may differ on the proper content of this acknowledgment.
On this [date], before me personally came [owner or operator] to me known, who, being by me duly sworn, did depose and say that she/he resides at [address], that she/he is [title] of [corporation], the corporation described in and which executed the above instrument; that she/he knows the seal of said corporation; that the seal affixed to such instrument is such corporate seal; that it was so affixed by order to the Board of Directors of said corporation, and that she/he signed her/his name thereto by like order.
(b) A surety bond guaranteeing payment into a trust fund, as specified in § 144.63 of this chapter, must be worded as follows, except that instructions in brackets are to be replaced with the relevant information and the brackets deleted:
Principal: [legal name and business address of owner or operator].
Type of organization: [insert “individual,” “joint venture,” “partnership,” or “corporation”].
Surety(ies): [name(s) and business address(es)].
EPA Identification Number, name, address, and plugging and abandonment amount(s) for each facility guaranteed by this bond [indicate plugging and abandonment amounts separately]: ___
Total penal sum of bond: $___
Surety's bond number: ___
Know All Persons By These Presents, That we, the Principal and Surity(ies) hereto are firmly bound to the U.S. Environmental Protection Agency (hereinafter called EPA), in the above penal sum for the payment of which we bind ourselves, our heirs, executors, administrators, successors, and assigns jointly and severally; provided that, where the Surety(ies) are corporations acting as co-surties, we, the Sureties, bind ourselves in such sum “jointly and severally” only for the purpose of allowing a joint action or actions against any or all of us, and for all other purposes each Surety binds itself, jointly and severally with the Principal, for the payment of such sum only as is set forth opposite the name of such Surety, but if no limit of liability is indicated, the limit of liability shall be the full amount of the penal sum.
Whereas said Principal is required, under the Underground Injection Control Regulations (UIC), to have a permit or comply with requirements to operate under rule in order to own or operate each injection well identified above, and
Whereas said Principal is required to provide financial assurance for plugging and abandonment as a condition of the permit or provisions to operate under rule, and
Whereas said Principal shall establish a standby trust fund as is required when a surety bond is used to provide such financial assurance;
Now, therefore, the conditions of the obligation are such that if the Principal shall faithfully, before the beginning of plugging and abandonment of each injection well identified above, fund the standby trust fund in the amount(s) identified above for the injection well,
Or if the Principal shall fund the standby trust fund in such amount(s) within 15 days after an order to begin plugging and abandonment is issued by an EPA Regional Administrator or a U.S. district court or other court of competent jurisdiction,
Or, if the Principal shall provide alternate financial assurance, as specified in subpart F of 40 CFR part 144, as applicable, and obtain the EPA Regional Administrator's written approval of such assurance, within 90 days after the date of notice of cancellation is received by both the Principal and the EPA Regional Administrator(s) from the Surety(ies), then this obligation shall be null and void, otherwise it is to remain in full force and effect.
The Surety(ies) shall become liable on this bond obligation only when the Principal has failed to fulfill the conditions described above. Upon notification by an EPA Regional Administrator that the Principal has failed to perform as guaranteed by this bond, the Surety(ies) shall place funds in the amount guaranteed for the injection well(s) into the standby trust funds as directed by the EPA Regional Administrator.
The liability of the Surety(ies) shall not be discharged by any payment or succession of payments hereunder, unless and until such payment or payments shall amount in the aggregate to the penal sum of the bond, but in no event shall the obligation of the Surety(ies) hereunder exceed the amount of said penal sum.
The Surety(ies) may cancel the bond by sending notice of cancellation by certified mail to the Principal and to the EPA Regional Administrator(s) for the Region(s) in which the injection well(s) is (are) located, provided, however, that that cancellation shall not occur during the 120 days beginning on the date of receipt of the notice of cancellation by both the Principal and the EPA Regional Administrator(s), as evidenced by the return receipts.
The Principal may terminate this bond by sending written notice to the Surety(ies), provided, however, that no such notice shall become effective until the Surety(ies) receive(s) written authorization for termination of the bond by the EPA Regional Administrator(s) of the Region(s) in which the bonded facility(ies) is (are) located.
[The following paragraph is an optional rider that may be included but is not required.]
Principal and Surety(ies) hereby agree to adjust the penal sum of the bond yearly so that it guarantees a new plugging and abandonment amount, provided that the penal sum does not increase by more than 20 -percent in any one year, and no decrease in the penal sum takes place without the writ-ten permission of the EPA Regional Administrator(s).
In Witness Whereof, the Principal and Surety(ies) have executed this Financial Guarantee Bond and have affixed their seals on the date set forth above.
The persons whose signatures appear below hereby certify that they are authorized to execute this surety bond on behalf of the Principal and Surety(ies) and that the wording of this surety bond is identical to the wording specified in 40 CFR 144.70(b) as such regulations were constituted on the date this bond was executed.
State of incorporation: ___.
Liability limit: $___.
Bond premium: $___.
(c) A surety bond guaranteeing performance of plugging and abandonment, as specified in § 144.63(c), must be worded as follows, except that the instructions in brackets are to be replaced with the relevant information and the brackets deleted:
Date bond executed: ___.
Effective date: ___.
Principal: [legal name and business address of owner or operator].
Type of organization: [insert “individual,” “joint venture,” “partnership,” or “corporation”].
State of incorporation: ___.
Surety(ies): [name(s) and business address(es)]
EPA Identification Number, name, address, and plugging and abandonment amounts(s) for each injection well guaranteed by this bond [indicate plugging and abandonment amounts for each well]:
Total penal sum of bond: $___.
Surety's bond number: ___.
Know All Persons By These Presents, That We, the Principal and Surety(ies) hereto are firmly bound to the U.S. Environmental Protection Agency [hereinafter called EPA], in the above penal sum for the payment of which we bind ourselves, our heirs, executors, administrators, successors, and assigns jointly and severally; provided that, where the Surety(ies) are corporations acting as co-sureties, we, the Sureties, bind ourselves in such sum “jointly and severally” only for the purpose of allowing a joint action or actions against any or all of us, and for all other purposes each Surety binds itself, jointly and severally with the Principal, for the payment of such sum only as is set forth opposite the name of such Surety, but if no limit of liability is indicated, the limit of liability shall be the full amount of the penal sum.
Whereas said Principal is required, under the Undergound Injection Control Regulations, as amended, to have a permit or comply with provisions to operate under rule for each injection well identified above, and
Whereas said Principal is required to provide financial assurance for plugging and abandonment as a condition of the permit or approval to operate under rule, and
Whereas said Principal shall establish a standby trust fund as is required when a -surety bond is used to provide such financial -assurance;
Now, Therefore, the conditions of this obligation are such that if the Principal shall faithfully perform plugging and abandonment, whenever required to do so, of each injection well for which this bond guarantees plugging and abandonment, in accordance with the plugging and abandonment plan and other rquirements of the permit or provisions for operating under rule and other requirements of the permit or provisions for operating under rule as may be amended, pursuant to all applicable laws, statutes, rules and regulations, as such laws, statutes, rules, and regulations may be amended,
Or, if the Principal shall provide alternate financial assurance as specified in subpart F of 40 CFR part 144, and obtain the EPA Regional Administrator's written approval of such assurance, within 90 days after the date of notice of cancellation is received by both the Principal and the EPA Regional Administrator(s) from the Surety(ies), then this obligation shall be null and void, otherwise it is to remain in full force and effect.
The Surety(ies) shall become liable on this bond obligation only when the Principal has failed to fulfill the conditions described above.
Upon notification by an EPA Regional Administrator that the Principal has been found in violation of the plugging and abandonment requirements of 40 CFR part 144, for an injection well which this bond guarantees performances of plugging and abandonment, the Surety(ies) shall either perform plugging and abandonment in accordance with the plugging and abandonment plan and other permit requirements or provisions for operating under rule and other requirements or place the amount for plugging and abandonment into a standby trust fund as directed by the EPA Regional Administrator.
Upon notification by an EPA Regional Administrator that the Principal has failed to provide alternate financial assurance as specified in subpart F of 40 CFR part 144, and obtain written approval of such assurance from the EPA Regional Administrator(s) during the 90 days following receipt by both the Principal and the EPA Regional Administrator(s) of a notice of cancellation of the bond, the Surety(ies) shall place funds in the amount guaranteed for the injection well(s) into the standby trust fund as directed by the EPA Regional Administrator.
The surety(ies) hereby waive(s) notification of amendments to plugging and abandonment plans, permits, applicable laws, statutes, rules, and regulations and agrees that no such amendment shall in any way alleviate its (their) obligation on this bond.
The liability of the Surety(ies) shall not be discharged by any payment or succession of payments hereunder, unless and until such payment or payments shall amount in the aggregate to the penal sum of the bond, but in no event shall the obligation of the Surety(ies) hereunder exceed the amount of said penal sum.
The Surety(ies) may cancel the bond by sending notice by certified mail to the owner or operator and to the EPA Regional Administrator(s) for the Region(s) in which the injection well(s) is (are) located, provided, however, that cancellation shall not occur during the 120 days beginning on the date of receipt of the notice of cancellation by both the Principal and the EPA Regional Administrator(s), as evidenced by the return receipts.
The principal may terminate this bond by sending written notice to the Surety(ies), provided, however, that no such notice shall become effective until the Surety(ies) receive(s) written authorization for termination of the bond by the EPA Regional Administrator(s) of the EPA Region(s) -in which the bonded injection well(s) is (are) located.
[The following paragraph is an optional rider that may be included but is not required.]
Principal and Surety(ies) hereby agree to adjust the penal sum of the bond yearly so that it guarantees a new plugging and abandonment amount, provided that the penal sum does not increase by more than 20 -percent in any one year, and no decrease -in the penal sum takes place without the -written permission of the EPA Regional Administrator(s).
In Witness Whereof, The Principal and Surety(ies) have executed this Performance Bond and have affixed their seals on the date set forth above.
The persons whose signatures appear below hereby certify that they are authorized to execute this surety bond on behalf of the Principal and Surety(ies) and that the wording on this surety bond is identical to the wording specified in 40 CFR 144.70(c) as such regulation was constituted on the date this bond was executed.
Principal.
State of incorporation:
Liability limit: $___.
Corporate seal:
Bond premium: $___.
(d) A letter of credit, as specified in § 144.63(d) of this chapter, must be worded as follows, except that instructions in brackets are to be replaced with the relevant information and the brackets deleted:
Regional Administrator(s)
U.S. Environmental Protection Agency.
Dear Sir or Madam:
We hereby establish our Irrevocable Standby Letter of Credit No. ___ in your favor, at the request and for the account of [owner's or operator's name and address] up to the aggregate amount of [in words] U.S. dollars $___, available upon presentation [insert, if more than one Regional Administrator is a beneficiary, “by any one of you”] of
(1) Your sight draft, bearing reference to this letter of credit No. ___, and
(2) Your signed statement reading as follows: “I certify that the amount of the draft is payable pursuant to regulations issued under authority of the Safe Drinking Water Act.”
This letter of credit is effective as of [date] and shall expire on [date at least 1 year later], but such expiration date shall be automatically extended for a period of [at least 1 year] on [date] and on each successive expiration date, unless, at least 120 days before the current expiration date, we notify both you and [owner's or operator's name] by certified mail that we have decided not to extend this letter of credit beyond the current expiration date. In the event you are so notified, any unused portion of the credit shall be available upon presentation of your sight draft for 120 days after the date of receipt by both you and [owner's or operator's name], as shown on the signed return -receipts.
Whenever this letter of credit is drawn on under and in compliance with the terms of this credit, we shall duly honor such draft upon presentation to us, and we shall deposit the amount of the draft directly into the standby trust fund of [owner's or operator's name] in accordance with your instructions.
We certify that the wording of this letter of credit is identical to the wording specified in 40 CFR 144.70(d) as such regulations were constituted on the date shown immediately below.
This credit is subject to [insert “the most recent edition of the Uniform Customs and Practice for Documentary Credits, published and copyrighted by the International Chamber of Commerce,” or “the Uniform Commercial Code”].
(e) A certificate of insurance, as specified in § 144.63(e) of this chapter, must be worded as follows, except that instructions in brackets are to be replaced with the relevant information and the brackets deleted:
Certificate of Insurance for Plugging and Abandonment
Name and Address of Insurer (herein called the “insurer”):
Name and Address of Insurer (herein called the “insurer”):
Injection Wells covered: [list for each well: The EPA Identification Number, name, address, and the amount of insurance for plugging and abandonment (these amounts for all injection wells covered must total the face amount shown below).]
The insurer hereby certifies that it has issued to the Insured the policy of insurance identified above to provide financial assurance for plugging and abandonment for the injection wells identified above. The Insurer further warrants that such policy conforms in all respects with the requirements of 40 CFR 144.63(e), as applicable and as such regulations were constituted on the date shown immediately below. It is agreed that any provision of the policy inconsistent with such regulations is hereby amended to eliminate such inconsistency.
Whenever requested by the EPA Regional Administrator(s) of the U.S. Environmental Protection Agency, the Insurer agrees to furnish to the EPA Regional Administrator(s) a duplicate original of the policy listed above, including all endorsements thereon.
I hereby certify that the wording of this certificate is identical to the wording specified in 40 CFR 144.70(e) as such regulations were constituted on the date shown immediately below.
[Signature of witness or notary:]
(f) A letter from the chief financial officer, as specified in § 144.63(f) of this chapter, must be worded as follows, except that instructions in brackets are
[Address to Regional Administrator of every Region in which injection wells for which financial responsibility is to be demonstrated through the financial test are -located.]
I am the chief financial officer of [name and address of firm.] This letter is in support of this firm's use of the financial test to demonstrate financial assurance, as specified in subpart F of 40 CFR part 144.
[Fill out the following four paragraphs regarding injection wells and associated cost estimates. If your firm has no injection wells that belong in a particular paragraph, write “None” in the space indicated. For each injection well, include its EPA Identification Number, name, address, and current plugging and abandonment cost estimate.]
1. This firm is the owner or operator of the following injection wells for which financial assurance for plugging and abandonment is demonstrated through the financial test specified in subpart F of 40 CFR part 144. The current plugging and abandonment cost estimate covered by the test is shown for each injection well: ___.
2. This firm guarantees, through the corporate guarantee specified in subpart F of 40 CFR part 144, the plugging and abandonment of the following injection wells owned or operated by subsidaries of this firm. The current cost estimate for plugging and abandonment so guaranteed is shown for each injection well: ___.
3. In States where EPA is not administering the financial requirements of subpart F of 40 CFR part 144, this firm, as owner or operator or guarantor, is demonstrating financial assurance for the plugging and abandoment of the following injection wells through the use of a test equivalent or substantially equivalent to the financial test specified in subpart F of 40 CFR part 144. The current plugging and abandonment cost estimate covered by such a test is shown for each injection well: ___.
4. This firm is the owner or operator of the following injection wells for which financial assurance for plugging and abandonment is not demonstrated either to EPA or a State through the financial test or any other financial assurance mechanism specified in subpart F of 40 CFR part 144 or equivalent or substantially equivalent State mechanisms. The current plugging and abandonment cost estimate not covered by such financial assurance is shown for each injection well: ___.
This firm [insert “is required” or “is not required”] to file a Form 10K with the Securities and Exchange Commission (SEC) for the latest fiscal year.
The fiscal year of this firm ends on [month, day]. The figures for the following items marked with an asterisk are derived from this firm's independently audited, year-end financial statements for the latest completed fiscal year, ended [date].
[Fill in Alternative I if the criteria of paragraph (f)(1)(i) of § 144.63 of this chapter are used. Fill in Alternative II if the criteria of paragraph (f)(1)(ii) of § 144.63 of this chapter are used.]
I hereby certify that the wording of this letter is identical to the wording specified in 40 CFR 144.70(f) as such regulations were constituted on the date shown immediately below.
(g) A corporate guarantee as specified in § 144.63(e) must be worded as follows except that instructions in brackets are to be replaced with the relevant information and the bracketed material deleted:
Guarantee made this __ day of ___, -19__, by [name of guaranteeing entity], a business corporation organized under the laws of the State of ____, herein referred to as guarantor, to the United States Environmental Protection Agency (EPA), obligee, on behalf of our subsidiary [owner or operator] of [business address].
1. Guarantor meets or exceeds the financial test criteria and agrees to comply with the reporting requirements for guarantors as specified in 40 CFR 144.63(e).
2. [Owner or operator] owns or operates the following Class I hazardous waste injection well covered by this guarantee: [List for each facility: EPA Identification Number, name, and address. Indicate for each whether guarantee is for closure, post-closure care, or both.]
3. “Plugging and abandonment plan” as used below refers to the plans maintained as required by 40 CFR part 144 for the plugging and abandonment of injection wells as identified above.
4. For value received from [owner or operator], guarantor guarantees to EPA that in the event that [owner or operator] fails to perform [“plugging and abandonment”] of the above facility(ies) in accordance with the plugging and abandonment plan and other requirements when required to do so, the guarantor will do so or fund a trust fund as specified in 40 CFR 144.63 in the name of [owner or operator] in the amount of the adjusted plugging and abandonment cost estimates prepared as specified in 40 CFR 144.62.
5. Guarantor agrees that, if at the end of any fiscal year before termination of this guarantee, the guarantor fails to meet the financial test criteria, guarantor will send within 90 days, by certified mail, notice to the EPA Regional Administrator(s) for the Region(s) in which the facility(ies) is (are) located and to [owner or operator] that he intends to provide alternate financial assurance as specified in 40 CFR 144.63 in the name of [owner or operator]. Within 30 days after sending such notice, the guarantor will establish such financial assurance if [owner or operator] has not done so.
6. The guarantor agrees to notify the Regional Administrator, by certified mail, of a voluntary or involuntary case under Title 11, U.S. Code, naming guarantor as debtor, within 10 days after its commencement.
7. Guarantor agrees that within 30 days after being notified by an EPA Regional Administrator of a determination that guarantor no longer meets the financial test criteria or that he is disallowed from continuing as a guarantor of plugging and adandonment, he will establish alternate financial assurance, as specified in 40 CFR 144.63, in the name of [owner or operator] if [owner or operator] has not done so.
8. Guarantor agrees to remain bound under this guarantee notwithstanding any or all of the following: amendment or modification of the plugging and abandonment plan, the extension or reduction of the time of performance of plugging and abandonment or any other modification or alteration of an obligation of [owner or operator] pursuant to 40 CFR part 144.
9. Guarantor agrees to remain bound under this guarantee for so long as [owner or operator] must comply with the applicable financial assurance requirements of 40 CFR part 144 for the above-listed facilities, except that guarantor may cancel this guarantee by sending notice by certified mail, to the EPA Regional Administrator(s) for the Region(s) in which the facility(ies) is (are) located and to [owner or operator], such cancellation to become effective no earlier than 120 days after actual receipt of such notice by both EPA and [owner or operator] as evidenced by the return receipts.
10. Guarantor agrees that if [owner or operator] fails to provide alternate financial assurance and obtain written approval of such assurance from the EPA Regional Administrator(s) within 90 days after a notice of cancellation by the guarantor is received by both the EPA Regional Administrator(s) and [owner or operator], guarantor will provide alternate financial assurance as specified in 40 CFR 144.63 in the name of [owner or operator].
11. Guarantor expressly waives notice of acceptance of this guarantee by the EPA or by [owner or operator]. Guarantor also expressly waives notice of amendments or modifications of the plugging and abandonment plan.
I hereby certify that the wording of this guarantee is identical to the wording specified in 40 CFR 144.70(f).
Effective date: ___.
Signature of witness or notary: ___
This subpart tells you what requirements apply if you own or operate a Class V injection well. You may also be required to follow additional requirements listed in the rest of this part. Where they may apply, these other requirements are referenced rather than repeated. The requirements described in this subpart and elsewhere in this part are to protect underground sources of drinking water and are part of the Underground Injection Control (UIC) Program established under the Safe Drinking Water Act. This subpart is written in a special format to make it easier to understand the regulatory requirements. Like other EPA regulations, it establishes enforceable legal requirements.
As described in § 144.6, injection wells are classified as follows:
(a)
(2) Other industrial and municipal disposal wells which inject fluids beneath the lowermost formation containing, within one quarter mile of the well bore, an underground source of drinking water;
(3) Radioactive waste disposal wells which inject fluids below the lowermost formation containing an underground source of drinking water within one quarter mile of the well bore.
(b)
(1) Which are brought to the surface in connection with natural gas storage operations, or conventional oil or natural gas production and may be commingled with waste waters from gas plants which are an integral part of production operations, unless those waters are classified as a hazardous waste at the time of injection.
(2) For enhanced recovery of oil or natural gas; and
(3) For storage of hydrocarbons which are liquid at standard temperature and pressure.
(c)
(1) Mining of sulfur by the Frasch process;
(2)
(3) Solution mining of salts or potash.
(d)
(2) Wells used by generators of hazardous waste or of radioactive waste, by owners and operators of hazardous waste management facilities, or by owners or operators of radioactive waste disposal sites to dispose of hazardous waste or radioactive waste
(3) Wells used by generators of hazardous waste or owners or operators of hazardous waste management facilities to dispose of hazardous waste, which cannot be classified under paragraph (a)(1) or (d)(1) and (2) of this section (e.g., wells used to dispose of hazardous waste into or above a formation which contains an aquifer which has been exempted pursuant to 40 CFR 146.04).
(e)
This subpart applies to you if you own or operate a Class V well, for example:
(1) Air conditioning return flow wells used to return to the supply aquifer the water used for heating or cooling in a heat pump;
(2) Large capacity cesspools including multiple dwelling, community or regional cesspools, or other devices that receive sanitary wastes, containing human excreta, which have an open bottom and sometimes perforated sides. The UIC requirements do not apply to single family residential cesspools nor to non-residential cesspools which receive solely sanitary waste and have the capacity to serve fewer than 20 persons a day.
(3) Cooling water return flow wells used to inject water previously used for cooling;
(4) Drainage wells used to drain surface fluids, primarily storm runoff, into a subsurface formation;
(5) Dry wells used for the injection of wastes into a subsurface formation;
(6) Recharge wells used to replenish the water in an aquifer;
(7) Salt water intrusion barrier wells used to inject water into a fresh aquifer to prevent the intrusion of salt water into the fresh water;
(8) Sand backfill and other backfill wells used to inject a mixture of water and sand, mill tailings or other solids into mined out portions of subsurface mines whether what is injected is a radioactive waste or not.
(9) Septic system wells used to inject the waste or effluent from a multiple dwelling, business establishment, community or regional business establishment septic tank. The UIC requirements do not apply to single family residential septic system wells, nor to non-residential septic system wells which are used solely for the disposal of sanitary waste and have the capacity to serve fewer than 20 persons a day.
(10) Subsidence control wells (not used for the purpose of oil or natural gas production) used to inject fluids into a non-oil or gas producing zone to reduce or eliminate subsidence associated with the overdraft of fresh water;
(11) Injection wells associated with the recovery of geothermal energy for heating, aquaculture and production of electric power;
(12) Wells used for solution mining of conventional mines such as stopes leaching;
(13) Wells used to inject spent brine into the same formation from which it was withdrawn after extraction of halogens or their salts;
(14) Injection wells used in experimental technologies.
(15) Injection wells used for in situ recovery of lignite, coal, tar sands, and oil shale.
(16) Motor vehicle waste disposal wells that receive or have received fluids from vehicular repair or maintenance activities, such as an auto body repair shop, automotive repair shop, new and used car dealership, specialty repair shop (
If you own or operate any type of Class V well, the regulations below require that you cannot allow movement of fluid into USDWs that might cause endangerment, you must comply with other Federal UIC requirements in 40 CFR parts 144 through 147, and you must comply with any other measures required by your State or EPA Regional Office UIC Program to protect USDWs, and you must properly close your well when you are through using it. You also must submit basic information about your well, as described in § 144.83.
(a)
(2) If the Director of the UIC Program in your State or EPA Region learns that your injection activity may endanger USDWs, he or she may require you to close your well, require you to get a permit, or require other actions listed in § 144.12(c), (d), or (e).
(b)
(c)
(d)
Yes, you need to provide basic “inventory information” about your well to the UIC Director, if you haven’t already. You also need to provide any additional information that your UIC Program Director requests in accordance with the provisions of the UIC regulations.
(a)
This information is requested on national form “Inventory of Injection Wells,” OMB No. 2040-0042.
(1) The requirements differ depending on your well status and location, as described in the following table:
(2) If your well is in a Primacy State or a DI Program State, here is the information you must submit:
(i) No matter what type of Class V well you own or operate, you must submit at least the following information for each Class V well: facility name and location; name and address of legal contact; ownership of facility; nature and type of injection well(s); and operating status of injection well(s).
(ii)
(A) Sand or other backfill wells (40 CFR 144.81(8) and 146.5(e)(8) of this chapter);
(B) Geothermal energy recovery wells (40 CFR 144.81(11) and 146.5 (e)(12) of this chapter);
(C) Brine return flow wells (40 CFR 144.81(13) and 146.5 (e)(14) of this chapter);
(D) Wells used in experimental technology (40 CFR 144.81(14) and 146.5 (e)(15) of this chapter);
(E) Municipal and industrial disposal wells other than Class I; and
(F) Any other Class V wells at the discretion of the Regional Administrator.
(iii) You must provide a list of all wells owned or operated along with the following information for each well. (A single description of wells at a single facility with substantially the same characteristics is acceptable).
(A) Location of each well or project given by Township, Range, Section, and Quarter-Section, or by latitude and longitude to the nearest second, according to the conventional practice in your State;
(B) Date of completion of each well;
(C) Identification and depth of the underground formation(s) into which each well is injecting;
(D) Total depth of each well;
(E) Construction narrative and schematic (both plan view and cross-sectional drawings);
(F) Nature of the injected fluids;
(G) Average and maximum injection pressure at the wellhead;
(H) Average and maximum injection rate; and
(I) Date of the last inspection.
(3) Regardless of whether your well is in a Primacy State or DI Program you are responsible for knowing about, understanding, and complying with these inventory requirements.
(b)
(1) Such information requirements may include, but are not limited to:
(i) Perform ground water monitoring and periodically submit your monitoring results;
(ii) Analyze the fluids you inject and periodically submit the results of your analyses;
(iii) Describe the geologic layers through which and into which you are injecting; and
(iv) Conduct other analyses and submit other information, if needed to protect underground sources of drinking water.
(2) If the Director requires this other information, he or she will request it from you in writing, along with a brief statement on why the information is required. This written notification also will tell you when to submit the information.
(3) You are prohibited from using your injection well if you fail to comply with the written request within the time frame specified. You can start injecting again only if you receive a permit.
No, unless you fall within an exception described below:
(a)
(b)
(1) You fail to comply with the prohibition of fluid movement standard in § 144.12(a) and described in § 144.82(a) (in which case, you have to get a permit, close your well, and/or comply with other conditions determined by the UIC Program Director in your State or EPA Region);
(2) You own or operate a Class V large-capacity cesspool (in which case, you must close your well as specified in the additional requirements below) or a Class V motor vehicle waste disposal well in a ground water protection area or sensitive ground water area (in which case, you must either close your well or get a permit as specified in the additional requirements in this subsection). New motor vehicle waste disposal wells and new cesspools are prohibited as of April 5, 2000;
(3) You are specifically required by the UIC Program Director in your State or EPA Region to get a permit (in which case, rule authorization expires upon the effective date of the permit issued, or you are prohibited from injecting into your well upon:
(i) Failure to submit a permit application in a timely manner as specified in a notice from the Director; or
(ii) Upon the effective date of permit denial);
(4) You have failed to submit inventory information to your UIC Program Director, as described in § 144.83(a) (in which case, you are prohibited from injecting into your well until you comply with the inventory requirements); or
(5) If you are in a DI State and you received a request from your UIC Program Director for additional information under § 144.83(b), and have failed to comply with the request in a timely manner (in which case, you are prohibited from injecting into your well until you get a permit).
(a)
(b)
(c)
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(a) You are subject to these new requirements if you own or operate an existing motor vehicle well and you are located in a ground water protection area or an other sensitive ground water area. If your State or EPA Region fails to identify these areas within the specified time frames these requirements apply to all existing motor vehicle waste disposal wells within your State.
(b)
(i) The new requirements in this subpart will apply to all existing motor vehicle waste disposal wells in the State and owners and operators of motor vehicle waste disposal wells located outside of completed assessments for ground water protection areas must close their well or receive a permit by January 1, 2005.
(ii) EPA may grant a State an extension for up to one year from the January 1, 2004 deadline if the State is making reasonable progress in completing the source water assessments for ground water protection areas. States must apply for the extension by June 1, 2003. If a State fails to complete the assessments for the remaining ground water protection areas by the extended date the rule requirements will apply to all motor vehicle waste disposal wells in the State and owners and operators of motor vehicle waste disposal wells located outside of ground water protection areas with completed assessments must close their well or receive a permit by January 1, 2006.
(2) The UIC Program Director may extend the compliance deadline for specific motor vehicle waste disposal wells for up to one year if the most efficient compliance option for the well is connection to a sanitary sewer or installation of new treatment technology.
(c)
(d)
(e)
(f)
(g) [Reserved]
(h)
The additional requirements are specified in the following tables:
The following describes the requirements for closing your Class V injection well.
(a)
(2) Closure does not mean that you need to cease operations at your facility, only that you need to close your well. A number of alternatives are available for disposing of waste fluids. Examples of alternatives that may be available to motor vehicle stations include: recycling and reusing wastewater as much as possible; collecting and recycling petroleum-based fluids, coolants, and battery acids drained from vehicles; washing parts in a self-contained, recirculating solvent sink, with spent solvents being recovered and replaced by the supplier; using absorbents to clean up minor leaks and spills, and placing the used materials in approved waste containers and disposing of them properly; using a wet vacuum or mop to pick up accumulated rain or snow melt, and if allowed, connecting floor drains to a municipal sewer system or holding tank, and if allowed, disposing of the holding tank contents through a publicly owned treatment works. You should check with the publicly owned treatment works you might use to see if they would accept your wastes. Alternatives that may be available to owners and operators of a large-capacity cesspool include: conversion to a septic system; connection to sewer; and installation of an on-site treatment unit.
(b)
42 U.S.C. 300f
(a) This part specifies the procedures EPA will follow in approving, revising, and withdrawing State programs under section 1422 (underground injection control—UIC) of SDWA, and includes the elements which must be part of submissions to EPA for program approval and the substantive provisions which must be present in State programs for them to be approved.
(b) State submissions for program approval must be made in accordance with the procedures set out in subpart C. This includes developing and submitting to EPA a program description (§ 145.23), an Attorney General's Statement (§ 145.24), and a Memorandum of Agreement with the Regional Administrator (§ 145.25).
(c) The substantive provisions which must be included in State programs to obtain approval include requirements for permitting, compliance evaluation, enforcement, public participation, and sharing of information. The requirements are found in subpart B. Many of the requirements for State programs are made applicable to States by cross-referencing other EPA regulations. In particular, many of the provisions of parts 144 and 124 are made applicable to States by the references contained in § 145.11.
(d) Upon submission of a complete program, EPA will conduct a public hearing, if interest is shown, and determine whether to approve or disapprove the program taking into consideration the requirements of this part, the Safe Drinking Water Act and any comments received.
(e) Upon approval of a State program, the Administrator shall suspend the issuance of Federal permits for those activities subject to the approved State program.
(f) Any State program approved by the Administrator shall at all times be conducted in accordance with the requirements of this part.
(g) Nothing in this part precludes a State from:
(1) Adopting or enforcing requirements which are more stringent or
(2) Operating a program with a greater scope of coverage than that required under this part. Where an approved State program has a greater scope of coverage than required by Federal law the additional coverage is not part of the federally approved program.
(h) Section 1451 of the SDWA authorizes the Administrator to delegate primary enforcement responsibility for the Underground Injection Control Program to eligible Indian Tribes. An Indian Tribe must establish its eligibility to be treated as a State before it is eligible to apply for Underground Injection Control grants and primary enforcement responsibility. All requirements of parts 124, 144, 145, and 146 that apply to States with UIC primary enforcement responsibility also apply to Indian Tribes except where specifically noted.
The definitions of part 144 apply to all subparts of this part.
(a) All State programs under this part must have legal authority to implement each of the following provisions and must be administered in conformance with each; except that States are not precluded from omitting or modifying any provisions to impose more stringent requirements.
(1) Section 144.5(b)—(Confidential information);
(2) Section 144.6—(Classification of injection wells);
(3) Section 144.7—(Identification of underground sources of drinking water and exempted aquifers);
(4) Section 144.8—(Noncompliance reporting);
(5) Section 144.11—(Prohibition of unauthorized injection);
(6) Section 144.12—(Prohibition of movement of fluids into underground sources of drinking water);
(7) Section 144.13—(Elimination of Class IV wells);
(8) Section 144.14—(Requirements for wells managing hazardous waste);
(9) Sections 144.21-144.26—(Authorization by rule);
(10) Section 144.31—(Application for a permit);
(11) Section 144.32—(Signatories);
(12) Section 144.33—(Area Permits);
(13) Section 144.34—(Emergency permits);
(14) Section 144.35—(Effect of permit);
(15) Section 144.36—(Duration);
(16) Section 144.38—(Permit transfer);
(17) Section 144.39—(Permit modification);
(18) Section 144.40—(Permit termination);
(19) Section 144.51—(Applicable permit conditions);
(20) Section 144.52—(Establishing permit conditions);
(21) Section 144.53(a)—(Schedule of compliance);
(22) Section 144.54—(Monitoring requirements);
(23) Section 144.55—(Corrective Action);
(24) Section 124.3(a)—(Application for a permit);
(25) Section 124.5 (a), (c), (d), and (f)—(Modification of permits);
(26) Section 124.6 (a), (c), (d), and (e)—(Draft Permit);
(27) Section 124.8—(Fact sheets);
(28) Section 124.10 (a)(1)(ii), (a)(1)(iii), (a)(1)(v), (b), (c), (d), and (e)—(Public notice);
(29) Section 124.11—(Public comments and requests for hearings);
(30) Section 124.12(a)—(Public hearings); and
(31) Section 124.17 (a) and (c)—(Response to comments).
(32) Section 144.88—(What are the additional requirements?);
(b)(1) States need not implement provisions identical to the provisions listed in paragraphs (a)(1) through (a)(32) of this section. Implemented provisions must, however, establish requirements at least as stringent as the corresponding listed provisions. While States may impose more stringent requirements, they may not make one requirement more lenient as a tradeoff for making another requirement more stringent; for example, by requiring
(2) State programs may, if they have adequate legal authority, implement any of the provisions of parts 144 and 124. See, for example § 144.37(d) (continuation of permits) and § 124.4 (consolidation of permit processing).
(a) State programs shall have procedures for receipt, evaluation, retention and investigation for possible enforcement of all notices and reports required of permittees and other regulated persons (and for investigation for possible enforcement of failure to submit these notices and reports).
(b) State programs shall have inspection and surveillance procedures to determine, independent of information supplied by regulated persons, compliance or noncompliance with applicable program requirements. The State shall maintain:
(1) A program which is capable of making comprehensive surveys of all facilities and activities subject to the State Director's authority to identify persons subject to regulation who have failed to comply with permit application or other program requirements. Any compilation, index, or inventory of such facilities and activities shall be made available to the Regional Administrator upon request;
(2) A program for periodic inspections of the facilities and activities subject to regulation. These inspections shall be conducted in a manner designed to:
(i) Determine compliance or noncompliance with issued permit conditions and other program requirements;
(ii) Verify the accuracy of information submitted by permittees and other regulated persons in reporting forms and other forms supplying monitoring data; and
(iii) Verify the adequacy of sampling, monitoring, and other methods used by permittees and other regulated persons to develop that information;
(3) A program for investigating information obtained regarding violations of applicable program and permit requirements; and
(4) Procedures for receiving and ensuring proper consideration of information submitted by the public about violations. Public effort in reporting violations shall be encouraged and the State Director shall make available information on reporting procedures.
(c) The State Director and State officers engaged in compliance evaluation shall have authority to enter any site or premises subject to regulation or in which records relevant to program operation are kept in order to copy any records, inspect, monitor or otherwise investigate compliance with permit conditions and other program requirements. States whose law requires a search warrant before entry conform with this requirement.
(d) Investigatory inspections shall be conducted, samples shall be taken and other information shall be gathered in a manner [e.g., using proper “chain of custody” procedures] that will produce evidence admissible in an enforcement proceeding or in court.
(a) Any State agency administering a program shall have available the following remedies for violations of State program requirements:
(1) To restrain immediately and effectively any person by order or by suit in State court from engaging in any unauthorized activity which is endangering or causing damage to public health or environment;
This paragraph requires that States have a mechanism (e.g., an administrative cease and desist order or the ability to seek a temporary restraining order) to stop any unauthorized activity endangering public health or the environment.
(2) To sue in courts of competent jurisdiction to enjoin any threatened or continuing violation of any program requirement, including permit conditions, without the necessity of a prior revocation of the permit;
(3) To assess or sue to recover in court civil penalties and to seek criminal remedies, including fines, as follows:
(i) For all wells except Class II wells, civil penalties shall be recoverable for
(ii) Criminal fines shall be recoverable in at least the amount of $5,000 per day against any person who willfully violates any program requirement, or for Class II wells, pipeline (production) severance shall be imposable against any person who willfully violates any program requirement.
In many States the State Director will be represented in State courts by the State Attorney General or other appropriate legal officer. Although the State Director need not appear in court actions he or she should have power to request that any of the above actions be brought.
(b)(1) The maximum civil penalty or criminal fine (as provided in paragraph (a)(3) of this section) shall be assessable for each instance of violation and, if the violation is continuous, shall be assessable up to the maximum amount for each day of violation.
(2) The burden of proof and degree of knowledge or intent required under State law for establishing violations under paragraph (a)(3) of this section, shall be no greater than the burden of proof or degree of knowledge or intent EPA must provide when it brings an action under the Safe Drinking Water Act.
For example, this requirement is not met if State law includes mental state as an element of proof for civil violations.
(c) A civil penalty assessed, sought, or agreed upon by the State Director under paragraph (a)(3) of this section shall be appropriate to the violation.
To the extent that State judgments or settlements provide penalties in amounts which EPA believes to be substantially inadequate in comparison to the amounts which EPA would require under similar facts, EPA, when authorized by the applicable statute, may commence separate actions for penalties.
In addition to the requirements of this paragraph, the State may have other enforcement remedies. The following enforcement options, while not mandatory, are highly recommended:
Procedures for assessment by the State of the costs of investigations, inspections, or monitoring surveys which lead to the establishment of violations;
Procedures which enable the State to assess or to sue any persons responsible for unauthorized activities for any expenses incurred by the State in removing, correcting, or terminating any adverse effects upon human health and the environment resulting from the unauthorized activity, or both; and
Procedures for the administrative assessment of penalties by the Director.
(d) Any State administering a program shall provide for public participation in the State enforcement process by providing either:
(1) Authority which allows intervention as of right in any civil or administrative action to obtain remedies specified in paragraph (a) (1), (2) or (3) of this section by any citizen having an interest which is or may be adversely affected; or
(2) Assurance that the State agency or enforcement authority will:
(i) Investigate and provide written responses to all citizen complaints submitted pursuant to the procedures specified in § 145.12(b)(4);
(ii) Not oppose intervention by any citizen when permissive intervention may be authorized by statute, rule, or regulation; and
(iii) Publish notice of and provide at least 30 days for public comment on any proposed settlement of a State enforcement action.
(e) To the extent that an Indian Tribe does not assert or is precluded from asserting criminal enforcement authority the Administrator will assume primary enforcement responsibility for criminal violations. The Memorandum of Agreement in § 145.25 shall reflect a system where the Tribal agency will refer such violations to the Administrator in an appropriate and timely manner.
(a) Any information obtained or used in the administration of a State program shall be available to EPA upon
(b) EPA shall furnish to States with approved programs the information in its files not submitted under a claim of confidentiality which the State needs to implement its approved program. EPA shall furnish to States with approved programs information submitted to EPA under a claim of confidentiality, which the State needs to implement its approved program, subject to the conditions in 40 CFR part 2.
(a) States shall submit to the Administrator a proposed State UIC program complying with § 145.22 of this part within 270 days of the date of promulgation of the UIC regulations on June 24, 1980. The administrator may, for good cause, extend the date for submission of a proposed State UIC program for up to an additional 270 days.
(b) States shall submit to the Administrator 6 months after the date of promulgation of the UIC regulations a report describing the State's progress in developing a UIC program. If the Administrator extends the time for submission of a UIC program an additional 270 days, pursuant to § 145.21(a), the State shall submit a second report six months after the first report is due. The Administrator may prescribe the manner and form of the report.
(c) The requirements of § 145.21 (a) and (b) shall not apply to Indian Tribes.
(d) EPA will establish a UIC program in any State which does not comply with paragraph (a) of this section. EPA will continue to operate a UIC program in such a State until the State receives approval of a UIC program in accordance with the requirements of this part.
States which are authorized to administer the NPDES permit program under section 402 of CWA are encouraged to rely on existing statutory authority, to the extent possible, in developing a State UIC program. Section 402(b)(1)(D) of CWA requires that NPDES States have the authority “to issue permits which control the disposal of pollutants into wells.” In many instances, therefore, NPDES States will have existing statutory authority to regulate well disposal which satisfies the requirements of the UIC program. Note, however, that CWA excludes certain types of well injections from the definition of “pollutant.” If the State's statutory authority contains a similar exclusion it may need to be modified to qualify for UIC program approval.
(e) If a State can demonstrate to EPA's satisfaction that there are no underground injections within the State for one or more classes of injection wells (other than Class IV wells) subject to SDWA and that such injections cannot legally occur in the State until the State has developed an approved program for those classes of injections, the State need not submit a program to regulate those injections and a partial program may be approved. The demonstration of legal prohibition shall be made by either explicitly banning new injections of the class not covered by the State program or providing a certification from the State Attorney General that such new injections cannot legally occur until the State has developed an approved program for that class. The State shall submit a program to regulate both those classes of injections for which a demonstration is not made and class IV wells.
(f) When a State UIC program is fully approved by EPA to regulate all classes of injections, the State assumes primary enforcement authority under section 1422(b)(3) of SDWA. EPA retains primary enforcement responsibility whenever the State program is disapproved in whole or in part. States which have partially approved programs have authority to enforce any violation of the approved portion of their program. EPA retains authority
(g) A State can assume primary enforcement responsibility for the UIC program, notwithstanding § 145.21(3), when the State program is unable to regulate activities on Indian lands within the State. EPA will administer the program on Indian lands if the State does not seek this authority.
(a) Any State that seeks to administer a program under this part shall submit to the Administrator at least three copies of a program submission. The submission shall contain the following:
(1) A letter from the Governor of the State requesting program approval;
(2) A complete program description, as required by § 145.23, describing how the State intends to carry out its responsibilities under this part;
(3) An Attorney General's statement as required by § 145.24;
(4) A Memorandum of Agreement with the Regional Administrator as required by § 145.25;
(5) Copies of all applicable State statutes and regulations, including those governing State administrative procedures;
(6) The showing required by § 145.31(b) of the State's public participation activities prior to program submission.
(b) Within 30 days of receipt by EPA of a State program submission, EPA will notify the State whether its submission is complete. If EPA finds that a State's submission is complete, the statutory review period (i.e., the period of time allotted for formal EPA review of a proposed State program under the Safe Drinking Water Act) shall be deemed to have begun on the date of receipt of the State's submission. If EPA finds that a State's submission is incomplete, the statutory review period shall not begin until all the necessary information is received by EPA.
(c) If the State's submission is materially changed during the statutory review period, the statutory review period shall begin again upon receipt of the revised submission.
(d) The State and EPA may extend the statutory review period by agreement.
Any State that seeks to administer a program under this part shall submit a description of the program it proposes to administer in lieu of the Federal program under State law or under an interstate compact. The program description shall include:
(a) A description in narrative form of the scope, structure, coverage and processes of the State program.
(b) A description (including organization charts) of the organization and structure of the State agency or agencies which will have responsibility for administering the program, including the information listed below. If more than one agency is responsible for administration of a program, each agency must have statewide jurisdiction over a class of activities. The responsibilities of each agency must be delineated, their procedures for coordination set forth, and an agency may be designated as a “lead agency” to facilitate communications between EPA and the State agencies having program responsibility. When the State proposes to administer a program of greater scope of coverage than is required by Federal law, the information provided under this paragraph shall indicate the resources dedicated to administering the Federally required portion of the program.
(1) A description of the State agency staff who will carry out the State program, including the number, occupations, and general duties of the employees. The State need not submit complete job descriptions for every employee carrying out the State program.
(2) An itemization of the estimated costs of establishing and administering the program for the first two years after approval, including cost of the personnel listed in paragraph (b)(1) of this section, cost of administrative support, and cost of technical support.
(3) An itemization of the sources and amounts of funding, including an estimate of Federal grant money, available to the State Director for the first two years after approval to meet the costs listed in paragraph (b)(2) of this section, identifying any restrictions or limitations upon this funding.
(c) A description of applicable State procedures, including permitting procedures and any State administrative or judicial review procedures.
(d) Copies of the permit form(s), application form(s), reporting form(s), and manifest format the State intends to employ in its program. Forms used by States need not be identical to the forms used by EPA but should require the same basic information. The State need not provide copies of uniform national forms it intends to use but should note its intention to use such forms.
States are encouraged to use uniform national forms established by the Administrator. If uniform national forms are used, they may be modified to include the State Agency's name, address, logo, and other similar information, as appropriate, in place of EPA's.
(e) A complete description of the State's compliance tracking and enforcement program.
(f) A State UIC program description shall also include:
(1) A schedule for issuing permits within five years after program approval to all injection wells within the State which are required to have permits under this part and part 144;
(2) The priorities (according to criteria set forth in 40 CFR 146.09) for -issuing permits, including the number -of permits in each class of injection -well which will be issued each year -during the first five years of program -operation;
(3) A description of how the Director will implement the mechanical integrity testing requirements of 40 CFR 146.08, including the frequency of testing that will be required and the number of tests that will be reviewed by the Director each year;
(4) A description of the procedure whereby the Director will notify owners and operators of injection wells of the requirement that they apply for and obtain a permit. The notification required by this paragraph shall require applications to be filed as soon as possible, but not later than four years after program approval for all injection wells requiring a permit;
(5) A description of any rule under which the Director proposes to authorize injections, including the text of the rule;
(6) For any existing enhanced recovery and hydrocarbon storage wells which the Director proposes to authorize by rule, a description of the procedure for reviewing the wells for compliance with applicable monitoring, reporting, construction, and financial responsibility requirements of §§ 144.51 and 144.52, and 40 CFR part 146;
(7) A description of and schedule for the State's program to establish and maintain a current inventory of injection wells which must be permitted under State law;
(8) Where the Director had designated underground sources of drinking water in accordance with § 144.7(a), a description and identification of all such designated sources in the State;
(9) A description of aquifers, or parts thereof, which the Director has identified under § 144.7(b) as exempted aquifers, and a summary of supporting data;
(10) A description of and schedule for the State's program to ban Class IV wells prohibited under § 144.13; and
(11) A description of and schedule for the State's program to establish an inventory of Class V wells and to assess the need for a program to regulate Class V wells.
(12)
(a) Any State that seeks to administer a program under this part shall submit a statement from the State Attorney General (or the attorney for those State or interstate agencies which have independent legal counsel) that the laws of the State, or an interstate compact, provide adequate authority to carry out the program described under § 145.23 and to meet the requirements of this part. This statement shall include citations to the specific statutes, administrative regulations, and, where appropriate, judicial decisions which demonstrate adequate authority. State statutes and regulations cited by the State Attorney General or independent legal counsel shall be in the form of lawfully adopted State statutes and regulations at the time the statement is signed and shall be fully effective by the time the program is approved. To qualify as “independent legal counsel” the attorney signing the statement required by this section must have full authority to independently represent the State agency in court on all matters pertaining to the State program.
EPA will supply States with an -Attorney General's statement format on -request.
(b) When a State seeks authority over activities on Indian lands, the statement shall contain an appropriate analysis of the State's authority.
(a) Any State that seeks to administer a program under this part shall submit a Memorandum of Agreement. The Memorandum of Agreement shall be executed by the State Director and the Regional Administrator and shall become effective when approved by the Administrator. In addition to meeting the requirements of paragraph (b) of this section, the Memorandum of Agreement may include other terms, conditions, or agreements consistent with this part and relevant to the administration and enforcement of the State's regulatory program. The Administrator shall not approve any Memorandum of Agreement which contains provisions which restrict EPA's statutory oversight responsibility.
(b) The Memorandum of Agreement shall include the following:
(1) Provisions for the prompt transfer from EPA to the State of pending permit applications and any other information relevant to program operation not already in the possession of the State Director (e.g., support files for permit issuance, compliance reports, etc.). When existing permits are transferred from EPA to State for administration, the Memorandum of Agreement shall contain provisions specifying a procedure for transferring the administration of these permits. If a State lacks the authority to directly administer permits issued by the Federal government, a procedure may be established to transfer responsibility for these permits.
For example, EPA and the State and the permittee could agree that the State would issue a permit(s) identical to the outstanding Federal permit which would simultaneously be terminated.
(2) Provisions specifying classes and categories of permit applications, draft permits, and proposed permits that the State will send to the Regional Administrator for review, comment and, where applicable, objection.
(3) Provisions specifying the frequency and content of reports, documents and other information which the State is required to submit to EPA. The State shall allow EPA to routinely review State records, reports, and files relevant to the administration and enforcement of the approved program. State reports may be combined with grant reports where appropriate.
(4) Provisions on the State's compliance monitoring and enforcement program, including:
(i) Provisions for coordination of compliance monitoring activities by
(ii) Procedures to assure coordination of enforcement activities.
(5) When appropriate, provisions for joint processing of permits by the State and EPA, for facilities or activities which require permits from both EPA and the State under different programs. See § 124.4.
(6) Provisions for modification of the Memorandum of Agreement in accordance with this part.
(c) The Memorandum of Agreement, the annual program and grant and the State/EPA Agreement should be consistent. If the State/EPA Agreement indicates that a change is needed in the Memorandum of Agreement, the Memorandum of Agreement may be amended through the procedures set forth in this part. The State/EPA Agreement may not override the Memorandum of Agreement.
Detailed program priorities and specific arrangements for EPA support of the State program will change and are therefore more appropriately negotiated in the context of annual agreements rather than in the MOA. However, it may still be appropriate to specify in the MOA the basis for such detailed agreements, e.g., a provision in the MOA specifying that EPA will select facilities in the State for inspection annually as part of the State/EPA agreement.
(a) Prior to submitting an application to the Administrator for approval of a State UIC program, the State shall issue public notice of its intent to adopt a UIC program and to seek program approval from EPA. This public notice shall:
(1) Be circulated in a manner calculated to attract the attention of interested persons. Circulation of the public notice shall include publication in enough of the largest newspapers in the State to attract Statewide attention and mailing to persons on appropriate State mailing lists and to any other persons whom the agency has reason to believe are interested;
(2) Indicate when and where the State's proposed program submission may be reviewed by the public;
(3) Indicate the cost of obtaining a copy of the submission;
(4) Provide for a comment period of not less than 30 days during which interested persons may comment on the proposed UIC program;
(5) Schedule a public hearing on the State program for no less than 30 days after notice of the hearing is published;
(6) Briefly outline the fundamental aspects of the State UIC program; and
(7) Identify a person that an interested member of the public may contact for further information.
(b) After complying with the requirements of paragraph (a) of this section any State may submit a proposed UIC program under section 1422 of SDWA and § 145.22 of this part to EPA for approval. Such a submission shall include a showing of compliance with paragraph (a) of this section; copies of all written comments received by the State; a transcript, recording or summary of any public hearing which was held by the State; and a responsiveness summary which identifies the public participation activities conducted, describes the matters presented to the public, summarizes significant comments received, and responds to these comments. A copy of the responsiveness summary shall be sent to those who testified at the hearing, and others upon request.
(c) After determining that a State's submission for UIC program approval is complete the Administrator shall issue public notice of the submission in the
(1) Indicate that a public hearing will be held by EPA no earlier than 30 days after notice of the hearing. The notice may require persons wishing to present testimony to file a request with the Regional Administrator, who may cancel the public hearing if sufficient public interest in a hearing is not expressed;
(2) Afford the public 30 days after the notice to comment on the State's submission; and
(3) Note the availability of the State submission for inspection and copying by the public.
(d) The Administrator shall approve State programs which conform to the applicable requirements of this part.
(e) Within 90 days of the receipt of a complete submission (as provided in § 145.22) or material amendment thereto, the Administrator shall by rule either fully approve, disapprove, or approve in part the State's UIC program taking into account any comments submitted. The Administrator shall give notice of this rule in the
(a) Either EPA or the approved State may initiate program revision. Program revision may be necessary when the controlling Federal or State statutory or regulatory authority is modified or supplemented. The state shall keep EPA fully informed of any proposed modifications to its basic statutory or regulatory authority, its forms, procedures, or priorities.
(b) Revision of a State program shall be accomplished as follows:
(1) The State shall submit a modified program description, Attorney General's statement, Memorandum of Agreement, or such other documents as EPA determines to be necessary under the circumstances.
(2) Whenever EPA determines that the proposed program revision is substantial, EPA shall issue public notice and provide an opportunity to comment for a period of at least 30 days. The public notice shall be mailed to interested persons and shall be published in the
(3) The Administrator shall approve or disapprove program revisions based on the requirements of this part and of the Safe Drinking Water Act.
(4) A program revision shall become effective upon the approval of the Administrator. Notice of approval of any substantial revision shall be published in the
(c) States with approved programs shall notify EPA whenever they propose to transfer all or part of any program from the approved State agency to any other State agency, and shall identify any new division of responsibilities among the agencies involved. The new agency is not authorized to administer the program until approval by the Administrator under paragraph (b) of this section. Organizational charts required under § 145.23(b) shall be revised and resubmitted.
(d) Whenever the Administrator has reason to believe that circumstances have changed with respect to a State program, he may request, and the State shall provide, a supplemental Attorney General's statement, program description, or such other documents or information as are necessary.
(e) The State shall submit the information required under paragraph (b)(1) of this section within 270 days of any amendment to this part or 40 CFR part 144, 146, or 124 which revises or adds any requirement respecting an approved UIC program.
(a) The Administrator may withdraw program approval when a State program no longer complies with the requirements of this part, and the State
(1) When the State's legal authority no longer meets their requirements of this part, including:
(i) Failure of the State to promulgate or enact new authorities when necessary; or
(ii) Action by a State legislature or court striking down or limiting State authorities.
(2) When the operation of the State program fails to comply with the requirements of this part, including:
(i) Failure to exercise control over activities required to be regulated under this part, including failure to issue permits;
(ii) Repeated issuance of permits which do not conform to the requirements of this part; or
(iii) Failure to comply with the public participation requirements of this part.
(3) When the State's enforcement program fails to comply with the requirements of this part, including:
(i) Failure to act on violations of permits or other program requirements;
(ii) Failure to seek adequate enforcement penalties or to collect administrative fines when imposed; or
(iii) Failure to inspect and monitor activities subject to regulation.
(4) When the State program fails to comply with the terms of the Memorandum of Agreement required under § 145.24.
(a) A State with a program approved under this part may voluntarily transfer program responsibilities required by Federal law to EPA by taking the following actions, or in such other manner as may be agreed upon with the Administrator.
(1) The State shall give the Administrator 180 days notice of the proposed transfer and shall submit a plan for the orderly transfer of all relevant program information not in the possession of EPA (such as permits, permit files, compliance files, reports, permit applications) which are necessary for EPA to administer the program.
(2) Within 60 days of receiving the notice and transfer plan, the Administrator shall evaluate the State's transfer plan and shall identify any additional information needed by the Federal government for program administration and/or identify any other deficiencies in the plan.
(3) At least 30 days before the transfer is to occur the Administrator shall publish notice of the transfer in the
(b) Approval of a State UIC program may be withdrawn and a Federal program established in its place when the Administrator determines, after holding a public hearing, that the State program is not in compliance with the requirements of SDWA and this part.
(1)
(2)
(3)
The Administrator is authorized to treat an Indian Tribe as eligible to apply for primary enforcement responsibility for the Underground Injection Control Program if it meets the following criteria:
(a) The Indian Tribe is recognized by the Secretary of the Interior.
(b) The Indian Tribe has a Tribal governing body which is currently “carrying out substantial governmental duties and powers” over a defined area, (
(c) The Indian Tribe demonstrates that the functions to be performed in regulating the underground injection wells that the applicant intends to regulate are within the area of the Indian Tribal government's jurisdiction.
(d) The Indian Tribe is reasonably expected to be capable, in the Administrator's judgment, of administering (in a manner consistent with the terms and purposes of the Act and all applicable regulations) an effective Underground Injection Control Program.
An Indian Tribe may apply to the Administrator for a determination that it meets the criteria of section 1451 of the Act. The application shall be concise and -describe how the Indian Tribe will -meet each of the requirements of § 145.52. The application shall consist of the following:
(a) A statement that the Tribe is recognized by the Secretary of the -Interior.
(b) A descriptive statement demonstrating that the Tribal governing body is currently carrying out substantial governmental duties and powers over a defined area. The statement should:
(1) Describe the form of the Tribal government;
(2) Describe the types of governmental functions currently performed by the Tribal governing body such as, but not limited to, the exercise of police powers affecting (or relating to) the health, safety, and welfare of the affected population; taxation; and the exercise of the power of eminent domain; and
(3) Identify the sources of the Tribal government's authority to carry out the governmental functions currently being performed.
(c) A map or legal description of the area over which the Indian Tribe asserts jurisdiction; a statement by the Tribal Attorney General (or equivalent official) which describes the basis for the Tribe's jurisdictional assertion (including the nature or subject matter of the asserted jurisdiction); a copy of those documents such as Tribal constitutions, by-laws, charters, executive orders, codes, ordinances, and/or resolutions which the Tribe believes are relevant to its assertions regarding jurisdiction; and a description of the locations of the underground -injection wells the Tribe proposes to regulate.
(d) A narrative statement describing the capability of the Indian Tribe to administer an effective Underground
(1) A description of the Indian Tribe's previous management experience which may include, the administration of programs and services authorized under the Indian Self-Determination and Education Assistance Act (25 U.S.C. 450
(2) A list of existing environmental or public health programs administered by the Tribal governing body and a copy of related Tribal laws, regulations and policies.
(3) A description of the Indian Tribe's accounting and procurement systems.
(4) A description of the entity (or entities) which exercise the executive, legislative, and judicial functions of the Tribal government.
(5) A description of the existing, or proposed, agency of the Indian Tribe which will assume primary enforcement responsibility, including a description of the relationship between owners/operators of the underground injection wells and the agency.
(6) A description of the technical and administrative capabilities of the staff to administer and manage an effective Underground Injection Control Program or a plan which proposes how the Tribe will acquire additional administrative and/or technical expertise. The plan must address how the Tribe will obtain the funds to acquire the additional administrative and technical -expertise.
(e) The Adminstrator may, in his discretion, request further documentation necessary to support a Tribe's eligibility.
(f) If the Administrator has previously determined that a Tribe has met the prerequisites that make it eligible to assume a role similar to that of a State as provided by statute under the Safe Drinking Water Act, the Clean Water Act, or the Clean Air Act, then that Tribe need provide only that information unique to the Underground Injection Control program (§ 145.76(c) and (d)(6)).
(a) The Administrator shall process a completed application of an Indian Tribe in a timely manner. He shall promptly notify the Indian Tribe of receipt of the application.
(b) A tribe that meets the requirements of § 145.52 is eligible to apply for development grants and primary enforcement responsibility for an Underground Injection Control program and the associated funding under section 1443(b) of the Act and primary enforcement responsibility for the Underground Injection Control Program under sections 1422 and/or 1425 of the Act.
Safe Drinking Water Act, 42 U.S.C. 300f
(a) This part sets forth technical criteria and standards for the Underground Injection Control Program. This part should be read in conjunction with 40 CFR parts 124, 144, and 145, which also apply to UIC programs. 40 CFR part 144 defines the regulatory framework of EPA administered permit programs. 40 CFR part 145 describes the elements of an approvable State program and procedures for EPA approval of State participation in the permit programs. 40 CFR part 124 describes the procedures the Agency will use for issuing permits under the covered programs. Certain of these procedures will also apply to State-administered programs as specified in 40 CFR part 145.
(b) Upon the approval, partial approval or promulgation of a State UIC program by the Administrator, any underground injection which is not authorized by the Director by rule or by permit is unlawful.
The Safe Drinking Water Act, 42 U.S.C. 300f
The following definitions apply to the underground injection control program.
(1)(i) Which supplies any public water system; or
(ii) Which contains a sufficient quantity of ground water to supply a public water system; and
(A) Currently supplies drinking water for human consumption; or
(B) Contains fewer than 10,000 mg/l total dissolved solids; and
(2) Which is not an exempted aquifer.
An aquifer or a portion thereof which meets the criteria for an “underground source of drinking water” in § 146.3 may be determined under 40 CFR 144.8 to be an “exempted aquifer” if it meets the following criteria:
(a) It does not currently serve as a source of drinking water; and
(b) It cannot now and will not in the future serve as a source of drinking water because:
(1) It is mineral, hydrocarbon or geothermal energy producing, or can be demonstrated by a permit applicant as part of a permit application for a Class II or III operation to contain minerals or hydrocarbons that considering their quantity and location are expected to be commercially producible.
(2) It is situated at a depth or location which makes recovery of water for drinking water purposes economically or technologically impractical;
(3) It is so contaminated that it would be economically or technologically impractical to render that water fit for human consumption; or
(4) It is located over a Class III well mining area subject to subsidence or catastrophic collapse; or
(c) The total dissolved solids content of the ground water is more than 3,000 and less than 10,000 mg/l and it is not reasonably expected to supply a public water system.
Injection wells are classified as -follows:
(a)
(2) Other industrial and municipal disposal wells which inject fluids beneath the lowermost formation containing, within one quarter mile of the well bore, an underground source of drinking water.
(3) Radioactive waste disposal wells which inject fluids below the lowermost formation containing an underground source of drinking water within one quarter mile of the well bore.
(b)
(1) Which are brought to the surface in connection with conventional oil or natural gas production and may be commingled with waste waters from gas plants which are an integral part of production operations, unless those waters are classified as a hazardous waste at the time of injection.
(2) For enhanced recovery of oil or natural gas; and
(3) For storage of hydrocarbons which are liquid at standard temperature and pressure.
(c)
(1) Mining of sulfur by the Frasch process;
(2) In situ production of uranium or other metals. This category includes only in-situ production from ore bodies which have not been conventionally mined. Solution mining of conventional mines such as stopes leaching is included in Class V.
(3) Solution mining of salts or potash.
(d)
(2) Wells used by generators of hazardous waste or of radioactive waste,
(3) Wells used by generators of hazardous waste or owners or operators of hazardous waste management facilities to dispose of hazardous waste, which cannot be classified under § 146.05(a)(1) or § 146.05(d) (1) and (2) (e.g., wells used to dispose of hazardous wastes into or above a formation which contains an aquifer which has been exempted pursuant to § 146.04).
(e)
(1) Air conditioning return flow wells used to return to the supply aquifer the water used for heating or cooling in a heat pump;
(2) Cesspools including multiple dwelling, community or regional cesspools, or other devices that receive wastes which have an open bottom and sometimes have perforated sides. The UIC requirements do not apply to single family residential cesspools nor to non-residential cesspools which receive solely sanitary wastes and have the capacity to serve fewer than 20 persons a day.
(3) Cooling water return flow wells used to inject water previously used for cooling;
(4) Drainage wells used to drain surface fluid, primarily storm runoff, into a subsurface formation;
(5) Dry wells used for the injection of wastes into a subsurface formation;
(6) Recharge wells used to replenish the water in an aquifer;
(7) Salt water intrusion barrier wells used to inject water into a fresh water aquifer to prevent the intrusion of salt water into the fresh water;
(8) Sand backfill and other backfill wells used to inject a mixture of water and sand, mill tailings or other solids into mined out portions of subsurface mines whether what is injected is a radioactive waste or not.
(9) Septic system wells used to inject the waste or effluent from a multiple dwelling, business establishment, community or regional business establishment septic tank. The UIC requirements do not apply to single family residential septic system wells, nor to non-residential septic system wells which are used solely for the disposal of sanitary waste and have the capacity to serve fewer than 20 persons a day.
(10) Subsidence control wells (not used for the purpose of oil or natural gas production) used to inject fluids into a non-oil or gas producing zone to reduce or eliminate subsidence associated with the overdraft of fresh water;
(11) Radioactive waste disposal wells other than Class IV;
(12) Injection wells associated with the recovery of geothermal energy for heating, aquaculture and production of electric power.
(13) Wells used for solution mining of conventional mines such as stopes leaching;
(14) Wells used to inject spent brine into the same formation from which it was withdrawn after extraction of halogens or their salts;
(15) Injection wells used in experimental technologies.
(16) Injection wells used for in situ recovery of lignite, coal, tar sands, and oil shale.
The area of review for each injection well or each field, project or area of the State shall be determined according to either paragraph (a) or (b) of this section. The Director may solicit input from the owners or operators of injection wells within the State as to which method is most appropriate for each geographic area or field.
(a)
(i) In the case of application(s) for well permit(s) under § 122.38 that area the radius of which is the lateral distance in which the pressures in the injection zone may cause the migration of the injection and/or formation fluid
(ii) In the case of an application for an area permit under § 122.39, the proj-ect area plus a circumscribing area the width of which is the lateral distance from the perimeter of the project area, in which the pressures in the injection zone may cause the migration of the injection and/or formation fluid into an underground source of drinking water.
(2) Computation of the zone of endangering influence may be based upon the parameters listed below and should be calculated for an injection time period equal to the expected life of the injection well or pattern. The following modified Theis equation illustrates one form which the mathematical model may take.
(i) The injection zone is homogenous and isotropic;
(ii) The injection zone has infinite area extent;
(iii) The injection well penetrates the entire thickness of the injection zone;
(iv) The well diameter is infinitesimal compared to “r” when injection time is longer than a few minutes; and
(v) The emplacement of fluid into the injection zone creates instantaneous increase in pressure.
(b)
(2) In the case of an application for an area permit under § 122.39 a fixed width of not less than one-fourth (
(c) If the area of review is determined by a mathematical model pursuant to paragraph (a) of this section, the permissible radius is the result of such calculation even if it is less than one-fourth (
In determining the adequacy of corrective action proposed by the applicant under 40 CFR 144.55 and in determining the additional steps needed to prevent fluid movement into underground sources of drinking water, the following criteria and factors shall be considered by the Director:
(a) Nature and volume of injected fluid;
(b) Nature of native fluids or by-products of injection;
(c) Potentially affected population;
(d) Geology;
(e) Hydrology;
(f) History of the injection operation;
(g) Completion and plugging records;
(h) Abandonment procedures in effect at the time the well was abandoned; and
(i) Hydraulic connections with underground sources of drinking water.
(a) An injection well has mechanical integrity if:
(1) There is no significant leak in the casing, tubing or packer; and
(2) There is no significant fluid movement into an underground source of drinking water through vertical channels adjacent to the injection well bore.
(b) One of the following methods must be used to evaluate the absence of significant leaks under paragraph (a)(1) of this section:
(1) Following an initial pressure test, monitoring of the tubing-casing annulus pressure with sufficient frequency to be representative, as determined by the Director, while maintaining an annulus pressure different from atmospheric pressure measured at the surface;
(2) Pressure test with liquid or gas; or
(3) Records of monitoring showing the absence of significant changes in the relationship between injection pressure and injection flow rate for the following Class II enhanced recovery wells:
(i) Existing wells completed without a packer provided that a pressure test has been performed and the data is available and provided further that one pressure test shall be performed at a time when the well is shut down and if the running of such a test will not cause further loss of significant amounts of oil or gas; or
(ii) Existing wells constructed without a long string casing, but with surface casing which terminates at the base of fresh water provided that local geological and hydrological features allow such construction and provided further that the annular space shall be visually inspected. For these wells, the Director shall prescribe a monitoring program which will verify the absence of significant fluid movement from the injection zone into an USDW.
(c) One of the following methods must be used to determine the absence of significant fluid movement under paragraph (a)(2) of this section:
(1) The results of a temperature or noise log; or
(2) For Class II only, cementing records demonstrating the presence of adequate cement to prevent such migration; or
(3) For Class III wells where the nature of the casing precludes the use of the logging techniques prescribed at paragraph (c)(1) of this section, cementing records demonstrating the presence of adequate cement to prevent such migration;
(4) For Class III wells where the Director elects to rely on cementing records to demonstrate the absence of significant fluid movement, the monitoring program prescribed by § 146.33(b) shall be designed to verify the absence of significant fluid movement.
(d) The Director may allow the use of a test to demonstrate mechanical integrity other than those listed in paragraphs (b) and (c)(2) of this section with the written approval of the Administrator. To obtain approval, the Director shall submit a written request to the Administrator, which shall set forth the proposed test and all technical data supporting its use. The Administrator shall approve the request if it will reliably demonstrate the mechanical integrity of wells for which its use is proposed. Any alternate method approved by the Administrator shall be published in the
(e) In conducting and evaluating the tests enumerated in this section or others to be allowed by the Director, the owner or operator and the Director shall apply methods and standards generally accepted in the industry. When the owner or operator reports the results of mechanical integrity tests to the Director, he shall include a description of the test(s) and the method(s) used. In making his/her evaluation, the Director shall review monitoring and other test data submitted since the previous evaluation.
(f) The Director may require additional or alternative tests if the results presented by the owner or operator under § 146.8(e) are not satisfactory to the Director to demonstrate that there is no movement of fluid into or between USDWs resulting from the injection activity.
In determining priorities for setting times for owners or operators to submit applications for authorization to inject under the procedures of § 144.31 (a), (c), (g) or § 144.22(f), the Director shall base these priorities upon consideration of the following factors:
(a) Injection wells known or suspected to be contaminating underground sources of drinking water;
(b) Injection wells known to be injecting fluids containing hazardous contaminants;
(c) Likelihood of contamination of underground sources of drinking water;
(d) Potentially affected population;
(e) Injection wells violating existing State requirements;
(f) Coordination with the issuance of permits required by other State or Federal permit programs;
(g) Age and depth of the injection well; and
(h) Expiration dates of existing State permits, if any.
(a) Requirements for Class I, II and III wells. (1) Prior to abandoning Class I, II and III wells, the well shall be plugged with cement in a manner which will not allow the movement of fluids either into or between underground sources of drinking water. The Director may allow Class III wells to use other plugging materials if the Director is satisfied that such materials will prevent movement of fluids into or between underground sources of drinking water.
(2) Placement of the cement plugs shall be accomplished by one of the following:
(i) The Balance method;
(ii) The Dump Bailer method;
(iii) The Two-Plug method; or
(iv) An alternative method approved by the Director, which will reliably provide a comparable level of protection to underground sources of drinking water.
(3) The well to be abandoned shall be in a state of static equilibrium with the mud weight equalized top to bottom, either by circulating the mud in the well at least once or by a comparable method prescribed by the Director, prior to the placement of the cement plug(s).
(4) The plugging and abandonment plan required in 40 CFR 144.51(o) and 144.52(a)(6) shall, in the case of a Class III project which underlies or is in an aquifer which has been exempted under § 146.04, also demonstrate adequate protection of USDWs. The Director shall prescribe aquifer cleanup and monitoring where he deems it necessary and feasible to insure adequate protection of USDWs.
(b) Requirements for Class IV wells. Prior to abandoning a Class IV well, the owner or operator shall close the well in accordance with 40 CFR 144.23(b).
(c) Requirements for Class V wells. (1) Prior to abandoning a Class V well, the owner or operator shall close the well in a manner that prevents the movement of fluid containing any contaminant into an underground source of drinking water, if the presence of that contaminant may cause a violation of any primary drinking water regulation under 40 CFR part 141 or may otherwise adversely affect the health of persons. Closure requirements for motor vehicle waste disposal wells and large-capacity cesspools are reiterated at § 144.89.
(2) The owner or operator shall dispose of or otherwise manage any soil, gravel, sludge, liquids, or other materials removed from or adjacent to the well in accordance with all applicable
This subpart establishes criteria and standards for underground injection control programs to regulate Class I nonhazardous wells.
(a) All Class I wells shall be sited in such a fashion that they inject into a formation which is beneath the lowermost formation containing, within one quarter mile of the well bore, an underground source of drinking water.
(b) All Class I wells shall be cased and cemented to prevent the movement of fluids into or between underground sources of drinking water. The casing and cement used in the construction of each newly drilled well shall be designed for the life expectancy of the well. In determining and specifying casing and cementing requirements, the following factors shall be considered:
(1) Depth to the injection zone;
(2) Injection pressure, external pressure, internal pressure, and axial loading;
(3) Hole size;
(4) Size and grade of all casing strings (wall thickness, diameter, nominal weight, length, joint specification, and construction material);
(5) Corrosiveness of injected fluid, formation fluids, and temperatures;
(6) Lithology of injection and confining intervals; and
(7) Type or grade of cement.
(c) All Class I injection wells, except those municipal wells injecting non-corrosive wastes, shall inject fluids through tubing with a packer set immediately above the injection zone, or tubing with an approved fluid seal as an alternative. The tubing, packer, and fluid seal shall be designed for the expected service.
(1) The use of other alternatives to a packer may be allowed with the written approval of the Director. To obtain approval, the operator shall submit a written request to the Director, which shall set forth the proposed alternative and all technical data supporting its use. The Director shall approve the request if the alternative method will reliably provide a comparable level of protection to underground sources of drinking water. The Director may approve an alternative method solely for an individual well or for general use.
(2) In determining and specifying requirements for tubing, packer, or alternatives the following factors shall be considered:
(i) Depth of setting;
(ii) Characteristics of injection fluid (chemical content, corrosiveness, and density);
(iii) Injection pressure;
(iv) Annular pressure;
(v) Rate, temperature and volume of injected fluid; and
(vi) Size of casing.
(d) Appropriate logs and other tests shall be conducted during the drilling and construction of new Class I wells. A descriptive report interpreting the results of such logs and tests shall be prepared by a knowledgeable log analyst and submitted to the Director. At a minimum, such logs and tests shall include:
(1) Deviation checks on all holes constructed by first drilling a pilot hole, and then enlarging the pilot hole by reaming or another method. Such checks shall be at sufficiently frequent intervals to assure that vertical avenues for fluid migration in the form of diverging holes are not created during drilling.
(2) Such other logs and tests as may be needed after taking into account the availability of similar data in the area of the drilling site, the construction plan, and the need for additional information, that may arise from time to time as the construction of the well progresses. In determining which logs and tests shall be required, the following logs shall be considered for use in the following situations:
(i) For surface casing intended to protect underground sources of drinking water:
(A) Resistivity, spontaneous potential, and caliper logs before the casing is installed; and
(B) A cement bond, temperature, or density log after the casing is set and cemented.
(ii) For intermediate and long strings of casing intended to facilitate -injection:
(A) Resistivity, spontaneous potential, porosity, and gamma ray logs before the casing is installed;
(B) Fracture finder logs; and
(C) A cement bond, temperature, or density log after the casing is set and cemented.
(e) At a minimum, the following information concerning the injection formation shall be determined or calculated for new Class I wells:
(1) Fluid pressure;
(2) Temperature;
(3) Fracture pressure;
(4) Other physical and chemical characteristics of the injection matrix; and
(5) Physical and chemical characteristics of the formation fluids.
(a)
(1) Except during stimulation injection pressure at the wellhead shall not exceed a maximum which shall be calculated so as to assure that the pressure in the injection zone during injection does not initiate new fractures or propagate existing fractures in the injection zone. In no case shall injection pressure initiate fractures in the confining zone or cause the movement of injection or formation fluids into an underground source of drinking water.
(2) Injection between the outermost casing protecting underground sources of drinking water and the well bore is prohibited.
(3) Unless an alternative to a packer has been approved under § 146.12(c), the annulus between the tubing and the long string of casings shall be filled with a fluid approved by the Director and a pressure, also approved by the Director, shall be maintained on the annulus.
(b)
(1) The analysis of the injected fluids with sufficient frequency to yield representative data of their characteristics;
(2) Installation and use of continuous recording devices to monitor injection pressure, flow rate and volume, and the pressure on the annulus between the tubing and the long string of casing;
(3) A demonstration of mechanical integrity pursuant to § 146.8 at least once every five years during the life of the well; and
(4) The type, number and location of wells within the area of review to be used to monitor any migration of fluids into and pressure in the underground sources of drinking water, the parameters to be measured and the frequency of monitoring.
(c)
(1) Quarterly reports to the Director on:
(i) The physical, chemical and other relevant characteristics of injection fluids;
(ii) Monthly average, maximum and minimum values for injection pressure, flow rate and volume, and annular pressure; and
(iii) The results of monitoring prescribed under paragraph (b)(4) of this section.
(2) Reporting the results, with the first quarterly report after the completion, of:
(i) Periodic tests of mechanical integrity;
(ii) Any other test of the injection well conducted by the permittee if required by the Director; and
(iii) Any well work over.
(d)
(2) When prescribing a monitoring system the Director may also require:
(i) Continuous monitoring for pressure changes in the first aquifer overlying the confining zone. When such a well is installed, the owner or operator shall, on a quarterly basis, sample the aquifer and analyze for constituents specified by the Director;
(ii) The use of indirect, geophysical techniques to determine the position of the waste front, the water quality in a formation designated by the Director, or to provide other site specific data;
(iii) Periodic monitoring of the ground water quality in the first aquifer overlying the injection zone;
(iv) Periodic monitoring of the ground water quality in the lowermost USDW; and
(v) Any additional monitoring necessary to determine whether fluids are moving into or between USDWs.
This section sets forth the information which must be considered by the Director in authorizing Class I wells. For an existing or converted new Class I well the Director may rely on the existing permit file for those items of information listed below which are current and accurate in the file. For a newly drilled Class I well, the Director shall require the submission of all the information listed below. For both existing and new Class I wells certain maps, cross-sections, tabulations of wells within the area of review and other data may be included in the application by reference provided they are current, readily available to the Director (for example, in the permitting agency's files) and sufficiently identified to be retrieved. In cases where EPA issues the permit all the information in this section must be submitted to the Administrator.
(a) Prior to the issuance of a permit for an existing Class I well to operate or the construction or conversion of a new Class I well the Director shall consider the following:
(1) Information required in 40 CFR 144.31 and 144.31(g);
(2) A map showing the injection well(s) for which a permit is sought and the applicable area of review. Within the area of review, the map must show the number, or name, and location of all producing wells, dry holes, surface bodies of water, springs, mines (surface and subsurface), quarries, water wells and other pertinent surface features including residences and roads. The map should also show faults, if known or suspected. Only information of public record is required to be included on this map;
(3) A tabulation of data on all wells within the area of review which penetrate into the proposed injection zone. Such data shall include a description of each well's type, construction, date drilled, location, depth, record of plugging and/or completion, and any additional information the Director may require;
(4) Maps and cross sections indicating the general vertical and lateral limits of all underground sources of drinking water within the area of review, their position relative to the injection formation and the direction of water movement, where known, in each underground source of drinking water which may be affected by the proposed injection;
(5) Maps and cross sections detailing the geologic structure of the local area;
(6) Generalized maps and cross sections illustrating the regional geologic setting;
(7) Proposed operating data:
(i) Average and maximum daily rate and volume of the fluid to be injected;
(ii) Average and maximum injection pressure; and
(iii) Source and an analysis of the chemical, physical, radiological and biological characteristics of injection fluids;
(8) Proposed formation testing program to obtain an analysis of the chemical, physical and radiological characteristics of and other information on the receiving formation;
(9) Proposed stimulation program;
(10) Proposed injection procedure;
(11) Schematic or other appropriate drawings of the surface and subsurface construction details of the well.
(12) Contingency plans to cope with all shut-ins or well failures so as to prevent migration of fluids into any underground source of drinking water;
(13) Plans (including maps) for meeting the monitoring requirements in § 146.13(b);
(14) For wells within the area of review which penetrate the injection zone but are not properly completed or plugged, the corrective action proposed to be taken under 40 CFR 144.55;
(15) Construction procedures including a cementing and casing program, logging procedures, deviation checks, and a drilling, testing, and coring program; and
(16) A certificate that the applicant has assured, through a performance bond or other appropriate means, the resources necessary to close, plug or abandon the well as required by 40 CFR 122.42(g).
(b) Prior to granting approval for the operation of a Class I well the Director shall consider the following information:
(1) All available logging and testing program data on the well;
(2) A demonstration of mechanical integrity pursuant to § 146.8;
(3) The anticipated maximum pressure and flow rate at which the permittee will operate;
(4) The results of the formation testing program;
(5) The actual injection procedure;
(6) The compatibility of injected waste with fluids in the injection zone and minerals in both the injection zone and the confining zone; and
(7) The status of corrective action on defective wells in the area of review.
(c) Prior to granting approval for the plugging and abandonment of a Class I well the Director shall consider the following information:
(1) The type and number of plugs to be used;
(2) The placement of each plug including the elevation of the top and bottom;
(3) The type and grade and quantity of cement to be used;
(4) The method for placement of the plugs; and
(5) The procedure to be used to meet the requirement of § 146.10(c).
This subpart establishes criteria and standards for underground injection control programs to regulate Class II wells.
(a) All new Class II wells shall be sited in such a fashion that they inject into a formation which is separated from any USDW by a confining zone that is free of known open faults or fractures within the area of review.
(b)(1) All Class II injection wells shall be cased and cemented to prevent movement of fluids into or between underground sources of drinking water. The casing and cement used in the construction of each newly drilled well shall be designed for the life expectancy of the well. In determining and specifying casing and cementing requirements, the following factors shall be considered:
(i) Depth to the injection zone;
(ii) Depth to the bottom of all USDWs; and
(iii) Estimated maximum and average injection pressures;
(2) In addition the Director may consider information on:
(i) Nature of formation fluids;
(ii) Lithology of injection and confining zones;
(iii) External pressure, internal pressure, and axial loading;
(iv) Hole size;
(v) Size and grade of all casing strings; and
(vi) Class of cement.
(c) The requirements in paragraph (b) of this section need not apply to existing or newly converted Class II wells located in existing fields if:
(1) Regulatory controls for casing and cementing existed for those wells
(2) Well injection will not result in the movement of fluids into an underground source of drinking water so as to create a significant risk to the health of persons.
(d) The requirements in paragraph (b) of this section need not apply to newly drilled wells in existing fields if;
(1) They meet the requirements of the State for casing and cementing applicable to that field at the time of submission of the State program to the Administrator; and
(2) Well injection will not result in the movement of fluids into an underground source of drinking water so as to create a significant risk to the health of persons.
(e) Where a State did not have regulatory controls for casing and cementing prior to the time of the submission of the State program to the Administrator, the Director need not apply the casing and cementing requirements in paragraph (b) of this section if he submits as a part of his application for primacy, an appropriate plan for casing and cementing of existing, newly converted, and newly drilled wells in existing fields, and the Administrator approves the plan.
(f) Appropriate logs and other tests shall be conducted during the drilling and construction of new Class II wells. A descriptive report interpreting the results of that portion of those logs and tests which specifically relate to (1) an USDW and the confining zone adjacent to it, and (2) the injection and adjacent formations shall be prepared by a knowledgeable log analyst and submitted to the director. At a minimum, these logs and tests shall include:
(1) Deviation checks on all holes constructed by first drilling a pilot hole and then enlarging the pilot hole, by reaming or another method. Such checks shall be at sufficiently frequent intervals to assure that vertical avenues for fluid movement in the form of diverging holes are not created during drilling.
(2) Such other logs and tests as may be needed after taking into account the availability of similar data in the area of the drilling site, the construction plan, and the need for additional -information that may arise from time to time as the construction of the well progresses. In determining which logs and tests shall be required the following shall be considered by the Director in setting logging and testing requirements:
(i) For surface casing intended to protect underground sources of drinking water in areas where the lithology has not been determined:
(A) Electric and caliper logs before casing is installed; and
(B) A cement bond, temperature, or density log after the casing is set and cemented.
(ii) for intermediate and long strings of casing intended to facilitate injection:
(A) Electric porosity and gamma ray logs before the casing is installed;
(B) Fracture finder logs; and
(C) A cement bond, temperature, or density log after the casing is set and cemented.
(g) At a minimum, the following information concerning the injection formation shall be determined or calculated for new Class II wells or projects:
(1) Fluid pressure;
(2) Estimated fracture pressure;
(3) Physical and chemical characteristics of the injection zone.
(a)
(1) Injection pressure at the wellhead shall not exceed a maximum which shall be calculated so as to assure that the pressure during injection does not initiate new fractures or propagate existing fractures in the confining zone adjacent to the USDWs. In no case shall injection pressure cause the movement of injection or formation fluids into an underground source of drinking water
(2) Injection between the outermost casing protecting underground sources
(b)
(1) Monitoring of the nature of injected fluids at time intervals sufficiently frequent to yield data representative of their characteristics;
(2) Observation of injection pressure, flow rate, and cumulative volume at least with the following frequencies:
(i) Weekly for produced fluid disposal operations;
(ii) Monthly for enhanced recovery operations;
(iii) Daily during the injection of liquid hydrocarbons and injection for withdrawal of stored hydrocarbons; and
(iv) Daily during the injection phase of cyclic steam operations
(3) A demonstration of mechanical integrity pursuant to § 146.8 at least once every five years during the life of the injection well;
(4) Maintenance of the results of all monitoring until the next permit review (see 40 CFR 144.52(a)(5)); and
(5) Hydrocarbon storage and enhanced recovery may be monitored on a field or project basis rather than on an individual well basis by manifold monitoring. Manifold monitoring may be used in cases of facilities consisting of more than one injection well, operating with a common manifold. Separate monitoring systems for each well are not required provided the owner/operator demonstrates that manifold monitoring is comparable to individual well monitoring.
(c)
(2) Owners or operators of hydrocarbon storage and enhanced recovery projects may report on a field or project basis rather than an individual well basis where manifold monitoring is used.
This section sets forth the information which must be considered by the Director in authorizing Class II wells. Certain maps, cross-sections, tabulations of wells within the area of review, and other data may be included in the application by reference provided they are current, readily available to the Director (for example, in the permitting agency's files) and sufficiently identified to be retrieved. In cases where EPA issues the permit, all the information in this section is to be submitted to the Administrator.
(a) Prior to the issuance of a permit for an existing Class II well to operate or the construction or conversion of a new Class II well the Director shall consider the following:
(1) Information required in 40 CFR 144.31 and 144.31(g);
(2) A map showing the injection well or project area for which a permit is sought and the applicable area of review. Within the area of review, the map must show the number or name and location of all existing producing wells, injection wells, abandoned wells, dry holes, and water wells. The map may also show surface bodies of waters, mines (surface and subsurface), quarries and other pertinent surface features including residences and roads, and faults if known or suspended. Only information of public record and pertinent information known to the applicant is required to be included on this map. This requirement does not apply to existing Class II wells; and
(3) A tabulation of data reasonably available from public records or otherwise known to the applicant on all
(4) Proposed operating data:
(i) Average and maximum daily rate and volume of fluids to be injected.
(ii) Average and maximum injection pressure; and
(iii) Source and an appropriate analysis of the chemical and physical characteristics of the injection fluid.
(5) Appropriate geological data on the injection zone and confining zone including lithologic description, geological name, thickness and depth;
(6) Geologic name and depth to bottom of all underground sources of drinking water which may be affected by the injection;
(7) Schematic or other appropriate drawings of the surface and subsurface construction details of the well;
(8) In the case of new injection wells the corrective action proposed to be taken by the applicant under 40 CFR 122.44;
(9) A certificate that the applicant has assured through a performance bond or other appropriate means, the resources necessary to close plug or abandon the well as required by 40 CFR 122.42(g);
(b) In addition the Director may consider the following:
(1) Proposed formation testing program to obtain the information required by § 146.22(g);
(2) Proposed stimulation program;
(3) Proposed injection procedure;
(4) Proposed contingency plans, if any, to cope with well failures so as to prevent migration of contaminating fluids into an underground source of drinking water;
(5) Plans for meeting the monitoring requirements of § 146.23(b).
(c) Prior to granting approval for the operation of a Class II well the Director shall consider the following information:
(1) All available logging and testing program data on the well;
(2) A demonstration of mechanical integrity pursuant to § 146.8;
(3) The anticipated maximum pressure and flow rate at which the permittee will operate.
(4) The results of the formation testing program;
(5) The actual injection procedure; and
(6) For new wells the status of corrective action on defective wells in the area of review.
(d) Prior to granting approval for the plugging and abandonment of a Class II well the Director shall consider the following information:
(1) The type, and number of plugs to be used;
(2) The placement of each plug including the elevation of top and bottom;
(3) The type, grade, and quantity of cement to be used;
(4) The method of placement of the plugs; and
(5) The procedure to be used to meet the requirements of § 146.10(c).
This subpart establishes criteria and standards for underground injection control programs to regulate Class III wells.
(a) All new Class III wells shall be cased and cemented to prevent the migration of fluids into or between underground sources of drinking water. The Director may waive the cementing requirement for new wells in existing projects or portions of existing projects where he has substantial evidence that no contamination of underground sources of drinking water would result. The casing and cement used in the construction of each newly drilled well shall be designed for the life expectancy of the well. In determining and specifying casing and cementing requirements, the following factors shall be considered:
(1) Depth to the injection zone;
(2) Injection pressure, external pressure, internal pressure, axial loading, etc.;
(3) Hole size;
(4) Size and grade of all casing strings (wall thickness, diameter, nominal weight, length, joint specification, and construction material);
(5) Corrosiveness of injected fluids and formation fluids;
(6) Lithology of injection and confining zones; and
(7) Type and grade of cement.
(b) Appropriate logs and other tests shall be conducted during the drilling and construction of new Class III wells. A descriptive report interpreting the results of such logs and tests shall be prepared by a knowledgeable log analyst and submitted to the Director. The logs and tests appropriate to each type of Class III well shall be determined based on the intended function, depth, construction and other characteristics of the well, availability of similar data in the area of the drilling site and the need for additional information that may arise from time to time as the construction of the well progresses. Deviation checks shall be conducted on all holes where pilot holes and reaming are used, unless the hole will be cased and cemented by circulating cement to the surface. Where deviation checks are necessary they shall be conducted at sufficiently frequent intervals to assure that vertical avenues for fluid migration in the form of diverging holes are not created during drillings.
(c) Where the injection zone is a formation which is naturally water-bearing the following information concerning the injection zone shall be determined or calculated for new Class III wells or projects:
(1) Fluid pressure;
(2) Fracture pressure; and
(3) Physical and chemical characteristics of the formation fluids.
(d) Where the injection formation is not a water-bearing formation, the information in paragraph (c)(2) of this section must be submitted.
(e) Where injection is into a formation which contains water with less than 10,000 mg/l TDS monitoring wells shall be completed into the injection zone and into any underground sources of drinking water above the injection zone which could be affected by the mining operation. These wells shall be located in such a fashion as to detect any excursion of injection fluids, process by-products, or formation fluids outside the mining area or zone. If the operation may be affected by subsidence or catastrophic collapse the monitoring wells shall be located so that they will not be physically affected.
(f) Where injection is into a formation which does not contain water with less than 10,000 mg/l TDS, no monitoring wells are necessary in the injection stratum.
(g) Where the injection wells penetrate an USDW in an area subject to subsidence or catastrophic collapse an adequate number of monitoring wells shall be completed into the USDW to detect any movement of injected fluids, process by-products or formation fluids into the USDW. The monitoring wells shall be located outside the physical influence of the subsidence or catastrophic collapse.
(h) In determining the number, location, construction and frequency of monitoring of the monitoring wells the following criteria shall be considered:
(1) The population relying on the USDW affected or potentially affected by the injection operation;
(2) The proximity of the injection operation to points of withdrawal of drinking water;
(3) The local geology and hydrology;
(4) The operating pressures and whether a negative pressure gradient is being maintained;
(5) The nature and volume of the injected fluid, the formation water, and the process by-products; and
(6) The injection well density.
(a)
(1) Except during well stimulation injection pressure at the wellhead shall be calculated so as to assure that the pressure in the injection zone during injection does not initiate new fractures or propagate existing fractures in the injection zone. In no case, shall injection pressure initiate fractures in the confining zone or cause the migration of injection or formation fluids into an underground source of drinking water.
(2) Injection between the outermost casing protecting underground sources of drinking water and the well bore is prohibited.
(b)
(1) Monitoring of the nature of injected fluids with sufficient frequency to yield representative data on its characteristics. Whenever the injection fluid is modified to the extent that the analysis required by § 146.34(a)(7)(iii) is incorrect or incomplete, a new analysis as required by § 146.34(a)(7)(iii) shall be provided to the Director.
(2) Monitoring of injection pressure and either flow rate or volume semi-monthly, or metering and daily recording of injected and produced fluid volumes as appropriate.
(3) Demonstration of mechanical integrity pursuant to § 146.08 at least once every five years during the life of the well for salt solution mining.
(4) Monitoring of the fluid level in the injection zone semi-monthly, where appropriate and monitoring of the parameters chosen to measure water quality in the monitoring wells required by § 146.32(e), semi-monthly.
(5) Quarterly monitoring of wells required by § 146.32(g).
(6) All Class III wells may be monitored on a field or project basis rather than an individual well basis by manifold monitoring. Manifold monitoring may be used in cases of facilities consisting of more than one injection well, operating with a common manifold. Separate monitoring systems for each well are not required provided the owner/operator demonstrates that manifold monitoring is comparable to individual well monitoring.
(c)
(1) Quarterly reporting to the Director on required monitoring;
(2) Results of mechanical integrity and any other periodic test required by the Director reported with the first regular quarterly report after the completion of the test; and
(3) Monitoring may be reported on a project or field basis rather than individual well basis where manifold monitoring is used.
This section sets forth the information which must be considered by the Director in authorizing Class III wells. Certain maps, cross sections, tabulations of wells within the area of review, and other data may be included in the application by reference provided they are current, readily available to the Director (for example, in the permitting agency's files) and sufficiently identified to be retrieved. In cases where EPA issues the permit, all the information in this section must be submitted to the Administrator.
(a) Prior to the issuance of a permit for an existing Class III well or area to operate or the construction of a new Class III well the Director shall consider the following:
(1) Information required in 40 CFR 144.31 and 144.31(g);
(2) A map showing the injection well or project area for which a permit is sought and the applicable area of review. Within the area of review, the
(3) A tabulation of data reasonably available from public records or otherwise known to the applicant on wells within the area of review included on the map required under paragraph (a)(2) of this section which penetrate the proposed injection zone. Such data shall include a description of each well's type, construction, date drilled, location, depth, record of plugging and completion, and any additional information the Director may require. In cases where the information would be repetitive and the wells are of similar age, type, and construction the Director may elect to only require data on a representative number of wells.
(4) Maps and cross sections indicating the vertical limits of all underground sources of drinking water within the area of review, their position relative to the injection formation, and the direction of water movement, where known, in every underground source of drinking water which may be affected by the proposed injection:
(5) Maps and cross sections detailing the geologic structure of the local area;
(6) Generalized map and cross sections illustrating the regional geologic setting;
(7) Proposed operating data:
(i) Average and maximum daily rate and volume of fluid to be injected;
(ii) Average and maximum injection pressure; and
(iii) Qualitative analysis and ranges in concentrations of all constituents of injected fluids. The applicant may request Federal confidentiality as specified in 40 CFR part 2. If the information is proprietary an applicant may, in lieu of the ranges in concentrations, choose to submit maximum concentrations which shall not be exceeded. In such a case the applicant shall retain records of the undisclosed concentrations and provide them upon request to the Director as part of any enforcement investigation.
(8) Proposed formation testing program to obtain the information required by § 146.32(c).
(9) Proposed stimulation program;
(10) Proposed injection procedure;
(11) Schematic or other appropriate drawings of the surface and subsurface construction details of the well;
(12) Plans (including maps) for meeting the monitoring requirements of § 146.33(b);
(13) Expected changes in pressure, native fluid displacement, direction of movement of injection fluid;
(14) Contingency plans to cope with all shut-ins or well failures so as to prevent the migration of contaminating fluids into underground sources of drinking water;
(15) A certificate that the applicant has assured, through a performance bond, or other appropriate means, the resources necessary to close, plug, or abandon the well as required by 40 CFR 144.52(a)(7) and
(16) The corrective action proposed to be taken under 40 CFR 144.55.
(b) Prior to granting approval for the operation of a Class III well the Director shall consider the following information:
(1) All available logging and testing data on the well;
(2) A satisfactory demonstration of mechanical integrity for all new wells and for all existing salt solution wells pursuant to § 146.08;
(3) The anticipated maximum pressure and flow rate at which the permittee will operate;
(4) The results of the formation testing program;
(5) The actual injection procedures; and
(6) The status of corrective action on defective wells in the area of review.
(c) Prior to granting approval for the plugging and abandonment of a Class III well the Director shall consider the following information:
(1) The type and number of plugs to be used;
(2) The placement of each plug including the elevation of the top and bottom;
(3) The type, grade, and quantity of cement to be used;
(4) The method of placement of the plugs; and
(5) The procedure to be used to meet the requirements of § 146.10(c).
This subpart sets forth criteria and standards for underground injection control programs to regulate all injection not regulated in subparts B, C, D, and E.
(a) Generally, wells covered by this subpart inject non-hazardous fluids into or above formations that contain underground sources of drinking water. It includes all wells listed in § 146.5(e) but is not limited to those types of injection wells.
(b) It also includes wells not covered in Class IV that inject radioactive material listed in 10 CFR part 20, appendix B, table II, column 2.
(a) This subpart establishes criteria and standards for underground injection control programs to regulate Class I hazardous waste injection wells. Unless otherwise noted this subpart supplements the requirements of subpart A and applies instead of subpart B to Class I hazardous waste injection wells.
(b)
(a) All Class I hazardous waste injection wells shall be sited such that they inject into a formation that is beneath the lowermost formation containing within one quarter mile of the well bore an underground source of drinking water.
(b) The siting of Class I hazardous waste injection wells shall be limited to areas that are geologically suitable. The Director shall determine geologic suitability based upon:
(1) An analysis of the structural and stratigraphic geology, the hydrogeology, and the seismicity of the region;
(2) An analysis of the local geology and hydrogeology of the well site, including, at a minimum, detailed information regarding stratigraphy, structure and rock properties, aquifer hydrodynamics and mineral resources; and
(3) A determination that the geology of the area can be described confidently and that limits of waste fate
(c) Class I hazardous waste injection wells shall be sited such that:
(1) The injection zone has sufficient permeability, porosity, thickness and areal extent to prevent migration of fluids into USDWs.
(2) The confining zone:
(i) Is laterally continuous and free of transecting, transmissive faults or fractures over an area sufficient to prevenet the movement of fluids into a USDW; and
(ii) Contains at least one formation of sufficient thickness and with lithologic and stress characteristics capable of preventing vertical propagation of fractures.
(d) The owner or operator shall demonstrate to the satisfaction of the Director that:
(1) The confining zone is separated from the base of the lowermost USDW by at least one sequence of permeable and less permeable strata that will provide an added layer of protection for the USDW in the event of fluid movement in an unlocated borehole or transmissive fault; or
(2) Within the area of review, the piezometric surface of the fluid in the injection zone is less than the piezometric surface of the lowermost USDW, considering density effects, injection pressures and any significant pumping in the overlying USDW; or
(3) There is no USDW present.
(4) The Director may approve a site which does not meet the requirements in paragraphs (d) (1), (2), or (3) of this section if the owner or operator can demonstrate to the Director that because of the geology, nature of the waste, or other considerations, abandoned boreholes or other conduits would not cause endangerment of USDWs.
For the purposes of Class I hazardous waste wells, this section shall apply to the exclusion of § 146.6. The area of review for Class I hazardous waste injection wells shall be a 2-mile radius around the well bore. The Director -may specify a larger area of review based on the calculated cone of influence of the well.
For the purposes of Class I hazardous waste wells, this section shall apply to the exclusion of §§ 144.55 and 146.07.
(a) The owner or operator of a Class I hazardous waste well shall as part of the permit application submit a plan to the Director outlining the protocol used to:
(1) Identify all wells penetrating the confining zone or injection zone within the area of review; and
(2) Determine whether wells are adequately completed or plugged.
(b) The owner or operator of a Class I hazardous waste well shall identify the location of all wells within the area of review that penetrate the injection zone or the confining zone and shall submit as required in § 146.70(a):
(1) A tabulation of all wells within the area of review that penetrate the injection zone or the confining zone; and
(2) A description of each well or type of well and any records of its plugging or completion.
(c) For wells that the Director determines are improperly plugged, completed, or abandoned, or for which plugging or completion information is unavailable, the applicant shall also submit a plan consisting of such steps or modification as are necessary to prevent movement of fluids into or between USDWs. Where the plan is adequate, the Director shall incorporate it into the permit as a condition. Where the Director's review of an application indicates that the permittee's plan is inadequate (based at a minimum on the factors in paragraph (e) of this section), the Director shall:
(1) Require the applicant to revise the plan;
(2) Prescribe a plan for corrective action as a condition of the permit; or
(3) Deny the application.
(d) Requirements:
(1) Existing injection wells. Any permit issued for an existing Class I hazardous waste injection well requiring corrective action other than pressure limitations shall include a compliance schedule requiring any corrective action accepted or prescribed under paragraph (c) of this section. Any such compliance schedule shall provide for
(2) New injection wells. No owner or operator of a new Class I hazardous waste injection well may begin injection until all corrective actions required under this section have been taken.
(3) The Director may require pressure limitations in lieu of plugging. If pressure limitations are used in lieu of plugging, the Director shall require as a permit condition that injection pressure be so limited that pressure in the injection zone at the site of any improperly completed or abandoned well within the area of review would not be sufficient to drive fluids into or between USDWs. This pressure limitation shall satisfy the corrective action requirement. Alternatively, such injection pressure limitation may be made part of a compliance schedule and may be required to be maintained until all other required corrective actions have been implemented.
(e) In determining the adequacy of corrective action proposed by the applicant under paragraph (c) of this section and in determining the additional steps needed to prevent fluid movement into and between USDWs, the following criteria and factors shall be considered by the Director:
(1) Nature and volume of injected fluid;
(2) Nature of native fluids or byproducts of injection;
(3) Geology;
(4) Hydrology;
(5) History of the injection operation;
(6) Completion and plugging records;
(7) Closure procedures in effect at the time the well was closed;
(8) Hydraulic connections with USDWs;
(9) Reliability of the procedures used to identify abandoned wells; and
(10) Any other factors which might affect the movement of fluids into or between USDWs.
(a)
(1) Prevent the movement of fluids into or between USDWs or into any unauthorized zones;
(2) Permit the use of appropriate testing devices and workover tools; and
(3) Permit continuous monitoring of injection tubing and long string casing as required pursuant to §146.67(f).
(b)
(c)
(i) Depth to the injection zone;
(ii) Injection pressure, external pressure, internal pressure and axial loading;
(iii) Hole size;
(iv) Size and grade of all casing strings (well thickness, diameter, nominal weight, length, joint specification and construction material);
(v) Corrosiveness of injected fluid, formation fluids and temperature;
(vi) Lithology of injection and confining zones;
(vii) Type or grade of cement; and
(viii) Quantity and chemical composition of the injected fluid.
(2) One surface casing string shall, at a minimum, extend into the confining bed below the lowest formation that contains a USDW and be cemented by circulating cement from the base of
(3) At least one long string casing, using a sufficient number of centralizers, shall extend to the injection zone and shall be cemented by circulating cement to the surface in one or more stages:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure; and
(ii) In a quantity no less than 120% of the calculated volume necessary to fill the annular space. The Director may require more than 120% when the geology or other circumstances warrant it.
(4) Circulation of cement may be accomplished by staging. The Director may approve an alternative method of cementing in cases where the cement cannot be recirculated to the surface, provided the owner or operator can demonstrate by using logs that the cement is continuous and does not allow fluid movement behind the well bore.
(5) Casings, including any casing connections, must be rated to have sufficient structural strength to withstand, for the design life of the well:
(i) The maximum burst and collapse pressures which may be experienced during the construction, operation and closure of the well; and
(ii) The maximum tensile stress which may be experienced at any point along the length of the casing during the construction, operation, and closure of the well.
(6) At a minimum, cement and cement additivies must be of sufficient quality and quantity to maintain integrity over the design life of the well.
(d)
(2) In determining and specifying requirements for tubing and packer, the following factors shall be considered:
(i) Depth of setting;
(ii) Characteristics of injection fluid (chemical content, corrosiveness, temperature and density);
(iii) Injection pressure;
(iv) Annular pressure;
(v) Rate (intermittent or continuous), temperature and volume of injected fluid;
(vi) Size of casing; and
(vii) Tubing tensile, burst, and collapse strengths.
(3) The Director may approve the use of a fluid seal if he determines that the following conditions are met:
(i) The operator demonstrates that the seal will provide a level of protection comparable to a packer;
(ii) The operator demonstrates that the staff is, and will remain, adequately trained to operate and maintain the well and to identify and interpret variations in parameters of concern;
(iii) The permit contains specific limitations on variations in annular pressure and loss of annular fluid;
(iv) The design and construction of the well allows continuous monitoring of the annular pressure and mass balance of annular fluid; and
(v) A secondary system is used to monitor the interface between the annulus fluid and the injection fluid and the permit contains requirements for testing the system every three months and recording the results.
(a) During the drilling and construction of a new Class I hazardous waste injection well, appropriate logs and tests shall be run to determine or verify the depth, thickness, porosity, permeability, and rock type of, and the salinity of any entrained fluids in, all relevant geologic units to assure conformance with performance standards in § 146.65, and to establish accurate baseline data against which future measurements may be compared. A descriptive report interpreting results of such logs and tests shall be prepared by a knowledgeable log analyst and submitted to the Director. At a minimum, such logs and tests shall include:
(1) Deviation checks during drilling on all holes constructed by drilling a pilot hole which are enlarged by reaming or another method. Such checks shall be at sufficiently frequent intervals to determine the location of the borehole and to assure that vertical avenues for fluid movement in the
(2) Such other logs and tests as may be needed after taking into account the availability of similar data in the area of the drilling site, the construction plan, and the need for additional information that may arise from time to time as the construction of the well progresses. At a minimum, the following logs shall be required in the following situations:
(i) Upon installation of the surface casing:
(A) Resistivity, spontaneous potential, and caliper logs before the casing is installed; and
(B) A cement bond and variable density log, and a temperature log after the casing is set and cemented.
(ii) Upon installation of the long string casing:
(A) Resistivity, spontaneous potential, porosity, caliper, gamma ray, and fracture finder logs before the casing is installed; and
(B) A cement bond and variable density log, and a temperature log after the casing is set and cemented.
(iii) The Director may allow the use of an alternative to the above logs when an alternative will provide equivalent or better information; and
(3) A mechanical integrity test consisting of:
(i) A pressure test with liquid or gas;
(ii) A radioactive tracer survey;
(iii) A temperature or noise log;
(iv) A casing inspection log, if required by the Director; and
(v) Any other test required by the Director.
(b) Whole cores or sidewall cores of the confining and injection zones and formation fluid samples from the injection zone shall be taken. The Director may accept cores from nearby wells if the owner or operator can demonstrate that core retrieval is not possible and that such cores are representative of conditions at the well. The Director may require the owner or operator to core other formations in the borehole.
(c) The fluid temperature, pH, conductivity, pressure and the static fluid level of the injection zone must be recorded.
(d) At a minimum, the following information concerning the injection and confining zones shall be determined or calculated for Class I hazardous waste injection wells:
(1) Fracture pressure;
(2) Other physical and chemical characteristics of the injection and confining zones; and
(3) Physical and chemical characteristics of the formation fluids in the injection zone.
(e) Upon completion, but prior to operation, the owner or operator shall conduct the following tests to verify hydrogeologic characteristics of the injection zone:
(1) A pump test; or
(2) Injectivity tests.
(f) The Director shall have the opportunity to witness all logging and testing by this subpart. The owner or operator shall submit a schedule of such activities to the Director 30 days prior to conducting the first test.
(a) Except during stimulation, the owner or operator shall assure that injection pressure at the wellhead does not exceed a maximum which shall be calculated so as to assure that the pressure in the injection zone during injection does not initiate new fractures or propagate existing fractures in the injection zone. The owner or operator shall assure that the injection pressure does not initiate fractures or propagate existing fractures in the confining zone, nor cause the movement of injection or formation fluids into a USDW.
(b) Injection between the outermost casing protecting USDWs and the well bore is prohibited.
(c) The owner or operator shall maintain an annulus pressure that exceeds the operating injection pressure, unless the Director determines that such a requirement might harm the integrity of the well. The fluid in the annulus shall be noncorrosive, or shall contain a corrosion inhibitor.
(d) The owner or operator shall maintain mechanical integrity of the injection well at all times.
(e) Permit requirements for owners or operators of hazardous waste wells which inject wastes which have the potential to react with the injection formation to generate gases shall include:
(1) Conditions limiting the temperature, pH or acidity of the injected waste; and
(2) Procedures necessary to assure that pressure imbalances which might cause a backflow or blowout do not occur.
(f) The owner or operator shall install and use continuous recording devices to monitor: the injection pressure; the flow rate, volume, and temperature of injected fluids; and the pressure on the annulus between the tubing and the long string casing, and shall install and use:
(1) Automatic alarm and automatic shut-off systems, designed to sound and shut-in the well when pressures and flow rates or other parameters approved by the Director exceed a range and/or gradient specified in the permit; or
(2) Automatic alarms, designed to sound when the pressures and flow rates or other parameters approved by the Director exceed a rate and/or gradient specified in the permit, in cases where the owner or operator certifies that a trained operator will be on-site at all times when the well is operating.
(g) If an automatic alarm or shutdown is triggered, the owner or operator shall immediately investigate and identify as expeditiously as possible the cause of the alarm or shutoff. If, upon such investigation, the well appears to be lacking mechanical integrity, or if monitoring required under paragraph (f) of this section otherwise indicates that the well may be lacking mechanical integrity, the owner or operator shall:
(1) Cease injection of waste fluids unless authorized by the Director to continue or resume injection.
(2) Take all necessary steps to determine the presence or absence of a leak; and
(3) Notify the Director within 24 hours after the alarm or shutdown.
(h) If a loss of mechanical integrity is discovered pursuant to paragraph (g) of this section or during periodic mechanical integrity testing, the owner or operator shall:
(1) Immediately cease injection of waste fluids;
(2) Take all steps reasonably necessary to determine whether there may have been a release of hazardous wastes or hazardous waste constituents into any unauthorized zone;
(3) Notify the Director within 24 hours after loss of mechanical integrity is discovered;
(4) Notify the Director when injection can be expected to resume; and
(5) Restore and demonstrate mechanical integrity to the satisfaction of the Director prior to resuming injection of waste fluids.
(i) Whenever the owner or operator obtains evidence that there may have been a release of injected wastes into an unauthorized zone:
(1) The owner or operator shall immediately case injection of waste fluids, and:
(i) Notify the Director within 24 hours of obtaining such evidence;
(ii) Take all necessary steps to identify and characterize the extent of any release;
(iii) Comply with any remediation plan specified by the Director;
(iv) Implement any remediation plan approved by the Director; and
(v) Where such release is into a USDW currently serving as a water supply, place a notice in a newspaper of general circulation.
(2) The Director may allow the operator to resume injection prior to completing cleanup action if the owner or operator demonstrates that the injection operation will not endanger USDWs.
(j) The owner or operator shall notify the Director and obtain his approval prior to conducting any well workover.
Testing and monitoring requirements shall at a minimum include:
(a) Monitoring of the injected wastes. (1) The owner or operator shall develop and follow an approved written waste analysis plan that describes the procedures to be carried out to obtain a detailed chemical and physical analysis of a representative sample of the waste, including the quality assurance procedures used. At a minimum, the plan shall specify:
(i) The paramenters for which the waste will be analyzed and the rationale for the selection of these parameters;
(ii) The test methods that will be used to test for these parameters; and
(iii) The sampling method that will be used to obtain a representative sample of the waste to be analyzed.
(2) The owner or operator shall repeat the analysis of the injected wastes as described in the waste analysis plan at frequencies specified in the waste analysis plan and when process or operating changes occur that may significantly alter the characteristics of the waste stream.
(3) The owner or operator shall conduct continuous or periodic monitoring of selected parameters as required by the Director.
(4) The owner or operator shall assure that the plan remains accurate and the analyses remain representative.
(b) Hydrogeologic compatibility determination. The owner or operator shall submit information demonstrating to the satisfaction of the Director that the waste stream and its anticipated reaction products will not alter the permeability, thickness or other relevant characteristics of the confining or injection zones such that they would no longer meet the requirements specified in § 146.62.
(c) Compatibility of well materials. (1) The owner or operator shall demonstrate that the waste stream will be compatible with the well materials with which the waste is expected to come into contact, and submit to the Director a description of the methodology used to make that determination. Compatibility for purposes of this requirement is established if contact with injected fluids will not cause the well materials to fail to satisfy any design requirement imposed under § 146.65(b).
(2) The Director shall require continuous corrosion monitoring of the construction materials used in the well for wells injecting corrosive waste, and may require such monitoring for other waste, by:
(i) Placing coupons of the well construction materials in contact with the waste stream; or
(ii) Routing the waste stream through a loop constructed with the material used in the well; or
(iii) Using an alternative method approved by the Director.
(3) If a corrosion monitoring program is required:
(i) The test shall use materials identical to those used in the construction of the well, and such materials must be continuously exposed to the operating pressures and temperatures (measured at the well head) and flow rates of the injection operation; and
(ii) The owner or operator shall monitor the materials for loss of mass, thickness, cracking, pitting and other signs of corrosion on a quarterly basis to ensure that the well components meet the minimum standards for material strength and performance set forth in § 146.65(b).
(d)
(1) The long string casing, injection tube, and annular seal shall be tested by means of an approved pressure test with a liquid or gas annually and whenever there has been a well workover;
(2) The bottom-hole cement shall be tested by means of an approved radioactive tracer survey annually;
(3) An approved temperature, noise, or other approved log shall be run at least once every five years to test for movement of fluid along the borehole. The Director may require such tests whenever the well is worked over;
(4) Casing inspection logs shall be run whenever the owner or operator conducts a workover in which the injection string is pulled, unless the Director waives this requirement due to well construction or other factors which limit the test's reliability, or based upon the satisfactory results of a casing inspection log run within the previous five years. The Director may require that a casing inspection log be run every five years, if he has reason to believe that the integrity of the long string casing of the well may be adversely affected by naturally-occurring or man-made events;
(5) Any other test approved by the Director in accordance with the procedures in § 146.8(d) may also be used.
(e)
(2) When prescribing a monitoring system the Director may also require:
(i) Continuous monitoring for pressure changes in the first aquifer overlying the confining zone. When such a well is installed, the owner or operator shall, on a quarterly basis, sample the aquifer and analyze for constituents specified by the Director;
(ii) The use of indirect, geophysical techniques to determine the position of the waste front, the water quality in a formation designated by the Director, or to provide other site specific data;
(iii) Periodic monitoring of the ground water quality in the first aquifer overlying the injection zone;
(iv) Periodic monitoring of the ground water quality in the lowermost USDW; and
(v) Any additional monitoring necessary to determine whether fluids are moving into or between USDWs.
(f) The Director may require seismicity monitoring when he has reason to believe that the injection activity may have the capacity to cause seismic disturbances.
Reporting requirements shall, at a minimum, include:
(a) Quarterly reports to the Director containing:
(1) The maximum injection pressure;
(2) A description of any event that exceeds operating parameters for annulus pressure or injection pressure as specified in the permit;
(3) A description of any event which triggers an alarm or shutdown device required pursuant to § 146.67(f) and the response taken;
(4) The total volume of fluid injected;
(5) Any change in the annular fluid volume;
(6) The physical, chemical and other relevant characteristics of injected fluids; and
(7) The results of monitoring prescribed under § 146.68.
(b) Reporting, within 30 days or with the next quarterly report whichever comes later, the results of:
(1) Periodic tests of mechanical integrity;
(2) Any other test of the injection well conducted by the permittee if required by the Director; and
(3) Any well workover.
This section sets forth the information which must be evaluated by the Director in authorizing Class I hazardous waste injection wells. For a new Class I hazardous waste injection well, the owner or operator shall submit all the information listed below as part of the permit application. For an existing or converted Class I hazardous waste injection well, the owner or operator shall submit all information listed below as part of the permit application except for those items of information which are current, accurate, and available in the existing permit file. For both existing and new Class I hazardous waste injection wells, certain maps, cross-sections, tabulations of wells within the area of review and other data may be included in the application by reference provided they are current and readily available to the Director (for example, in the permitting agency's files) and sufficiently identifiable to be retrieved. In cases where EPA issues the permit, all the information in this section must be submitted to the Administrator or his designee.
(a) Prior to the issuance of a permit for an existing Class I hazardous waste injection well to operate or the construction or conversion of a new Class I hazardous waste injection well, the Director shall review the following to
(1) Information required in § 144.31;
(2) A map showing the injection well for which a permit is sought and the applicable area of review. Within the area of review, the map must show the number or name and location of all producing wells, injection wells, abandoned wells, dry holes, surface bodies of water, springs, mines (surface and subsurface), quarries, water wells and other pertinent surface features, including residences and roads. The map should also show faults, if known or suspected;
(3) A tabulation of all wells within the area of review which penetrate the proposed injection zone or confining zone. Such data shall include a description of each well's type, construction, date drilled, location, depth, record of plugging and/or completion and any additional information the Director may require;
(4) The protocol followed to identify, locate and ascertain the condition of abandoned wells within the area of review which penetrate the injection or the confining zones;
(5) Maps and cross-sections indicating the general vertical and lateral limits of all underground sources of drinking water within the area of review, their position relative to the injection formation and the direction of water movement, where known, in each underground source of drinking water which may be affected by the proposed injection;
(6) Maps and cross-sections detailing the geologic structure of the local area;
(7) Maps and cross-sections illustrating the regional geologic setting;
(8) Proposed operating data;
(i) Average and maximum daily rate and volume of the fluid to be injected; and
(ii) Average and maximum injection pressure;
(9) Proposed formation testing program to obtain an analysis of the chemical, physical and radiological characteristics of and other information on the injection formation and the confining zone;
(10) Proposed stimulation program;
(11) Proposed injection procedure;
(12) Schematic or other appropriate drawings of the surface and subsurface construction details of the well;
(13) Contingency plans to cope with all shut-ins or well failures so as to prevent migration of fluids into any USDW;
(14) Plans (including maps) for meeting monitoring requirements of § 146.68;
(15) For wells within the area of review which penetrate the injection zone or the confining zone but are not properly completed or plugged, the corrective action to be taken under § 146.64;
(16) Construction procedures including a cementing and casing program, well materials specifications and their life expectancy, logging procedures, deviation checks, and a drilling, testing and coring program; and
(17) A demonstration pursuant to part 144, subpart F, that the applicant has the resources necessary to close, plug or abandon the well and for post-closure care.
(b) Prior to the Director's granting approval for the operation of a Class I hazardous waste injection well, the owner or operator shall submit and the Director shall review the following information, which shall be included in the completion report:
(1) All available logging and testing program data on the well;
(2) A demonstration of mechanical integrity pursuant to § 146.68;
(3) The anticipated maximum pressure and flow rate at which the permittee will operate;
(4) The results of the injection zone and confining zone testing program as required in § 146.70(a)(9);
(5) The actual injection procedure;
(6) The compatibility of injected waste with fluids in the injection zone and minerals in both the injection zone and the confining zone and with the materials used to construct the well;
(7) The calculated area of review based on data obtained during logging and testing of the well and the formation, and where necessary revisions to the information submitted under § 146.70(a) (2) and (3).
(8) The status of corrective action on wells identified in § 146.70(a)(15).
(c) Prior to granting approval for the plugging and abandonment (i.e., closure) of a Class I hazardous waste injection well, the Director shall review the information required in §§ 146.71(a)(4) and 146.72(a).
(d) Any permit issued for a Class I hazardous waste injection well for disposal on the premises where the waste is generated shall contain a certification by the owner or operator that:
(1) The generator of the hazardous waste has a program to reduce the volume or quantity and toxicity of such waste to the degree determined by the generator to be economically practicable; and
(2) Injection of the waste is that practicable method of disposal currently available to the generator which minimizes the present and future threat to human health and the environment.
(a)
(1) The owner or operator shall submit the plan as a part of the permit -application and, upon approval by the Director, such plan shall be a condition of any permit issued.
(2) The owner or operator shall submit any proposed significant revision to the method of closure reflected in the plan for approval by the Director no later than the date on which notice of closure is required to be submitted to the Director under paragraph (b) of this section.
(3) The plan shall assure financial responsibility as required in § 144.52(a)(7).
(4) The plan shall include the following information:
(i) The type and number of plugs to be used;
(ii) The placement of each plug including the elevation of the top and bottom of each plug;
(iii) The type and grade and quantity of material to be used in plugging;
(iv) The method of placement of the plugs;
(v) Any proposed test or measure to be made;
(vi) The amount, size, and location (by depth) of casing and any other materials to be left in the well;
(vii) The method and location where casing is to be parted, if applicable;
(viii) The procedure to be used to meet the requirements of paragraph (d)(5) of this section;
(ix) The estimated cost of closure; and
(x) Any proposed test or measure to be made.
(5) The Director may modify a closure plan following the procedures of § 124.5.
(6) An owner or operator of a Class I hazardous waste injection well who ceases injection temporarily, may keep the well open provided he:
(i) Has received authorization from the Director; and
(ii) Has described actions or procedures, satisfactory to the Director, that the owner or operator will take to ensure that the well will not endanger USDWs during the period of temporary disuse. These actions and procedures shall include compliance with the technical requirements applicable to active injection wells unless waived by the Director.
(7) The owner or operator of a well that has ceased operations for more than two years shall notify the Director 30 days prior to resuming operation of the well.
(b)
(c)
(1) A statement that the well was closed in accordance with the closure plan previously submitted and approved by the Director; or
(2) Where actual closure differed from the plan previously submitted, a written statement specifying the differences between the previous plan and the actual closure.
(d)
(2) Prior to well closure, appropriate mechanical integrity testing shall be conducted to ensure the integrity of that portion of the long string casing and cement that will be left in the ground after closure. Testing methods may include:
(i) Pressure tests with liquid or gas;
(ii) Radioactive tracer surveys;
(iii) Noise, temperature, pipe evaluation, or cement bond logs; and
(iv) Any other test required by the Director.
(3) Prior to well closure, the well shall be flushed with a buffer fluid.
(4) Upon closure, a Class I hazardous waste well shall be plugged with cement in a manner that will not allow the movement of fluids into or between USDWs.
(5) Placement of the cement plugs shall be accomplished by one of the following:
(i) The Balance Method;
(ii) The Dump Bailer Method;
(iii) The Two-Plug Method; or
(iv) An alternate method, approved by the Director, that will reliably provide a comparable level of protection.
(6) Each plug used shall be appropriately tagged and tested for seal and stability before closure is completed.
(7) The well to be closed shall be in a state of static equilibrium with the mud weight equalized top to bottom, either by circulating the mud in the well at least once or by a comparable method prescribed by the Director, prior to the placement of the cement plug(s).
(a) The owner or operator of a Class I hazardous waste well shall prepare, maintain, and comply with a plan for post-closure care that meets the requirements of paragraph (b) of this section and is acceptable to the Director. The obligation to implement the post-closure plan survives the termination of a permit or the cessation of injection activities. The requirement to maintain an approved plan is directly enforceable regardless of whether the requirement is a condition of the permit.
(1) The owner or operator shall submit the plan as a part of the permit application and, upon approval by the Director, such plan shall be a condition of any permit issued.
(2) The owner or operator shall submit any proposed significant revision to the plan as appropriate over the life of the well, but no later than the date of the closure report required under § 146.71(c).
(3) The plan shall assure financial responsibility as required in § 146.73.
(4) The plan shall include the following information:
(i) The pressure in the injection zone before injection began;
(ii) The anticipated pressure in the injection zone at the time of closure;
(iii) The predicted time until pressure in the injection zone decays to the point that the well's cone of influence no longer intersects the base of the lowermost USDW;
(iv) Predicted position of the waste front at closure;
(v) The status of any cleanups required under § 146.64; and
(vi) The estimated cost of proposed post-closure care.
(5) At the request of the owner or operator, or on his own initiative, the Director may modify the post-closure plan after submission of the closure report following the procedures in § 124.5.
(b) The owner or operator shall:
(1) Continue and complete any cleanup action required under § 146.64, if applicable;
(2) Continue to conduct any groundwater monitoring required under the permit until pressure in the injection zone decays to the point that the well's cone of influence no longer intersects the base of the lowermost USDW. The Director may extend the period of post-closure monitoring if he determines that the well may endanger a USDW.
(3) Submit a survey plat to the local zoning authority designated by the Director. The plat shall indicate the location of the well relative to permanently surveyed benchmarks. A copy of the plat shall be submitted to the Regional Administrator of the appropriate EPA Regional Office.
(4) Provide appropriate notification and information to such State and local authorities as have cognizance over drilling activities to enable such State and local authorities to impose appropriate conditions on subsequent drilling activities that may penetrate the well's confining or injection zone.
(5) Retain, for a period of three years following well closure, records reflecting the nature, composition and volume of all injected fluids. The Director shall require the owner or operator to deliver the records to the Director at the conclusion of the retention period, and the records shall thereafter be retained at a location designated by the Director for that purpose.
(c) Each owner of a Class I hazardous waste injection well, and the owner of the surface or subsurface property on or in which a Class I hazardous waste injection well is located, must record a notation on the deed to the facility property or on some other instrument which is normally examined during title search that will in perpetuity provide any potential purchaser of the property the following information:
(1) The fact that land has been used to manage hazardous waste;
(2) The name of the State agency or local authority with which the plat was filed, as well as the address of the Regional Environmental Protection Agency Office to which it was submitted;
(3) The type and volume of waste injected, the injection interval or intervals into which it was injected, and the period over which injection occurred.
The owner or operator shall demonstrate and maintain financial responsibility for post-closure by using a trust fund, surety bond, letter of credit, financial test, insurance or corporate guarantee that meets the specifications for the mechanisms and instruments revised as appropriate to cover closure and post-closure care in 40 CFR part 144, subpart F. The amount of the funds available shall be no less than the amount identified in § 146.72(a)(4)(vi). The obligation to maintain financial responsibility for post-closure care survives the termination of a permit or the cessation of injection. The requirement to maintain financial responsibility is enforceable regardless of whether the requirement is a condition of the permit.
42 U.S.C. 300h; and 42 U.S.C. 6901
(a) This part sets forth the applicable Underground Injection Control (UIC) programs for each of the states, territories, and possessions identified pursuant to the Safe Drinking Water Act (SDWA) as needing a UIC program.
(b) The applicable UIC program for a State is either a State-administered program approved by EPA, or a federally-administered program promulgated by EPA. In some cases, the UIC program may consist of a State-administered program applicable to some classes of wells and a federally-administered program applicable to other classes of wells. Approval of a State program is based upon a determination by the Administrator that the program meets the requirements of section 1422 or section 1425 of the Safe Drinking Water Act and the applicable provisions of parts 124, 144, and 146 of this chapter. A federally-administered program is promulgated in those instances where the state has failed to submit a program for approval or where the submitted program does not meet the minimum statutory and regulatory requirements.
(c) In the case of State programs approved by EPA pursuant to section 1422 of the SDWA, each State subpart describes the major elements of such programs, including State statutes and regulations, Statement of Legal Authority, Memorandum of Agreement, and Program Description. State statutes and regulations that contain standards, requirements, and procedures applicable to owners or operators have been incorporated by reference pursuant to regulations of the Office of the Federal Register. Material incorporated by reference is available for inspection in the appropriate EPA Regional Office, in EPA Headquarters, and at the Office of the Federal Register Information Center, Room 8301, 800 North Capitol Street, NW., suite 700, Washington, DC. Other State statutes and regulations containing standards and procedures that constitute elements of the State program but do not apply directly to owners or operators have been listed but have not been incorporated by reference.
(d) In the case of State programs promulgated under section 1422 that are to be administered by EPA, the State subpart makes applicable the provisions of parts 124, 144, and 146, and provides additional requirements pertinent to the specific State program.
(e) Regulatory provisions incorporated by reference (in the case of approved State programs) or promulgated by EPA (in the case of EPA-administered programs), and all permit conditions or permit denials issued pursuant to such regulations, are enforceable by the Administrator pursuant to section 1423 of the SDWA.
(f) The information requirements located in the following sections have been cleared by the Office of Management and Budget: Sections 147.104, 147.304, 147.754, 147.904, 147.1154, 147.1354, 147.1454, 147.1654, 147.1954, and 147.2154.
The OMB clearance number is No. 2040-0042.
The provisions in this part and the various applications thereof are distinct and severable. If any provision of this part or the application thereof to any person or circumstances is held invalid, such invalidity shall not affect other provisions or application of such provision to other persons or circumstances which can be given effect without the invalid provision or application.
The UIC program for Class II wells in the State of Alabama, except those on Indian lands, is the program administered by the State Oil and Gas Board of Alabama, approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Code of Alabama Sections 9-17-1 through 9-17-109 (Cumm. Supp. 1989);
(2) State Oil and Gas Board of Alabama Administrative Code, Oil and Gas Report 1 (supplemented through May 1989), Rules and Regulations Governing the Conservation of Oil and Gas in Alabama, and Oil and Gas Statutes of Alabama with Oil and Gas Board Forms, § 400-1-2 and § 400-1-5-.04.
(b) The Memorandum of Agreement between EPA Region IV and the Alabama Oil and Gas Board, signed by the EPA Regional Administrator on June 15, 1982.
(c)
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
The UIC program for Class I, III, IV and V wells in the State of Alabama, except those on Indian lands, is the program administered by the Alabama Department of Environmental Management, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Alabama Water Pollution Control Act, Code of Alabama 1975, sections 22-
(2) Regulations, Policies and Procedures of the Alabama Water Im-provement Commission, Title I (Reg-u-la-tions) (Rev. December 1980), as amended May 17, 1982, to add Chapter 9, Underground Injection Control Regulations (effective June 10, 1982), as amended April 6, 1983 (effective May 11, 1983).
(b) The Memorandum of Agreement between EPA Region IV and the Alabama Department of Environment Management, signed by the EPA Regional Administrator on May 24, 1983.
(c)
(2) Letter from Attorney, Alabama Water Improvement Commission, to Regional Administrator, EPA Region IV, “Re: AWIC Response to Phillip Tate's (U.S. EPA, Washington) Comments on AWIC's Final Application for Class I, III, IV, and V UIC Program,” September 21, 1982;
(3) Letter from Alabama Chief Assistant Attorney General to Regional Counsel, EPA Region IV, “Re: Status of Independent Legal Counsel in Alabama Water Improvement Commission's Underground Injection Control Program,” September 14, 1982.
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
The UIC program for hydraulic fracturing of coal beds in the State of Alabama, except those on Indian lands, is the program administered by the State Oil and Gas Board of Alabama, approved by EPA pursuant to Section 1425 of the SDWA on December 22, 1999 and effective on January 19, 2000. The Alabama program consists of the following elements, as submitted to EPA in the State's program application:
(a)
(b) Addendum One, Underground Injection Control Program, Memorandum of Agreement Between the State of Alabama and the USEPA Region 4, signed by the Supervisor, Alabama State Oil and Gas Board on December 10, 1999, and the Regional Administrator, U.S. Environmental Protection Agency Region 4, on December 13, 1999.
(c)
(d) The Program Description for the Regulation of Hydraulic Fracturing of Coal Beds As required by 40 CFR 145.23—State Oil and Gas Board of Alabama, including Appendices A through F.
(a)
(b)
The UIC program for Class II wells in the State of Alaska, other than those on Indian lands, is the program administered by the Alaska Oil and Gas Conservation Commission approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Alaska Statutes, Alaska Oil and Gas Conservation Act, Title 31, §§ 31.05.005 through 31.30.010 (1979 and Cum. Supp. 1984);
(2) Alaska Statutes, Administrative Procedures Act, Title 44, §§ 44.62.010 through 44.62.650 (1984);
(3) Alaska Administrative Code, Alaska Oil and Gas Conservation Commission, 20 AAC 25.005 through 20 AAC 25.570 (Supp. 1986).
(b)
(c)
(d) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a) This section identifies any aquifers or their portions exempted in accordance with §§ 144.7(b) and 146.4 of this chapter at the time of program promulgation. EPA may in the future exempt other aquifers or portions, according to applicable procedures, without codifying such exemptions in this section. An updated list of exemptions will be maintained in the Regional office.
(b) The following aquifers are exempted in accordance with the provisions of §§ 144.7(b) and 146.4 of this chapter for Class II injection activities only:
(1) The portions of aquifers in the Kenai Peninsula, greater than the indicated depths below the ground surface, and described by a
(i) Swanson River Field—1700 feet.
(ii) Beaver Creek Field—1650 feet.
(iii) Kenai Gas Field—1300 feet.
(2) The portion of aquifers beneath Cook Inlet described by a
(i) Granite Point.
(ii) McArthur River Field.
(iii) Middle Ground Shoal Field.
(iv) Trading Bay Field.
(3) The portions of aquifers on the North Slope described by a
Maximum injection pressure. The owner or operator shall limit injection pressure to the lesser of:
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable; or
(b) A value for well head pressure calculated by using the following formula:
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish maximum injection pressures after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within 1 year of the effective date of this program.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) as needed to protect USDWs.
(a)
(b)
The UIC program for Class I, III, IV and V wells in the State of Arkansas, except those wells on Indian lands, is the program administered by the Arkansas Department of Pollution Control and Ecology approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Arkansas Water and Air Pollution Control Act, Act 472 of 1949 as amended, Arkansas Statutes Annotated sections 82-1901 through 82-1943 (1976);
(2) Act 105 of 1939, Arkansas Statutes Annotated sections 53-101 through 53-130 (1971 and Supp. 1981); Act 937 of 1979, Arkansas Statutes Annotated sections 53-1301 through 53-1320 (Supp. 1981); Act 523 of 1981;
(3) Arkansas Underground Injection Control Code, Department of Pollution Control and Ecology, promulgated January 22, 1982;
(4) General Rule and Regulations, Arkansas Oil and Gas Commission (Order No. 2-39, revised July 1972);
(5) Arkansas Hazardous Waste Management Code, Department of Pollution Control and Ecology, promulgated August 21, 1981.
(b) The Memorandum of Agreement and Addendum No. 1 to the Memorandum of Agreement, between EPA Region VI and the Arkansas Department of Pollution Control and Ecology
(c)
(2) Letter from Chief Attorney, Arkansas Department of Pollution Control and Ecology, to Acting Regional Counsel, EPA Region VI, “Re: Addendum to Legal Statement—Underground Injection Control Program,” October 13, 1981;
(3) Letter from General Counsel, Arkansas Oil and Gas Commission, to Acting Regional Counsel, EPA Region VI, “Re: Supplemental Addendum to Legal Statement—Underground Injection Control Program,” October 20, 1981;
(4) Letter from Chief Attorney, Arkansas Department of Pollution Control and Ecology, to Attorney, Office of Regional Counsel, EPA Region VI (re: status as independent legal counsel), December 31, 1981;
(5) Letter from General Counsel, Arkansas Oil and Gas Commission, to Acting Regional Counsel, EPA Region VI, “Re: Supplemental Addendum to Legal Statement—Underground Injection Control Program,” January 13, 1982;
(6) Letter from Chief Counsel, Arkansas Department of Pollution Control and Ecology, to Acting Regional Counsel, EPA Region VI, “Re: Addendum to Legal Statement—Underground Injection Control Program,” February 15, 1982;
(7) Letter from Chief Counsel, Arkansas Department of Pollution Control and Ecology, to Acting Regional Counsel, EPA Region VI, “Re: Addendum to Legal Statement—Underground Injection Control Program,” May 13, 1982.
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for Class II wells in the State of California, except those on Indian lands, is the program administered by the California Division of Oil and Gas, approved by EPA pursuant to SDWA section 1425.
(a)
(1) California Laws for Conservation of Petroleum and Gas, California Public Resources Code Div. 3, Chapt. 1, §§ 3000-3359 (1989);
(2) California Administrative Code, title 14, §§ 1710 to 1724.10 (May 28, 1988).
(b) The Memorandum of Agreement between EPA Region IX and the California Division of Oil and Gas, signed by the EPA Regional Administrator on September 29, 1982.
(c)
(2) Letter from California Deputy Attorney General to Chief of California Branch, EPA Region IX, “Re: California Application for Primacy, Class II UIC Program,” December 3, 1982.
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
Maximum injection pressure. The owner or operator shall limit injection pressure to the lesser of:
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable; or
(b) A value for well head pressure calculated by using the following formula:
The UIC program for Class II wells in the State of Colorado, except those wells on Indian Lands, is the program administered by the Colorado Oil and Gas Commission approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the FR on April 2, 1984 (49 FR 13040); the effective date of this program is April 2, 1984. This program consists of the following elements, as submitted to EPA in the State's program application:
(a)
(1) Colorado Revised Statutes, 1989 replacement volume, Section 34-60-101 through 34-60-123;
(2) Colorado Revised Statutes, 1989 replacement volume, Section 25-8-101 through 25-8-612;
(3) Rules and Regulations, Rules of Practice and Procedure, and Oil and Gas Conservation Act (As Amended) Department of Natural Resources, Oil and Gas Conservation Commission of the State of Colorado (revised July 1989);
(4) Oil and Gas Conservation Commission Revised Rules and Regulations in the 300, 400, 500, and 600 series, effective March 20, 1989.
(b)
(c)
(2) Letter from Colorado Assistant Attorney General to the Acting Regional Counsel, EPA Region VIII, “Re: Class II Well Injection Control Program of Colorado Oil and Gas Conservation Commission”, April 29, 1983;
(3) Letter from Colorado Assistant Attorney General to the Acting Regional Counsel, EPA Region VIII, “Re: Class II Underground Injection Control Program of Colorado Oil and Gas Conservation Commission, interpretation of C.R.S. 1973, 34-60-110”, July 11, 1983;
(4) Letter from Colorado Assistant Attorney General to the Acting Regional Counsel, EPA Region VIII, “Re: Class II Well Underground Injection Control Program of Colorado Oil and Gas Conservation Commission”, February 17, 1984;
(5) Memorandum from Colorado Assistant Attorney General to the Acting Regional Counsel, EPA Region VIII, “Re: Authority to set and enforce maximum pressure for injecting fluids into Class II wells with existing permits”, March 7, 1984.
(d)
(1) Application and accompanying materials for approval of Colorado's UIC program for Class II wells submitted by the Director of the Colorado Oil and Gas Conservation Commission to the Regional Administrator, May 3, 1983;
(2) Supplemental amendment to Colorado's application for primacy for the UIC program for Class II wells describing the process through which the State will ensure enforceable limits for maximum injection pressure, describing the Commission's plan of administration for Class II wells, and describing Mechanical Integrity Test procedures for Class II wells, March 7, 1984;
(3) Official correspondence concerning various program issues between the Colorado Oil and Gas Conservation Commission and EPA Region VIII, for the period from March 7, 1984 to May 8, 1989.
(a)
(b)
(a) This section identifies any aquifers of their portions exempted in accordance with §§ 144.7(b) and 146.4 of this chapter at the time of program promulgation. EPA may in the future exempt other aquifers or portions according to applicable procedures without codifying such exemptions in this section. An updated list of exemptions will be maintained in the Regional office.
(b) For all aquifers into which existing Class II wells are injecting, those portions within a
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable; or
(b) A value for wellhead pressure calculated by using the following formula;
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirements of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes rules for maximum injection pressures based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within one year of the effective date of this program.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistent to deterioration from formation and injection fluids; and
(iii) In quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) as needed to protect USDWs.
(a) The owner or operator converting an existing well to an injection well shall check the condition of the casing with one of the following logging tools:
(1) A Pipe analysis log; or
(2) A Caliper log.
(b) The owner or operator of a new injection well cased with plastic (PVC, ABS, and others) casings shall:
(1) Not construct a well deeper than 500 feet;
(2) Use cement and additives compatible with such casing material;
(3) Cement the annular space above the injection interval from the bottom of the blank casing to the surface.
(c) The owner or operator of a newly drilled well shall install centralizers as directed by the Regional Administrator.
(d) The owner or operator shall as required by the Regional Administrator:
(1) Protect USDWs by:
(i) Setting surface casing 50 feet below the base of the lowermost USDW;
(ii) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(iii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may approve alternate casing and cementing practices provided that the owner or operator demonstrates that such practices will adequately protect USDWs.
(e)
(f) The applicant must give separate notice of intent to apply for a permit to each owner or tenant of the land within one-quarter mile of the site. The addresses of those to whom notice is given, and a description of how notice is given, shall be submitted with the permit application. The notice shall include:
(1) Name and address of applicant;
(2) A brief description of the planned injection activities, including well location, name and depth of the injection zone, maximum injection pressure and volume, and fluid to be injected;
(3) EPA contact person; and
(4) A statement that opportunity to comment will be announced after EPA prepares a draft permit. This requirement may be waived by the Regional Administrator when he determines that individual notice to all land owners and tenants would be impractical.
The UIC program for all classes of wells in the State of Connecticut, -except those wells on Indian lands, is the program administered by the Con-nect-i-cut Department of Environmental Protection approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the FR on March 26, 1984 (49 FR 11179); the effective date of this program is March 26, 1984. This program consists of the following elements, as submitted to EPA in the State's program application:
(a)
(1) Connecticut General Statutes Annotated, title 22a (Environmental Protection), chapter 439, sections 22a-1 through 22a-27 (1985 and Cumm. Supp. 1990);
(2) Connecticut General Statutes Annotated, Title 22a (Environmental Protection), Chapter 446K (1985 and Cumm. Supp. 1990).
(b)
(c)
(2) Addendum to the Statement from the Attorney General of the State of Connecticut, signed by the Attorney General on May 10, 1983.
(d)
(a)
(b)
The UIC program for all classes of wells in the State of Delaware, except those wells on Indian lands, is the program administered by the Delaware Department of Natural Resources and Environmental Control approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the FR on April 5, 1984 (49 FR 13525); the effective date of this program is May 7, 1984. This program consists of the following elements, as submitted to EPA in the State's program application:
(a)
(1) Delaware Environmental Protection Act, (Environmental Control) 7 Delaware Code Annotated, Chapter 60, Sections 6001-6060 (Revised 1974 and Cumm. Supp. 1988);
(2) State of Delaware Regulations Governing Underground Injection Control, parts 122, 124 and 146 (Department of Natural Resources and Environmental Control), effective August 15, 1983.
(b)
(c)
(d)
(a)
(b)
(a)
(b)
The UIC program for Class I, III, IV, and V wells in the State of Florida, except for those on Indian lands is administered by the Florida Department of Environmental Regulations, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Florida Air and Water Pollution Control Act, Florida Statutes Annotated sections 403.011 through 403.90 (1973 and Supp. 1983);
(2) Chapter 17-28, Underground Injection Control, Florida Administrative Code (April 27, 1989).
(b)
(1) Administrative Procedures Act, Florida Statutes Chapter 120;
(2) Florida Administrative Code, Chapter 17-1 (1982) (Administrative Procedures Act);
(3) Florida Administrative Code, Chapter 17-3 (1982) (Water Quality Standards);
(4) Florida Administrative Code, Chapter 17-4 (1982) (Permits);
(5) Florida Administrative Code, Chap-ter 28-5 (1982) (Decisions De-ter-min-ing Substantial Interests);
(6) Florida Administrative Code, Chapter 28-6 (1982) (Licensing);
(c) The Memorandum of Agreement between EPA Region IV and the Florida Department of Environmental Regulation, signed by the EPA Regional Administrator on March 31, 1983.
(d)
(2) “Addendum to Statement of Legal Authority for Implementation of Underground Injection Control Program” and accompanying certifications, signed by Acting General Counsel for the Florida Department of Environmental Regulation, September 20, 1982.
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressure greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within 1 year of the effective date of this program.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) Comply with other requirements which the Regional Administrator may specify either in addition to or in lieu of the requirements set forth in paragraphs (b)(1) through (3) of this section as needed to protect USDWs.
(c)
The UIC program for all classes of wells in the State of Georgia, except those wells on Indian lands, is the program administered by the Georgia Department of Natural Resources, Environmental Protection Division approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Oil and Gas and Deep Drilling Act of 1975, Official Code of Georgia Annotated (O.C.G.A.) §§ 12-4-40 through 12-4-53 (1988);
(2) Ground Water Use Act of 1972, O.C.G.A. §§ 12-5-90 through 12-5-107 (1988);
(3) Water Well Standards Act of 1985, O.C.G.A. §§ 12-5-120, through 12-5-138 (1988);
(4) Georgia Administrative Procedure Act, O.C.G.A. §§ 50-13-1 through 50-13-22 (Reprinted from the O.C.G.A. and 1988 Cumm. Supp.);
(5) Georgia Water Quality Control Act, O.C.G.A. §§ 12-5-20 through 12-5-53 (1988);
(6) Georgia Hazardous Waste Management Act, O.C.G.A. §§ 12-8-60 through 12-8-83 (1988);
(7) Georgia Safe Drinking Water Act of 1977, O.C.G.A. §§ 12-5-170 through 12-5-193 (1988);
(8) Rules of Georgia Department of Natural Resources, Environmental Protection Division, Water Quality Control, GA. COMP. R. & REGS. Chapter 391-3-6-.13 (Revised July 28, 1988).
(b)
(c)
(2) Underground Injection Control Program, Attorney General's Statement, February 4, 1982;
(3) Amended Attorney General's Statement Relating to Authority of the State of Georgia to Implement an Underground Injection Control Program, April 22, 1983;
(4) Letter to EPA Office of General Counsel from Senior Assistant Attorney General “Re: State UIC Program”, July 13, 1983.
(d)
(a)
(b)
(a)
(b)
The UIC program for Class I, II, III, IV, and V wells in the State of Idaho, other than those on Indian lands, is the program administered by the Idaho Department of Water Resources, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Public Writings, Title 9, Chapter 3, Idaho Code, sections 9-301 through 9-302 (Bobbs-Merrill 1979);
(2) Crimes and Punishments, Title 18, Chapter 1, Idaho Code, sections 18-113 through 18-114 (Bobbs-Merrill 1979 and Supp. 1984);
(3) Department of Health and Welfare, Title 39, Chapter 1, Idaho Code, Chapter 39-108 (Bobbs-Merrill 1977);
(4) Drainage-Water Rights and Reclamation, Title 42, Chapter 2, Idaho Code sections 42-237(e); section 42-238 (Bobbs-Merrill 1977 and Supp. 1984);
(5) Department of Water Resources-Water Resources Board, Title 42, Chapter 17, Idaho Code, sections 42-1701, 42-1703, 42-1735 (Bobbs-Merrill 1977, section 42-1701A (Supp. 1984);
(6) Director of Department of Water Resources, Title 42, Chapter 18, Idaho Code, sections 42-1801 through 42-1805 (Bobbs-Merrill 1977);
(7) Waste Disposal and Injection Wells, Title 42, Chapter 39, Idaho Code, sections 42-3901 through 42-3914 (Bobbs-Merrill 1977), sections 42-3915 through 42-3919 (Supp. 1984);
(8) Idaho Trade Secrets Act, Title 48, Chapter 8, Idaho Code, sections 48-801 through 48-807 (Bobbs-Merrill 1977 and Supp. 1984);
(9) Administrative Procedure, Title 67, Chapter 52, Idaho Code, sections
(10) Idaho Radiation Control Regulations (IRCR section 1-9002.70; sections 1-9100 through 1-9110, Department of Health and Welfare (May 1981);
(11) Rules and Regulations: Construction and Use of Injection Wells, Idaho Department of Water Resources, Rules 1 through 14 (August 1984);
(12) Rules and Regulations: Practice and Procedures, Idaho Department of Water Resources, Rules 1 through 14 (October 1983).
(b) The Memorandum of Agreement between EPA and Region X and the Idaho Department of Water Resources signed by the EPA Regional Administrator on February 11, 1985.
(c)
(2) Letter from David J. Barber, Deputy Attorney General, Idaho Department of Water Resources to Harold Scott, EPA, Region 10, revising the Attorney General's Statement, February 14, 1985.
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for Class I, III, IV and V wells in the State of Illinois, -except those on Indian lands, is the -program administered by the Illinois Environmental Protection Agency, approved by EPA pursuant to section 1422 of the SDWA. Notice of the ap-pro-val was published in the
(a)
(1) Illinois Environmental Protection Act, Illinois ch. 111
(2) Illinois Pollution Control Board Rules and Regulations at Title 35, Illinois Administrative Code, Chapter I, Part 700, Outline of Waste Disposal Regulations; Part 702, RCRA and UIC Permit Programs; Part 704, UIC Permit
(b) The Memorandum of Agreement between EPA Region V and the Illinois Environmental Protection Agency, signed by the EPA Regional Administrator on March 22, 1984.
(c)
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
The UIC program for Class II wells in the State of Illinois, except those on Indian lands, is the program administered by the Illinois Environmental Protection Agency, approved by EPA pursuant to section 1425 of the SDWA. Notice of the approval was published in the
(a)
(1) Conservation of Oil and Gas, etc., Illinois Revised Statutes ch. 96
(2) Illinois Environmental Protection Act, Illinois Revised Statutes ch. 111
(3) Illinois Revised Statutes ch. 100
(4) Illinois Department of Mines and Minerals Regulations for the Oil and Gas Division, Rules I, II, IIA, III, V, VII, and IX (1981).
(b) The Memorandum of Agreement between EPA Region V and the Illinois Department of Mines and Minerals, signed by the EPA Regional Administrator on March 22, 1984.
(c)
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for Class II injection wells in the State of Indiana on non-Indian lands is the program administered by the Indiana Department of Natural Resources (INDR) approved by the EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the FR on August 19, 1991; the effective date of this program is August 19, 1991. This program consists of the following elements, as submitted to EPA in the State's program application:
(a)
(1) Indiana Code, title 4, article 21.5, chapters 1 through 6 (1988).
(2) West's Annotated Indiana Code, title 13, article 8, chapters 1 through 15 (1990 and Cumm. Supp. 1990).
(3) Indiana Administrative Code, title 310, article 7, rules 1 through 3 (Cumm. Supp. 1991).
(b)
(c)
(d) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable; or
(b) A value for well head pressure calculated by using the following formula:
(a)
(b)
The UIC program for Class I, III, IV and V wells in the State of Kansas, except those on Indian lands as described in § 147.860, is the program administered by the Kansas Department of Health and Environment, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Chapter 28, Article 46, Underground Injection Control Regulations, Kansas Administrative Regulations §§ 28-46-1 through 28-46-42 (1986 and Supp. 1987);
(2) Chapter 28, Article 43, Construction, operation, monitoring and abandonment of salt solution mining wells, Kansas Administrative Regulations §§ 28-43-1 through 28-43-10 (1986);
(3) Kansas Statutes Annotated §§ 65-161, 65-164 through 65-166a, 65-171d (1980 and Cumm. Supp. 1989).
(b)
(c)
(2) Addendum No. 1 of the Memorandum of Agreement, signed by the EPA Regional Administrator on August 29, 1983.
(d)
(2) “Supplemental Statement of Attorney General”, signed by the Attorney General of the State of Kansas, undated (one page).
(e)
The UIC program for Class II wells in the State of Kansas, except those on Indian lands as described in § 147.860, is the program administered by the Kansas Corporation Commission and the Kansas Department of Health and Environment, approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(b)
(a)
(b)
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable or;
(b) A value for well head pressure calculated by using the following formula:
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within 1 year of the effective date of this program.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between and the casing the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) of this section, as needed to protect USDWs.
Notwithstanding the alternatives presented in § 146.6 of this chapter, the area of review shall be a minimum fixed radius as described in § 146.6(b) of this chapter.
The UIC program for Class I, II, III, IV, and V wells in the State of Louisiana, except those wells on Indian lands, is the program administered by the Louisiana Department of Natural Resources approved by EPA pursuant to sections 1422 and 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Louisiana Revised Statutes Annotated sections 30:1-30:24 (1975 and Supp. 1982);
(2) Underground Injection Control Program Regulations for Class I, III, IV, and V wells, Statewide Order No. 29-N-1 (February 20, 1982), as amended June 1, 1985 and January 20, 1986;
(3)(i) Statewide Order Governing the Drilling for and Producing of Oil and Gas in the State of Louisiana, Statewide Order No. 29-B (August 26, 1974) (Composite Order Incorporating Amendments through March 1, 1974);
(ii) Amendments to Statewide Order No. 29-B (Off-site Disposal of Drilling Mud and Salt Water Generated from Drilling and Production of Oil and Gas Wells) (effective July 20, 1980);
(iii) Amendment to Statewide Order No. 29-B (Amendment concerning the use of Tables 5A and 6A, etc.) (December 15, 1980, effective January 1, 1981);
(iv) Amendment to Statewide Order No. 29-B (Amendment concerning the underground injection control of saltwater disposal wells, enhanced recovery injection wells, and liquid hydrocarbon storage wells) (effective February 20, 1982);
(v) Amendment to Statewide Order No. 29-B (Amendment concerning the offsite disposal of drilling mud and saltwater) (effective May 20, 1983);
(vi) Amendment to Statewide Order No. 29-B (Amendment concerning disposal of nonhazardous oilfield waste) (March 20, 1984, effective May 20, 1984);
(vii) Amendment to Statewide Order No. 29-B (Amendment concerning the administrative approval of injectivity
(4) (i) Statewide Order adopting rules and regulations pertaining to the use of salt dome cavities (i.e., storage chambers) for storage of liquid and/or gaseous hydrocarbons, etc., Statewide Order No. 29-M (July 6, 1977, effective July 20, 1977);
(ii) Supplement to Statewide Order No. 29-M (October 2, 1978);
(iii) Second Supplement to Statewide Order No. 29-M (June 8, 1979).
(b)(1) The Memorandum of Agreement (Class I, III, IV, and V wells) between EPA Region VI and the Louisiana Department of Natural Resources, Office of Conservation, signed by the EPA Regional Administrator on March 17, 1982 and amended by Addendum 1 and Addendum 2 on November 3, 1989;
(2) The Memorandum of Agreement (Class II wells) between EPA Region VI and the Louisiana Department of Natural Resources, Office of Conservation, signed by the EPA Regional Administrator on March 17, 1982.
(c)
(2) Letter from Attorney General of Louisiana to EPA, “Re: Louisiana Underground Injection Control Program Authorization for State of Louisiana” (Class II Wells), January 13, 1982 (5 pages).
(3) Letter from Attorney General of Louisiana to EPA, “Re: Class I Hazardous Waste Injection Well Regulatory Program; Attorney General's Statement, October 9, 1989 (9 pages);
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for all classes of wells in the State of Maine, except those on Indian lands, is the program administered by the Maine Department of Environmental Protection approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Maine Revised Statutes Annotated title 38, sections 361-A, 363-B, 413, 414, 414-A, 420, and 1317-A (1978);
(2) Rules to Control the Subsurface Discharge of Pollutants by Well Injection, Rules of the Department of Environmental Protection, Chapter 543 (adopted June 22, 1983, effective July 4, 1983).
(b) The Memorandum of Agreement between EPA Region I and the Maine Department of Environmental Protection, signed by the EPA Regional Administrator on May 16, 1983.
(c)
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for Class I, II, III, IV, and V wells in the State of Maryland, except those wells on Indian lands, is the program administered by the Maryland Department of the Environment approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the FR on April 19, 1984 (49 FR 15553); the effective date of this program is June 4, 1984. This program consists of the following elements, as submitted to EPA in the State's program application:
(a)
(1) Code of Maryland Regulations, Title 26, Subtitle 08, Chapter 07 promulgated and effective as of March 1, 1989;
(2) Code of Maryland Regulations, Title 26, Subtitle 08, Chapter 01, promulgated and effective as of March 1, 1989;
(3) Code of Maryland Regulations, Title 26, Subtitle 08, Chapter 02, promulgated and effective as of March 1, 1989;
(4) Code of Maryland Regulations, Title 26, Subtitle 08, Chapter 03, promulgated and effective as of March 1, 1989;
(5) Code of Maryland Regulations, Title 26, Subtitle 08, Chapter 04, promulgated and effective as of March 1, 1989;
(6) Code of Maryland Regulations, Title 26, Subtitle 13, Chapter 05, section .19, promulgated and effective as of August 1, 1989;
(7) Code of Maryland Regulations, Title 26, Subtitle 01, Chapter 02, promulgated and effective as of March 1, 1989;
(8) Code of Maryland Regulations, Title 26, Subtitle 01, Chapter 04, promulgated and effective as of March 1, 1989.
(b)
(c)
(d)
(a)
(b)
The UIC program for all classes of wells in the State of Massachusetts, except those on Indian lands, is the program administered by the Massachusetts Department of Environmental Protection, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Massachusetts General Laws Annotated chapter 21, sections 27, 43, and 44 (West 1981);
(2) Code of Massachusetts Regulations, title 310, sections 23.01-23.11 as amended April 26, 1982.
(b) The Memorandum of Agreement between EPA Region I and the Massachusetts Department of Environmental Quality Engineering, signed by the EPA Regional Administrator on August 18, 1982.
(c)
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
(a)
(b)
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable; or
(b) A value for well head pressure calculated by using the following formula:
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regonal Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes field rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within 1 year following the effective date of this program.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3)
(a)
(b)
(a)
(b)
(a)
(b)
(c)
The UIC program for Class I, III, IV and V wells in the State of Mississippi, except those on Indian lands, is the program administered by the Mississippi Department of Natural Resources approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Mississippi Air and Water Pollution Control Law, Mississippi Code Annotated sections 49-17-1 through 49-17-29 (1972) and Supp. 1983);
(2) Mississippi Department of Natural Resources, Bureau of Pollution Control, Underground Injection Control Program Regulations (adopted February 11, 1982);
(3) Mississippi Department of Natural Resources, Bureau of Pollution Control, State of Mississippi Wastewater Permit Regulations for National Pollutant Discharge Elimination System (NPDES), Underground Injection Control (UIC), and State Operating Permits (adopted May 1, 1974; amended February 11, 1982).
(b) The Memorandum of Agreement between EPA Region IV and the Mississippi Department of Natural Resources, signed by the EPA Regional Administrator on February 8, 1983.
(c)
(2) Letter from Attorney General of Mississippi (by Special Assistant Attorney General) to Executive Director, Mississippi Department of Natural Resources, “Re: Authority to Regulate and Take Samples from Underground Injection Systems,” October 18, 1982;
(3) Letter from Attorney General of Mississippi (by Special Assistant Attorney General) to Regional Administrator, EPA Region IV, “Re: Public Participation in State Enforcement Actions, UIC Program,” June 10, 1983.
(d) The Program Description and any other materials submitted as part of the application or supplements thereto.
The UIC program for Class II wells in the State of Mississippi, other than those on Indian lands, is the program administered by the State Oil and Gas Board of Mississippi approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a) Incorporation by reference. The requirements set forth in the State statutes and regulations cited in this paragraph are hereby incorporated by reference and made a part of the applicable UIC program under the SDWA for the State of Mississippi. This incorporation by reference was approved by the Director of the Federal Register in accordance with 5 U.S.C. 552(a).
(1) Mississippi Code Annotated, section 5-9-9 (Supp. 1988).
(2) Mississippi Code Annotated, sections 53-1-1 through 53-1-47, inclusive and sections 53-1-71 through 53-1-77, inclusive (1972 and Supp. 1988).
(3) Mississippi Code Annotated, sections 53-3-1 through 53-3-165, inclusive (1972 and Supp. 1988).
(4) State Oil and Gas Board Statewide Rules and Regulations, Rules 1 through 65, inclusive (Aug. 1, 1987, as amended, Sept. 17, 1987).
(b) The Memorandum of Agreement between EPA Region IV and the State Oil and Gas Board of Mississippi signed by the Regional Administrator on October 31, 1988.
(c) Statement of legal authority. Statement from the Attorney General signed on October 1, 1987 with amendments to the Statement signed August 5, 1988 and September 15, 1988 by the Special Assistant Attorney General.
(d) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
The UIC program for all classes of wells in the State of Missouri, except those on Indian lands, is administered by the Missouri Department of Natural Resources, approved by EPA pursuant to section 1422 and 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Vernon's Annotated Missouri Statutes sections 259.010 to 259.240 (Supp. 1984);
(2) Missouri Code of State Regulations, title 10, division 50, chapters 1 and 2 (June 1984);
(3) Vernon's Annotated Missouri Statutes chapter 204, §§ 204.006 through 204.470 (1983 and Cumm. Supp. 1990).
(b) The Memorandum of Agreement between EPA Region VII and the Missouri Department of Oil and Gas, signed by the EPA Regional Administrator on December 3, 1982.
(c)
(2) Addendum to Opinion Letter No. 63 (1982), signed by Attorney General of Missouri, October 28, 1982.
(3) Opinion No. 127-83, signed by Attorney General of Missouri, July 11, 1983.
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
The UIC program for Class I, III, IV, and V wells in the State of Missouri, other than those on Indian lands, is the program administered by the Missouri Department of Natural Resources, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Revised Statutes of the State of Missouri, Volume 2, sections 204.016, 204.026, 204.051, 204.056 and Volume V, section 577.155 (1978 and Cumm. Supp. 1984);
(2) Missouri Code of State Regulations, title 10, division 20, Chapter 6, sections 20-6.010, 20-6.020, 20-6.070, 20-6.080, 20-6.090, and title 10, division -20, Chapter 7, section 20-7.031 (1977, amended 1984).
(b)
(1) Revised Statutes of the State of Missouri, chapters 204, 260, 536, 557, 558 and 560; sections 640.130.1 and 1.020 (1978 and Cumm. Supp. 1984);
(2) Rule 52.12 Vernon's Annotated Missouri Rules (1978);
(3) Missouri Code of State Regulations, title 10, division 20, Chapters 1 through 7 (1977, amended 1984).
(c) The Memorandum of Agreement between EPA Region VII and the Missouri Department of Natural Resources, signed by the EPA Regional Administrator on October 10, 1984.
(d)
(e) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for Class II injection wells in the State of Montana, except for those in Indian Country, is the program administered by the Montana Board of Oil and Gas Conservation (MBOGC) approved by the EPA pursuant to Section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Montana Statutory Requirements Applicable to the Underground Injection Control Program, August, 1996.
(2) Montana Regulatory Requirements Applicable to the Underground Injection Control Program, August, 1996.
(b)
(2) Letter dated May 24, 1996, from the Administrator of the MBOGC and the attached addendum (Addendum No. 1-96) to the MOA between MBOGC and EPA Region VIII, signed by the Acting EPA Regional Administrator on August 14, 1996.
(c)
(2) MBOGC independent counsel's certification of Montana's UIC program for Class II wells dated July 24, 1995.
(3) Letter dated March 8,1996, from MBOGC independent counsel to USEPA, Region VIII; “Re: EPA comments of November 29, 1995, on Montana Class II primacy application.”
(4) Letter dated March 8, 1996, from the Administrator of the MBOGC and the attached proposed replacement language for the MOA; “Re: Responses to EPA comments on Montana Class II Primacy Application.”
(d)
(1) Application and accompanying materials for approval of Montana's UIC program for Class II wells submitted by the Governor of Montana, August 3, 1995.
(2) [Reserved]
(a)
(b)
Those portions of aquifers within one-quarter mile of existing Class II wells are exempted for the purpose of Class II injection activities only.
A complete listing of the exemptions and their location is available for review in the EPA Regional Office, 1860 Lincoln Street, Denver, Colorado. An updated list of exemptions will be maintained in the Regional -Office.
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable or
(b) A value for well head pressure calculated by using the following formula:
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator established rules for maximum injection pressure based on data provided pursuant to paragraph (ii) below the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within 1 year of the effective date of this program.
(b)
(1) Isolate all USDWs by placing cement between the outermost casing and the well bore as follows:
(i) If the injection well is east of the 108th meridian, cement the outermost casing from a point 50 feet into a major shale formation underlying the uppermost USDW to the surface. For the purpose of this paragraph, major shale formations are defined as the Bearpaw, Clagget, and Colorado formations.
(ii) If the injection well is west of the 108th meridian, cement the outermost casing to a depth of 1,000 feet, or to the base of the lowermost USDW in use as a source of drinking water whichever is deeper. The Regional Administrator may allow an owner or operator to -cement to a lesser depth if he can -demonstrate to the satisfaction of the Regional Administrator that no USDW will be affected by the injection -facilities.
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deteriortion from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) of this section, as needed to protect USDWs.
(a)
(b) The applicant must give separate notice of intent to apply for a permit to each owner or tenant of the land within one-quarter mile of the site. This requirement may be waived by the Regional Administrator where individual notice to all land owners and tenants would be impractical. The addresses of those to whom notice is given, and a description of how notice was given, shall be submitted with the permit application. The notice shall -include:
(1) Name and address of applicant;
(2) A brief description of the planned injection activities, including well location, name and depth of the injection zone, maximum injection pressure and volume, and fluid to be injected;
(3) EPA contact person; and
(4) A statement that opportunity to comment will be announced after EPA prepares a draft permit.
(c) Owners and operators on or within one-half mile of Indian lands shall provide notice as specified in paragraph (b) of this section, except that such notice shall be provided within a one-half mile radius of the site.
The following is an informational listing of state requirements incorporated by reference in Subpart BB of part 147 of the Code of Federal Regulations:
(a) The statutory provisions include:
(1) Montana Code annotated, 1995, Title 2, Chapter 15:
Section 2-15-121. Allocation for administrative purposes only.
Section 2-15-124. Quasi-judicial boards.
Section 2-15-3303. Board of oil and gas conservation-composition—allocation—quasi-judicial.
(2) Montana Code annotated, 1995, Title 82, Chapter 10:
Section 82-10-101. Action for accounting for royalty.
Section 82-10-102. Remedy not exclusive.
Section 82-10-103. Obligation to pay royalties as essence of contract-interest.
Section 82-10-104. Payment of royalties-form of record required.
Section 82-10-105 through 82-10-109 reserved.
Section 82-10-110. Division order-definition-effect.
Section 82-10-201. Authorization for lease and terms-land not subject to leasing.
Section 82-10-202. Acreage pooling.
Section 82-10-203. Interference with normal use of land prohibited.
Section 82-10-204. Lease of acquired oil and gas interests.
Section 82-10-301. Definitions.
Section 82-10-302. Policy.
Section 82-10-303. Use of eminent domain to acquire underground reservoirs.
Section 82-10-304. Certificate of board required prior to use of eminent domain.
Section 82-10-305. Proceedings.
Section 82-10-401. Notice required before abandonment of well-owner's option.
Section 82-10-402. Inventory of abandoned wells and seismic operations-reclamation procedures.
Section 82-10-501. Purpose-legislative findings.
Section 82-10-502. Definitions.
Section 82-10-503. Notice of drilling operations.
Section 82-10-504. Surface damage and disruption payments-penalty for late payment.
Section 82-10-505. Liability for damages to property.
Section 82-10-506. Notification of injury.
Section 82-10-0507. Agreement—offer of settlement.
Section 82-10-508. Rejection—legal action.
Section 82-10-509 and 82-10-510. Reserved.
Section 82-10-511. Remedies cumulative.
(3) Montana Code annotated, 1995, Title 82, Chapter 11:
Section 82-11-101. Definitions.
Section 82-11-102. Oil or gas wells not public utilities.
Section 82-11-103. Lands subject to law.
Section 82-11-104. Construction-no conflict with board of land commissioners’ authority.
Section 82-11-105 through 82-11-110 reserved.
Section 82-11-111. Powers and duties of board.
Section 82-11-112. Intergovernmental cooperation.
Section 82-11-113. Role of board in implementation of national gas policy.
Section 82-11-114. Appointment of examiners.
Section 82-11-115. Procedure to make determinations.
Section 82-11-116. Public access.
Section 82-11-117. Confidentiality of records.
Section 82-11-118. Fees for processing applications.
Section 82-11-119 through 82-11-120 reserved.
Section 82-11-121. Oil and gas waste prohibited.
Section 82-11-122. Notice of intention to drill or conduct seismic operations-notice to surface owner.
Section 82-11-123. Requirements for oil and gas operations.
Section 82-11-124. Requirement relating to waste prevention.
Section 82-11-125. Availability of cores or chips, cuttings, and bottom-hole temperatures to board.
Section 82-11-126. Availability of facilities to bureau of mines.
Section 82-11-127. Prohibited activity.
Section 82-11-128 through 82-11-130 reserved.
Section 82-11-131. Privilege and license tax.
Section 82-11-132. Statements to treasurer and payment of tax.
Section 82-11-133. Penalty for late payment.
Section 82-11-134. Permit fees.
Section 82-11-135. Money earmarked for board expenses.
Section 82-11-136. Expenditure of funds from bonds for plugging wells.
Section 82-11-137. Class II injection well operating fee.
Section 82-11-138 through 82-11-140 reserved.
Section 82-11-141. Administrative procedure.
Section 82-11-142. Subpoena power-civil actions.
Section 82-11-143. Rehearing.
Section 82-11-144. Court review.
Section 82-11-145. Injunction or restraining order.
Section 82-11-146. Appeal.
Section 82-11-147. Violations.
Section 82-11-148. Criminal penalties.
Section 82-11-149. Civil penalties.
Section 82-11-150. Legal assistance.
Section 82-11-151. Emergencies-notice and hearing.
Section 82-11-152 through 82-11-160 reserved.
Section 82-11-161. Oil and gas production damage mitigation account-statutory appropriation.
Section 82-11-162. Release of producing oil or gas well from drilling bond-fee.
Section 82-11-163. Landowner's bond on noncommercial well.
Section 82-11-164. Lien created.
Section 82-11-165 through 82-11-170 reserved.
Section 82-11-171. Terminated.
Section 82-11-201. Establishment of well spacing units.
Section 82-11-202. Pooling of interest within spacing unit.
Section 82-11-203. Pooling agreements not in violation of antitrust laws.
Section 82-11-204. Hearing on operation of pool as unit.
Section 82-11-205. Board order for unit operation-criteria.
Section 82-11-206. Terms and conditions of plan for unit operations.
Section 82-11-207. Approval of plan for unit operations by persons paying costs.
Section 82-11-208. Board orders-amendment.
Section 82-11-209. Units established by previous order.
Section 82-11-210. Unit operations-less than whole of pool.
Section 82-11-211. Operations considered as done by all owners in unit.
Section 82-11-212. Property rights and operator's lien.
Section 82-11-213. Contract not terminated by board order.
Section 82-11-214. Title to oil and gas rights not affected by board order.
Section 82-11-215. Unit operation not restraint of trade.
Section 82-11-216. No creation of relationship between parties in unit.
Section 82-11-301. Authorization to join interstate compact for conservation of oil and gas.
Section 82-11-302. Interstate oil and gas compact.
Section 82-11-303. Extension of expiration date.
Section 82-11-304. Governor as member of Interstate Oil Compact Commission.
Section 82-11-305. Limitation on power of representative.
Section 82-11-306. Expenses of representative.
(b) The regulatory provisions include: Administrative Rules of Montana Board of Oil and Gas Conservation, Chapter 22, revised March 1996:
Rule 36.22.101. Organizational Rule.
Rule 36.22.201. Procedural Rules.
Rule 36.22.202. Environmental Policy Act Procedural Rules.
Rule 36.22.301. Effective Scope of Rules.
Rule 36.22.302. Definitions.
Rule 36.22.303. Classification of Wildcat or Exploratory Wells.
Rule 36 22.304. Inspection of Record, Properties, and Wells.
Rule 36.22.305. Naming of Pools.
Rule 36.22.306. Organization of Reports.
Rule 36.22.307. Adoption of Forms.
Rule 36.22.308. Seal of Board.
Rule 36.22.309. Referral of Administrative Decisions.
Rule 36.22.401. Office and Duties of Petroleum Engineer.
Rule 36.22.402. Office and Duties of Administrator.
Rule 36.22.403. Office and Duties of Geologist.
Rule 36.22.501. Shot Location Limitations.
Rule 36.22.502. Plugging and Abandonment.
Rule 36.22.503. Notification.
Rule 36.22.504. Identification.
Rule 36.22.601. Notice of Intention and Permit to Drill.
Rule 36.22.602. Notice of Intention to Drill and Application for Permit to Drill.
Rule 36.22.603. Permit Fees.
Rule 36.22.604. Permit Issuance - Expiration - Extension.
Rule 36.22.605. Transfer of Permits.
Rule 36.22.606. Notice and Eligibility Statement for Drilling or Recompletion in Unit Operations.
Rule 36.22.607. Drilling Permits Pending Special Field Rules.
Rule 36.22.701. Spacing Units - General.
Rule 36.22.702. Spacing of Wells.
Rule 36.22.703. Horizontal Wells.
Rule 36.22.1001. Rotary Drilling Procedure.
Rule 36.22.1002. Cable Drilling Procedure.
Rule 36.22.1003. Vertical Drilling Required Deviation.
Rule 36.22.1004. Dual Completion of Wells.
Rule 36.22.1005. Drilling Waste Disposal and Surface Restoration.
Rules 36.22.1006 through 36.22.1010. Reserved.
Rule 36.22.1011. Well Completion and Recompletion Reports.
Rule 36.22.1012. Samples of Cores and Cuttings.
Rule 36.22.1013. Filing of Completion Reports, Well Logs, Analyses, Reports, and Surveys.
Rule 36.22.1014. Blowout Prevention and Well Control Equipment.
Rule 36.22.1101. Fire Hazard Prevention.
Rule 36.22.1102. Fire Walls Required.
Rule 36.22.1103. Notification and Report of Emergencies and Undesirable Incidents.
Rule 36.22.1104. Control and Cleanup.
Rule 36.22.1105. Solid Waste.
Rule 36.22.1201. Surface Equipment.
Rule 36.22.1202. Identification.
Rule 36.22.1203. Chokes Required.
Rule 36.22.1204. Separators Required.
Rule 36.22.1205. Vacuum Pumps Prohibited.
Rule 36.22.1206. Tubing Required.
Rule 36.22.1207. Earthen Pits and Open Vessels.
Rule 36.22.1208. Producing from Different Pools Through the Same Casing.
Rules 36.22.1209 through 36.22.1212. Reserved.
Rule 36.22.1213. Reservoir or Pool Surveys.
Rule 36.22.1214. Subsurface Pressure Tests.
Rule 36.22.1215. Stabilized Production Test.
Rule 36.22.1216. Gas Oil Ratio Tests.
Rule 36.22.1217. Water Production Report.
Rule 36.22.1218. Gas to be Metered.
Rule 36.22.1219. Gas Waste Prohibited.
Rule 36.22.1220. Associated Gas Flaring Limitation—Application to exceed—Board Review and Action.
Rule 36.22.1221. Burning of Waste Gas Required.
Rule 36.22.1222. Hydrogen Sulfide Gas.
Rule 36.22.1223. Fencing, Screening, and Netting of Pits.
Rules 36.22.1224 and 36.22.1425. Reserved.
Rule 36.22.1226. Disposal of Water.
Rule 36.22.1227. Earthen Pits and Ponds.
Rule 36.22.1228. Disposal by Injection.
Rule 36.22.1229. Water Injection and Gas Repressuring.
Rule 36.22.1230. Application Contents and Requirements.
Rule 36.22.1231. Notice of Application Objections.
Rule 36.22.1232. Board Authorization.
Rule 36.22.1233. Notice of Commencement or Discontinuance—Plugging of Abandoned Wells.
Rule 36.22.1234. Record Required.
Rules 36.22.1235 through 36.22.1239. Reserved.
Rule 36.22.1240. Report of Well Status Change.
Rule 36.22.1241. Service Company Reports.
Rule 36.22.1242. Reports by Producers.
Rule 36.22.1243. Reports from Transporters, Refiners, and Gasoline or Extraction Plants.
Rule 36.22.1244. Producer's Certificate of Compliance.
Rule 36.22.1245. Illegal Production.
Rule 36.22.1301. Notice and Approval of Intention to Abandon Report.
Rule 36.22.1302. Notice of Abandonment.
Rule 36.22.1303. Well Plugging Requirement.
Rule 36.22.1304. Plugging Methods and Procedure.
Rule 36.22.1305. Exception for Fresh Water Wells.
Rule 36.22.1306. Approval for Pulling Casing and Reentering Wells.
Rule 36.22.1307. Restoration of Surface.
Rule 36.22.1308. Plugging and Restoration Bond.
Rule 36.22.1309. Subsequent Report of Abandonment.
Rule 36.22.1401. Definitions.
Rule 36.22.1402. Underground Injection.
Rule 36.22.1403. Application Contents and Requirements Rules.
Rule 36.22.1404 and 36.22.1405. Reserved.
Rule 36.22.1406. Corrective Action.
Rule 36.22.1407. Signing the Application.
Rule 36.22.1408. Financial Responsibility.
Rule 36.22.1409. Hearings.
Rule 36.22.1410. Notice of Application.
Rule 36.22.1411. Board Authorization.
Rules 36.22.1412 and 36.22.1413. Reserved.
Rule 36.22.1414. Notice of Commencement or Discontinuance—Plugging of Abandoned Wells.
Rule 36.22.1415. Records Required.
Rule 36.22.1416. Mechanical Integrity.
Rule 36.22.1417. Notification of Tests—Reporting Results.
Rule 36.22.1418. Exempt Aquifers.
Rule 36.22.1419. Tubingless Completions.
Rules 36.22.1420 and 36.22.1421. Reserved.
Rule 36.22.1422. Permit Conditions.
Rule 36.22.1423. Injection Fee—Well Classification.
Rule 36.22.1601. Who May Apply for Determination.
Rule 36.22.1602. Application Requirements and Contents.
Rule 36.22.1603. Documents and Technical Data Supporting Application.
Rule 36.22.1604. Docket Number.
Rule 36.22.1605. List of Applications—Public Access.
Rule 36.22.1606. Objections to Applications.
Rule 36.22.1607. Deadlines for Action Determinations.
Rule 36.22.1608. Deficient Applications.
Rule 36.22.1609. Board Action on Applications.
Rule 36.22.1610. Special Findings and Determinations New Onshore Production Wells Under Section 103.
Rule 36.22.1611. Special Findings and Determinations Stripper Well Production.
The UIC program for Class II wells in the State of Nebraska, except those on Indian lands, is the program administered by the Nebraska Oil and Gas Conservation Commission, approved by EPA pursuant to section 1425 of the SDWA.
(a)
(1) Rules and Regulations of the Nebraska Oil and Gas Conservation Commission, Rules 1 through 6 (as published by the Commission, May 1981);
(2) Revised Statutes of Nebraska, sections 57-903 and 57-906 (Reissue 1988).
(b)
(1) Chapter 57, Oil and Gas Conservation, Revised Statutes of Nebraska sections 57-901 through 57-922 (Reissue 1985).
(c) The Memorandum of Agreement between EPA Region VII and the Nebraska Oil and Gas Conservation Commission, signed by the EPA Regional Administrator on July 12, 1982.
(d)
(2) “Re: Nebraska Underground Injection Control Program, Addendum to Attorney General's Statement for Class II Wells,” signed by Assistant Attorney General for Attorney General of Nebraska,” undated.
(e) The Program Description and any other materials submitted as part of
The UIC program for Class I, III, IV, and V wells in the State of Nebraska, except those on Indian lands, is the program administered by the Nebraska Department of Environmental Control, approved by EPA pursuant to section 1422 of the SDWA.
(a)
(1) Nebraska Environmental Protection Act, Revised Statutes of Nebraska sections 81-1502, 81-1506, 81-1519, and 81-1520 (Reissue 1987);
(2) Nebraska Department of Environmental Control, Title 122—Rules and Regulations for Underground Injection and Mineral Production Wells, Effective Date: February 16, 1982, Amended Dates: November 12, 1983, March 22, 1984; as amended by amendment approved by the Governor on January 2, 1989.
(b)
(1) Nebraska Environmental Protection Act, Nebraska Revised Statutes sections 81-1502, 81-1506, 81-1519, and 81-1520 (Reissue 1987 and Cumm. Supp. 1988);
(c)(1) The Memorandum of Agreement between EPA Region VII and the Nebraska Department of Environmental Control, signed by the EPA Regional Administrator on July 12, 1982.
(2) Addendum to Underground Injection Control Memorandum of Agreement signed by the EPA Regional Administrator on July 12, 1982.
(3) Amendments to the Memorandum of Agreement signed by the EPA Regional Administrator on November 22, 1983.
(d)
(2) Letter from Attorney General (of Nebraska), by Assistant Attorney General, to Director, (Nebraska) Department of Environmental Control, August 7, 1981;
(3) Letter from Attorney General (of Nebraska), by Assistant Attorney General, to Director, (Nebraska) Department of Environmental Control, April 29, 1982;
(4) Letter from Attorney General (of Nebraska), by Assistant Attorney General, to Legal Counsel, (Nebraska) Department of Environmental Control, October 18, 1983.
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
The UIC program for all classes of underground injection wells in the State of Nevada, other than those on Indian lands, is the program administered by the Nevada Division of Environmental Protection approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
Copies may be inspected at the Environmental Protection Agency, Region IX, 215 Fremont Street, San Francisco, California 99105, or at the Office of the Federal Register, 800 North Capitol Street NW., suite 700, Washington, DC.
(1) Nevada Revised Statutes [NRS], Volume 25, Chapters 445.131 through 445.354, Inclusive. 1987.
(2) Nevada Revised Statutes [NRS], Volume 29, Chapters 534A.010 through 534A.090, Inclusive. 1987.
(3) Nevada Revised Statutes [NRS], Volume 28, Chapters 522.010 through 522.190, Inclusive. 1987.
(4) Nevada Administrative Code [NAC], Underground Injection Control Regulations, Sections 1 through 96.1, Inclusive. July 22, 1987, revised September 3, 1987 (amending NAC Chapter 445).
(5) Nevada Administrative Code [NAC], Regulations and Rules of Practice and Procedure adopted Pursuant to NRS 534A, Sections 1 through 69, Inclusive. November 12, 1985 (amending NAC Chapter 534A).
(6) Nevada Administrative Code [NAC], Regulations and Rules of Practice and Procedure adopted Pursuant to NRS 522.010 through 522.625, Inclusive. July 22, 1987 (amending NAC Chapter 522).
(b) The Memorandum of Agreement between EPA Region 9 and the Nevada Department of Conservation and Natural Resources signed by the EPA Regional Administrator on April 6, 1988.
(c)
(d) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable; or
(b) A value for well head pressure calculated by using the formula:
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes field rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within one year following the effective date of this program.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) of this section, as needed to protect USDWs.
The UIC program for all classes of wells in the State of New Hampshire, except those wells on Indian lands, is the program administered by the New Hampshire Department of Environmental Services, approved by the EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the FR on September 21, 1982 (47 FR
(a)
(1) New Hampshire Revised Statutes Annotated section 149:8 III(a) (1978);
(2) New Hampshire Code of Administrative Rules, Part Wc 410 (Protection of Groundwaters of the State, sections Ws 410.1 through Ws 410.16) (Issue Ws 3-82).
(b)(1) The Memorandum of Agreement between EPA Region I and the New Hampshire Water Supply and Pollution Control Commission, signed by the EPA Regional Administrator on August 23, 1982;
(2) Amendment No. 1 to the Memorandum of Agreement, signed by the EPA Regional Administrator on July 16, 1982.
(c)
(2) Letter from Attorney General of New Hampshire to Regional Administrator, EPA Region I, “Re: Attorney General's Statement—Underground Injection Control Program,” July 1, 1982.
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for all classes of wells in the State of New Jersey, except those on Indian lands, is the program administered by the New Jersey Department of Environmental Protection, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the Federal Register on July 15, 1983 (48 FR 32343); the effective date of this program is August 15, 1983. This program consists of the following elements, as submitted to EPA in the State's program application.
(a)
(1) Water Pollution Control Act, New Jersey Statutes Annotated sections 58:10A-1 through 58:10A-20 (West 1982 and Supp. 1990);
(2) New Jersey Administrative Code, sections 7:14A-1.1 through 1.9 (subchapter 1), 7:14A-2.1 through 2.15 (subchapter 2), 7:14A-5.1 through 5.17, (subchapter 5) (amended March 1988).
(b)(1) The Memorandum Agreement between EPA Region II and the New Jersey Department of Environmental Protection, signed by the EPA Regional Administrator on September 9, 1982;
(2) Letter from Commissioner, New Jersey Department of Environmental Protection, to Regional Administrator, EPA Region II, March 21, 1983.
(c)
(2) Letter from Attorney General of New Jersey (by Deputy Attorney General) to Commissioner, Department of Environmental Protection, “Re: New Jersey Pollutant Discharge Elimination System—Underground Injection Control,” April 15, 1983 (six pages);
(3) Letter from Attorney General of New Jersey (by Assistant Attorney General) to Commissioner, Department of Environmental Protection, “Re: New Jersey Pollutant Discharge Elimination System—Underground Injection Control,” April 15, 1983 (two pages).
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for Class II wells in the State of New Mexico, except for those on Indian lands, is the program administered by the New Mexico Energy and Minerals Department, Oil Conservation Division, approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Oil and Gas Act, New Mexico Statutes Annotated sections 70-2-1 through --36 (1978);
(2)
(b)(1) The Memorandum of Agreement between EPA Region VI and the New Mexico Energy and Minerals Department, Oil Conservation Division, signed by the EPA Regional Administrator on December 10, 1981;
(2) Addendum No. 1 to the Memorandum of Agreement, signed by the EPA Regional Administrator on June 28, 1982;
(3) Addendum No. 2 to the Memorandum of Agreement, signed by the EPA Regional Administrator on November 18, 1982;
(4) Letter from Director, Oil Conservation Division, New Mexico Energy and Minerals Department, and Assistant Attorney General of New Mexico, to Regional Administrator, EPA Region VI, November 6, 1981.
(c)
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
The UIC program for Class I, III, IV and V injection wells in the State of New Mexico, except for those on Indian lands, is the program administered by the New Mexico Water Quality Control Commission, the Environmental Improvement Division, and the Oil Conservation Division, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) New Mexico Water Quality Control Commission Regulations (WQCC 82-1) sections 1-100 through 5-300 (September 20, 1982).
(b)
(1) Water Quality Act, New Mexico Statutes Annotated sections 74-6-1 through 74-6-13 (1978 and Supp. 1982);
(2) Geothermal Resources Conservation Act, New Mexico Statutes Annotated sections 71-5-1 through 71-5-24 (1978 and Supp. 1982);
(3) Surface Mining Act, New Mexico Statutes Annotated sections 69-25A-1 through 69-25A-35 (1978 and Supp. 1980).
(c)(1) The Memorandum of Agreement between EPA Region VI and the New Mexico Water Quality Control Commission, the Environmental Improvement Division, and the Oil Conservation Division, signed by the EPA Regional Administrator on April 13, 1983;
(2) Letter from the Director, Environmental Improvement Division and the Director, Oil Conservation Division, to Regional Administrator, EPA Region IV, “Re: New Mexico Underground Injection Control Program—Clarification,” February 10, 1983.
(d)
(e) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
(a)
(b)
(a) This section identifies any aquifer or their portions exempted in accordance with §§ 144.7(b) and 146.4 of this chapter at the time of program promulgation. EPA may in the future exempt other aquifers or portions, according to applicable procedures, without codifying such exemptions in this section. An updated list of exemptions will be maintained in the Regional office.
(b) The following portions of aquifers are exempted in accordance with the provisions of §§ 144.7(b) and 146.4 of this chapter for Class II injection activities only:
(1) The Bradford First, Second, and Third Sand Members and the Kane Sand Member in the Bradford Field in Cattaraugus County.
(2) The Chipmunk Oil field in Cattaraugus County.
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable; or
(b) A value for well head pressure calculated by using the following formula:
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure, or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within one year of the effective date of this program.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(iii) For wells as described in § 146.8(b)(3)(ii), installing a smaller diameter pipe inside the existing injection tubing and setting it on an appropriate packer; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 50 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) of this section as needed to protect USDWs.
(a) The owner or operator of a Class I well authorized by permit shall install or shall ensure that the well has:
(1) Surface casing present;
(i) Extending from the surface to a depth at least 50 feet below the base of the lowermost USDW; and
(ii) Cemented back to the surface by recirculating the cement; and
(2) Long string casing and tubing;
(i) Extending to the injection zone; and
(ii) Cemented back to 50 feet above the base of the next largest casing string.
(b) The owner or operator of a new Class II well authorized by permit shall:
(1) Install surface casing from the surface to at least 50 feet below the base of the lowermost USDW.
(2) Cement the casing by recirculating to the surface or by using no less than 120% of the calculated annular volume.
(3) For new enhanced recovery wells, install tubing or long string casing extending to the injection zone.
(4) For new salt water disposal wells, install long string casing and tubing extending to the injection zone.
(5) Isolate any injection zone by placing sufficient cement to fill the calculated volume to a point 50 feet above the injection zone.
(c) The Regional Administrator may specify casing and cementing requirements other than those listed in paragraphs (a) and (b) of this section on a case by case basis as conditions of the permit.
The UIC program for all classes of wells in the State of North Carolina, except those wells on Indian lands, is the program administered by the North Carolina Department of Environment, Health and Natural Resources approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Administrative Procedure Act, N.C. GEN. STAT. 150B-1 through 150B-64 (1987 and Cumm. Supp. 1989);
(2) North Carolina Well Construction Act, N.C. GEN. STAT. §§ 87-83 through 87-99 (1989 and Cumm. Supp. 1989);
(3) Water and Air Resources, N.C. GEN. STAT. §§ 143-211 through 143-215.10 (1987 and Cumm. Supp. 1989);
(4) Solid Waste Management, N.C. GEN. STAT. §§ 130A-290 through 130A-309.03 (1989);
(5) North Carolina Drinking Water Act, N.C. GEN. STAT. §§ 130A-311 through 130A-332 (1989);
(6) Sanitary Sewage Systems, N.C. GEN. STAT. §§ 130A-333 through 130A-335 (1989).
(b)
(1) N.C. ADMIN. CODE, Title 15, r. 02L.0100
(2) N.C. ADMIN. CODE, Title 15, r. 02L.0100
(c)
(d)
(2) Amendment to Underground Injection Control Program, Attorney General's Statement (February 9, 1984).
(e)
(a)
(b)
The UIC program for Class II wells in the State of North Dakota, except those on Indian lands, is the program administered by the North Dakota Industrial Commission, approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) North Dakota Century Code, Chapter 38-08 (Control of Gas and Oil Resources, 1987 and Supp. 1989);
(2) North Dakota Administrative Code, Chapter 43-02-05 (Underground Injection Control, as published in
(3) North Dakota Administrative Code, Chapter 43-02-03 (General Rules, as published in
(b) The Memorandum of Agreement between EPA Region VIII and the North Dakota Industrial Commission, Oil and Gas Division, signed by the
(c)
(d) The Program Description and other materials submitted as part of the application or as supplements thereto.
The UIC program for Class I, III, IV, and V wells in the State of North Dakota, except those on Indian lands, is the program administered by the North Dakota Department of Health, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) North Dakota Century Code Sections 38-12-01, 38-12-03 (1980);
(2) North Dakota Century Code, Sections 61-28-02 and 61-28-06 (1989);
(3) North Dakota Administrative Code Sections 33-25-01-01 through 33-25-01-18 (North Dakota State Health Department Underground Control Program) (1983);
(4) North Dakota Administrative Code, Chapter 43-02-02 (Subsurface Mineral Exploration and Development) (August 1986), and Chapter 43-02-02.1 (Underground Injection Control Program) (March 1, 1984);
(5) North Dakota Administrative Code Sections 43-02-02-1-01 through 43-02-02-1-18 (North Dakota Geological Survey—Undergound Injection Control Program) (1984);
(b)
(1) North Dakota Environmental Law Enforcement Act of 1975, North Dakota Century Code Sections 32-40-01 to 32-40-11 (1976);
(2) North Dakota Century Code, Ch. 38-12 (Regulation, Development, and Production of Subsurface Minerals) (1979);
(3) North Dakota Century Code Chapter 61-28 (Control, Prevention and Abatement of Pollution of Surface Waters) (1989);
(4) North Dakota Administrative Code Article 33-22 (Practice and Procedure) (1983).
(c) The Memorandum of Agreement between EPA Region VIII and the North Dakota Department of Health, signed by the EPA Regional Administrator on May 18, 1984.
(d) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
The UIC program for Class II wells in the State of Ohio, except for those on Indian lands, is the program administered by the Ohio Department of Natural Resources, approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Ohio Revised Code Annotated, sections 1509.01 through 1509.22 (Page 1978 and Supp. 1982);
(2) Rules of the Division of Oil and Gas, Ohio Administrative Code sections 1501:91-01, through 1501: 9-11-13 (1983).
(b) The Memorandum of Agreement between EPA Region V and the Ohio Department of Natural Resources.
(c)
(d) The Program Description and any other materials submitted as part of the application or as supplements thereto.
The UIC program for Class I, III, IV, and V wells in the State of Ohio, other than those on Indian lands, is the program administered by the Ohio Department of Natural Resources and -the Ohio Environmental Protection Agency, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Ohio Revised Code Annotated, sections 1509.01, 1509.03, 1509.221 (Supp. 1983);
(2) Rules of the Division of Oil and Gas, Ohio Administrative Code, sections 1501:9-7-01 through 7-14 (1984);
(3) Ohio Revised Code Annotated, sections 6111.04, 6111.043, 6111.044 (Supp. 1983);
(4) Rules of the Ohio Environmental Protection Agency, Ohio Administrative Code, sections 3745-34-01 through 34-41; 3745-9-01 through 9-11 (Director Ohio EPA Order, June 18, 1984).
(b)
(1) Ohio Revised Code, Chapter 119 (1978 Replacement Part);
(2) Ohio Code Supplement, sections 6111.041, 6111.042, 6111.045 (Supp. 1982).
(c) (1) The Memorandum of Agreement between EPA Region V and the Ohio Department of Natural Resources, signed by the EPA Regional Administrator on March 30, 1984;
(2) Memorandum of Agreement between the Ohio Department of Natural Resources and the Ohio Environmental Protection Agency, Related to the -Underground Injection Control Program for the State of Ohio, signed August 1, 1984.
(d)
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
The owner or operator shall limit injection pressure to the lesser of:
(a) A value which will not exceed -the operating requirements of § 144.28(f)(3)(i); or
(b) A value for well head pressure calculated by using the following formula:
(a)
(b)
The UIC program for Class I, III, IV, and V wells in the State of Oklahoma, except those on Indian lands, is the program administered by the Oklahoma State Department of Health, approved by EPA pursuant to SDWA section 1422. Notice of this approval was published in the
(a)
(1) Oklahoma Statutes title 63 sections 1-901, 1-903 (1981);
(2) Oklahoma Controlled Industrial Waste Disposal Act, Oklahoma Statute Annotated title 63 sections 1-2002, 1-2014 (West Supp. 1983-1984);
(3)
(b)
(1) Oklahoma Open Meeting Act, Oklahoma Statutes title 25 sections 301 through 314 (Supp. 1978);
(2) Oklahoma Statutes Annotated title 63 sections 1-101 to 1-114, 1-901 to 1-911, 1-1601
(3) Oklahoma Statutes Annotated title 75 sections 301 to 327 (West 1976 and Supp. 1982).
(c) (1) The Memorandum of Agreement between EPA Region VI and the Oklahoma State Department of Health, signed by the EPA Regional Administrator on April 13, 1982;
(2) Memorandum of Understanding between the Oklahoma State Department of Health and the Oklahoma Corporation Commission (OCC), signed by members of the OCC on February 12, 1982;
(3) Memorandum of Understanding between the Oklahoma State Department of Health and the Oklahoma Department of Mines (ODM), signed by the Deputy Chief Mine Inspector, ODM, on February 15, 1982.
(d)
(e) The Program Description and any other materials submitted as part of the application or as supplements thereto.
The UIC program for Class II wells in the State of Oklahoma, including the lands of the Five Civilized Tribes, but not including those on other Indian lands, is the program administered by the Oklahoma Corporation Commission approved by EPA pursuant to SDWA section 1425. Notice of this approval was published in the
(a)
(b)
(1) Oklahoma Statutes, title 17 sections 51-53; title 52 sections 86.1-86.5, 139-153, 243, 307-318.1 (1971).
(2) OCC-OGR Rules No. 1-101-3-303.
(c) (1) The Memorandum of Agreement between EPA Region VI and the Oklahoma Corporation Commission, signed by the EPA Regional Administrator on April 13, 1981;
(2) Letter from the Manager, Underground Injection Control, Oklahoma Corporation Commission, to EPA, June 18, 1981.
(d)
(e) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for all classes of wells in the State of Oregon, except those on Indian lands, is administered by the Oregon Department of Environmental Quality, approved by EPA pursuant to section 1422 and section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Oregon Revised Statutes, Title 16, chapter 164, section 164.785; Title 36, chapter 468, sections 468.005, 468.065 to 468.070, 468.700 to 468.815; Title 43, chapter 520 sections 520.005, 520.095, 520.155—520.330 (1983);
(2) Oregon Administrative Rules, Chapter 340, Division 44, sections 340-44-005 through 340-44-055 (October 1983); Chapter 340, Division 45, sections 340-45-005 through 340-45-075 (January 1990); Chapter 632, Division 10, sections 632-10-002 through 632-10-235 (May 1986); Chapter 632, Division 20, sections 632-20-005 through 632-20-180 (May 1984).
(b)
(1) Oregon Revised Statutes, Chapter 183 (1987); 192.420, 192.500, 459.460(3), 468.005 through 468.605, and 468.780 through 468.997; Chapters 516 and 522 (1983);
(2) Oregon Administrative Rules, chapter 137, Div. 3 (July 1982); chapter 340, Div. 11 (April 1988); chapter 340, Div. 12 (March 1989); chapter 340, Div. 14 (November 1983); chapter 340, Div. 52 (November 1983); chapter 632, Div. 1 (June 1980); chapter 632, Div. 20 (January 1981).
(c)(1) The Memorandum of Agreement between EPA Region X and the Oregon Department of Environmental Quality, signed by the EPA Regional Administrator on May 3, 1984.
(d)
(2) Opinion of the Attorney General, Oregon, 35 Op. Attorney General 1042 (1972).
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a)
(b)
(a) This section identifies any aquifers or their portions exempted in accordance with §§ 144.7(b) and 146.4 of this chapter at the time of program promulgation. EPA may in the future exempt other aquifers or portions, according to applicable procedures, without codifying such exemptions in this section. An updated list of exemptions will be maintained in the Regional -office.
(b) Those portions of the following oil bearing aquifers, which would otherwise meet the definition of a USDW, are exempted in accordance with the
(1) The Sugar Run and Bradford series of oil producing sands of the Bradford Field, in McKean County; including the Bradford, West Branch, Stack, Bennett Brook, Marilla Brook, Brooder Hollow, Cyclone, Minard Run, Minard Run School, and Sugar Run (or Watsonville) Pools.
(2) The Bradford Third oil producing sand of the Guffey Field in McKean County.
(3) The Bradford series of oil producing sands of the Lewis Run Field in McKean County.
(4) The Bradford series of oil producing sands of the Windfall Field and Kings Run Pool in McKean County.
(5) The Red Valley member of the Second Sand formation of the Venango Group of oil producing sands in the Foster-Reno Field in Venango County; including the Foster, Bully Hill, Victory, Bredinsburg, Egypt Corners, Reno, Monarch Park and Seneca Pools.
(6) The Glade and Clarendon oil producing sands of the Morrison Run Field and Elk Run Pool in Warren County.
(7) The Clarendon and Glade oil producing sands of the Clarendon Field in Warren County.
(8) The Bradford Third oil producing sand in the Shinglehouse Field, including the Kings Run, Janders Run and Ceres Pools in Potter and McKean Counties.
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable or
(b) A value for well head pressure calculated by using the following formula:
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The information shall be submitted to the Regional Administrator within one year of the effective date of this regulation.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(iii) For wells as described in § 146.8(b)(3)(ii), installing a smaller diameter pipe inside the existing injection tubing and setting it on an appropriate packer; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 50 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) of this section as needed to protect USDWs.
(a) The owner or operator of a Class I well authorized by permit shall install or shall ensure that the well has:
(1) Surface casing present;
(i) Extending from the surface to a depth at least 50 feet below the base of the lowermost USDW; and
(ii) Cemented back to the surface by recirculating the cement; and
(2) Long string casing and tubing;
(i) Extending to the injection zone; and
(ii) Cemented back to 50 feet above the base of the next largest casing string.
(b) The owner or operator of a new Class II well authorized by permit shall:
(1) Install surface casing from the surface to at least 50 feet below the base of the lowermost USDW.
(2) Cement the casing by recirculating to the surface or by using no less than 120% of the calculated annular volume.
(3) For new enhanced recovery wells, install tubing or long string casing extending to the injection zone.
(4) For new salt water disposal wells, install long string casing and tubing extending to the injection zone.
(5) Isolate any injection zone by placing sufficient cement to fill the calculated volume to a point 50 feet above the injection zone.
(c) The Regional Administrator may specify casing and cementing requirements other than those listed in paragraphs (a) and (b) of this section on a case by case basis as conditions of the permit.
The UIC program for all classes of wells in Rhode Island, except those on Indian lands, is the program administered by the Rhode Island Department of Environmental Management, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Rhode Island Gen. Laws sections 46-12-1, 46-12-5, and 46-12-28 (Supp. 1983);
(2) “Underground Injection Control Program Rules and Regulations.” State of Rhode Island and Providence Plantations Department of Environmental Management. Division of Water Resources (as received by the Secretary of State, May 21, 1984).
(b)
(1) Rhode Island General Laws, Section 10-20-1
(2) Rhode Island General Laws, Section 23-19.1-1
(3) Rhode Island General Laws, Section 42-17.1
(4) Rhode Island General Laws, Section 42-35-1
(5) Rhode Island General Laws, Section 46-12-1
(6) Hazardous Waste Management -Facility Operating Permit Rules and Regulations—Landfills, at last amended November 2, 1981 (hereinafter referred to as the “Hazardous Waste Regulation”);
(7) Water Quality Regulations for Water Pollution Control, effective November 19, 1981; and
(8) Administrative Rules of Practices and Procedure for Department of Environmental Management, effective November 12, 1980.
(c) (1) The Memorandum of Agreement between EPA Region I and the Rhode Island Department of Environmental Management, signed by the EPA Regional Administrator on March 29, 1984;
(2) Letter from Director, Rhode Island Department of Environmental Management, to Regional Administrator, EPA Region I, amending Section III, C of the Memorandum of Agreement, April 25, 1984.
(d)
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
The UIC program for all classes of wells in the State of South Carolina, except for those on Indian lands, is the program administered by the South Carolina Department of Health and Environmental Control, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Pollution Control Act, S.C. Code Ann. Sections 48-1-10, 48-1-90, 48-1-100,
(2) South Carolina Department of Health and Environmental Control, Ground-Water Protection Division, Underground Injection Control Regulations, R-61-87, Effective Date: June 24, 1983 Published in South Carolina State Register, Volume 7, Issue 6; Amended Date: March 23, 1984, as amended by notice in South Carolina State Register, Volume 8, Issue 3.
(b)
(1) Pollution Control Act, S.C. Code Ann. Sections 48-1-10 to 48-1-350 (Law. Co-op. 1976 and Supp. 1983).
(2) State Safe Drinking Water Act, S.C. Code Ann. Sections 44-55-10 to 44-55-100 (Law. Co-op. 1976 and Supp. 1983).
(3) Administrative Procedures Act, S.C. Code Ann. Sections 1-23-10 et seq., and 1-23-310 to 1-23-400 (Law. Co-op. 1976 and Supp. 1983).
(4) S.C. Code Ann. Sections 15-5-20, 15-5-200 (Law. Co-op. 1976 and Supp. 1983).
(c)(1) The Memorandum of Agreement between EPA Region IV and the South Carolina Department of Health and Environmental Control signed by the EPA Regional Administrator on May 29, 1984.
(d)
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
The UIC program for Class II wells in the State of South Dakota, except those on Indian lands, is the program administered by the South Dakota Department of Water and Natural Resources, approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) South Dakota Codified Laws, sections 45-9-2, 45-9-4, 45-9-11, 45-9-13, 45-9-14, 45-9-15 (1983).
(2) Administrative Rules of South Dakota, sections 74:10:02 through 74:10:07, 74:10:09, and 74:10:11 published by the South Dakota Code Commission, as revised through October 4, 1987.
(b)
(1) South Dakota Codified Laws, Chapter 45-9 (sections not cited above) (1983); 1-26 (1981).
(c)(1) The Memorandum of Agreement between EPA Region VIII and the South Dakota Department of Water and Natural Resources, signed by the EPA Regional Administrator on July 18, 1984.
(d)
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a) This section identifies any aquifers or their portions exempted in accordance with §§ 144.7(b) and 146.4 of this chapter at the time of program promulgation. EPA may in the future exempt other aquifers or their portions, according to applicable procedures, without codifying such exemptions in this section. An updated list of exemptions will be maintained in the Regional office.
(b) Those portions of all aquifers located on Indian Lands, which meet the definition of USDW and into which existing Class II wells are injecting, are exempted within a
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comments, and opportunity for a public hearings, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at a pressure greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating provided he submits a request in writing to the Regional Administrator, and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii)(A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes field rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit to the Regional Administrator data acceptable to the Regional administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operation pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone; and/or
(4) Comply with other requirements which the Regional Administrator may specify in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) of this section as needed to protect USDWs.
(a) The owner or operator converting an existing well to an injection well shall check the condition of the casing with one of the following logging tools;
(1) A pipe analysis log; or
(2) A caliper log.
(b) The owner or operator of a new injection well cased with plastic (PVC, ABS, or others) casings shall:
(1) Not construct a well deeper than 500 feet;
(2) Use cement and additives compatible with such casing material; and
(3) Cement the annular space above the injection intermal from the bottom of the blank casing to the surface.
(c) The owner or operator of a newly drilled well shall install centralizers as directed by the Regional Administrator.
(d) The owner or operator shall as required by the Regional Administrator:
(1) Protect USDWs by:
(i) Setting surface casing 50 feet below the lowermost USDW;
(ii) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(iii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure; and
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may approve alternate casing and cementing practices provided that the owner or operator demonstrates that such practices will adequately protect USDWs.
(e)
(f) The applicant must give separate notice of intent to apply for a permit to each owner of record of the land within one-quarter mile of the site. The addresses of those to whom notice is given and the description of how notice was given shall be submitted with the permit application. The notice shall include:
(1) The name and address of applicant;
(2) A brief description of the planned injection activities, including well location, name and depth of the injection zone, maximum injection pressure and volume, and fluid to be injected;
(3) The EPA contact person; and
(4) A statement that opportunity to comment will be announced after EPA prepares a draft permit.
(a)
(b)
(a) A value which will not exceed the operating requirements of § 144.28(f)(3) (i) or (ii) as applicable or
(b) A value for well head pressure calculated by using the following formula:
(a)
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure; or
(ii) May inject at pressures greater than those specified in paragraph (a)(1)(i) of this section for the field or formation in which he is operating, provided he submits a request in writing to the Regional Administrator and demonstrates to the satisfaction of the Regional Administrator that such injection pressure will not violate the requirement of § 144.28(f)(3)(ii) (A) and (B). The Regional Administrator may grant such a request after notice, opportunity for comment, and opportunity for a public hearing, according to the provisions of part 124, subpart A of this chapter.
(2) Prior to such time as the Regional Administrator establishes rules for maximum injection pressure based on data provided pursuant to paragraph (a)(2)(ii) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within one year of the effective date of this regulation.
(b)
(1) Protect USDWs by:
(i) Cementing surface casing by recirculating the cement to the surface from a point 50 feet below the lowermost USDW; or
(ii) Isolating all USDWs by placing cement between the outermost casing and the well bore; and
(2) Isolate any injection zones by placing sufficient cement to fill the calculated space between the casing and the well bore to a point 250 feet above the injection zone; and
(3) Use cement:
(i) Of sufficient quantity and quality to withstand the maximum operating pressure;
(ii) Which is resistant to deterioration from formation and injection fluids; and
(iii) In a quantity no less than 120% of the calculated volume necessary to cement off a zone.
(4) The Regional Administrator may specify other requirements in addition to or in lieu of the requirements set forth in paragraphs (b) (1) through (3) of this section, as needed to protect USDWs.
Notwithstanding the alternatives presented in § 146.6 of this chapter, the area of review shall be a minimum fixed radius as described in § 146.6(b) of this chapter.
(a)
(1) Injection Well Act, Texas Water Code sections 27.002, 27.011 (Vernon Supp. 1984);
(b)
(1) Texas Water Code Annotated, Chapter 5 (Vernon 1972 and Supp. 1982);
(2) Injection Well Act, Texas Water Code Annotated, Chapter 27 (Vernon 1972 and Supp. 1982);
(3) Rules of Texas Department of Water Resources, Chapter 27; Rules -of Texas Water Development Board, -Chapter 22.
(c) The Memorandum of Agreement between EPA Region VI and the Texas Department of Water Resources, signed by the EPA Regional Administrator on October 11, 1981.
(d)
(e) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(f) Certain Class V wells are under the UIC program of the Texas Railroad Commission approved on April 23, 1982, under the authorities cited in § 147.2201 of this part.
The UIC program for Class II wells in the State of Texas, except for those wells on Indian lands, is the program administered by the Railroad Commission of Texas, approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Injection Well Act, Texas Water Code Annotated sections 27.031 and 27.033 (Vernon Supp. 1984);
(2) Texas Natural Resources Code Annotated sections 85.041, 85.045, 85.046 and 85.052 (Vernon 1978 and Supp. 1982);
(3) Rules Having Statewide General Application to Oil, Gas, and Geothermal Resource Operations, sections .051.02.02.000 to .051.02.02.080 (Railroad Commission of Texas, Oil and Gas Division, Revised 12-22-81), amended as follows:
(i) Amendment to 16 TAC section 3.9 (section .051.02.02.009) issued December 21, 1981, effective April 1, 1982;
(ii) Amendment to 16 TAC section 3.46 (section .051.02.02.046) issued December 21, 1981, effective April 1, 1982.
(iii) Amendment to 16 TAC section 3.71 (section .051.02.02.074) issued December 21, 1981, effective April 1, 1982.
(b)
(1) Texas Water Code, Chapters 26, 27 and 29 (Vernon 1972 and Supp. 1982);
(2) Texas Natural Resources Code, Chapters 81, 85-89, 91 and 141 (Vernon 1978 and Supp. 1982);
(3) General Rules of Practice and Procedure, Subchapters A-J (Railroad Commission of Texas, adopted November 24, 1975, revised December 1980).
(c)(1) The Memorandum of Agreement between EPA Region VI and the Railroad Commission of Texas, signed by the EPA Regional Administrator on March 24, 1982.
(2) Letter from Director of Underground Injection Control, Railroad Commission of Texas, to Chief, Ground Water Protection Section, EPA Region VI, “Re: Letter of Clarification—UIC Program Application,” March 21, 1982.
(d)
(e) The Program Description and any other materials submitted as part of the application or as supplements thereto.
(a)
(b)
The UIC program for Class I, III, IV, and V wells in the State of Utah, except those on Indian lands, is administered by the Utah Department of Health, Division of Environmental Health, approved by EPA pursuant to Section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Utah Water Pollution Control Act, Utah Code Annotated, Title 26, Chapter 11, Sections 2, 8, and 10 (1989);
(2) Underground Injection Control Regulations; Utah Administrative Code, Section R448-7 (effective as of January 2, 1990);
(3) Underground Injection Control Program (adopted January 20, 1982 and revised effective July 20, 1990) (Officially submitted to EPA by the Executive Secretary of Utah Water Pollution Control Committee on August 16, 1990).
(b)
(1) Utah Pollution Control Act, Utah Code Annotated, Sections 26-11-1 through -20 (Supp. 1990);
(c)(1) The revised Memorandum of Agreement between EPA, Region VIII and the Utah Department of Health, Division of Environmental Health, signed by the Regional Administrator on October 3, 1990.
(2) Letter from Director, Utah Department of Health, Division of Environmental Health, Bureau of Water Pollution Control, to EPA Region VIII, Re: Underground Injection Control Program—Utah, March 15, 1982;
(3) Letter from the Executive Secretary of the Utah Water Pollution Control Committee to EPA Region VIII, “Re: Utah UIC Class I Well Program Changes,” August 16, 1990;
(d)
(2) Letter from Assistant Attorney General of Utah to Chief, Drinking Water Branch, EPA Region VIII, June 18, 1982;
(3) Addendum to Underground Injection Control Program, Attorney General's Statement signed by Attorney General of Utah, August 10, 1990.
(e) The Program Description (revised June 19, 1990) and any other materials submitted as part of the application or supplements thereto.
The UIC program for Class II wells in the State of Utah, except those on Indian lands, is the program administered by the Utah Department of Natural Resources, Division of Oil, Gas, and Mining, approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(1) Utah Code Annotated, 1953, section 40-6-1 through 40-6-18, as amended 1988 and Cumm. Supp. 1990;
(2) The Oil and Gas Conservation General Rules, adopted under the authority of the Oil and Gas Conservation Act, 40-6-1
(b)
(c)(1) The Memorandum of Agreement between EPA, Region VIII and
(2) Letter from Director, Division of Oil, Gas and Mining, Utah Department of Natural Resources and Energy, to Regional Administrator, EPA Region VIII, “Re: Aquifer Exemption Process,” June 16, 1982;
(3) “Memorandum of Understanding” between Utah Department of Health and Utah Department of Natural Resources, dated March 5, 1981;
(4) “Second Addition to Agreement between the Department of Health and the Department of Natural Resources and Energy,” dated December 15, 1981.
(d)
(2) Letter from Assistant Attorney General, State of Utah, to EPA Region VIII, undated, received in the EPA Office of Regional Counsel June 10, 1982.
(3) Memorandum to Director, Division of Oil, Gas and Mining from Assistant Attorney General regarding Underground Injection Control Program, January 8, 1985.
(e) The Program Description and any other materials submitted as part of the application or amendments thereto.
(a)
(b)
The UIC program for all classes of wells in the State of Vermont, except those wells on Indian lands, is the -program administered by the Vermont Department of Environmental Conservation, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the FR on June 22, 1984; the effective date of this program is July 6, 1984. This program consists of the following elements:
(a)
(1) Vt. Stat. Ann. tit. 10, sections 1251, 1259, 1263 (1973 and Supp. 1981), Effective date: July 1, 1982.
(2) Vermont Department of Water Resources and Environmental Engineering, Chapter 13 Water Pollution Control Regulations, Subchapter 13.UIC—Underground Injection Control, Discharges to Injection Wells, Effective Date: June 21, 1984.
(b)
(1) Vt. Stat. Ann. tit. 10, sections 1251 through 1283 (1973 and Supp. 1981).
(2) Vt. Stat. Ann. tit. 10, sections 901 through 911 (1973 and Supp. 1981).
(3) Vt. Stat. Ann. tit. 3, sections 801 through 847 (1973 and Supp. 1981).
(c)(1) The Memorandum of Agreement between EPA Region I and the Vermont Agency of Environmental Conservation signed by the EPA Regional Administrator on January 16, 1984.
(d)
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a)
(b)
The UIC program for Class I, II, III, IV, and V wells in the State of Washington other than those on Indian lands, is the program administered by the Washington Department of Ecology, approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Revised Code of Washington section 90.48.020, 90.48.080, 90.48.160, and 90.48.162 (Bureau of National Affairs, 1983 Laws);
(2) Washington Administrative Code sections 173-218-010 to 173-218-110 (Bureau of National Affairs, 2/29/84);
(3) Washington Administrative Code sections 344-12-001 to 344-12-262 (1983 Ed.)
(4) Washington Administrative Code Chapter 173-160 (reprinted May 1988).
(b)
(1) Revised Code of Washington, chapter 34.04 (Bureau of National Affairs, 1981 Laws), entitled “Administrative Procedure act”;
(2) Revised Code of Washington, chapter 43.21A (Bureau of National Affairs, 1980 Laws), entitled “Department of Ecology,” as amended by 1983 Washington Laws, Chapter 270;
(3) Revised Code of Washington, chapter 70.105 (Bureau of National Affairs, 1983 Laws), entitled “Hazardous Waste Disposal”;
(4) Revised Code of Washington, chapter 78.52 (Bureau of National Affairs, 1983 Laws), entitled “Oil and Gas Conservation”;
(5) Revised Code of Washington, chapter 90.48 (Bureau of National Affairs, 1986 Laws), entitled “Water Pollution Control.”
(c)(1) The Memorandum of Agreement between EPA Region X and the Washington Department of Ecology, signed by the EPA Regional Administrator on May 14, 1984;
(2) Memorandum of Agreement between the Washington Department of Ecology and Oil and Gas Conservation Committee, Related to the Underground Injection Control Program for the State of Washington, signed March 23, 1984;
(3) Memorandum of Agreement between the Washington Department of Ecology and Washington Department of Natural Resources, Related to the Underground Injection Control Program for the State of Washington, signed March 23, 1984;
(4) Memorandum of Agreement between the Washington Department of Ecology and Department of Social and Health Services, Related to the Underground Injection Control Program for the State of Washington, signed March 23, 1984;
(d)
(e) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a) The UIC program for the Colville Indian Reservation consists of a prohibition of all Class I, II, III and IV injection wells and of a program administered by EPA for Class V wells. This program consists of the UIC program requirements of 40 CFR part 124, 144 and 146 and any additional requirements set forth in the remainder of this subpart. Injection well owners and EPA shall comply with these requirements. The prohibition on Class I-IV wells is effective November 25, 1988. No owner or operator shall construct, operate, maintain, convert, or conduct any other injection activity thereafter using Class I-IV wells.
(b) Owners and operators of Class I, II, III or IV wells in existence on the effective date of the program shall cease injection immediately. Within 60 days of the effective date of the program, the owner or operator shall submit a plan and schedule for plugging and abandoning the well for the Director's approval. The owner or operator shall
(a)
(b)
The UIC program for Class I, II, III, IV, and V wells in the State of Wisconsin, other than those on Indian lands as described in § 147.2510, is the program administered by the Wisconsin Department of Natural Resources, approved by EPA pursuant to SDWA section 1422. Notice of this approval was published in the
(a)
(1) Wisconsin Statutes Annotated §§ 147.015, 147.02 and 147.04 (West 1974 and Supp. 1983);
(2) Chapter NR 112, Well Construction and Pump Installation, Wisconsin Administrative Code §§ NR 112.03 and 112.20 (October 1981), as amended by Natural Resources Board Order No. WQ-25-82, approved by the Natural Resources Board on August 25, 1982;
(3) Chapter NR 113, Servicing Septic Tanks, Seepage Pits, Grease Traps or Privies, Wisconsin Administrative Code §§ NR 113.07-113.08 (1979), as amended by Natural Resources Board Order No. WQ-25-82, approved by the Wisconsin Natural Resources Board on August 25, 1982;
(4) Chapter NR 181, Hazardous Waste Management, Wisconsin Administrative Code §§ NR 181.04-181.415 (1981), as amended June 1985;
(5) Chapter NR 210, Sewage Treatment Works, Wisconsin Administrative Code § 210.05 Natural Resources Board Order No. WQ-25-82, approved by the Wisconsin Natural Resources Board on August 25, 1982;
(6) Chapter NR 214, Land Application and Disposal of Liquid Industrial Wastes and By-Products, Wisconsin Administrative Code §§ 214.03 and 214.08 (1983).
(b)
(1) Chapter 144, Water, Sewage, Refuse, Mining and Air Pollution, Wisconsin Statutes Annotated (West 1974 and Supp. 1983);
(2) Chapter 147, Pollution Discharge Elimination, Wisconsin Statutes Annotated (West 1974 and Supp. 1983);
(3) Chapter 162, Pure Drinking Water, Wisconsin Statutes Annotated (West 1974 and Supp. 1983);
(4) Laws of 1981, Chapter 20, § 2038 (Re: heat pump injection);
(5) Wisconsin Statutes 803.09(1) (West 1977) (intervention as of right in civil actions).
(c)
(d)
(2) Letter from Assistant Attorney General, State of Wisconsin, to EPA Region, “Re: Amendments to Attorney General's Statement-UIC,” June 30, 1983.
(e)
(a)
(b)
(c)
The UIC program for Class I, III, IV and V wells in the State of Wyoming, except those on Indian lands is the program administered by the Wyoming Department of Environmental Quality approved by EPA pursuant to section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) Wyoming Environmental Quality Act, Wyoming Statutes sections 35-11-101 through 35-11-115, and 35-11-301 through 35-11-305 (1977 Republished Edition and 1989 Cumm. Supp.);
(2) Water Quality Rules and Regulations, Wyoming Department of Environmental Quality, Chapter III: Regulations for Permit to Construct, Install or Modify Public Facilities Capable or, (sic) Causing or Contributing to Pollution (certified copy, signed December 21, 1983);
(3) Water Quality Rules and Regulations, Wyoming Department of Environmental Quality, Chapter VIII: Quality Standards for Groundwaters of Wyoming (certified copy, signed April 9, 1980);
(4) Water Quality Rules and Regulations, Wyoming Department of Environmental Quality, Chapter IX: Wyoming Groundwater Pollution Control Permit (certified copy, signed April 9, 1980);
(5) Water Quality Rules and Regulations, Wyoming Department of Environmental Quality, Chapter XIII: Prohibitions of Permits for New Hazardous Waste Injection Wells (certified copy, signed August 25, 1989);
(6) Land Quality Rules and Regulations, Wyoming Department of Environmental Quality, Chapter XXI: In Situ Mining (effective March 26, 1981).
(b)
(1) Article 9, Underground Water, Wyoming Statutes sections 41-3-901 through 41-3-938 (September 1982);
(2) Wyoming Administrative Procedure Act, Wyoming Statutes sections 9-4-101 through 9-4-115 (1988);
(3) Department of Environmental Quality Rules of Practice and Procedure (1982).
(c)(1) The Memorandum of Agreement between EPA, Region VIII and the Wyoming Department of Environmental Quality, signed by the EPA Regional Administrator on April 26, 1983.
(2) Letter from Regional Administrator, EPA Region VIII, to Governor of Wyoming, May 21, 1982, with Attachment (regarding aquifer exemptions);
(3) Letter from Governor of Wyoming to Regional Administrator, EPA Region VIII, “Re: Underground Injection Control (UIC) Program—Aquifer Exemption Issues,” June 7, 1982;
(4) Letter from Regional Administrator, EPA Region VIII to Governor of Wyoming, “Re: Underground Injection Control (UIC) Program—Aquifer Exemption Issues,” June 25, 1982;
(5) Letter from Director, Wyoming Department of Environmental Quality, to Acting Director, Water Management Division, EPA Region VIII, December 1, 1982.
(d)
(2) Letter from Attorney General for the State of Wyoming to Acting Regional Counsel, EPA Region VIII, “Re: Wyoming Assumption of the UIC Program—$36, Chapter IX, Wyoming Water Quality Rules and Regulations,” November 24, 1982.
(e) The Program Description and any other materials submitted as part of the application or amendment thereto.
The UIC program for Class II wells in the State of Wyoming, except those on Indian lands, is the program administered by the Wyoming Oil and Gas Conservation Commission approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the FR on November 23, 1982 (47 FR 52434); the effective date of this program is December 23, 1982. This program consists of the following elements as submitted to EPA in the State's program application:
(a)
(1) Rules and Regulations of the Wyoming Oil and Gas Conservation Commission, including Rules of Practice and Procedure, as published by the Wyoming Oil and Gas Conservation Commission, August 7, 1990;
(2) Title 30, Chapter 5, Wyoming Statutes, sections 30-5-101 through 30-5-126
(b)
(2) Amendment No. 1 to the Memorandum of Agreement, dated December 22, 1982;
(3) Amendment No. 2 to the Memorandum of Agreement, dated January 25, 1990;
(4) Letter from State Oil and Gas Supervisor, Wyoming Oil and Gas Conservation Commission, to the Acting Director, Water Management Division, EPA Region VIII, “Re: Application for Primacy in the Regulation of Class II Injection Wells,” March 8, 1982;
(5) Letter from State Oil and Gas Supervisor, Wyoming Oil and Gas Conservation Commission, to EPA Region VIII, “Re: Regulation of Liquid Hydrocarbon Storage Wells Under the UIC Program,” July 1, 1982;
(6) Memorandum of Agreement Between the Wyoming State Board of Control, State Engineer, Oil and Gas Conservation Commission, and the Department of Environmental Quality, dated October 14, 1981.
(c)
(2) Letter from special Assistant Attorney General for the State of Wyoming to Assistant Regional Counsel, EPA Region VIII, May 13, 1982;
(3) Letter from special Assistant Attorney General for the State of Wyoming to Assistant Regional Counsel, EPA Region VIII, July 1, 1982.
(d)
(a)
(b)
In accordance with §§ 144.7(b) and 146.4 of this chapter, those portions of aquifers currently being used for injection in connection with Class II (oil and gas) injection operations on the Wind River Reservation, which are described below, are hereby exempted for the purpose of Class II injection activity. This exemption applies only to the aquifers tabulated below, and includes those portions of the aquifers defined on the surface by an outer boundary of those quarter-quarter sections dis-sected by a line drawn parallel to, but one-quarter mile outside, the field boundary, and is restricted to extend no further than one-quarter mile outside the Reservation boundary. Maps showing the exact boundaries of the field may be consulted at the EPA's Region 8 Office, and at the EPA Headquarters in Washington, DC.
In accordance with § 144.7(b) and § 146.4 of this chapter, the aquifers described in the following table are hereby exempted from the definition of an underground source of drinking water, as defined in 40 CFR 144.3:
The UIC program for all classes of wells in the territory of Guam, except those on Indian lands, is the program administered by the Guam Environmental Protection Agency, approved by EPA pursuant to SDWA section 1422. Notice of this approval was published in the
(a)
(1) Water Resources Conservation Act, Government Code of Guam sections 57021-57025, Public Law 9-31 (March 9, 1967), as amended by Public Law 9-76 (July 29, 1967), as amended by Public Law 12-191 (December 30, 1974);
(2) Water Pollution Control Act, Government Code of Guam sections 57042 and 57045, Public Law 9-76 (July 29, 1967), as amended by Public Law 9-212 (August 5, 1968), as amended by Public Law 10-31 (March 10, 1969), as amended by Public Law 12-191 (December 30, 1974);
(3) Guam Environmental Protection Agency, Underground Injection Control Regulations, Chapters 1-9, as revised by amendments adopted September 24, 1982;
(4) Guam Environmental Protection Agency, Water Quality Standards, Section I-IV (approved September 25, 1981, effective November 16, 1981).
(b)
(1) Government Code of Guam, Title XXV, Chapters I-III (sections 24000-24207);
(2) Government Code of Guam, Title LXI, Chapters I-III (sections 57000-57051);
(3) Government Code of Guam, Title LXI, Chapters VI (sections 57120-57142);
(4) Government Code of Guam, Title LXI, Chapters VIII (sections 57170-57188);
(5) Government Code of Guam, Title LXI, Chapters XII (sections 57285-57299);
(c) The Memorandum of Agreement between EPA, Region IX and the Guam Environmental Protection Agency signed by the Regional Administrator on January 14, 1983.
(d)
(2) Letter from Attorney General of Guam to Regional Administrator, Region IX, “Re: Additional comments to be incorporated into the May 12, 1982, Attorney General's Statement for Underground Injection Control Program,” September 2, 1982.
(e) The Program Description and any other materials submitted as part of the application or amendments thereto.
(a)
(b)
The Underground Injection Control Program for all classes of wells in the Commonwealth of Puerto Rico, other than those on Indian lands, is the program administered by Puerto Rico's Environmental Quality Board (EQB), approved by the EPA pursuant to the Safe Drinking Water Act (SDWA) section 1422. This program consists of the following elements, as submitted to EPA in the Commonwealth's program application.
(a)
(1) Underground Injection Control Regulations of the Commonwealth of Puerto Rico, Parts I through V and appendices A and B, adopted September 14, 1983 (Amended July 20, 1988).
(2) Puerto Rico Public Policy Environmental Act (PRPPE), Title 12 Laws of Puerto Rico Annotated (LPRA) Chapters 121 and 131, 1977 edition, as amended 1988 edition, and Chapter 122, 1988 edition.
(b) Memorandum of Agreement. The Memorandum of Agreement between EPA Region II and the Commonwealth of Puerto Rico's EQB signed by the Regional Administrator on August 23, 1991.
(c) Statement of legal authority. (1) Attorney General's statement on the Commonwealth of Puerto Rico's Authority to apply for, assume and carry out the UIC Program, dated June 26, 1987. (2) Letter from the Governor of the Commonwealth of Puerto Rico requesting the program, dated July 16, 1987.
(d) Program description. The Description of the Commonwealth of Puerto Rico's Underground Injection Control Program, dated with the effective date October 30, 1986.
(a) Contents. The UIC program for all classes of wells on Indian lands in the Commonwealth of Puerto Rico is administered by EPA. This program consists of the UIC program requirements of 40 CFR parts 124, 144, 146, 148 and any additional requirements set forth in the remainder of this subpart. Injection well owners and operators and
(b) Effective date. The effective date for the UIC program on Indian Lands in the Commonwealth of Puerto Rico is November 25, 1988.
(a)
(b)
(a)
(b)
The UIC program for Class I, II, III, IV, and V wells in the Commonwealth of the Northern Mariana Islands, other than those on Indian lands, is the program administered by the Commonwealth of the Northern Mariana Islands Division of Environmental Quality approved by EPA pursuant to Section 1422 of the SDWA. Notice of this approval was published in the
(a)
(1) CNMI Environmental Protection Act, 2 CMC sections 3101,
(2) CNMI Coastal Resources Management Act, 2 CMC sections 1501,
(3) CNMI Drinking Water Regulations, Commonwealth Register, Volume 4, Number 4 (August 15, 1982);
(4) CNMI Underground Injection Control Regulations, Commonwealth Register, Volume 6, Number 5 (May 15, 1984, amended November 15, 1984, January 15, 1985);
(5) CNMI Coastal Resources Management Regulations, Commonwealth Register, Volume 6, Number 12, December 17, 1984.
(b)(1) The Memorandum of Agreement between EPA Region IX and the Commonwealth of the Northern Mariana Islands Division of Environmental Quality, signed by the EPA Regional Administrator on May 3, 1985;
(c)
(d) The Program Description and any other materials submitted as part of the original application or as supplements thereto.
(a)
(b)
(a)
(b)
Safe Drinking Water Act, 42 U.S.C. 300h.
This subpart sets forth the rules and permitting requirements for the Osage Mineral Reserve, Osage County, Oklahoma, Underground Injection Control Program. The regulations apply to owners and operators of Class II injection wells located on the Reserve, and to EPA.
Most of the following terms are defined in § 144.3, and have simply been reproduced here for the convenience of the reader. This section also includes definitions of some terms unique to the Osage program. Terms used in this subpart are defined as follows:
(a) Which are brought to the surface in connection with conventional oil or natural gas production and may be commingled with waste waters from gas plants which are an integral part of
(b) For enhanced recovery of oil or natural gas; and
(c) For storage of hydrocarbons which are liquid at standard temperature and pressure.
(a)(1) Which supplies any public water system; or
(2) Which contains a sufficient quantity of ground water to supply a public water system; and
(i) Currently supplies drinking water for human consumption; or
(ii) Contains fewer than 10,000 mg/1 total dissolved solids; and
(b) Which is not an exempted aquifer.
(a) Any underground injection, except as authorized by permit or rule issued under the UIC program, is prohibited. The construction or operation of any well required to have a permit is prohibited until the permit has been issued.
(b) No owner or operator shall construct, operate, maintain, convert, plug, or abandon any injection well, or conduct any other injection activity, in a manner that allows the movement of fluid containing any contaminant into underground sources of drinking water, if the presence of that contaminant may cause the violation of any primary drinking water regulation under 40 CFR part 142 or may otherwise adversely affect the health of persons. The applicant for a permit shall have the burden of showing that the requirements of this paragraph are met.
(c) Injection between the outermost casing protecting underground sources of drinking water and the well bore is prohibited.
(a) The area of review for an injection well or project will be a fixed radius of one-forth of a mile from the well, field or project.
(b) The zone of endangering influence is the lateral area around the injection well or project in which the injection zone pressures may cause movement of fluid into an underground source of drinking water (USDW) if there are improperly sealed, completed or abandoned wells present. A zone of endangering influence may be determined by EPA through the use of an appropriate formula that addresses the relevant geologic, hydrologic, engineering and operational features of the well, field, or project.
The owner/operator shall notify the Osage UIC office within 30 days of the date injection has terminated. The well must be plugged within 1 year after termination of injection. The Regional Administrator may extend the time to plug, but only if no fluid movement into a USDW will occur, and the operator has presented a viable plan for utilizing the well within a reasonable time.
(a) Until an injection well has been properly plugged and abandoned, annual reports to the Regional Administrator on well status, and mechanical integrity tests as outlined in §§ 147.2912 and 147.2920 will be required, whether or not injection has ceased.
(b) All wells shall be plugged to prevent movement of fluid into an USDW.
(c) The owner/operator shall notify the Osage UIC office by certified mail at least 5 days prior to the commencement of plugging operations. The Osage UIC office may waive or reduce the 5-day notice requirement when a qualified EPA representative is available to witness the plugging operation. The following information must be submitted as part of the notification:
(1) Type and number of plugs to be used;
(2) Elevation of top and bottom of each plug;
(3) Method of plug placement; and
(4) Type, grade and quantity of cement to be used.
(d) The well shall be kept full of mud as casing is removed. No surface casing shall be removed without written approval from the Regional Administrator.
(e)(1) If surface casing is adequately set and cemented through all freshwater zones (set to at least 50 feet below the base of freshwater), a plug shall be set at least 50 feet below the shoe of the casing and extending at least 50 feet above the shoe of the -casing, or
(2) If the surface casing and cementing is inadequate, the well bore shall be filled with cement from a point 50 feet below the base of fresh water to a point 50 feet above the shoe of the surface casing, and any additional plugs as required by the Osage UIC office and/or the Osage Agency.
(3) In all cases, the top 20 feet of the well bore below 3 feet of ground surface shall be filled with cement. Surface casing shall be cut off 3 feet below ground surface and covered with a secure steel cap on top of the surface pipe. The remaining 3 feet shall be filled with dirt.
(f)(1) Except as provided in paragraph (f)(2) of this section, each producing or receiving formation shall be sealed off with a 50-foot cement plug placed at the base of the formation and a 50-foot cement plug placed at the top of the formation.
(2) The requirement in paragraph (f)(1) of this section does not apply if the producing/receiving formation is already sealed off from the well bore with adequate casing and cementing behind casing, and casing is not to be removed, or the only openings from the producing/receiving formation into the well bore are perforations in the casing, and the annulus between the casing and the outer walls of the well is filled with cement for a distance of 50 feet below the base of the formation and 50 feet above the top of the formation. When such conditions exist, a bridge plug capped with 10 feet of cement set at the top of the producing formation may be used.
(g) When specified by the Osage UIC office, any uncased hole below the shoe of any casing to be left in the well shall be filled with cement to a depth of at least 50 feet below the casing shoe, or the bottom of the hole, and the casing above the shoe shall be filled with cement to at least 50 feet above the shoe of the casing. If the well has a screen or liner which is not to be removed, the well bore shall be filled with cement from the base of the screen or liner to at least 50 feet above the top of the screen or liner.
(h) All intervals between cement plugs in the well bore shall be filled with mud.
(i) A report containing copies of the cementing tickets shall be submitted to BIA within 10 days of plugging completion.
(j) A surety bond must be on file with the Bureau of Indian Affairs (BIA), and shall not be released until the well has been properly plugged and the Regional Administrator has agreed to the release of the bond.
(a) An emergency permit may be issued if:
(1) There will be an imminent health hazard unless an emergency permit is issued; or
(2) There will be a substantial and irretrievable loss of oil and gas resources, timely application for a permit could not practicably have been made, and injection will not result in movement of fluid into an USDW; or
(3) There will be a substantial delay in oil or gas production, and injection will not result in movement of fluid into an USDW.
(b)
(ii) Emergency permits issued to prevent a substantial and irretrievable loss of oil or gas resources shall be for no longer than 90 days, unless a complete permit application has been submitted during that time; in which case the emergency permit may be extended until a final decision on the permit application has been made.
(iii) Emergency permits to avoid a substantial delay in oil or gas production shall be issued only after a complete permit application has been submitted and shall be effective until a final decision on the permit application is made.
(2) Notice of the emergency permit will be given by the Regional Administrator according to the notice procedure for a draft permit within 10 days after issuance.
(3) An emergency permit may be oral or written. If oral, a written emergency permit must be issued within five calendar days.
(a) The following information cannot be claimed confidential by the submitter:
(1) Name and address of permit applicant or permittee.
(2) Information concerning the existence, absence or level of contaminants in drinking water.
(b) Other information claimed as confidential will be processed in accordance with 40 CFR -part 2.
(a) After notice and opportunity for a public hearing, the Administrator may designate any aquifer or part of an aquifer as an exempted aquifer.
(b) An aquifer or its portion that meets the definition of a USDW may be exempted by EPA from USDW status if the following conditions are met:
(1) It does not currently serve as a source of drinking water, and
(2) It cannot now and will not in the future serve as a source of drinking water because:
(i) It is hydrocarbon producing, or can be demonstrated by a permit applicant as a part of a permit application for a Class II operation to contain hydrocarbons that are expected to be commercially producible (based on historical production or geologic information); or
(ii) It is situated at a depth or location which makes recovery of water for drinking water purposes economically or technologically impractical; or
(iii) It is so contaminated that it would be economically or technologically impractical to render that water fit for human consumption; or
(3) The Total Dissolved Solids content of the groundwater is more than 3,000 and less than 10,000 mg/1 and it is not reasonably expected to supply a public water system.
All existing Class II injection wells (wells authorized by BIA and constructed or completed on or before the effective date of the Osage UIC program) are hereby authorized. Owners or operators of wells authorized by rule must comply with the provisions of §§ 147.2903, 147.2905, 147.2907, and 147.2910 through 147.2915.
Existing Class II injuction wells are authorized for the life of the well, subject to the obligation to obtain a permit if specifically required by the Regional Administrator pursuant to § 147.2915.
All Class II wells shall be cased and cemented to prevent movement of fluids into USDWs. The Regional Administrator shall review inventory information, data submitted in permit applications, and other records, to determine the adequacy of construction (completion) or existing injection wells. At the Regional Administrator's discretion, well casing and cementing may be considered adequate if it meets the BIA requirements that were in effect at the time of construction (completion) and will not result in movement of fluid into an USDW. If the Regional Administrator determines that the construction of a well authorized by rule is inadequate, he shall require a permit, or he shall notify the owner/operator and the owner/operator shall correct the problem according to instructions from the Regional Administrator. All corrections must be completed within one year of owner/operator notification of inadequacies.
(a) Each well authorized by rule must have mechanical integrity. Mechanical integrity must be demonstrated within five years of program adoption. The Regional Administrator will notify the well owner/operator three months before proof of mechanical integrity must be submitted to EPA. The owner/operator must contact the Osage UIC office at least five days prior to testing. The owner/operator may perform the mechanical integrity test prior to receiving notice from the Regional Administrator, provided the Osage UIC office is notified at least five days in advance. Conditions of both paragraphs (a)(1) and (a)(2) of this section must be met.
(1) There is no significant leak in the casing, tubing or packer. This may be shown by the following:
(i) Performance of a pressure test of the casing/tubing annulus to at least 200 psi, or the pressure specified by the
(ii) Maintaining a positive gauge pressure on the casing/tubing annulus (filled with liquid) and monitoring the pressure monthly and reporting of the pressure information annually; or
(iii) Radioactive tracer survey; or
(iv) For enhanced recovery wells, records of monitoring showing the absence of significant changes in the relationship between injection pressure and injection flow rate at the well head, following an initial pressure test as described by paragraph (a)(1)(i) or (v) of this section; or
(v) Testing or monitoring programs approved by the Regional Administrator on a case-by-case basis, and
(2) There is no significant fluid movement into a USDW through vertical channels adjacent to the well bore. This may be shown by any of the following:
(i) Cementing records (need not be reviewed every five years);
(ii) Tracer survey (in appropriate hydrogeologic settings; must be used in conjunction with at least one of the other alternatives);
(iii) Temperature log;
(iv) Noise log; or
(v) Other tests deemed acceptable by the Regional Administrator.
(b) Injection pressure at the wellhead shall be limited so that it does not initiate new fractures or propagate existing fractures in the confining zone adjacent to any UDSW.
(1) For existing Class II salt water disposal wells, The owner/operator shall, except during well stimulation, use an injection pressure at the wellhead no greater than the pressure calculated by using the following formula:
(2) For existing Class II enhanced recovery wells, the owner or operator:
(i) Shall use an injection pressure no greater than the pressure established by the Regional Administrator for the field or formation in which the well is located. The Regional Administrator shall establish such a maximum pressure after notice, opportunity for comment, and opportunity for a public hearing according to the provisions of part 124, subpart A of this chapter, and will inform owners and operators in writing of the applicable maximum pressure.
(ii) Prior to such time as the Regional Administrator establishes rules for maximum injection pressures based on data provided pursuant to paragraph (b)(2)(ii)(B) of this section the owner/operator shall:
(A) Limit injection pressure at the wellhead to a value which will not initiate new fractures or propagate existing fractures in the confining zone adjacent to any USDW; and
(B) Submit data acceptable to the Regional Administrator which defines the fracture pressure of the formation in which injection is taking place. A single test may be submitted on behalf of two or more operators conducting operations in the same formation, if the Regional Administrator approves such submission. The data shall be submitted to the Regional Administrator within one year of the effective date of this program.
(c) Injection wells or projects which have exhibited failure to confine injected fluids to the authorized injection zone or zones may be subject to restriction of injection volume and pressure, or shut-down, until the failure has been identified and corrected.
(a) The owner/operator has the duty to submit inventory information to the Regional Administrator upon request. Such request may be a general request to all operators in the County (e.g., public notice, or mailout requesting verification of information).
(b) The operator shall monitor the injection pressure (psi) and rate (bb1/day) at least monthly, with the results reported annually. The annual report shall specify the types of methods used to generate the monitoring data.
(c) The owner/operator shall notify the Osage UIC office within 30 days of any mechanical failure or down-hole problems involving well integrity, well workovers, or any noncompliance. As required, operators must apply for and obtain a workover permit from the Bureau of Indian Affairs Osage Agency before reentering an injection well. If the condition may endanger an USDW, the owner/operator shall notify the Osage UIC office orally within 24 hours, with written notice including plans for testing and/or repair to be submitted within five days. If all the information is not available within five days, a followup report must be submitted within 30 days.
(d) The owner/operator shall determine the nature of injected fluids initially, when the nature of injected fluids is changed or when new constituents are added. The records should reflect the source of character of the new fluid and the date changes were made.
(e) The owner/operator shall retain all monitoring records for three years, unless an enforcement action is pending, and then until three years after the enforcement action has been resolved.
Based on the Regional Administrator's discretion, corrective action to prevent movement of fluid into an USDW may be required for improperly sealed, completed or abandoned wells (i.e., wells or well bores which may provide and avenue for fluid migration into a USDW) within the zone of endangering influence (as defined in § 147.2904, Area of Review) of an injection well authorized by rule.
(a) EPA will notify the operator when corrective action is required. Corrective action may include:
(1) Well modifications:
(i) Recementing;
(ii) Workover;
(iii) Reconditioning;
(iv) Plugging or replugging;
(2) Limitations on injection pressure to prevent movement of fluid into an USDW;
(3) A more stringent monitoring program; and/or
(4) Periodic testing of other wells to determine if significant movement of fluid has occurred.
(b) If the monitoring discussed in paragraph (a) (3) or (4) of this section indicate the potential endangerment of an USDW, then action as described in paragraph (a) (1) or (2) of this section must be taken.
(a) The Regional Administrator may require the owner or operator of any well authorized by rule to apply for an individual or area permit. The Regional Administrator shall notify the owner/operator in writing that a permit application is required. The notice shall contain:
(1) Explanation of need for application;
(2) Application form and, if appropriate, a list of additional information to be submitted; and
(3) Deadline for application submission.
(b) Cases in which the Regional Administrator may require a permit include:
(1) The owner or operator is not in compliance with provisions of the rule;
(2) Injection well is no longer within the category of wells authorized by rule;
(3) Protection of USDWs requires that the injection operation be regulated by requirements which are not contained in the rule; or
(4) Discretion of Regional Administrator.
(c) Injection is no longer authorized by rule upon the effective date of a permit or permit denial, or upon failure of the owner/operator to submit an application in a timely manner as specified in the notice described in paragraph (a) of this section.
(d) Any owner/operator authorized by rule may request to be excluded from the coverage of the rules by applying for an individual or area UIC permit.
The owner or operator of a new Class II injection well or any other Class II well required to have a permit in the Osage Mineral Reserve shall comply with the requirements of §§ 147.2903, 147.2907, 147.2918, through 147.2928.
Unless otherwise specified in the permit, the permits will be in effect until the well is plugged and abandoned or the permit terminated. The Regional Administrator will review each issued permit at least once every five years to determine whether it should be modified or terminated.
(a) The owner/operator must submit the original and three copies of the permit application, with two complete sets of attachments, to the Osage UIC office. The application should be signed by the owner/operator or a duly authorized representative. The application should also include appropriate forms (i.e., BIA's Application for Operation or Report on Wells and EPA's permit application). The applicant has the burden of proof to show that the proposed injection activities will not endanger USDWs.
(b) The application shall include the information listed below. Information required by paragraphs (b) (5), (7), or (9) of this section that is contained in EPA or BIA files may be included in the application by reference.
(1) Map using township-range sections showing the area of review and identifying all wells of public record penetrating the injection interval.
(2) Tabulation of data on the wells identified in paragraph (b)(1) of this section, including location, depth, date drilled, and record of plugging and/or completion.
(3) Operating data:
(i) Maximum and average injection rate;
(ii) Maximum and average injection pressure;
(iii) Whether operation is on cyclic or continuous operation basis; and
(iv) Source and appropriate analysis of injected fluids, including total dissolved solids, chlorides, and additives.
(4) Geologic data on the injection and confining zones, including faults, geological name, thickness permeability, depth and lithologic description.
(5) Depth to base of fresh water.
(6) Schematic drawings of the surface and subsurface details of the well, showing:
(i) Total depth or plug-back depth;
(ii) Depth to top and bottom of injection interval;
(iii) Depths to tops and bottoms of casing and cemented intervals, and amount of cement to be used;
(iv) Size of casing and tubing, and depth of packer; and
(v) Hole diameter.
(7) Proof that surety bond has been filed with the BIA Superintendent in accordance with 25 CFR 226.6. A surety bond must be maintained until the well has been properly plugged.
(8) Verification of public notice, consisting of a list showing the names, addresses, and date that notice of permit application was given or sent to:
(i) The surface land owner;
(ii) Tenants on land where injection well is located or proposed to be located; and
(iii) Each operator of a producing lease within one-half mile of the well location.
(9) All available logging and testing data on the well (for existing wells, i.e., wells to be converted or wells previously authorized by rule).
(a) All Class II wells shall be sited so that they inject into a formation that
(b) All Class II wells shall be cased and cemented to prevent movement of fluids into or between USDWs. Requirements shall be based on the depth to base of fresh water, and the depth to the injection zone. Newly drilled Class II wells must have surface casing set and cemented to at least 50 feet below the base of fresh water, or the equivalent (e.g., long string cemented to surface). At the Regional Administrator's discretion, the casing and cementing of wells to be converted may be considered adequate if they meet the BIA requirements that were in effect at the time of construction (completion), and will not result in movement of fluid into a USDW.
(c) Owner/operators shall provide a standard female fitting with cut-off valves, connected to the tubing and the tubing/casing annulus so that the injection pressure and annulus pressure may be measured by an EPA representative by attaching a gauge having a standard male fitting.
(d) No owner or operator may begin construction of a new well until a permit authorizing such construction has been issued, unless such construction is otherwise authorized by an area permit.
(a) For new Class II wells, injection shall be through adequate tubing and packer. Packer shall be run on the tubing and set inside the casing within 75 feet of the top of the injection interval. For existing Class II, wells, injection shall be through adequate tubing and packer, or according to alternative operating requirements approved by the Regional Administrator, as necessary to prevent the movement of fluid into a USDW.
(b) Each well must have mechanical integrity. Mechanical integrity of the injection well must be shown prior to operation. The owner/operator must notify the Osage UIC office at least five days prior to mechanical integrity testing. Conditions of both paragraphs (b) (1) and (2) of this section must be met.
(1) There is no significant leak in the casing, tubing or packer. This may be shown by the following:
(i) Performance of a pressure test of the casing/tubing annulus to at least 200 psi, or the pressure specified by the Regional Administrator, to be repeated thereafter, at five year intervals, for the life of the well (Pressure tests conducted during well operation shall maintain an injection/annulus pressure differential of at least 100 psi throughout the tubing length); or
(ii) Maintaining a positive gauge pressure on the casing/tubing annulus (filled with liquid) and monitoring the pressure monthly and reporting of the pressure information annually; or
(iii) Radioactive tracer survey; or
(iv) For enhanced recovery wells, record of monitoring showing the absence of significant changes in the relationship between injection pressure and injection flow rate at the wellhead, following an initial pressure test as described by paragraph (b)(1) (i) or (v) of this section; or
(v) Testing or monitoring programs approved by the Administrator on a case-by-case basis, and
(2) There is no significant fluid movement into a USDW through vertical channels adjacent to the well bore. This may be shown by any of the following:
(i) Cementing records (need not be reviewed every five years);
(ii) Tracer survey (in appropriate hydrogelogic settings; must be used in conjunction with at least one of the other alternatives);
(iii) Temperature log;
(iv) Noise log; or
(v) Other tests deemed acceptable by the Administrator.
(c) Injection pressure at the wellhead shall be limited so that it does not initiate new fractures or propagate existing fractures in the confining zone adjacent to any UDSW.
(d) Injection wells or projects which have exhibited failure to confine injected fluids to the authorized injection zone or zones may be subject to restriction of injected volume and pressure or shut-in, until the failure has been identified and corrected.
(e) Operation shall not commence until proof has been submitted to the
The permit may, when appropriate, specify a schedule of compliance leading to compliance with the Safe Drinking Water Act and the Osage UIC regulations.
(a) Any schedule of compliance shall require compliance as soon as possible, and in no case later than three years after the effective date of the permit.
(b) If a permit establishes a schedule of compliance which exceeds one year from the date of permit issuance, the schedule shall set forth interim requirements and the dates for their achievement.
(1) The time between interim dates shall not exceed one year.
(2) If the time necessary for completion of any interim requirement is more than 1 year and is not readily divisible into stages for completion, the permit shall specify interim dates for the submission of reports of progress toward completion of the interim requirements and indicate a projected completion date.
(c) The permit shall be written to require that if a schedule of compliance is applicable, progress reports be submitted no later than 30 days following each interim date and the final date of compliance.
(a) The owner/operator shall notify the Osage UIC office within 30 days of the date on which injection commenced.
(b) The operator shall monitor the injection pressure (psi) and rate (bbl/day) at least monthly, with the results reported annually. The annual reports shall specify the types or methods used to generate the monitoring data.
(c) The owner/operator shall notify the Osage UIC office within 30 days of any mechanical failure or down-hole problems involving well integrity, well workovers, or any noncompliance. (Operators should note the obligation to apply for and obtain a workover permit from the Bureau of Indian Affairs Osage Agency before reentering an injection well.) If the condition may endanger an USDW, the owner/operator shall notify the Osage UIC officer -orally within 24 hours, with written notice including plans for testing and/or repair to be submitted within five days. If all the information is not available within five days, a followup report must be submitted within 30 days.
(d) The owner/operator shall retain all monitoring records for three years, unless an enforcement action is pending, and then until three years after the enforcement action has been resolved.
(e) The owner/operator shall notify the Osage UIC office in writing of a transfer of ownership at least 10 days prior to such transfer.
All improperly sealed, completed or abandoned wells (i.e., wells or well bores which may provide an avenue for movement of fluid into an UDSW) within the zone of endangering influence (as defined in § 147.2904, Area of Review) that penetrate the injection zone of a Class II well, must have corrective action taken to prevent movement of fluid into a USDW.
(a) EPA will review completion and plugging records of wells within the zone of endangering influence that penetrate the injection zone and will notify the operator when corrective action is required. Corrective action may include:
(1) Well modifications, including:
(i) Recementing;
(ii) Workover;
(iii) Reconditioning; and/or
(iv) Plugging or replugging;
(2) Permit conditions to limit injection pressure so as to prevent movement of fluid into a USDW;
(3) A more stringent monitoring program; and/or
(4) Periodic testing of other wells within the area of review to determine if significant movement of fluid has occurred. If the monitoring discussed in paragraph (a)(3) or (a)(4) of this section indicates the potential endangerment
(b) If the Regional Administrator has demonstrable knowledge that wells within the zone of endangering influence will not serve as conduits for fluid movement into a USDW, the permit may be approved without requiring corrective action. However, additional monitoring shall be required to confirm that no significant migration will occur.
(a) Area permits may be issued for more than one injection well if the following conditions are met:
(1) All existing wells are described and located in the permit application;
(2) All wells are within the same well field, project, reservoir or similar unit;
(3) All wells are of similar construction; and
(4) All wells are operated by the same owner/operator.
(b) Area permits shall specify:
(1) The area within which injection is authorized; and
(2) The requirements for construction, monitoring, reporting, operation and abandonment for all wells authorized by the permit.
(c) Area permits can authorize the construction and operation of new wells within the permit area, if:
(1) The permittee notifies the Regional Administrator in the annual report of when and where any new wells have or will be drilled;
(2) The new wells meet the criteria outlined in paragraphs (a) and (b) of this section; and
(3) The effects of the new wells were addressed in the permit application and approved by the Regional Administrator.
(a) The permittee must comply with all permit conditions, except as authorized by an emergency permit (described in § 147.2906). Noncompliance is grounds for permit modification, permit termination or enforcement action.
(b) The permittee has a duty to halt or reduce activity in order to maintain compliance with permit conditions.
(c) The permittee shall take all reasonable steps to mitigate any adverse environmental impact resulting from noncompliance.
(d) The permittee shall properly operate and maintain all facilities installed or used to meet permit conditions. Proper operation and maintenance also includes adequate operator staffing and training, adequate funding, and adequate engineering capability available.
(e) This permit may be modified or terminated for cause (see §§ 147.2927 and 147.2928). The filing of a request by the permittee for a permit modification or termination, or a notification of planned changes or anticipated noncompliance, does not stay any permit condition.
(f) This permit does not convey any property rights, or any exclusive -privilege.
(g) The permittee shall furnish, within a reasonable time, information that the Regional Administrator requests, for determination of permit compliance, or if cause exists, for permit modification or termination.
(h) The permittee shall allow EPA representatives, upon presentation of appropriate credentials or other documentation, to:
(1) Enter permittee's premises where a regulated activity is conducted or located, or where records required by this permit are kept;
(2) Have access to and copy records required by this permit;
(3) Inspect any facilities, equipment, practices or operations regulated or required by this permit; and
(4) Sample or monitor any substances or parameters at any location for purpose of assuring compliance with this permit or the SDWA.
(i)
(1) Samples and monitoring data shall be representative of injection -activity.
(2) Permittee shall retain monitoring records for three years.
(3) Monitoring records shall include:
(i) Date, exact place and time of sampling or measurement;
(ii) Individual(s) who preformed the measurements;
(iii) Date(s) analyses were performed;
(iv) Individual(s) who performed the analyses;
(v) Analytical techniques or methods used, including quality assurance techniques employed to insure the generation of reliable data; and
(vi) Results of analyses.
(j)
“I certify under penalty of law that I have personally examined and am familiar with the information submitted in this document and all attachments and that, based on my inquiry of those individuals immediately responsible for obtaining the information, I believe that the information is true, accurate, and complete. I am aware that there are significant penalties for submitting false information, including the possibility of fine and imprisonment.”
(k)
(2) The permittee shall give advance notice to the Regional Administrator of any planned changes which may result in noncompliance.
(3) This permit is not transferable to any person except after notice to the Regional Administrator in accordance with § 147.2926.
(l) A new injection well shall not commence injection until construction is complete and the Regional Administrator has been notified of completion of construction and has given his approval to commence injection.
(a) Permits may be transferred to another permittee:
(1) If the current permittee notifies the Regional Administrator at least 10 days before the proposed transfer date; and
(2) If the notice includes a written agreement between the existing and new permittees containing:
(i) A specific date for transfer of permit responsibility, coverage and liability; and
(ii) Assurance that the new permittee has a surety bond on file with BIA; and
(3) If the Regional Administrator does not respond with a notice to the existing permittee that the permit will be modified.
(b) If the conditions in paragraph (a) of this section are met, the transfer is effective on the date specified in paragraph (a)(2)(i) of this section.
(a) Permits may be modified for the following causes only (with the exceptions listed in paragraph (b) of this section regarding minor modifications):
(1) There are substantial changes to the facility or activity which occurred after permit issuance that justify revised or additional permit conditions.
(2) The Regional Administrator has received information (e.g., from monitoring reports, inspections) which warrants a modified permit.
(3) The regulations or standards on which the permit was based have changed.
(4) The Regional Administrator has received notice of a proposed permit transfer.
(5) An interested person requests in writing that a permit be modified, and the Regional Administrator determines that cause for modification exists.
(6) Cause exists for termination under § 147.2928, but the Regional Administrator determines that permit modification is appropriate.
(b)
(2) Minor modifications consist of:
(i) Correcting typographical errors;
(ii) Requiring more frequent monitoring or reporting;
(iii) Changing ownership or operational control (see § 147.2926, Permit Transfers); or
(iv) Changing quantities or types of injected fluids, provided:
(A) The facility can operate within conditions of permit;
(B) The facility classification would not change.
(c)
(2) The draft permit shall follow the general permitting procedures (i.e., public comment period, etc.) before a final decision is made.
(3) Only the changed conditions shall be addressed in the draft permit or public review.
(a) Permits may be terminated for the following causes only:
(1) Noncompliance with any permit condition.
(2) Misrepresentation or failure to fully disclose any relevant facts.
(3) Determination that the permitted activity endangers human health or the environment.
(4) Interested person requests in writing that a permit be terminated and the Regional Administrator determines that request is valid.
(b)
(2) Notice of intent to terminate shall follow the general permitting procedures (i.e., public comment period, etc.) before a final decision is made.
(a)
(2) If the application is incomplete, the Regional Administrator shall:
(i) List the additional information needed;
(ii) Specify a date by which the information must be submitted; and
(iii) Notify the applicant when the application is complete.
(3) After an application is determined complete, the Regional Administrator may request additional information to clarify previously submitted information. The application will still be considered complete.
(4) If an applicant fails or refuses to correct deficiencies in the application, the permit may be denied and appropriate enforcement actions taken.
(b)
(2) A draft permit shall contain at least the following information:
(i) The standard permit conditions in § 147.2925;
(ii) Any monitoring and reporting requirements;
(iii) The construction and operation requirements; and
(iv) Plugging and abandonment requirements.
(c)
(2) The statement of basis shall briefly describe the draft permit conditions and the reasons for them. In the case of a notice of intent to deny or terminate, the statement of basis shall give reasons to support the tentative decision.
(3) The statement of basis shall be sent to the applicant, and to any other person who requests a copy.
(d)
(A) A permit application has been tentatively denied;
(B) A draft permit has been prepared;
(C) A hearing has been scheduled; or
(D) An appeal has been granted.
(ii) The applicant shall give public notice that he is submitting a permit application.
(iii) Public notice is not required when a request for permit modification or termination is denied. However, written notice will be given to the permittee and the requester.
(iv) Public notices may include more than one permit or action.
(2)(i) Public notice of a draft permit (including notice of intent to deny)
(ii) Public notice of a hearing shall be given at least 30 days before the hearing.
(3)(i) Public notice given by the Regional Administrator for the reasons listed in paragraph (d)(1)(i) of this section shall be mailed to the applicant, and published in a daily or weekly paper of general circulation in the affected area.
(ii) Notice of application submission required by paragraph (d)(1)(ii) of this section shall be given to the surface landowner, tenants on the land where an injection well is located or is proposed to be located, and to each operator of a producing lease within one-half mile of the well location prior to submitting the application to the Regional Administrator.
(4) The notice of application submission in paragraphs (d)(1)(ii) and (d)(3)(ii) of this section shall contain:
(i) The applicant's name and address;
(ii) The legal location of the injection well;
(iii) Nature of activity;
(iv) A statement that EPA will be preparing a draft permit and that there will be an opportunity for public comment; and
(v) The name and phone number of EPA contact person.
(5) All other notices shall contain:
(i) The name, address, and phone number of the Osage UIC office and contact person for additional information and copies of the draft permit;
(ii) Name and address of permit applicant or permittee;
(iii) Brief description of nature of activity;
(iv) Brief description of comment period and comment procedures;
(v) Location of the information available for public review; and
(vi) In the case of a notice for a hearing the notice shall also include:
(A) Date, time, and location of hearing;
(B) Reference to date of previous notices of the same permit; and
(C) Brief description of the purpose of the hearing, including rules and procedures.
(e)
(2) The Regional Administrator shall consider all comments when making the final decision, and shall respond to comments after the decision is made. The response shall:
(i) Specify if any changes were made from the draft permit to the final permit decision, and why;
(ii) Briefly describe and respond to all significant comments on the draft permit made during the comment period, or hearing, if held; and
(iii) Be made available to the public.
(f)
(2) Any person may submit oral or written statements and data concerning the draft permit. The public comment period shall be automatically extended to the close of any public hearing held, or may be extended by the hearing officer at the hearing.
(3) A tape recording or written transcript of the hearing shall be made available to the public.
(g)
(i) Prepare a new draft permit;
(ii) Prepare a revised statement of basis; or
(iii) Reopen the comment period.
(2) Comments submitted during a reopened comment period shall be limited to the substantial new questions that caused its reopening.
(3) Public notice about any of the above actions shall be given and shall define the scope of the new questions raised.
(h)
(2) A final permit decision shall become effective 30 days after giving notice of the decision unless:
(i) A later date is specified in the -notice;
(ii) Review is requested under § 147.2929(j); or
(iii) No comments requested a change in the draft permit, in which case the permit is effective immediately upon issuance.
(i)
(j)
(2) A person may request review of a final permit decision within 30 days after a final permit decision has been issued. The 30-day period within which a person may request review begins with the service of notice of the Regional Administrator's final permit decision unless a later date is specified in that notice.
(3) The petition requesting review shall include:
(i) A demonstration that the petition is eligible under the requirements of paragraph (j)(1) of this section; and, when appropriate,
(ii) A showing that the condition in question is based on:
(A) A finding of fact or conclusion of law that is clearly erroneous; or
(B) An exercise of discretion or important policy consideration which -the Administrator, in his discretion, should review.
(4) The Administrator may also decide, on his initiative, to review any condition of any UIC permit issued under these requirements. The Administrator must act under this paragraph within 30 days of the date notice was given of the Regional Administrator's action.
(5) Within a reasonable time following the filing of the petition for review, the Administrator shall issue an order either granting or denying the request. To the extent that review is denied, the conditions of the final permit decision become final agency action.
(6) Public notice shall be given by the Regional Administrator of any grant of a review petition by the Administrator. Notice shall be sent to the applicant, the person requesting the review, appropriate persons on the Osage County mailing list and to newspapers of general circulation in the county. Included in the notice shall be a briefing schedule for the appeal and a statement that any interested person may file an amicus brief. Notice of denial of the review petition will be sent only to the person(s) requesting the review.
(7) A petition to the Administrator, under paragraphs (j) (1) and (2) of this section is a prerequisite to the seeking of judicial review of the final agency action. For purposes of judicial review, final agency action occurs when a final UIC permit is issued or denied by the Regional Administrator and agency review procedures are exhausted. A final permit decision shall be issued by the Regional Administrator:
(i) When the Administrator issues notice to the parties involved that review has been denied;
(ii) When the Administrator issues a decision on the merits of the appeal and the decision does not include a remand of the proceedings; or
(iii) Upon the completion of the remand proceedings if the proceedings are remanded, unless the Administrator's remand order specifically provides that the appeal of the remand decision will be required to exhaust the administrative remedies.
(a)
(b)
An applicant shall give public notice of his intention to apply for a permit as follows:
(a) Prior to submitting an application to the Director, the applicant shall give notice to each landowner, tenant, and operator of a producing lease within one-half mile of the well and to the affected Tribal Government. The notice shall include:
(1) Name and address of applicant;
(2) A brief description of the planned injection activities including well location, name and depth of the injection zone, maximum injection pressure and volume, and source and description of the fluid to be injected;
(3) Name, address, and phone number of the EPA contact person; and
(4) A statement that opportunity to comment will be announced to the public after EPA prepares a draft permit.
(b) In addition to the requirements of § 144.31(e) of this chapter, a permit applicant shall submit a description of the way the notice was given and the names and addresses of those to whom it was given.
(c) Upon written request and supporting documentation, the Director may waive the requirement in paragraph (a) of this section to give individual notice of intent to apply for permits in an area where it would be impractical. However, notice to the affected Tribal government shall not be waived.
(d) The Director shall also provide to the affected Tribal government all notices given to State governments under § 124.10(c) of this chapter.
(a)
(b)
Notwithstanding § 144.21(a)(3)(i)(B) of this chapter, authorization by rule for existing Class I and III wells will expire 90 days after the effective date of this UIC program unless a complete permit application has been submitted to the Director.
Notwithstanding §§ 144.24 and 146.51(b) of this chapter, owners and operators of wells used to dispose of radioactive waste (as defined in 10 CFR part 20, appendix B, table II, but not including high level and transuranic waste and spent nuclear fuel covered by 40 CFR part 191) shall comply with the permitting requirements pertaining to Class I wells in parts 124, 144 and 146 of this chapter, as modified and supplemented by this subpart.
(a)
(b)
(2) An owner or operator may inject at a pressure greater than that specified in paragraph (b)(1) of this section for the field or formation in which -he is operating after demonstrating in writing to the satisfaction of the Director that such injection pressure will not violate the requirements of § 144.28(f)(3)(ii) of this chapter. The Director may grant such a request after notice (including notice to the affected Tribe), opportunity for comment and opportunity for a public hearing according to the provisions of part 124, subpart A of this chapter.
(3) Prior to the time that the Director establishes rules for maximum injection pressure under paragraph (b)(1) of this section the owner or operator shall:
(i) Limit injection pressure to a value which will not exceed the operating requirements of § 144.28(f)(3)(ii); and
(ii) Submit data acceptable to the Director which defines the fracture pressure of the formation in which injection is taking place. A single submission may be made on behalf of two or more operators conducting operations in the same field and formation, if the Director approves. The data shall -be submitted to the Director within one year of the effective date of this program.
(a) Notwithstanding the requirements of § 144.31(c)(1) of this chapter, the owner or operator of an existing Class I or III well shall submit a complete permit application no later than 90 days after the effective date of the program.
(b) The topographic map (or other map if a topographic map is unavailable) required by § 144.31(e)(7) of this
The aquifer exemption criterion in § 146.4(c) of this chapter shall not be available for this program.
The area of review shall be defined as follows:
(a)
(b)
(1) An area defined by a radius two and one-half miles from the well or well field; or
(2) An area one-quarter mile from the well or well field where the well field production at the times exceeds injection to produce a net withdrawal; or
(3) A suitable distance, not less than one-quarter mile, proposed by the owner or operator and approved by the Director based upon a mathematical calculation such as that found in § 146.6(a)(2) of this chapter.
The monitoring of annulus pressure listed in § 146.8(b)(1) of this chapter will only be acceptable if preceded by a pressure test, using liquid or gas that clearly demonstrates that mechanical integrity exists at the time of the pressure test.
To meet the requirements of § 146.10(d) of this chapter, owners and operators of Class III uranium projects underlying or in aquifers containing up to 5,000 mg/l TDS which have been exempted under § 146.4 of this chapter shall:
(a) Include in the required plugging and abandonment plan a plan for aquifer clean-up and monitoring which demonstrates adequate protection of surrounding USDWs.
(1) The Director shall include in each such permit for a Class III uranium project the concentrations of contaminants to which aquifers must be cleaned up in order to protect surrounding USDWs.
(2) The concentrations will be set as close as is feasible to the original conditions.
(b) When requesting permission to plug a well, owners and operators shall submit for the Director's approval a schedule for the proposed aquifer cleanup, in addition to the information required by § 146.34(c).
(c) Cleanup and monitoring shall be continued until the owner or operator certifies that no constituent listed in the permit exceeds the concentrations required by the permit, and the Director notifies the permittee in writing that cleanup activity may be terminated.
In addition to the cementing requirement of § 146.12(b) of this chapter, owners and operators of Class I wells shall, through circulation, cement all casing to the surface.
(a) In addition to the information listed in § 146.14(a) of this chapter, the Director shall consider the following prior to issuing any Class I permit:
(1) Expected pressure changes, native fluid displacement, and direction of movement of the injected fluid; and
(2) Methods to be used for sampling, and for measurement and calculation of flow.
(b) In addition to the information listed in § 146.14(b) of this chapter, the Director shall consider any information required under § 146.14(a) of this chapter (as supplemented by this subpart) that has been gathered during construction.
(a) In addition to the requirements of § 146.32(c)(3) of this chapter, radiological characteristics of the formation fluids shall be provided to the Director.
(b) In addition to the requirements of § 146.32(e) of this chapter, the Director may require monitoring wells to be completed into USDWs below the injection zone if those USDWs may be affected by mining operations.
(a) In addition to the requirements of § 146.34(a) of this chapter, the following information shall be considered by the Director:
(1) Proposed construction procedures, including a cementing and casing program, logging procedures, deviation checks, and a drilling, testing and coring program.
(2) Depth to the proposed injection zone, and a chemical, physical and radiological analysis of the ground water in the proposed injection zone sufficient to define pre-injection water quality as required for aquifer cleanup by § 147.3011 of this subpart.
(3) An aquifer cleanup plan if required by § 147.3003(b) of this subpart.
(4) Any additional information that may be necessary to demonstrate that cleanup will reduce the level of contaminants in the surrounding USDWs as close as feasible to the original conditions.
(b) In addition to the requirements of § 146.34(b) of this chapter, the Director shall consider any information required under § 146.34(a) of this chapter (as supplemented by this subpart) that has been gathered during construction.
In addition to the criteria and standards applicable to Class V wells set forth in subpart F of part 146 of this chapter, owners and operators of wells that do not fall within the Class IV category but that are used to dispose of radioactive wastes (as defined in 10 CFR part 20, appendix B, table II, column 2, but not including high level and transuranic wastes and spent nuclear fuel covered by 40 CFR part 191) shall comply with all of the requirements applicable to Class I injection wells in 40 CFR parts 124, 144 and 146 as supplemented by this subpart.
The areas described by a one-quarter mile radius around the following Class II wells in the listed formations are exempted for the purpose of Class II injection.
(a)
(b)
(a) In addition to the notice requirements of § 124.10 of this chapter, the Director shall provide to the affected Tribal government all notices given to an affected State government under § 124.10(c) of this chapter.
(b)
(1) Owners and operators of Class I and III wells shall notify the affected Tribal government prior to submitting an application for a permit, shall publish such notice in at least two newspapers of general circulation in the area of the proposed well, and shall broadcast notice over at least one local radio station.
(2) The Director shall publish a notice of availability of a draft permit in at least two newspapers of general circulation in the area of the proposed well, and broadcast notice over at least one local radio station. The public notice shall allow at least 45 days for public comment.
(c)
(1) Owners and operators of Class II wells shall give notice of application for a permit to the affected Tribal government prior to submitting the application to the Director.
(2) In addition to the public notice required for each action listed in § 124.10(a) of this chapter, the Director shall also publish notice in a daily or weekly newspaper of general circulation in the affected area for actions concerning Class II wells.
In lieu of the requirements of § 144.28(c)(1) and (2) (i)-(iii) of this chapter, owners and operators of Class II wells shall comply with the plugging and abandonment provisions of § 147.3108 of this subpart.
Notwithstanding §§ 144.28(f)(2) and 146.12(c) of this chapter, owners and operators shall not use a fluid seal as an alternative to a packer.
(a) In addition to the notice required by § 144.28(j)(2) of this chapter, the owner or operator shall at the same time submit plugging information in conformance with § 147.3108 of this subpart including:
(1) Type and number of plugs;
(2) Elevation of top and bottom of each plug;
(3) Method of plug placement; and
(4) Type, grade and quantity of cement to be used.
(b) In addition to the permit conditions specified in §§ 144.51 and 144.52 of this chapter, each owner and operator shall submit and each permit shall contain the following information (in conformance with § 146.3108 of this subpart):
(1) Type and number of plugs;
(2) Elevation of top and bottom of each plug;
(3) Method of plug placement; and
(4) Type, grade and quantity of cement to be used.
(a) In lieu of the time periods for submitting a plugging report in § 144.28(k) of this chapter, owners and operators of Class I and III wells shall submit the report within 15 days of plugging the well and owners or operators of Class II wells within 30 days of plugging, or at the time of the next required operational report (whichever is less.) If the required operational report is due less than 15 days following completion of plugging, then the plugging report shall be submitted within 30 days for Class II wells and 15 days for Class I and III wells.
(b) In addition to the requirement of § 144.28(k)(1) of this chapter, owners and operators of Class II wells shall include a statement that the well was plugged in accordance with § 146.10 of this chapter and § 147.3109 of this subpart, and, if the actual plugging differed, specify the actual procedures used.
(c) The schedule upon which reports of plugging must be submitted are changed from those in § 144.51(o) to those specified in paragraph (a) of this section.
(a) When determining the area of review under § 146.6(b) of this chapter, the fixed radius shall be no less than one mile for Class I wells and one-half mile for Class II and III wells. In the case of an application for an area permit, determination of the area of review under § 146.6(b) shall be a fixed width of not
(b) However, in lieu of § 146.6(c) of this chapter, if the area of review is determined by a mathematical model pursuant to paragraph § 146.6(a) of this chapter, the permissible radius is the result of such calculation even if it is less than one mile for Class I wells and one-half for Class II and III wells.
(a) Monitoring of annulus pressure conducted pursuant to § 146.8(b)(1) shall be preceded by an initial pressure test. A positive gauge pressure on the casing/tubing annulus (filled with liquid) shall be maintained continuously. The pressure shall be monitored monthly.
(b) Pressure tests conducted pursuant to § 146.8(b)(2) of this chapter shall be performed with a pressure on the casing/tubing annulus of at least 200 p.s.i. unless otherwise specified by the Director. In addition, pressure tests conducted during well operation shall maintain an injection/annulus pressure differential of at least 100 p.s.i. throughout the tubing length.
(c) Monitoring of enhanced recovery wells conducted pursuant to § 146.8(b)(3), must be preceded by an initial pressure test that was conducted no more than 90 days prior to the commencement of monitoring.
In addition to the requirements of § 146.10 of this chapter, owners and operators shall comply with the following when plugging a well:
(a) For Class I and III wells:
(1) The well shall be filled with mud from the bottom of the well to a point one hundred (100) feet below the top of the highest disposal or injection zone and then with a cement plug from there to at least one hundred (100) feet above the top of the disposal or injection zone.
(2) A cement plug shall also be set from a point at least fifty (50) feet below the shoe of the surface casing to a point at least five (5) feet above the top of the lowest USDW.
(3) A final cement plug shall extend from a point at least thirty feet below the ground surface to a point five (5) feet below the ground surface.
(4) All intervals between plugs shall be filled with mud.
(5) The top plug shall clearly show by permanent markings inscribed in the cement or on a steel plate embedded in the cement the well permit number and date of plugging.
(b) For Class II wells:
(1) The well shall be kept full of mud as casing is removed. No surface casing shall be removed without written approval from the Director.
(2) If surface casing is adequately set and cemented through all USDWs (set to at least 50 feet below the base of the USDW), a plug shall be set at least 50 feet below the shoe of the casing and extending at least 50 feet above the shoe of the casing; or
(3) If the surface casing and cementing is inadequate, the well bore shall be filled with cement from a point at -least 50 feet below the base of the USDW to a point at least 50 feet above the shoe of the surface casing, and any additional plugs as required by the Director.
(4) In all cases, the top 20 feet of the well bore below 3 feet of ground surface shall be filled with cement. Surface casing shall be cut off 3 feet below ground surface and covered with a secure steel cap on top of the surface pipe. The remaining 3 feet shall be filled with dirt.
(5) Except as provided in sub-paragraph (b)(6) of this section, each producing or receiving formation shall be sealed off with at least a 50-foot cement plug placed at the base of the formation and at least a 50-foot cement plug placed at the top of the formation.
(6) The requirement in sub-paragraph (b)(5) of this section does not apply if the producing/receiving formation is already sealed off from the well bore with adequate casing and cementing behind casing, and casing is not to be removed, or the only openings from the producing/receiving formation into the well bore are perforations in the casing, and the annulus between the casing and the outer walls of the well is filled with cement for a distance of 50 feet above the top of the formation.
(7) When specified by the Director, any uncased hole below the shoe of any casing to be left in the well shall be filled with cement to a depth of at least 50 feet below the casing shoe, or the bottom of the hole, and the casing above the shoe shall be filled with cement to at least 50 feet above the shoe of the casing. If the well has a screen or liner which is not to be removed, the well bore shall be filled with cement from the base of the screen or liner to at least 50 feet above the top of the screen or liner.
(8) All intervals between cement plugs in the well bore must be filled with mud.
(c) For the purposes of this section mud shall be defined as: mud of not less than thirty-six (36) viscosity (API Full Funnel Method) and a weight of not less than nine (9) pounds per gallon.
The demonstrations of mechanical integrity required by § 146.14(b)(2) of this chapter prior to approval for the operation of a Class I well shall, for an existing well, be conducted no more than 90 days prior to application for the permit and the results included in the permit application. The owner or operator shall notify the Director at least seven days in advance of the time and date of the test so that EPA observers may be present.
Secs. 3004, Resource Conservation and Recovery Act, 42 U.S.C. 6901
(a) This part identifies wastes that are restricted from disposal into Class I wells and defines those circumstances under which a waste, otherwise prohibited from injection, may be injected.
(b) The requirements of this part apply to owners or operators of Class I hazardous waste injection wells used to inject hazardous waste.
(c) Wastes otherwise prohibited from injection may continue to be injected:
(1) If an extension from the effective date of a prohibition has been granted pursuant to § 148.4 with respect to such wastes; or
(2) If an exemption from a prohibition has been granted in response to a petition filed under § 148.20 to allow injection of restricted wastes with respect to those wastes and wells covered by the exemption; or
(3) If the waste is generated by a conditionally exempt small quantity generator, as defined in § 261.5; or
(d) Wastes that are hazardous only because they exhibit a hazardous characteristic, and which are otherwise prohibited under this part, or part 268 of this chapter, are not prohibited if the wastes:
(1) Are disposed into a nonhazardous or hazardous injection well as defined under 40 CFR § 146.6(a); and
(2) Do not exhibit any prohibited characteristic of hazardous waste identified in 40 CFR part 261, subpart C at the point of injection.
The prohibition of § 268.3 shall apply to owners or operators of Class I hazardous waste injection wells.
The owner or operator of a Class I hazardous waste injection well may submit an application to the Administrator for an extension of the effective date of any applicable prohibition established under subpart B of this part according to the procedures of § 268.5.
Generators of hazardous wastes that are disposed of into Class I injection wells must comply with the applicable requirements of § 268.7 (a) and (b). Owners or operators of Class I hazardous waste injection wells must comply with the applicable requirements of § 268.7(c).
(a) Effective August 8, 1988, the spent solvent wastes specified in § 261.31 as EPA Hazardous Waste Nos. F001, F002, F003, F004, and F005 are prohibited from underground injection unless the solvent waste is a solvent-water mixture or solvent-containing sludge containing less than 1 percent total F001-F005 solvent constituents listed in Table A of this section.
(b) Effective August 8, 1990, all spent F001-F005 solvent wastes containing less than 1 percent total F001-F005 solvent constituents listed in Table A of this section are prohibited from injection.
(c) Effective August 8, 1990, all spent F002 and F005 wastes containing solvent constituents listed in Table B of this section are prohibited from underground injection at off-site injection facilities.
(d) Effective November 8, 1990, the wastes specified in paragraph (c) of this section are prohibited from underground injection at on-site injection facilities.
(e) The requirements of paragraphs (a) and (b) of this section do not apply:
(1) If the wastes meet or are treated to meet the applicable standards specified in subpart D of part 268; or
(2) If an exemption from a prohibition has been granted in response to a petition under subpart C of this part; or
(3) During the period of extension of the applicable effective date, if an extension has been granted under § 148.4 of this part.
(a) Effective August 8, 1988, the dioxin-containing wastes specified in § 261.31 as EPA Hazardous Waste Nos. F020, F021, F022, F023, F026, F027, and F028, and prohibited from underground injection.
(b) The requirements of paragraph (a) of this section do not apply:
(1) If the wastes meet or are treated to meet the applicable standards specified in subpart D of part 268; or
(2) If an exemption from a prohibition has been granted in response to a petition under subpart C of this part; or
(3) During the period of extension of the applicable effective date, if an extension has been granted under § 148.4 of this part.
(a) Effective August 8, 1988, the hazardous wastes listed in 40 CFR 268.32 containing polychlorinated biphenyls at concentrations greater than or equal to 50 ppm or halogenated organic compounds at concentrations greater than or equal to 10,000 mg/kg are prohibited from underground injection.
(b) Effective August 8, 1990, the following hazardous wastes are prohibited from underground injection:
(1) Liquid hazardous wastes, including free liquids associated with any solid or sludge, containing free cyanides at concentrations greater than or equal to 1,000 mg/l;
(2) Liquid hazardous wastes, including free liquids associated with any solid or sludge, containing the following metals (or elements) or compounds of these metals (or elements) at concentrations greater than or equal to those specified below:
(i) Arsenic and/or compounds (as As) 500 mg/l;
(ii) Cadmium and/or compounds (as Cd) 100 mg/l;
(iii) Chromium (VI) and/or compounds (as Cr VI) 500 mg/l;
(iv) Lead and/or compounds (as Pb) 500 mg/l;
(v) Mercury and/or compounds (as Hg) 20 mg/l;
(vi) Nickel and/or compounds (as Ni) 134 mg/l;
(vii) Selenium and/or compounds (as Se) 100 mg/l; and
(viii) Thallium and/or compounds (as Tl) 130 mg/l;
(3) Liquid hazardous waste having a pH less than or equal to two (2.0); and
(4) Hazardous wastes containing halogenated organic compounds in total concentration less than 10,000 mg/kg but greater than or equal to 1,000 mg/kg.
(c) The requirements of paragraphs (a) and (b) of this section do not apply:
(1) If the wastes meet or are treated to meet the applicable standards specified in subpart D of part 268; or
(2) If an exemption from a prohibition has been granted in response to a petition under subpart C of this part; or
(3) During the period of extension of the applicable effective date, if an extension is granted under § 148.4 of this part.
(a) Effective June 7, 1989, the wastes specified in 40 CFR 261.31 as EPA Hazardous Waste numbers F006 (non-waste-waters) and the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste numbers K001, K015 (waste-waters), K016
(b) Effective June 8, 1989, the waste specified in 40 CFR 261.32 as EPA Hazardous Waste number K036 (waste-waters); and the wastes specified in 40 CFR 261.33 as P030, P039, P041, P063, P071, P089, P094, P097, U221, and U223 are prohibited from underground injection.
(c) Effective July 8, 1989, the wastes specified in 40 CFR 261.31 as EPA Hazardous Waste numbers F008 and F009 are prohibited from underground injection.
(d) Effective August 8, 1990, the wastes specified in 40 CFR 261.31 as EPA Hazardous Waste Number F006 (waste-waters) and F019; the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Numbers K004, K008, K015 (non-waste-waters), K017, K021 (wastewaters), K022 (waste-waters), K031, K035, K046 (reactive non-waste-waters and all waste-waters), K060 (waste-waters), K061 (waste-waters), K069 (calcium sulfate non-waste-waters and all waste-waters), K073, K083, K084, K085, K086 (all but solvent washes), K101 (high arsenic non-waste-waters), K102 (high arsenic non-waste-waters), and K106; and the wastes specified in 40 CFR part 261.33 as EPA Hazardous Waste Numbers P001, P004, P005, P010, P011, P012, P015, P016, P018, P020, P036, P037, P048, P050, P058, P059, P068, P069, P070, P081, P082, P084, P087, P092, P102, P105, P108, P110, P115, P120, P122, P123, U007, U009, U010, U012, U016, U018, U019, U022, U029, U031, U036, U037, U041, U043, U044, U046, U050, U051, U053, U061, U063, U064, U066, U067, U074, U077, U078, U086, U089, U103, U105, U108, U115, U122, U124, U129, U130, U133, U134, U137, U151, U154, U155, U157, U158, U159, U171, U177, U180, U185, U188, U192, U200, U209, U210, U211, U219, U220, U226, U227, U228, U237, U238, U248, and U249 are prohibited from underground injection at off-site injection facilities.
(e) Effective August 8, 1990, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste numbers K049, K050, K051, K052, K062, K071, and K104 are prohibited from underground injection.
(f) Effective November 8, 1990, the wastes specified in paragraph (d) of this section are prohibited from underground injection at on-site injection facilities.
(g) Effective June 7, 1991, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste numbers K016 (at concentrations less than 1%) are prohibited from underground injection.
(h) Effective June 8, 1991, the waste specified in 40 CFR 261.31 as EPA Hazardous Waste number F007; and the wastes specified in 40 CFR 261.32 as K011 (non-wastewaters) and K013 (non-wastewaters) are prohibited from underground injection.
(i) Effective May 8, 1992, the wastes specified in 40 CFR 261.32 and 261.33 as EPA Hazardous Waste Numbers K011 (waste-waters), K013 (waste-waters), and K014 are prohibited from underground injection.
(j) The requirements of paragraphs (a) through (i) of this section do not apply:
(1) If the wastes meet or are treated to meet the applicable standards specified in subpart D of part 268; or
(2) If an exemption from a prohibition has been granted in response to a petition under subpart C of this part; or
(3) During the period of extension of the applicable effective date, if an extension has been granted under § 148.4 of this part.
(a) Effective June 7, 1989, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste numbers K025 (non-wastewaters generated by the process described in the waste listing description and disposed after August 17, 1988, and not generated in the course of treating waste-water forms of these wastes) are prohibited from underground injection.
(b) Effective June 8, 1989, the wastes specified in 40 CFR 261.31 as EPA Hazardous Waste numbers F010, F024; the wastes specified in 40 CFR 261.32 as K009 (non-waste-waters), K010, K027, K028, K029 (non-waste-waters), K038, K039, K040, K043, K095 (non-waste-waters), K096 (non-waste-waters), K113, K114, K115, K116; and wastes specified in 40 CFR 261.33 as P029, P040, P043, P044, P062, P074, P085, P098, P104, P106, P111, U028, U058, U107, and U235 are prohibited from underground injection.
(c) Effective July 8, 1989, and continuing until December 8, 1989, the wastes specified in 40 CFR 261.31 as EPA Hazardous Waste numbers F011 and F012 are prohibited from underground injection pursuant to the treatment standards specified in §§ 268.41 and 268.43 applicable to F007, F008, and F009 waste-waters and non-waste-waters. Effective December 8, 1989, F011 (non-waste-waters) and F012 (non-waste-waters) are prohibited pursuant to the treatment standards specified in §§ 268.41 and 268.43 applicable to F011 and F012 wastewaters and non-waste-waters.
(d) Effective August 8, 1990, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Number K025 (waste-waters), K029 (waste-waters), K041, K042, K095 (waste-waters), K096 (waste-waters), K097, K098, and K105; and the wastes specified in 40 CFR part 261.33 as P002, P003, P007, P008, P014, P026, P027, P049, P054, P057, P060, P066, P067, P072, P107, P112, P113, P114, U002, U003, U005, U008, U011, U014, U015, U020, U021, U023, U025, U026, U032, U035, U047, U049, U057, U059, U060, U062, U070, U073, U080, U083, U092, U093, U094, U095, U097, U098, U099, U101, U106, U109, U110, U111, U114, U116, U119, U127, U128, U131, U135, U138, U140, U142, U143, U144, U146, U147, U149, U150, U161, U162, U163, U164, U165, U168, U169, U170, U172, U173, U174, U176, U178, U179, U189, U193, U196, U203, U205, U206, U208, U213, U214, U215, U216, U217, U218, U239, and U244 are prohibited from underground injection at off-site injection facilities.
(e) Effective June 8, 1991, the waste specified in 40 CFR 261.32 as EPA Hazardous Waste number K009 (waste-waters) is prohibited from underground injection.
(f) Effective November 8, 1990, the wastes specified in paragraph (d) of this section are prohibited from underground injection at on-site injection facilities.
(g) The requirements of paragraphs (a) through (f) of this section do not apply:
(1) If the wastes meet or are treated to meet the applicable standards specified in subpart D of part 268; or
(2) If an exemption from a prohibition has been granted in response to a petition under subpart C of this part; or
(3) During the period of extension of the applicable effective date, if an extension has been granted under § 148.4 of this part.
(a) Effective June 7, 1989, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste numbers K100 (non-waste-waters generated by the process described in the waste listing description and disposed after August 17, 1988, and not generated in the course of treating waste-water forms of these wastes) are prohibited from underground injection.
(b) Effective June 8, 1989, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste numbers K005 (non-waste-waters), K007 (non-waste-waters), K023, K093, K094; and the wastes specified in 40 CFR 261.33 as P013, P021, P099, P109, P121, U069, U087, U088, U102, and U190 are prohibited from underground injection.
(c) Effective August 8, 1990, the wastes identified in 40 CFR 261.31 as EPA Hazardous Waste Number F039 (non-waste-waters); the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Numbers K002, K003, K005 (waste-waters), K006, K007 (waste-waters), K026, K032, K033, K034, and K100 (waste-waters); the wastes specified in 40 CFR 261.33 as P006, P009, P017, P022, P023, P024, P028, P031, P033, P034, P038, P042, P045, P046, P047, P051, P056, P064, P065, P073, P075, P076, P077, P078, P088, P093, P095, P096, P101, P103, P116, P118, P119, U001, U004, U006, U017, U024, U027, U030, U033, U034, U038, U039, U042, U045, U048, U052, U055, U056, U068, U071, U072, U075, U076, U079, U081, U082, U084, U085, U090, U091, U096, U112, U113, U117, U118, U120, U121, U123, U125, U126, U132, U136, U141, U145, U148, U152, U153, U156, U160, U166, U167, U181, U182, U183, U184, U186, U187, U191, U194, U197, U201, U202, U204, U207, U222, U225, U234, U236, U240, U243, U246, and U247; and the wastes identified in 40 CFR 261.21, 261.23 or 261.24 as hazardous based on a characteristic alone, designated as D001, D004, D005, D006, D008, D009 (waste-waters), D010, D011, D012, D013, D014, D015, D016, D017, and newly listed waste F025 are prohibited from underground injection at off-site injection facilities.
(d) Effective August 8, 1990, mixed radioactive/hazardous waste in 40 CFR 268.10, 268.11, and 268.12, that are mixed radioactive and hazardous wastes, are prohibited from underground injection.
(e) Effective November 8, 1990, the wastes specified in paragraph (c) of this section are prohibited from underground injection at on-site injection facilities. These effective dates do not apply to the wastes listed in 40 CFR 148.12(b) which are prohibited from underground injection on August 8, 1990.
(f) Effective May 8, 1992, the waste identified in 40 CFR 261.31 as EPA Hazardous Waste Number F039 (waste-waters); the wastes identified in 40 CFR 261.22, 261.23 or 261.24 as hazardous based on a characteristic alone, designated as D002 (waste-waters and non-waste-waters), D003 (waste-waters and non-waste-waters), D007 (waste-waters and non-waste-waters), and D009 (non-waste-waters) are prohibited from underground injection. These effective dates do not apply to the wastes listed in 40 CFR 148.12(b) which are prohibited from underground injection on August 8, 1990.
(g) The requirements of paragraphs (a) through (f) of this section do not apply:
(1) If the wastes meet or are treated to meet the applicable standards specified in subpart D of part 268; or
(2) If an exemption from a prohibition has been granted in response to a petition under subpart C of this part; or
(3) During the period of extension of the applicable effective date, if an extension has been granted under § 148.4 of this part.
(a) Effective November 9, 1992, the wastes specified in 40 CFR part 261 as EPA hazardous waste numbers F037, F038, K107, K108, K109, K110, K111, K112, K117, K118, K123, K124, K125, K126, K131, K136, U328, U353, and U359 are prohibited from underground injection.
(b) Effective December 19, 1994 the wastes specified in 40 CFR 261.32 as EPA Hazardous waste numbers K141, K142, K143, K144, K145, K147, K148, K149, K150, and K151, are prohibited from underground injection.
(c) [Reserved]
(d) Effective June 30, 1995, the wastes specified in 40 CFR part 261 as EPA Hazardous waste numbers K117, K118, K131, and K132 are prohibited from underground injection.
(e) The requirements of paragraphs (a) and (b) of this section do not apply:
(1) If the wastes meet or are treated to meet the applicable standards specified in subpart D of part 268; or
(2) If an exemption from a prohibition has been granted in response to a
(3) During the period of extension of the applicable effective date, if an extension has been granted under § 148.4 of this part.
(a) Effective August 24, 1998, all newly identified D004-D011 wastes and characteristic mineral processing wastes, except those identified in paragraph (b) of this section, are prohibited from underground injection.
(b) Effective May 26, 2000, characteristic hazardous wastes from titanium dioxide mineral processing, and radioactive wastes mixed with newly identified D004-D011 or mixed with newly identified characteristic mineral processing wastes, are prohibited from underground injection.
(c) Effective August 11, 1997, the wastes specified in 40 CFR part 261 as EPA Hazardous waste numbers F032, F034, F035 are prohibited from underground injection.
(d) Effective May 12, 1999, the wastes specified in 40 CFR part 261 as EPA Hazardous waste numbers F032, F034, F035 that are mixed with radioactive wastes are prohibited from underground injection.
(e) On July 8, 1996, the wastes specified in 40 CFR 261.32 as EPA Hazardous waste numbers K156-K161, P127, P128, P185, P188-P192, P194, P196-P199, P201-P205, U271, U277-U280, U364-U367, U372, U373, U375-U379, U381-387, U389-U396, U400-U404, U407, and U409-U411 are prohibited from underground injection.
(f) On January 8, 1997, the wastes specified in 40 CFR 261.32 as EPA Hazardous waste number K088 is prohibited from underground injection.
(g) On April 8, 1998, the wastes specified in 40 CFR part 261 as EPA Hazardous waste numbers D018-043, and Mixed TC/Radioactive wastes, are prohibited from underground injection.
(h) [Reserved]
(i) Effective February 8, 1999, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Numbers K169, K170, K171, and K172 are prohibited from underground injection.
(j) Effective May 8, 2001, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Numbers K174 and K175 are prohibited from underground injection.
(k) Effective May 20, 2002, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Numbers K176, K177, and K178 are prohibited from underground injection.
(l) The requirements of paragraphs (a) through (k) of this section do not apply:
(1) If the wastes meet or are treated to meet the applicable standards specified in subpart D of 40 CFR part 268; or
(2) If an exemption from a prohibition has been granted in response to a petition under subpart C of this part; or
(3) During the period of extension of the applicable effective date, if an extension has been granted under § 148.4.
(a) Any person seeking an exemption from a prohibition under subpart B of this part for the injection of a restricted hazardous waste into an injection well or wells shall submit a petition to the Director demonstrating that, to a reasonable degree of certainty, there will be no migration of hazardous constituents from the injection zone for as long as the waste remains hazardous. This demonstration requires a showing that:
(1) The hydrogeological and geochemical conditions at the sites and the physiochemical nature of the waste stream(s) are such that reliable predictions can be made that:
(i) Fluid movement conditions are such that the injected fluids will not migrate within 10,000 years:
(A) Vertically upward out of the injection zone; or
(B) Laterally within the injection zone to a point of discharge or interface with an Underground Source of Drinking Water (USDW) as defined in 40 CFR part 146; or
(ii) Before the injected fluids migrate out of the injection zone or to a point of discharge or interface with USDW, the fluid will no longer be haz-ard-ous because of attenuation, trans-for-ma-tion, or im-mobi-li-za-tion of haz-ard-ous con-stit-u-ents within the injection zone by hy-drol-y-sis, chemical interactions or other means; and
(2) For each well the petition has:
(i) Demonstrated that the injection well's area of review complies with the substantive requirements of § 146.63;
(ii) Located, identified, and as-cer-tained the condition of all wells within the injection well's area of review (as specified in § 146.63) that pene-trate the injection zone or the con-fining zone by use of a pro-to-col acceptable to the Director that meets the sub-stan-tive requirements of § 146.64;
(iii) Submitted a corrective action plan that meets the substantive requirements of § 146.64, the implementation of which shall become a condition of petition approval; and
(iv) Submitted the results of pressure and radioactive tracer tests performed within one year prior to submission of the petition demonstrating the mechanical integrity of the well's long string casing, injection tube, annular seal, and bottom hole cement. In cases where the petition has not been approved or denied within one year after the initial demonstration of mechanical integrity, the Director may require the owner or operator to perform the tests again and submit the results of the new tests.
The requirements of § 148.20(a)(2) need not be incorporated in a permit at the time of petition approval.
(b) A demonstration under § 148.20(a)(1)(i) shall identify the strata within the injection zone which will confine fluid movement above the injection interval and include a showing that this strata is free of known transmissive faults of fractures and that there is a confining zone above the injection zone.
(c) A demonstration under § 148.20(a)(1)(ii) shall identify the strata within the injection zone where waste transformation will be accomplished and include a showing that this strata is free of known transmissive faults or fractures and that there is a confining zone above the injection zone.
(d) A demonstration may include a showing that:
(1) Treatment methods, the implementation of which shall become a condition of petition approval, will be utilized that reduce the toxicity or mobility of the wastes; or
(2) A monitoring plan, the implementation of which shall become a condition of petition approval, will be utilized to enhance confidence in one or more aspects of the demonstration.
(e) Any person who has been granted an exemption pursuant to this section may submit a petition for reissuance -of the exemption to include an ad-di-tional restricted waste or wastes or to mod-ify any conditions placed on the ex-emp-tion by the Director. The Director shall reissue the pet-i-tion if the petitioner complies with the re-quire-ments of paragraphs (a), (b) and (c) of this section.
(f) Any person who has been granted an exemption pursuant to this section may submit a petition to modify an exemption to include an additional (hazardous) waste or wastes. The Director may grant the modification if he determines, to a reasonable degree of certainty, that the additional waste or wastes will behave hydraulically and chemically in a manner similar to previously included wastes and that it will not interfere with the containment capability of the injection zone.
(a) Information submitted in support of § 148.20 must meet the following criteria:
(1) All waste analysis and any new testing performed by the petitioner shall be accurate and reproducible and performed in accordance with quality assurance standards;
(2) Estimation techniques shall be appropriate, and EPA-certified test protocols shall be used where available and appropriate;
(3) Predictive models shall have been verified and validated, shall be appropriate for the specific site, waste streams, and injection conditions of the operation, and shall be calibrated for existing sites where sufficient data are available;
(4) An approved quality assurance and quality control plan shall address all aspects of the demonstration;
(5) Reasonably conservative values shall be used whenever values taken from the literature or estimated on the basis of known information are used instead of site-specific measurements; and
(6) An analysis shall be performed to identify and assess aspects of the demonstration that contribute significantly to uncertainty. The petitioner shall conduct a sensitivity analysis to determine the effect that significant uncertainty may contribute to the demonstration. The demonstration shall then be based on conservative assumptions identified in the analysis.
(b) Any petitioner under § 148.20(a)(1)(i) shall provide sufficient site-specific information to support the demonstration, such as:
(1) Thickness, porosity, permeability and extent of the various strata in the injection zone;
(2) Thickness, porosity, permeability, extent, and continuity of the confining zone;
(3) Hydraulic gradient in the injection zone;
(4) Hydrostatic pressure in the injection zone; and
(5) Geochemical conditions of the site.
(c) In addition to the information in § 148.21(b), any petitioner under § 148.20(a)(1)(ii) shall provide sufficient waste-specific information to ensure reasonably reliant predictions about the waste transformation. The petitioner shall provide the information necessary to support the demonstration, such as:
(1) Description of the chemical processes or other means that will lead to waste transformation; and
(2) Results of laboratory experiments verifying the waste transformation.
(a) Any petition submitted to the Director pursuant to § 148.20(a) shall include the following components:
(1) An identification of the specific waste or wastes and the specific injection well or wells for which the demonstration will be made;
(2) A waste analysis to describe fully the chemical and physical characteristics of the subject wastes;
(3) Such additional information as is required by the Director to support the petition under §§ 148.20 and 148.21; and
(4) This statement signed by the petitioner or an authorized representative:
I certify under penalty of law that I have personally examined and am familiar with the information submitted in this petition and all attached documents, and that, based on my inquiry of those individuals immediately responsible for obtaining the information, I believe that submitted information is true, accurate, and complete. I am aware that there are significant penalties for submitting false information, including the possibility of fine and imprisonment.
(b) The Director shall provide public notice and an opportunity for public comment in accordance with the procedures in § 124.10 of the intent to approve or deny a petition. The final decision on a petition will be published in the
(c) If an exemption is granted it will apply only to the underground injection of the specific restricted waste or wastes identified in the petition into a Class I hazardous waste injection well or wells specifically identified in the petition (unless the exemption is modified or reissued pursuant to § 148.20(e) or (f).
(d) Upon request by any petitioner who obtains an exemption for a well under this subpart, the Director shall initiate and reasonably expedite the necessary procedures to issue or reissue a permit or permits for the hazardous waste well or wells covered by the exemption for a term not to exceed ten years.
(a) When considering whether to reissue a permit for the operation of a
(b) Whenever the Director determines that the basis for approval of a petition may no longer be valid, the Director shall require a new demonstration in accordance with § 148.20.
(a) The Director may terminate an exemption granted under § 148.20 for the following causes:
(1) Noncompliance by the petitioner with any condition of the exemption;
(2) The petitioner's failure in the petition or during the review and approval to disclose fully all relevant facts, or the petitioner's misrepresentation of any relevant facts at any time; or
(3) A determination that new information shows that the basis for -approval of the petition is no longer valid.
(b) The Director shall terminate an exemption granted under § 148.20 for the following causes:
(1) The petitioner's willful withholding during the review and approval of the petition of facts directly and materially relevant to the Director's decision on the petition;
(2) A determination that there has been migration from the injection zone or the well that is not in accordance with the terms of the exemption, except that the Director may at his discretion decide not to terminate where:
(i) The migration resulted from a mechanical failure of the well that can be corrected promptly through a repair to the injection well itself or from an undetected well or conduit that can be plugged promptly; and
(ii) The requirements of § 146.67(i) are satisfied.
(c) The Director shall follow the procedures in § 124.5 in terminating any exemption under this section.
Sec. 1424(e), Safe Drinking Water Act (42 U.S.C. 300h-3(e); sec. 1427 of the Safe Drinking Water Act, (42 U.S.C. 300h-6).
The purpose of this subpart is to provide criteria for identifying critical aquifer protection areas, pursuant to section 1427 of the Safe Drinking Water Act (SDWA).
(a)
(b)
(c)
(d)
A Critical Aquifer Protection Area is either:
(a) All or part of an area which was designated as a sole or principal source aquifer prior to June 19, 1986, and for which an areawide ground-water quality protection plan was approved, under section 208 of the Clean Water Act, prior to that date; or
(b) All or part of a major recharge area of a sole or principal source aquifer, designated before June 19, 1988, for which:
(1) The sole or principal source aquifer is particularly vulnerable to contamination due to the hydrogeologic characteristics of the unsaturated or saturated zone within the suggested critical aquifer protection area; and
(2) Contamination of the sole or principal source aquifer is reasonably -likely to occur, unless a program to reduce or prevent such contamination is implemented; and
(3) In the absence of any program to reduce or prevent contamination, reasonably foreseeable contamination would result in significant cost, taking into account:
(i) The cost of replacing the drinking water supply from the sole or principal source aquifer, and
(ii) Other economic costs and environmental and social costs resulting from such contamination.
This subpart sets forth, pursuant to sections 1424(e) and 1450 of the Public Health Service Act, as amended by the Safe Drinking Water Act, Pub. L. 93-523, regulations relating the Edwards Underground Reservoir which is the sole or principal drinking water source for the San Antonio area and which, if contaminated, would create a significant hazard to public health.
As used in this subpart and except as otherwise specifically provided, the term(s):
(a)
(b)
(c)
(d)
(e)
(f)
(g)
(h)
(i)
(j)
(k)
(a) Once an area is designated, no subsequent commitments of Federal financial assistance may be made to projects which the Administrator determines may contaminate the aquifer so as to create a significant hazard to public health.
(b) The Regional Administrator is hereby delegated the authority and assigned responsibility for carrying out the project review process assigned to the Administrator under section 1424(e) of the Act, except the final determination that a project may contaminate the aquifer through its recharge zone so as to create a significant hazard to public health.
(c) The Regional Administrator may review any project which he considers may potentially contaminate the aquifer through its recharge zone so as to create a significant hazard to public health.
After the area is designated under section 1424(e), Federal agencies, for projects, located in the recharge zone and streamflow source zones, are required to:
(a) Maintain a list of projects for which environmental impact statements will be prepared in accordance with the National Environmental Policy Act (NEPA);
(b) Revise the list at regular intervals and submit to EPA; and
(c) Make the list available to the public upon request.
Any person may submit a petition requesting the Regional Administrator to review a project to determine if such project may contaminate the aquifer through its recharge zone so as to -create a significant hazard to public health. Any such petition shall identify:
(a) The name, address, and telephone number of the individual, organization, or other entity submitting the petition;
(b) A brief statement of the requesting person's interest in the Regional Administrator's determination;
(c) The name of the project and Federal agency involved;
(d) Applicable action already taken by State and local agencies including establishment of regulations to prevent contamination of the aquifer and why,
(e) Any actions taken under the National Environmental Policy Act and why, in the petitioner's judgment, that action was inadequate in regard to evaluation of potential effect on the aquifer.
(f) The potential contaminants involved;
(g) The means by which the contaminant might enter the aquifer; and
(h) The potential impact of the proposed project.
(a) The Regional Administrator shall review under section 1424(e) all projects located in the recharge or streamflow source zone of the aquifer for which a draft or final EIS is submitted which may have an impact on ground water quality and which involve Federal financial assistance as defined in these regulations.
(b) Upon receipt of a public petition, the Regional Administrator shall decide whether the project which is the subject of the petition should be reviewed under section 1424(e).
(c) The Regional Administrator may decide to review a project upon his own motion.
(d) In determining whether to review a project upon receipt of a public petition or upon his own motion, the Regional Administrator shall consider whether the project is likely to directly or indirectly cause contamination of the aquifer through its recharge zone, taking into account any factors he deems relevant, including:
(1) The location of the project, and
(2) The nature of the project.
(e) In determining whether to review a project upon receipt of a public petition or upon his own motion, the Regional Administrator may consult with, or request information from, the Federal agency to which the project application has been made, the applicant seeking Federal assistance, appropriate State and local agencies, and other appropriate persons or entities.
(f) In determining whether to review a project which is the subject of a public petition, the Regional Administrator may request such additional information from the petitioner as he deems necessary.
(a)
(b)
In reviewing a project under section 1424(e), the Regional Administrator may request any additional information from the funding Federal agency which is pertinent to reaching a decision. If full evaluation of the groundwater impact of a project has not been submitted in accordance with the agency's NEPA procedures, the Regional Administrator may specifically request that the Federal agency submit a groundwater impact evaluation of whether the proposed project may contaminate the aquifer through its recharge zone so as to create a significant hazard to public health.
If there is significant public interest, the Regional Administrator may hold a public hearing with respect to any project or projects to be reviewed if he finds that such a hearing is necessary and would be helpful in clarifying the issues. Public hearings held under this
(a) As soon as practicable after the submission of public comments under section 1424(e) and information requested by the Environmental Protection Agency from the originating Federal agency, on the basis of such information as is available to him, the Regional Administrator shall review the project taking all relevant factors into account including:
(1) The extent of possible public health hazard presented by the project;
(2) Planning, design, construction, operation, maintenance and monitoring measures included in the project which would prevent or mitigate the possible health hazard;
(3) The extent and effectiveness of State or local control over possible contaminant releases to the aquifer;
(4) The cumulative and secondary impacts of the proposed project; and
(5) The expected environmental benefits of the proposed project.
(b) After reviewing the available information, the Regional Administrator shall:
(1) Determine that the risk of contamination of the aquifer through the recharge zone so as to create a significant hazard to public health is not sufficiently great so as to prevent commitment of Federal funding to the project; or
(2) Forward the information to the Administrator with his recommendation that the project may contaminate the aquifer through the recharge zone so as to create a significant hazard to public health.
(c) After receiving the available information forwarded by the Regional Administrator, the Administrator shall:
(1) Determine that the risk of contamination of the aquifer through the recharge zone so as to create a significant hazard to public health is not sufficiently great so as to prevent commitment of Federal funding to the project; or
(2) Determine that the project may contaminate the aquifer through the recharge zone so as to create a significant hazard to public health.
(d) Notice of any decisions by the Regional Administrator under paragraph (b)(1) of this section or by the Administrator under paragraphs (c)(1) and (2) of this section to prevent a commitment of Federal funding shall be published in the
If a project is redesigned in response to EPA's objections, the applicant for Federal financial assistance or the grantor agency may file a petition with the Regional Administrator for withdrawal of the determination that the project may contaminate the aquifer through the recharge zone so as to create a significant hazard to public health. Any such petition shall demonstrate how the project has been redesigned so as to justify the withdrawal of EPA's objections. If appropriate, the Regional Administrator may request public comments or hold an informal public hearing to consider the petition. After review of pertinent information, the Regional Administrator shall either deny the petition or recommend to the Administrator that the initial determination that a project may contaminate the aquifer be vacated. Upon receipt of a recommendation from the Regional Administrator that a determination be vacated, the Administrator shall either deny the petition or order that the initial determination be vacated. The final decision regarding a petition shall be published in the
After publication of a decision that a proposed project may contaminate a sole or principal source aquifer in a designated area through its recharge zone so as to create a significant hazard to public health, a commitment for Federal financial assistance may be entered into, if authorized under another provision of law, to plan or redesign such project to assure that it will not so contaminate the aquifer.
A list of CFR titles, subtitles, chapters, subchapters and parts and an alphabetical list of agencies publishing in the CFR are included in the CFR Index and Finding Aids volume to the Code of Federal Regulations which is published separately and revised annually.
Material Approved for Incorporation by Reference
Table of CFR Titles and Chapters
Alphabetical List of Agencies Appearing in the CFR
List of CFR Sections Affected
The Director of the Federal Register has approved under 5 U.S.C. 552(a) and 1 CFR Part 51 the incorporation by reference of the following publications. This list contains only those incorporations by reference effective as of the revision date of this volume. Incorporations by reference found within a regulation are effective upon the effective date of that regulation. For more information on incorporation by reference, see the preliminary pages of this volume.
All changes in this volume of the Code of Federal Regulations which were made by documents published in the
Title 40 was established at 36 FR 12213, June 29, 1971. For the period before January 1, 2001, see the “List of CFR Sections Affected, 1964-1972, 1973-1985, and 1986-2000,” published in ten separate volumes.