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Title 40—
Chapter I—Environmental Protection Agency appears in all thirty-four volumes. Regulations issued by the Council on Environmental Quality, including an Index to Parts 1500 through 1508, appear in the volume containing part 1000 to end. The OMB control numbers for title 40 appear in § 9.1 of this chapter.
For this volume, Cheryl E. Sirofchuck was Chief Editor. The Code of Federal Regulations publication program is under the direction of Michael L. White, assisted by Ann Worley.
(This book contains parts 136 to 149)
Nomenclature changes to chapter I appear at 65 FR 47324, 47325, Aug. 2, 2000, and at 66 FR 34375, 34376, June 28, 2001.
Secs. 301, 304(h), 307 and 501(a), Pub. L. 95-217, 91 Stat. 1566,
(a) The procedures prescribed herein shall, except as noted in §§ 136.4, 136.5, and 136.6, be used to perform the measurements indicated whenever the waste constituent specified is required to be measured for:
(1) 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
(2) Reports required to be submitted by dischargers under the NPDES established by parts 124 and 125 of this chapter; and
(3) Certifications issued by States pursuant to section 401 of the CWA, as amended.
(b) The procedure prescribed herein and in part 503 of title 40 shall be used to perform the measurements required for an application submitted to the Administrator or to a State for a sewage sludge permit under section 405(f) of the Clean Water Act and for recordkeeping and reporting requirements under part 503 of title 40.
As used in this part, the term:
(a)
(b)
(c)
(d)
(e)
(f)
(a) Parameters or pollutants, for which methods are approved, are listed
(b) The documents required in this section are incorporated by reference into this section with 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 documents may be obtained from the sources listed in paragraph (b) of this section. Documents may be inspected at EPA's Water Docket, EPA West, 1301 Constitution Avenue NW., Room B102, Washington, DC (Telephone: 202-566-2426); or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to:
(1) Environmental Monitoring and Support Laboratory, U.S. Environmental Protection Agency, Cincinnati OH (US EPA). Available at
(i) Microbiological Methods for Monitoring the Environment, Water, and Wastes. 1978. EPA/600/8-78/017, Pub. No. PB-290329/A.S.
(A) Part III Analytical Methodology, Section B Total Coliform Methods, page 108. Table IA, Note 3; Table IH, Note 3.
(B) Part III Analytical Methodology, Section B Total Coliform Methods, 2.6.2 Two-Step Enrichment Procedure, page 111. Table IA, Note 3; Table IH, Note 3.
(C) Part III Analytical Methodology, Section B Total Coliform Methods, 4 Most Probable Number (MPN) Method, page 114. Table IA, Note 3; Table IH, Note 3.
(D) Part III Analytical Methodology, Section C Fecal Coliform Methods, 2 Direct Membrane Filter (MF) Method, page 124. Table IA, Note 3; Table IH, Note 3.
(E) Part III, Analytical Methodology, Section C Fecal Coliform Methods, 5 Most Probable Number (MPN) Method, page 132. Table IA, Note 3; Table IH, Note 3.
(F) Part III Analytical Methodology, Section D Fecal Streptococci, 2 Membrane Filter (MF) Method, page 136. Table IA, Note 3; Table IH, Note 3.
(G) Part III Analytical Methodology, Section D Fecal Streptococci, 4 Most Probable Number Method, page 139. Table IA, Note 3; Table IH, Note 3.
(H) Part III Analytical Methodology, Section D Fecal Streptococci, 5 Pour Plate Method, page 143. Table IA, Note 3; Table IH, Note 3.
(ii) [Reserved]
(2) Environmental Monitoring and Support Laboratory, U.S. Environmental Protection Agency, Cincinnati OH (US EPA). Available at
(i) Method 300.1 (including Errata Cover Sheet, April 27, 1999), Determination of Inorganic Ions in Drinking Water by Ion Chromatography, Revision 1.0, 1997. Table IB, Note 52.
(ii) Method 551, Determination of Chlorination Disinfection Byproducts and Chlorinated Solvents in Drinking Water by Liquid-Liquid Extraction and Gas Chromatography With Electron-Capture Detection. 1990. Table IF.
(3) National Exposure Risk Laboratory-Cincinnati, U.S. Environmental Protection Agency, Cincinnati OH (US EPA). Available from
(i) Methods for the Determination of Inorganic Substances in Environmental Samples. August 1993. EPA/600/R-93/100, Pub. No. PB 94120821. Table IB, Note 52.
(A) Method 180.1, Determination of Turbidity by Nephelometry. Revision 2.0. Table IB, Note 52.
(B) Method 300.0, Determination of Inorganic Anions by Ion Chromatography. Revision 2.1. Table IB, Note 52.
(C) Method 335.4, Determination of Total Cyanide by Semi-Automated Colorimetry. Revision 1.0. Table IB, Notes 52 and 57.
(D) Method 350.1, Determination of Ammonium Nitrogen by Semi-Automated Colorimetry. Revision 2.0. Table IB, Notes 30 and 52.
(E) Method 351.2, Determination of Total Kjeldahl Nitrogen by Semi-Automated Colorimetry. Revision 2.0. Table IB, Note 52.
(F) Method 353.2, Determination of Nitrate-Nitrite Automated Colorimetry. Revision 2.0. Table IB, Note 52.
(G) Method 365.1, Determination of Phosphorus by Automated Colorimetry. Revision 2.0. Table IB, Note 52.
(H) Method 375.2, Determination of Sulfate by Automated Colorimetry. Revision 2.0. Table IB, Note 52.
(I) Method 410.4, Determination of Chemical Oxygen Demand by Semi-Automated Colorimetry. Revision 2.0. Table IB, Note 52.
(ii) Methods for the Determination of Metals in Environmental Samples, Supplement I. May 1994. EPA/600/R-94/111, Pub. No. PB 95125472. Table IB, Note 52.
(A) Method 200.7, Determination of Metals and Trace Elements in Water and Wastes by Inductively Coupled Plasma-Atomic Emission Spectrometry. Revision 4.4. Table IB, Note 52.
(B) Method 200.8, Determination of Trace Elements in Water and Wastes by Inductively Coupled Plasma Mass Spectrometry. Revision 5.3. Table IB, Note 52.
(C) Method 200.9, Determination of Trace Elements by Stabilized Temperature Graphite Furnace Atomic Absorption Spectrometry. Revision 2.2. Table IB, Note 52.
(D) Method 218.6, Determination of Dissolved Hexavalent Chromium in Drinking Water, Groundwater, and Industrial Wastewater Effluents by Ion Chromatography. Revision 3.3. Table IB, Note 52.
(E) Method 245.1, Determination of Mercury in Water by Cold Vapor Atomic Absorption Spectrometry. Revision 3.0. Table IB, Note 52.
(4) National Exposure Risk Laboratory-Cincinnati, U.S. Environmental Protection Agency, Cincinnati OH (US EPA). Available at
(i) EPA Method 200.5, Determination of Trace Elements in Drinking Water by Axially Viewed Inductively Coupled Plasma-Atomic Emission Spectrometry. Revision 4.2, October 2003. EPA/600/R-06/115. Table IB, Note 68.
(ii) EPA Method 525.2, Determination of Organic Compounds in Drinking Water by Liquid-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry. Revision 2.0, 1995. Table ID, Note 10.
(5) Office of Research and Development, Cincinnati OH. U.S. Environmental Protection Agency, Cincinnati OH (US EPA). Available at
(i) Methods for Benzidine, Chlorinated Organic Compounds, Pentachlorophenol, and Pesticides in Water and Wastewater. 1978. Table IC, Note 3; Table ID, Note 3.
(ii) Methods for Chemical Analysis of Water and Wastes. March 1979. EPA-600/4-79-020. Table IB, Note 1.
(iii) Methods for Chemical Analysis of Water and Wastes. Revised March 1983. EPA-600/4-79-020. Table IB, Note 1.
(A) Method 120.1, Conductance, Specific Conductance, µmhos at 25 °C. Revision 1982. Table IB, Note 1.
(B) Method 130.1, Hardness, Total (mg/L as CaCO
(C) Method 150.2, pH, Continuous Monitoring (Electrometric). December 1982. Table IB, Note 1.
(D) Method 160.4, Residue, Volatile, Gravimetric, Ignition at 550 °C. Issued 1971. Table IB, Note 1.
(E) Method 206.5, Arsenic, Sample Digestion Prior to Total Arsenic Analysis by Silver Diethyldithiocarbamate or Hydride Procedures. Issued 1978. Table IB, Note 1.
(F) Method 231.2, Gold, Atomic Absorption, Furnace Technique. Issued 1978. Table IB, Note 1.
(G) Method 245.2, Mercury, Automated Cold Vapor Technique. Issued 1974. Table IB, Note 1.
(H) Method 252.2, Osmium, Atomic Absorption, Furnace Technique. Issued 1978. Table IB, Note 1.
(I) Method 253.2, Palladium, Atomic Absorption, Furnace Technique. Issued 1978. Table IB, Note 1.
(J) Method 255.2, Platinum, Atomic Absorption, Furnace Technique. Issued 1978. Table IB, Note 1.
(K) Method 265.2, Rhodium, Atomic Absorption, Furnace Technique. Issued 1978. Table IB, Note 1.
(L) Method 279.2, Thallium, Atomic Absorption, Furnace Technique. Issued 1978. Table IB, Note 1.
(M) Method 283.2, Titanium, Atomic Absorption, Furnace Technique. Issued 1978. Table IB, Note 1.
(N) Method 289.2, Zinc, Atomic Absorption, Furnace Technique. Issued 1978. Table IB, Note 1.
(O) Method 310.2, Alkalinity, Colorimetric, Automated, Methyl Orange. Revision 1974. Table IB, Note 1.
(P) Method 351.1, Nitrogen, Kjeldahl, Total, Colorimetric, Automated Phenate. Revision 1978. Table IB, Note 1.
(Q) Method 352.1, Nitrogen, Nitrate, Colorimetric, Brucine. Issued 1971. Table IB, Note 1.
(R) Method 365.3, Phosphorus, All Forms, Colorimetric, Ascorbic Acid, Two Reagent. Issued 1978. Table IB, Note 1.
(S) Method 365.4, Phosphorus, Total, Colorimetric, Automated, Block
(T) Method 410.3, Chemical Oxygen Demand, Titrimetric, High Level for Saline Waters. Revision 1978. Table IB, Note 1.
(U) Method 420.1, Phenolics, Total Recoverable, Spectrophotometric, Manual 4-AAP With Distillation. Revision 1978. Table IB, Note 1.
(iv) Prescribed Procedures for Measurement of Radioactivity in Drinking Water. 1980. EPA-600/4-80-032. Table IE.
(A) Method 900.0, Gross Alpha and Gross Beta Radioactivity. Table IE.
(B) Method 903.0, Alpha-Emitting iRadio Isotopes. Table IE.
(C) Method 903.1, Radium-226, Radon Emanation Technique. Table IE.
(D) Appendix B, Error and Statistical Calculations. Table IE.
(6) Office of Science and Technology, U.S. Environmental Protection Agency, Washington DC (US EPA). Available at
(i) Method 1625C, Semivolatile Organic Compounds by Isotope Dilution GCMS. 1989. Table IF.
(ii) [Reserved]
(7) Office of Water, U.S. Environmental Protection Agency, Washington DC (US EPA). Available at
(i) Method 1631, Mercury in Water by Oxidation, Purge and Trap, and Cold Vapor Atomic Fluorescence Spectrometry. Revision E, August 2002. EPA-821-R-02-019, Pub. No. PB2002-108220. Table IB, Note 43.
(ii) Kelada-01, Kelada Automated Test Methods for Total Cyanide, Acid Dissociable Cyanide, and Thiocyanate. Revision 1.2, August 2001. EPA 821-B-01-009, Pub. No. PB 2001-108275. Table IB, Note 55.
(iii) In the compendium
(A) EPA Method 1666, Volatile Organic Compounds Specific to the Pharmaceutical Industry by Isotope Dilution GC/MS. Table IF, Note 1.
(B) EPA Method 1667, Formaldehyde, Isobutyraldehyde, and Furfural by Derivatization Followed by High Performance Liquid Chromatography. Table IF.
(C) Method 1671, Volatile Organic Compounds Specific to the Pharmaceutical Manufacturing Industry by GC/FID. Table IF.
(iv) Methods For The Determination of Nonconventional Pesticides In Municipal and Industrial Wastewater, Volume I. Revision I, August 1993. EPA 821-R-93-010A, Pub. No. PB 94121654. Tables ID, IG.
(A) Method 608.1, Organochlorine Pesticides. Table ID, Note 10; Table IG, Note 3.
(B) Method 608.2, Certain Organochlorine Pesticides. Table ID, Note 10; Table IG, Note 3.
(C) Method 614, Organophosphorus Pesticides. Table ID, Note 10; Table IG, Note 3.
(D) Method 614.1, Organophosphorus Pesticides. Table ID, Note 10; Table IG, Note 3.
(E) Method 615, Chlorinated Herbicides. Table ID, Note 10; Table IG, Note 3.
(F) Method 617, Organohalide Pesticides and PCBs. Table ID, Note 10; Table IG, Note 3.
(G) Method 619, Triazine Pesticides. Table ID, Note 10; Table IG, Note 3.
(H) Method 622, Organophosphorus Pesticides. Table ID, Note 10; Table IG, Note 3.
(I) Method 622.1, Thiophosphate Pesticides. Table ID, Note 10; Table IG, Note 3.
(J) Method 627, Dinitroaniline Pesticides. Table ID, Note 10; Table IG, Notes 1 and 3.
(K) Method 629, Cyanazine. Table IG, Note 3.
(L) Method 630, Dithiocarbamate Pesticides. Table IG, Note 3.
(M) Method 630.1, Dithiocarbamate Pesticides. Table IG, Note 3.
(N) Method 631, Benomyl and Carbendazim. Table IG, Note 3.
(O) Method 632, Carbamate and Urea Pesticides. Table ID, Note 10; Table IG, Note 3.
(P) Method 632.1, Carbamate and Amide Pesticides. Table IG, Note 3.
(Q) Method 633, Organonitrogen Pesticides. Table IG, Note 3.
(R) Method 633.1, Neutral Nitrogen-Containing Pesticides. Table IG, Note 3.
(S) Method 637, MBTS and TCMTB. Table IG, Note 3.
(T) Method 644, Picloram. Table IG, Note 3.
(U) Method 645, Certain Amine Pesticides and Lethane. Table IG, Note 3.
(V) Method 1656, Organohalide Pesticides. Table ID, Note 10; Table IG, Notes 1 and 3.
(W) Method 1657, Organophosphorus Pesticides. Table ID, Note 10; Table IG, Note 3.
(X) Method 1658, Phenoxy-Acid Herbicides. Table IG, Note 3.
(Y) Method 1659, Dazomet. Table IG, Note 3.
(Z) Method 1660, Pyrethrins and Pyrethroids. Table IG, Note 3.
(AA) Method 1661, Bromoxynil. Table IG, Note 3.
(BB) Ind-01. Methods EV-024 and EV-025, Analytical Procedures for Determining Total Tin and Triorganotin in Wastewater. Table IG, Note 3.
(v) Methods For The Determination of Nonconventional Pesticides In Municipal and Industrial Wastewater, Volume II. August 1993. EPA 821-R-93-010B, Pub. No. PB 94166311. Table IG.
(A) Method 200.9, Determination of Trace Elements by Stabilized Temperature Graphite Furnace Atomic Absorption Spectrometry. Table IG, Note 3.
(B) Method 505, Analysis of Organohalide Pesticides and Commercial Polychlorinated Biphenyl (PCB) Products in Water by Microextraction and Gas Chromatography. Table ID, Note 10; Table IG, Note 3.
(C) Method 507, The Determination of Nitrogen- and Phosphorus-Containing Pesticides in Water by Gas Chromatography with a Nitrogen-Phosphorus Detector. Table ID, Note 10; Table IG, Note 3.
(D) Method 508, Determination of Chlorinated Pesticides in Water by Gas Chromatography with an Electron Capture Detector. Table ID, Note 10; Table IG, Note 3.
(E) Method 515.1, Determination of Chlorinated Acids in Water by Gas Chromatography with an Electron Capture Detector. Table IG, Notes 2 and 3.
(F) Method 515.2, Determination of Chlorinated Acids in Water Using Liquid-Solid Extraction and Gas Chromatography with an Electron Capture Detector. Table IG, Notes 2 and 3.
(G) Method 525.1, Determination of Organic Compounds in Drinking Water by Liquids-Solid Extraction and Capillary Column Gas Chromatography/Mass Spectrometry. Table ID, Note 10; Table IG, Note 3.
(H) Method 531.1, Measurement of N-Methylcarbamoyloximes and N-Methylcarbamates in Water by Direct Aqueous Injection HPLC with Post-Column Derivatization. Table ID, Note 10; Table IG, Note 3.
(I) Method 547, Determination of Glyphosate in Drinking Water by Direct-Aqueous-Injection HPLC, Post-Column Derivatization, and Fluorescence Detection. Table IG, Note 3.
(J) Method 548, Determination of Endothall in Drinking Water by Aqueous Derivatization, Liquid-Solid Extraction, and Gas Chromatography with Electron-Capture Detector. Table IG, Note 3.
(K) Method 548.1, Determination of Endothall in Drinking Water by Ion-Exchange Extraction, Acidic Methanol Methylation and Gas Chromatography/Mass Spectrometry. Table IG, Note 3.
(L) Method 553, Determination of Benzidines and Nitrogen-Containing Pesticides in Water by Liquid-Liquid Extraction or Liquid-Solid Extraction and Reverse Phase High Performance Liquid Chromatography/Particle Beam/Mass Spectrometry Table ID, Note 10; Table IG, Note 3.
(M) Method 555, Determination of Chlorinated Acids in Water by High Performance Liquid Chromatography With a Photodiode Array Ultraviolet Detector. Table IG, Note 3.
(vi) In the compendium
(A) EPA Method 502.2, Volatile Organic Compounds in Water by Purge and Trap Capillary Column Gas Chromatography with Photoionization and Electrolytic Conductivity Detectors in Series. Table IF.
(B) [Reserved]
(vii) In the compendium
(A) EPA Method 524.2, Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry. Table IF.
(B) [Reserved]
(viii) Methods for Measuring the Acute Toxicity of Effluents and Receiving Waters to Freshwater and Marine Organisms, Fifth Edition. October 2002. EPA 821-R-02-012, Pub. No. PB2002-108488. Table IA, Note 26.
(ix) Short-Term Methods for Measuring the Chronic Toxicity of Effluents and Receiving Waters to Freshwater Organisms, Fourth Edition. October 2002. EPA 821-R-02-013, Pub. No. PB2002-108489. Table IA, Note 27.
(x) Short-Term Methods for Measuring the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms, Third Edition. October 2002. EPA 821-R-02-014, Pub. No. PB2002-108490. Table IA, Note 28.
(8) Office of Water, U.S. Environmental Protection Agency, Washington DC (US EPA). Available at
(i) Method 245.7, Mercury in Water by Cold Vapor Atomic Fluorescence Spectrometry. Revision 2.0, February 2005. EPA-821-R-05-001. Table IB, Note 17.
(ii) Method 1103.1:
(iii) Method 1106.1: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus-Esculin Iron Agar (mE-EIA). December 2009. EPA-621-R-09-015. Table IH, Note 23.
(iv) Method 1600: Enterococci in Water by Membrane Filtration Using membrane-Enterococcus Indoxyl-β-D-Glucoside Agar (mEI). December 2009. EPA-821-R-09-016. Table IA, Note 25; Table IH, Note 24.
(v) Method 1603:
(vi) Method 1604: Total Coliforms and
(vii) Method 1622:
(viii) Method 1623:
(ix) Method 1627, Kinetic Test Method for the Prediction of Mine Drainage Quality. December 2011. EPA-821-R-09-002. Table IB, Note 69.
(x) Method 1664, n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane Extractable Material (SGT-HEM; Non-polar Material) by Extraction and Gravimetry. Revision A, February 1999. EPA-821-R-98-002. Table IB, Notes 38 and 42.
(xi) Method 1664, n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated n-Hexane Extractable Material (SGT-HEM; Non-polar Material) by Extraction and Gravimetry. Revision B, February 2010. EPA-821-R-10-001. Table IB, Notes 38 and 42.
(xii) Method 1669, Sampling Ambient Water for Trace Metals at EPA Water Quality Criteria Levels. July 1996. Table IB, Note 43.
(xiii) Method 1680: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation using Lauryl Tryptose Broth (LTB) and EC Medium. April 2010. EPA-821-R-10-003. Table IA, Note 15.
(xiv) Method 1681: Fecal Coliforms in Sewage Sludge (Biosolids) by Multiple-Tube Fermentation using A-1 Medium. July 2006. EPA 821-R-06-013. Table IA, Note 20.
(xv) Method 1682:
(9) American National Standards Institute, 1430 Broadway, New York NY 10018.
(i) ANSI. American National Standard on Photographic Processing
(ii) [Reserved]
(10) American Public Health Association, 1015 15th Street NW., Washington, DC 20005. Standard Methods Online is available through the Standard Methods Web site (
(i) Standard Methods for the Examination of Water and Wastewater. 14th Edition, 1975. Table IB, Notes 17 and 27.
(ii) Standard Methods for the Examination of Water and Wastewater. 15th Edition, 1980, Table IB, Note 30; Table ID.
(iii) 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. Table IC, Note 6; Table ID, Note 6.
(iv) Standard Methods for the Examination of Water and Wastewater. 18th Edition, 1992. Tables IA, IB, IC, ID, IE, and IH.
(v) Standard Methods for the Examination of Water and Wastewater. 19th Edition, 1995. Tables IA, IB, IC, ID, IE, and IH.
(vi) Standard Methods for the Examination of Water and Wastewater. 20th Edition, 1998. Tables IA, IB, IC, ID, IE, and IH.
(vii) Standard Methods for the Examination of Water and Wastewater. 21st Edition, 2005. Table IB, Notes 17 and 27.
(viii) 2120, Color. 2001. Table IB.
(ix) 2130, Turbidity. 2001. Table IB.
(x) 2310, Acidity. 1997. Table IB.
(xi) 2320, Alkalinity. 1997. Table IB.
(xii) 2340, Hardness. 1997. Table IB.
(xiii) 2510, Conductivity. 1997. Table IB.
(xiv) 2540, Solids. 1997. Table IB.
(xv) 2550, Temperature. 2000. Table IB.
(xvi) 3111, Metals by Flame Atomic Absorption Spectrometry. 1999. Table IB.
(xvii) 3112, Metals by Cold-Vapor Atomic Absorption Spectrometry. 2009. Table IB.
(xviii) 3113, Metals by Electrothermal Atomic Absorption Spectrometry. 2004. Table IB.
(xix) 3114, Arsenic and Selenium by Hydride Generation/Atomic Absorption Spectrometry. 2009. Table IB.
(xx) 3120, Metals by Plasma Emission. 1999. Table IB.
(xxi) 3125, Metals by Inductively Coupled Plasma-Mass Spectrometry. 2009. Table IB.
(xxii) 3500-Al, Aluminum. 2001. Table IB.
(xxiii) 3500-As, Arsenic. 1997. Table IB.
(xxiv) 3500-Ca, Calcium. 1997. Table IB.
(xxv) 3500-Cr, Chromium. 2009. Table IB.
(xxvi) 3500-Cu, Copper. 1999. Table IB.
(xxvii) 3500-Fe, Iron. 1997. Table IB.
(xxviii) 3500-Pb, Lead. 1997. Table IB.
(xxix) 3500-Mn, Manganese. 1999. Table IB.
(xxx) 3500-K, Potassium. 1997. Table IB.
(xxxi) 3500-Na, Sodium. 1997. Table IB.
(xxxii) 3500-V, Vanadium. 1997. Table IB.
(xxxiii) 3500-Zn, Zinc. 1997. Table IB.
(xxxiv) 4110, Determination of Anions by Ion Chromatography. 2000. Table IB.
(xxxv) 4140, Inorganic Anions by Capillary Ion Electrophoresis. 1997. Table IB.
(xxxvi) 4500-B, Boron. 2000. Table IB.
(xxxvii) 4500-Cl
(xxxviii) 4500-Cl, Chlorine (Residual). 2000. Table IB.
(xxxix) 4500-CN
(xl) 4500-F
(xli) 4500-H
(xlii) 4500-NH
(xliii) 4500-NO
(xliv) 4500-NO
(xlv) 4500-N
(xlvi) 4500-O, Oxygen (Dissolved). 2001. Table IB.
(xlvii) 4500-P, Phosphorus. 1999. Table IB.
(xlviii) 4500-SiO
(xlix) 4500-S
(l) 4500-SO
(li) 4500-SO
(lii) 5210, Biochemical Oxygen Demand (BOD). 2001. Table IB.
(liii) 5220, Chemical Oxygen Demand (COD). 1997. Table IB.
(liv) 5310, Total Organic Carbon (TOC). 2000. Table IB.
(lv) 5520, Oil and Grease. 2001. Table IB.
(lvi) 5530, Phenols. 2005. Table IB.
(lvii) 5540, Surfactants. 2000. Table IB.
(lviii) 6200, Volatile Organic Compounds. 1997. Table IC.
(lix) 6410, Extractable Base/Neutrals and Acids. 2000. Tables IC, ID.
(lx) 6420, Phenols. 2000. Table IC.
(lxi) 6440, Polynuclear Aromatic Hydrocarbons. 2000. Table IC.
(lxii) 6630, Organochlorine Pesticides. 2000. Table ID.
(lxiii) 6640, Acidic Herbicide Compounds. 2001. Table ID.
(lxiv) 7110, Gross Alpha and Gross Beta Radioactivity (Total, Suspended, and Dissolved). 2000. Table IE.
(lxv) 7500, Radium. 2001. Table IE.
(lxvi) 9213, Recreational Waters. 2007. Table IH.
(lxvii) 9221, Multiple-Tube Fermentation Technique for Members of the Coliform Group. 2006. Table IA, Notes 12 and 14; Table IH, Notes 11 and 13.
(lxviii) 9222, Membrane Filter Technique for Members of the Coliform Group. 1997. Table IA; Table IH, Note 18.
(lxix) 9223, Enzyme Substrate Coliform Test. 2004. Table IA; Table IH.
(lxx) 9230, Fecal
(11) The Analyst, The Royal Society of Chemistry, RSC Publishing, Royal Society of Chemistry, Thomas Graham House, Science Park, Milton Road, Cambridge CB4 0WF, United Kingdom. (Also available from most public libraries.)
(i) Spectrophotometric Determination of Ammonia: A Study of a Modified Berthelot Reaction Using Salicylate and Dichloroisocyanurate. Krom, M.D. 105:305-316, April 1980. Table IB, Note 60.
(ii) [Reserved]
(12) Analytical Chemistry, ACS Publications, 1155 Sixteenth St. NW., Washington DC 20036. (Also available from most public libraries.)
(i) Spectrophotometric and Kinetics Investigation of the Berthelot Reaction for the Determination of Ammonia. Patton, C.J. and S.R. Crouch. 49(3):464-469, March 1977. Table IB, Note 60.
(ii) [Reserved]
(13) AOAC International, 481 North Frederick Avenue, Suite 500, Gaithersburg, MD 20877-2417.
(i) Official Methods of Analysis of AOAC International. 16th Edition, 4th Revision, 1998.
(A) 920.203, Manganese in Water, Persulfate Method. Table IB, Note 3.
(B) 925.54, Sulfate in Water, Gravimetric Method. Table IB, Note 3.
(C) 973.40, Specific Conductance of Water. Table IB, Note 3.
(D) 973.41, pH of Water. Table IB, Note 3.
(E) 973.43, Alkalinity of Water, Titrimetric Method. Table IB, Note 3.
(F) 973.44, Biochemical Oxygen Demand (BOD) of Water, Incubation Method. Table IB, Note 3.
(G) 973.45, Oxygen (Dissolved) in Water, Titrimetric Methods. Table IB, Note 3.
(H) 973.46, Chemical Oxygen Demand (COD) of Water, Titrimetric Methods. Table IB, Note 3.
(I) 973.47, Organic Carbon in Water, Infrared Analyzer Method. Table IB, Note 3.
(J) 973.48, Nitrogen (Total) in Water, Kjeldahl Method. Table IB, Note 3.
(K) 973.49, Nitrogen (Ammonia) in Water, Colorimetric Method. Table IB, Note 3.
(L) 973.50, Nitrogen (Nitrate) in Water, Brucine Colorimetric Method. Table IB, Note 3.
(M) 973.51, Chloride in Water, Mercuric Nitrate Method. Table IB, Note 3.
(N) 973.52, Hardness of Water. Table IB, Note 3.
(O) 973.53, Potassium in Water, Atomic Absorption Spectrophotometric Method. Table IB, Note 3.
(P) 973.54, Sodium in Water, Atomic Absorption Spectrophotometric Method. Table IB, Note 3.
(Q) 973.55, Phosphorus in Water, Photometric Method. Table IB, Note 3.
(R) 973.56, Phosphorus in Water, Automated Method. Table IB, Note 3.
(S) 974.27, Cadmium, Chromium, Copper, Iron, Lead, Magnesium, Manganese, Silver, Zinc in Water, Atomic Absorption Spectrophotometric Method. Table IB, Note 3.
(T) 977.22, Mercury in Water, Flameless Atomic Absorption Spectrophotometric Method. Table IB, Note 3.
(U) 991.15. Total Coliforms and
(V) 993.14, Trace Elements in Waters and Wastewaters, Inductively Coupled Plasma-Mass Spectrometric Method. Table IB, Note 3.
(W) 993.23, Dissolved Hexavalent Chromium in Drinking Water, Ground Water, and Industrial Wastewater Effluents, Ion Chromatographic Method. Table IB, Note 3.
(X) 993.30, Inorganic Anions in Water, Ion Chromatographic Method. Table IB, Note 3.
(ii) [Reserved]
(14) Applied and Environmental Microbiology, American Society for Microbiology, 1752 N Street NW., Washington DC 20036. (Also available from most public libraries.)
(i) New Medium for the Simultaneous Detection of Total Coliforms and
(ii) [Reserved]
(15) ASTM International, 100 Barr Harbor Drive, P.O. Box C700, West Conshohocken, PA 19428-2959, or online at
(i) Annual Book of ASTM Standards, Water, and Environmental Technology, Section 11, Volumes 11.01 and 11.02. 1994. Tables IA, IB, IC, ID, IE, and IH.
(ii) Annual Book of ASTM Standards, Water, and Environmental Technology, Section 11, Volumes 11.01 and 11.02. 1996. Tables IA, IB, IC, ID, IE, and IH.
(iii) Annual Book of ASTM Standards, Water, and Environmental Technology, Section 11, Volumes 11.01 and 11.02. 1999. Tables IA, IB, IC, ID, IE, and IH.
(iv) Annual Book of ASTM Standards, Water, and Environmental Technology, Section 11, Volumes 11.01 and 11.02. 2000. Tables IA, IB, IC, ID, IE, and IH.
(v) ASTM D511-08, Standard Test Methods for Calcium and Magnesium in Water. November 2008. Table IB.
(vi) ASTM D512-04, Standard Test Methods for Chloride Ion in Water. July 2004. Table IB.
(vii) ASTM D515-88, Test Methods for Phosphorus in Water, March 1989. Table IB.
(viii) ASTM D516-07, Standard Test Method for Sulfate Ion in Water, September 2007. Table IB.
(ix) ASTM D858-07, Standard Test Methods for Manganese in Water. August 2007. Table IB.
(x) ASTM D859-05, Standard Test Method for Silica in Water. February 2005. Table IB.
(xi) ASTM D888-09, Standard Test Methods for Dissolved Oxygen in Water. December 2009. Table IB.
(xii) ASTM D1067-06, Standard Test Methods for Acidity or Alkalinity of Water. January 2007. Table IB.
(xiii) ASTM D1068-05
(xiv) ASTM D1125-95 (Reapproved 1999), Standard Test Methods for Electrical Conductivity and Resistivity of Water. December 1995. Table IB.
(xv) ASTM D1126-02 (Reapproved 2007)
(xvi) ASTM D1179-04, Standard Test Methods for Fluoride Ion in Water. July 2004. Table IB.
(xvii) ASTM D1246-05, Standard Test Method for Bromide Ion in Water. February 2005. Table IB.
(xviii) ASTM D1252-06, Standard Test Methods for Chemical Oxygen Demand (Dichromate Oxygen Demand) of Water. February 2006. Table IB.
(xix) ASTM D1253-08, Standard Test Method for Residual Chlorine in Water. October 2008. Table IB.
(xx) ASTM D1293-99, Standard Test Methods for pH of Water. March 2000. Table IB.
(xxi) ASTM D1426-08, Standard Test Methods for Ammonia Nitrogen in Water. September 2008. Table IB.
(xxii) ASTM D1687-02 (Reapproved 2007)
(xxiii) ASTM D1688-07, Standard Test Methods for Copper in Water. August 2007. Table IB.
(xxiv) ASTM D1691-02 (Reapproved 2007)
(xxv) ASTM D1783-01 (Reapproved 2007), Standard Test Methods for Phenolic Compounds in Water. January 2008). Table IB.
(xxvi) ASTM D1886-08, Standard Test Methods for Nickel in Water. October 2008. Table IB.
(xxvii) ASTM D1889-00, Standard Test Method for Turbidity of Water. October 2000. Table IB.
(xxviii) ASTM D1890-96, Standard Test Method for Beta Particle Radioactivity of Water. April 1996. Table IE.
(xxix) ASTM D1943-96, Standard Test Method for Alpha Particle Radioactivity of Water. April 1996. Table IE.
(xxx) ASTM D1976-07, Standard Test Method for Elements in Water by Inductively-Coupled Argon Plasma Atomic Emission Spectroscopy. August 2007. Table IB.
(xxxi) ASTM D2036-09, Standard Test Methods for Cyanides in Water. October 2009. Table IB.
(xxxii) ASTM D2330-02, Standard Test Method for Methylene Blue Active Substances. August 2002. Table IB.
(xxxiii) ASTM D2460-97, Standard Test Method for Alpha-Particle-Emitting Isotopes of Radium in Water. October 1997. Table IE.
(xxxiv) ASTM D2972-08, Standard Tests Method for Arsenic in Water. October 2008. Table IB.
(xxxv) ASTM D3223-02 (Reapproved 2007)
(xxxvi) ASTM D3371-95, Standard Test Method for Nitriles in Aqueous Solution by Gas-Liquid Chromatography, February 1996. Table IF.
(xxxvii) ASTM D3373-03 (Reapproved 2007)
(xxxviii) ASTM D3454-97, Standard Test Method for Radium-226 in Water. February 1998. Table IE.
(xxxix) ASTM D3557-02 (Reapproved 2007)
(xl) ASTM D3558-08, Standard Test Method for Cobalt in Water. November 2008. Table IB.
(xli) ASTM D3559-08, Standard Test Methods for Lead in Water. October 2008. Table IB.
(xlii) ASTM D3590-02 (Reapproved 2006), Standard Test Methods for Total Kjeldahl Nitrogen in Water. February 2007. Table IB.
(xliii) ASTM D3645-08, Standard Test Methods for Beryllium in Water. October 2008. Table IB.
(xliv) ASTM D3695-95, Standard Test Method for Volatile Alcohols in Water by Direct Aqueous-Injection Gas Chromatography. April 1995. Table IF.
(xlv) ASTM D3859-08, Standard Test Methods for Selenium in Water. October 2008. Table IB.
(xlvi) ASTM D3867-04, Standard Test Method for Nitrite-Nitrate in Water. July 2004. Table IB.
(xlvii) ASTM D4190-08, Standard Test Method for Elements in Water by Direct-Current Plasma Atomic Emission Spectroscopy. October 2008. Table IB.
(xlviii) ASTM D4282-02, Standard Test Method for Determination of Free Cyanide in Water and Wastewater by Microdiffusion. August 2002. Table IB.
(xlix) ASTM D4327-03, Standard Test Method for Anions in Water by Chemically Suppressed Ion Chromatography. January 2003. Table IB.
(l) ASTM D4382-02 (Reapproved 2007)
(li) ASTM D4657-92 (Reapproved 1998), Standard Test Method for Polynuclear Aromatic Hydrocarbons in Water. January 1993. Table IC.
(lii) ASTM D4658-08, Standard Test Method for Sulfide Ion in Water. August 2008. Table IB.
(liii) ASTM D4763-88 (Reapproved 2001), Standard Practice for Identification of Chemicals in Water by Fluorescence Spectroscopy. September 1988. Table IF.
(liv) ASTM D4839-03, Standard Test Method for Total Carbon and Organic Carbon in Water by Ultraviolet, or
(lv) ASTM D5257-03, Standard Test Method for Dissolved Hexavalent Chromium in Water by Ion Chromatography. January 2003. Table IB.
(lvi) ASTM D5259-92, Standard Test Method for Isolation and Enumeration of Enterococci from Water by the Membrane Filter Procedure. October 1992. Table IH, Note 9.
(lvii) ASTM D5392-93, Standard Test Method for Isolation and Enumeration of
(lviii) ASTM D5673-05, Standard Test Method for Elements in Water by Inductively Coupled Plasma—Mass Spectrometry. July 2005. Table IB.
(lix) ASTM D5907-03, Standard Test Method for Filterable and Nonfilterable Matter in Water. July 2003. Table IB.
(lx) ASTM D6503-99, Standard Test Method for Enterococci in Water Using Enterolert. April 2000. Table IA Note 9, Table IH, Note 9.
(lxi) ASTM. D6508-00 (Reapproved 2005)
(lxii) ASTM. D6888-09, Standard Test Method for Available Cyanide with Ligand Displacement and Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and Amperometric Detection. October 2009. Table IB, Note 59.
(lxiii) ASTM. D6919-09, Standard Test Method for Determination of Dissolved Alkali and Alkaline Earth Cations and Ammonium in Water and Wastewater by Ion Chromatography. May 2009. Table IB.
(lxiv) ASTM. D7065-06, Standard Test Method for Determination of Nonylphenol, Bisphenol A, p-tert-Octylphenol, Nonylphenol Monoethoxylate and Nonylphenol Diethoxylate in Environmental Waters by Gas Chromatography Mass Spectrometry. January 2007. Table IC.
(lxv) ASTM. D7237-10, Standard Test Method for Free Cyanide with Flow Injection Analysis (FIA) Utilizing Gas Diffusion Separation and Amperometric Detection. June 2010. Table IB.
(lxvi) ASTM. D7284-08, Standard Test Method for Total Cyanide in Water by Micro Distillation followed by Flow Injection Analysis with Gas Diffusion Separation and Amperometric Detection. April 2008). Table IB.
(lxvii) ASTM. D7365-09a, Standard Practice for Sampling, Preservation, and Mitigating Interferences in Water Samples for Analysis of Cyanide. October 2009. Table II, Notes 5 and 6.
(lxviii) ASTM. D7511-09
(lxix) ASTM. D7573-09, Standard Test Method for Total Carbon and Organic Carbon in Water by High Temperature Catalytic Combustion and Infrared Detection. November 2009. Table IB.
(16) Bran & Luebbe Analyzing Technologies, Inc., Elmsford NY 10523.
(i) Industrial Method Number 378-75WA, Hydrogen Ion (pH) Automated Electrode Method, Bran & Luebbe (Technicon) Auto Analyzer II. October 1976. Table IB, Note 21.
(ii) [Reserved]
(17) CEM Corporation, P.O. Box 200, Matthews NC 28106-0200.
(i) Closed Vessel Microwave Digestion of Wastewater Samples for Determination of Metals. April 16, 1992. Table IB, Note 36.
(ii) [Reserved]
(18) Craig R. Chinchilla, 900 Jorie Blvd., Suite 35, Oak Brook IL 60523. Telephone: 630-645-0600.
(i) Nitrate by Discrete Analysis Easy (1-Reagent) Nitrate Method, (Colorimetric, Automated, 1 Reagent). Revision 1, November 12, 2011. Table IB, Note 62.
(ii) [Reserved]
(19) Hach Company, P.O. Box 389, Loveland CO 80537.
(i) Method 8000, Chemical Oxygen Demand. Hach Handbook of Water Analysis. 1979. Table IB, Note 14.
(ii) Method 8008, 1,10-Phenanthroline Method using FerroVer Iron Reagent for Water. 1980. Table IB, Note 22.
(iii) Method 8009, Zincon Method for Zinc. Hach Handbook for Water Analysis. 1979. Table IB, Note 33.
(iv) Method 8034, Periodate Oxidation Method for Manganese. Hach Handbook for Water Analysis. 1979. Table IB, Note 23.
(v) Method 8506, Bicinchoninate Method for Copper. Hach Handbook of Water Analysis. 1979. Table IB, Note 19.
(vi) Method 8507, Nitrogen, Nitrite—Low Range, Diazotization Method for Water and Wastewater. 1979. Table IB, Note 25.
(vii) Hach Method 10360, Luminescence Measurement of Dissolved Oxygen in Water and Wastewater and for Use in the Determination of BOD
(viii) m-ColiBlue24® Method, for total Coliforms and
(20) IDEXX Laboratories Inc., One Idexx Drive, Westbrook ME 04092.
(i) Colilert® Method. 2002. Table IA, Notes 17 and 18; Table IH, Notes 14, 15 and 16.
(ii) Colilert-18® Method. 2002. Table IA, Notes 17 and 18; Table IH, Notes 14, 15 and 16.
(iii) Enterolert® Method. 2002. Table IA, Note 24; Table IH, Note 12.
(iv) Quanti-Tray® Method. 2002. Table IA, Note 18; Table IH, Notes 14 and 16.
(v) Quanti-Tray®/2000 Method. 2002. Table IA, Note 18; Table IH, Notes 14 and 16.
(21) In-Situ Incorporated, 221 E. Lincoln Ave., Ft. Collins CO 80524. Telephone: 970-498-1500.
(i) In-Situ Inc. Method 1002-8-2009, Dissolved Oxygen Measurement by Optical Probe. 2009. Table IB, Note 64.
(ii) In-Situ Inc. Method 1003-8-2009, Biochemical Oxygen Demand (BOD) Measurement by Optical Probe. 2009. Table IB, Note 10.
(iii) In-Situ Inc. Method 1004-8-2009, Carbonaceous Biochemical Oxygen Demand (CBOD) Measurement by Optical Probe. 2009. Table IB, Note 35.
(22) Journal of Chromatography, Elsevier/North-Holland, Inc., Journal Information Centre, 52 Vanderbilt Avenue, New York NY 10164. (Also available from most public libraries.
(i) Direct Determination of Elemental Phosphorus by Gas-Liquid Chromatography. Addison, R.F. and R.G. Ackman. 47(3): 421-426, 1970. Table IB, Note 28.
(ii) [Reserved]
(23) Lachat Instruments, 6645 W. Mill Road, Milwaukee WI 53218, Telephone: 414-358-4200.
(i) QuikChem Method 10-204-00-1-X, Digestion and Distillation of Total Cyanide in Drinking and Wastewaters using MICRO DIST and Determination of Cyanide by Flow Injection Analysis. Revision 2.2, March 2005. Table IB, Note 56.
(ii) [Reserved]
(24) Leck Mitchell, Ph.D., P.E., 656 Independence Valley Dr., Grand Junction CO 81507. Telephone: 970-244-8661.
(i) Mitchell Method M5271, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Table IB, Note 66.
(ii) Mitchell Method M5331, Determination of Turbidity by Nephelometry. Revision 1.0, July 31, 2008. Table IB, Note 65.
(25) National Council of the Paper Industry for Air and Stream Improvements, Inc. (NCASI), 260 Madison Avenue, New York NY 10016.
(i) NCASI Technical Bulletin No. 253, An Investigation of Improved Procedures for Measurement of Mill Effluent and Receiving Water Color. December 1971. Table IB, Note 18.
(ii) [Reserved]
(26) Oceanography International Corporation, 512 West Loop, P.O. Box 2980, College Station TX 77840.
(i) OIC Chemical Oxygen Demand Method. 1978. Table IB, Note 13.
(ii) [Reserved]
(27) OI Analytical, Box 9010, College Station TX 77820-9010.
(i) Method OIA-1677-09, Available Cyanide by Ligand Exchange and Flow Injection Analysis (FIA). Copyright 2010. Table IB, Note 59.
(ii) Method PAI-DK01, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Titrimetric Detection. Revised December 22, 1994. Table IB, Note 39.
(iii) Method PAI-DK02, Nitrogen, Total Kjeldahl, Block Digestion, Steam Distillation, Colorimetric Detection. Revised December 22, 1994. Table IB, Note 40.
(iv) Method PAI-DK03, Nitrogen, Total Kjeldahl, Block Digestion, Automated FIA Gas Diffusion. Revised December 22, 1994. Table IB, Note 41.
(28) ORION Research Corporation, 840 Memorial Drive, Cambridge, Massachusetts 02138.
(i) ORION Research Instruction Manual, Residual Chlorine Electrode Model 97-70. 1977. Table IB, Note 16.
(ii) [Reserved]
(29) Technicon Industrial Systems, Tarrytown NY 10591.
(i) Industrial Method Number 379-75WE Ammonia, Automated Electrode Method, Technicon Auto Analyzer II. February 19, 1976. Table IB, Note 7.
(ii) [Reserved]
(30) Thermo Jarrell Ash Corporation, 27 Forge Parkway, Franklin MA 02038.
(i) Method AES0029. Direct Current Plasma (DCP) Optical Emission Spectrometric Method for Trace Elemental Analysis of Water and Wastes. 1986, Revised 1991. Table IB, Note 34.
(ii) [Reserved]
(31) Thermo Scientific, 166 Cummings Center, Beverly MA 01915. Telephone: 1-800-225-1480.
(i) Thermo Scientific Orion Method AQ4500, Determination of Turbidity by Nephelometry. Revision 5, March 12, 2009. Table IB, Note 67.
(ii) [Reserved]
(32) 3M Corporation, 3M Center Building 220-9E-10, St. Paul MN 55144-1000.
(i) Organochlorine Pesticides and PCBs in Wastewater Using Empore
(ii) [Reserved]
(33) U.S. Geological Survey (USGS), U.S. Department of the Interior, Reston, Virginia. Available from USGS Books and Open-File Reports (OFR) Section, Federal Center, Box 25425, Denver, CO 80225.
(i) OFR 76-177, Selected Methods of the U.S. Geological Survey of Analysis of Wastewaters. 1976. Table IE, Note 2.
(ii) OFR 91-519, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Organonitrogen Herbicides in Water by Solid-Phase Extraction and Capillary-Column Gas Chromatography/Mass Spectrometry With Selected-Ion Monitoring. 1992. Table ID, Note 14.
(iii) OFR 92-146, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Total Phosphorus by a Kjeldahl Digestion Method and an Automated Colorimetric Finish That Includes Dialysis. 1992. Table IB, Note 48.
(iv) OFR 93-125, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Inorganic and Organic Constituents in Water and Fluvial Sediments. 1993. Table IB, Note 51; Table IC, Note 9.
(v) OFR 93-449, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Chromium in Water by Graphite Furnace Atomic Absorption Spectrophotometry. 1993. Table IB, Note 46.
(vi) OFR 94-37, 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. 1994. Table ID, Note 9.
(vii) OFR 95-181, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Pesticides in Water by C-18 Solid-Phase Extraction and Capillary-Column Gas Chromatography/Mass Spectrometry With Selected-Ion Monitoring. 1995. Table ID, Note 11.
(viii) OFR 97-198, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Molybdenum in Water by Graphite Furnace Atomic Absorption Spectrophotometry. 1997. Table IB, Note 47.
(ix) OFR 98-165, 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. 1998. Table IB, Note 50.
(x) OFR 98-639, 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. 1999. Table IB, Note 49.
(xi) OFR 00-170, Methods of Analysis by the U.S. Geological Survey National
(xii) Water-Resources Investigation Report 01-4098, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Moderate-Use Pesticides and Selected Degradates in Water by C-18 Solid-Phase Extraction and Gas Chromatography/Mass Spectrometry. 2001. Table ID, Note 13.
(xiii) Water-Resources Investigations Report 01-4132, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Organic Plus Inorganic Mercury in Filtered and Unfiltered Natural Water With Cold Vapor-Atomic Fluorescence Spectrometry. 2001. Table IB, Note 71.
(xiv) Water-Resources Investigation Report 01-4134, Methods of Analysis by the U.S. Geological Survey National Water Quality Laboratory—Determination of Pesticides in Water by Graphitized Carbon-Based Solid-Phase Extraction and High-Performance Liquid Chormatography/Mass Spectrometry. 2001. Table ID, Note 12.
(xv) Methods for Determination of Inorganic Substances in Water and Fluvial Sediments, editors, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A1. 1979. Table IB, Note 8.
(xvi) Methods for Determination of Inorganic Substances in Water and Fluvial Sediments, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A1. 1989. Table IB, Note 2.
(xvii) Methods for the Determination of Organic Substances in Water and Fluvial Sediments. Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 5, Chapter A3. 1987. Table IB, Note 24; Table ID, Note 4.
(xviii) Techniques and Methods Book 5-B1, Determination of Elements in Natural-Water, Biota, Sediment and Soil Samples Using Collision/Reaction Cell Inductively Coupled Plasma-Mass Spectrometry. Chapter 1, Section B, Methods of the National Water Quality Laboratory, Book 5, Laboratory Analysis. 2006. Table IB, Note 70.
(xix) 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. 1989. Table IA, Note 4; Table IH, Note 4.
(xx) Water Temperature—Influential Factors, Field Measurement and Data Presentation, Techniques of Water-Resources Investigations of the U.S. Geological Survey, Book 1, Chapter D1. 1975. Table IB, Note 32.
(34) Waters Corporation, 34 Maple Street, Milford MA 01757, Telephone: 508-482-2131, Fax: 508-482-3625.
(i) Method D6508, Test Method for Determination of Dissolved Inorganic Anions in Aqueous Matrices Using Capillary Ion Electrophoresis and Chromate Electrolyte. Revision 2, December 2000. Table IB, Note 54.
(ii) [Reserved]
(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 recommendation of the Alternate Test Procedure Program Coordinator, Washington, DC.
(d) Under certain circumstances, the Administrator may approve additional alternate test procedures for nationwide use, upon recommendation by the Alternate Test Procedure Program Coordinator, Washington, DC.
(e) Sample preservation procedures, container materials, and maximum allowable holding times for parameters are cited in Tables IA, IB, IC, ID, IE, IF, IG, and IH are prescribed in Table II. Information in the table takes precedence over information in specific methods or elsewhere. Any person may apply for a change from the prescribed preservation techniques, container materials, and maximum holding times applicable to samples taken from a specific discharge. Applications for such limited use changes may be made by letters to the Regional Alternative
For
(a) A written application for review of an alternate test procedure (alternate method) for nationwide use may be made by letter via email or by hard copy in triplicate to the National Alternate Test Procedure (ATP) Program Coordinator (National Coordinator), Office of Science and Technology (4303T), Office of Water, U.S. Environmental Protection Agency, 1200 Pennsylvania Ave. NW., Washington, DC 20460. Any application for an alternate test procedure (ATP) under this paragraph (a) 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 test procedure is being requested.
(3) Provide a detailed description of the proposed alternate test procedure, together with references to published or other studies confirming the general applicability of the alternate test procedure for the analysis of the pollutant(s) or parameter(s) in wastewater discharges from representative and specified industrial or other categories.
(4) Provide comparability data for the performance of the proposed alternative test procedure compared to the performance of the reference method.
(b) The National Coordinator may request additional information and analyses from the applicant in order to determine whether the alternate test procedure satisfies the applicable requirements of this part.
(c)
(2) Where the National Coordinator approved an applicant's request for nationwide use of an alternate test procedure, the National Coordinator will notify the applicant that the National Coordinator will recommend rulemaking to approve the alternate test procedure. The National Coordinator will notify the Regional ATP Coordinator or permitting authorities that they may consider approval of this alternate test procedure for limited use in their Regions based on the information and data provided in the applicant's application. The Regional ATP Coordinator or permitting authority will grant approval on a case-by-case basis prior to use of the alternate test procedure for compliance analyses until the alternate test procedure is approved by publication in a final rule in the
(3) EPA will propose to amend 40 CFR Part 136 to include the alternate test procedure in § 136.3. 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 public comment, EPA shall publish in the
(5) Whenever the National Coordinator has approved an applicant's request for nationwide use of an alternate test procedure, any person may request an approval of the method for limited use under § 136.5 from the EPA Region.
(a) Any person may request the Regional Alternate Test Procedure (ATP) Coordinator or permitting authority to approve the use of an alternate test procedure in the Region.
(b) When the request for the use of an alternate test procedure concerns use in a State with an NPDES permit program approved pursuant to section 402 of the Act, the requestor shall first submit an application for limited use to the Director of the State agency having responsibility for issuance of NPDES permits within such State (
(c) Any application for approval of an alternate test procedure for limited use may be made by letter, email or by hard copy. The application shall include the following:
(1) Provide the name and address of the applicant and the applicable ID
(2) Identify the pollutant or parameter for which approval of an alternate test procedure is being requested.
(3) Provide justification for using testing procedures other than those specified in Tables IA through IH of § 136.3, or in the NPDES permit.
(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.
(5) Provide comparability data for the performance of the proposed alternate test procedure compared to the performance of the reference method.
(d)
(2) The Regional ATP Coordinator or permitting authority will forward a copy of every approval and rejection notification to the National Alternate Test Procedure Coordinator.
(a)
(2)
(3)
(4)
(5)
(6)
(b)
(2)
(i)
(A) The analyst may only rely on QC tests and QC acceptance criteria in a method if it includes wastewater matrix QC tests and QC acceptance criteria (e.g., matrix spikes) and both initial (start-up) and ongoing QC tests and QC acceptance criteria.
(B) If the approved method does not contain QC tests and QC acceptance criteria or if the QC tests and QC acceptance criteria in the method do not meet the requirements of this section, then the analyst must employ QC tests published in the “equivalent” of a Part 136 method that has such QC, or the essential QC requirements specified at 136.7, as applicable. If the approved method is from a compendium or VCSB and the QA/QC requirements are published in other parts of that organization's compendium rather than within the Part 136 method then that part of the organization's compendium must be used for the QC tests.
(C) In addition, the analyst must perform ongoing QC tests, including assessment of performance of the modified method on the sample matrix (e.g., analysis of a matrix spike/matrix spike duplicate pair for every twenty samples), and analysis of an ongoing precision and recovery sample (e.g., laboratory fortified blank or blank spike) and a blank with each batch of 20 or fewer samples.
(D) If the performance of the modified method in the wastewater matrix or reagent water does not meet or exceed the QC acceptance criteria, the method modification may not be used.
(ii)
(3)
(4)
(i) Changes between manual method, flow analyzer, and discrete instrumentation.
(ii) Changes in chromatographic columns or temperature programs.
(iii) Changes between automated and manual sample preparation, such as digestions, distillations, and extractions; in-line sample preparation is an acceptable form of automated sample preparation for CWA methods.
(iv) In general, ICP-MS is a sensitive and selective detector for metal analysis; however isobaric interference can cause problems for quantitative determination, as well as identification based on the isotope pattern. Interference reduction technologies, such as collision cells or reaction cells, are designed to reduce the effect of spectroscopic interferences that may bias results for the element of interest. The use of interference reduction technologies is allowed, provided the method performance specifications relevant to ICP-MS measurements are met.
(v) The use of EPA Method 200.2 or the sample preparation steps from EPA Method 1638, including the use of closed-vessel digestion, is allowed for EPA Method 200.8, provided the method performance specifications relevant to the ICP-MS are met.
(vi) Changes in pH adjustment reagents. Changes in compounds used to adjust pH are acceptable as long as they do not produce interference. For example, using a different acid to adjust pH in colorimetric methods.
(vii) Changes in buffer reagents are acceptable provided that the changes do not produce interferences.
(viii) Changes in the order of reagent addition are acceptable provided that the change does not alter the chemistry and does not produce an interference. For example, using the same reagents, but adding them in different order, or preparing them in combined or separate solutions (so they can be added separately), is allowed, provided reagent stability or method performance is equivalent or improved.
(ix) Changes in calibration range (provided that the modified range covers any relevant regulatory limit and the method performance specifications for calibration are met).
(x) Changes in calibration model. (A) Linear calibration models do not adequately fit calibration data with one or two inflection points. For example, vendor-supplied data acquisition and processing software on some instruments may provide quadratic fitting functions to handle such situations. If the calibration data for a particular analytical method routinely display quadratic character, using quadratic fitting functions may be acceptable. In such cases, the minimum number of calibrators for second order fits should be six, and in no case should concentrations be extrapolated for instrument responses that exceed that of the most concentrated calibrator. Examples of methods with nonlinear calibration functions include chloride by SM4500-
(B) As an alternative to using the average response factor, the quality of the calibration may be evaluated using the Relative Standard Error (RSE). The acceptance criterion for the RSE is the same as the acceptance criterion forRelative Standard Deviation (RSD), in the method. RSE is calculated as:
(C) Using the RSE as a metric has the added advantage of allowing the same numerical standard to be applied to the calibration model, regardless of the form of the model. Thus, if a method states that the RSD should be ≤20% for the traditional linear model through the origin, then the RSE acceptance limit can remain ≤20% as well. Similarly, if a method provides an RSD acceptance limit of ≤15%, then that same figure can be used as the acceptance limit for the RSE. The RSE may be used as an alternative to correlation coefficients and coefficients of determination for evaluating calibration curves for any of the methods at part 136. If the method includes a numerical criterion for the RSD, then the same numerical value is used for the RSE. Some older methods do not include any criterion for the calibration curve—for these methods, if RSE is used the value should be ≤20%. Note that the use of the RSE is included as an alternative to the use of the correlation coefficient as a measure of the suitability of a calibration curve. It is not necessary to evaluate both the RSE and the correlation coefficient.
(xi) Changes in equipment such as equipment from a vendor different from the one specified in the method.
(xii) The use of micro or midi distillation apparatus in place of macro distillation apparatus.
(xiii) The use of prepackaged reagents.
(xiv) The use of digital titrators and methods where the underlying chemistry used for the determination is similar to that used in the approved method.
(xv) Use of selected ion monitoring (SIM) mode for analytes that cannot be effectively analyzed in full-scan mode and reach the required sensitivity. False positives are more of a concern when using SIM analysis, so at a minimum, one quantitation and two qualifying ions must be monitored for each analyte (unless fewer than three ions with intensity greater than 15% of the base peak are available). The ratio of each of the two qualifying ions to the quantitation ion must be evaluated and should agree with the ratio observed in an authentic standard within ±20 percent. Analyst judgment must be applied to the evaluation of ion ratios because the ratios can be affected by co-eluting compounds present in the sample matrix. The signal-to-noise ratio of the least sensitive ion should be at least 3:1. Retention time in the sample should match within 0.05 minute of an authentic standard analyzed under identical conditions. Matrix interferences can cause minor shifts in retention time and may be evident as shifts in the retention times of the internal standards. The total scan time should be such that a minimum of
(xvi) Changes are allowed in purge-and-trap sample volumes or operating conditions. Some examples are:
(A) Changes in purge time and purge-gas flow rate. A change in purge time and purge-gas flow rate is allowed provided that sufficient total purge volume is used to achieve the required minimum detectible concentration and calibration range for all compounds. In general, a purge rate in the range 20-200 mL/min and a total purge volume in the range 240-880 mL are recommended.
(B) Use of nitrogen or helium as a purge gas, provided that the required sensitivities for all compounds are met.
(C) Sample temperature during the purge state. Gentle heating of the sample during purging (e.g., 40 °C) increases purging efficiency of hydrophilic compounds and may improve sample-to-sample repeatability because all samples are purged under precisely the same conditions.
(D) Trap sorbent. Any trap design is acceptable, provided that the data acquired meet all QC criteria.
(E) Changes to the desorb time. Shortening the desorb time (e.g., from4 minutes to 1 minute) may not affect compound recoveries, and can shorten overall cycle time and significantly reduce the amount of water introduced to the analytical system, thus improving the precision of analysis, especially for water-soluble analytes. A desorb time of four minutes is recommended, however a shorter desorb time may be used, provided that all QC specifications in the method are met.
(F) Use of water management techniques is allowed. Water is always collected on the trap along with the analytes and is a significant interference for analytical systems (GC and GC/MS). Modern water management techniques (e.g., dry purge or condensation points) can remove moisture from the sample stream and improve analytical performance.
(xvii) The following modifications are allowable when performing EPA Method 625: The base/neutral and acid fractions may be added together and analyzed as one extract, provided that the analytes can be reliably identified and quantified in the combined extracts; the pH extraction sequence may be reversed to better separate acid and neutral components; neutral components may be extracted with either acid or base components; a smaller sample volume may be used to minimize matrix interferences provided matrix interferences are demonstrated and documented; alternative surrogate and internal standard concentrations other than those specified in the method are acceptable, provided that method performance is not degraded; an alternative concentration range may be used for the calibration other than the range specified in the method; the solvent for the calibration standards may be changed to match the solvent of the final sample extract.
(xviii) If the characteristics of a wastewater matrix prevent efficient recovery of organic pollutants and prevent the method from meeting QC requirements, the analyst may attempt to resolve the issue by adding salts to the sample, provided that such salts do not react with or introduce the target pollutant into the sample (as evidenced by the analysis of method blanks, laboratory control samples, and spiked samples that also contain such salts), and that all requirements of paragraph (b)(2) of this section are met. Samples having residual chlorine or other halogen must be dechlorinated prior to the addition of such salts.
(xix) If the characteristics of a wastewater matrix result in poor sample dispersion or reagent deposition on equipment and prevent the analyst from meeting QC requirements, the analyst may attempt to resolve the issue by adding a inert surfactant that does not affect the chemistry of the method, such as Brij-35 or sodium dodecyl sulfate (SDS), provided that such surfactant does not react with or introduce the target pollutant into the sample (as evidenced by the analysis of method blanks, laboratory control samples, and spiked samples that also contain such surfactant) and that all requirements of paragraph (b)(1) and (b)(2) of this section are met. Samples having residual chlorine or other halogen must be dechlorinated prior to the addition of such surfactant.
(xx) The use of gas diffusion (using pH change to convert the analyte to gaseous form and/or heat to separate an analyte contained in steam from the sample matrix) across a hydrophobic semi-permeable membrane to separate the analyte of interest from the sample matrix may be used in place of manual or automated distillation in methods for analysis such as ammonia, total cyanide, total Kjeldahl nitrogen, and total phenols. These procedures do not replace the digestion procedures specified in the approved methods and must be used in conjunction with those procedures.
(xxi) Changes in equipment operating parameters such as the monitoring wavelength of a colorimeter or the reaction time and temperature as needed to achieve the chemical reactions defined in the unmodified CWA method. For example, molybdenum blue phosphate methods have two absorbance maxima, one at about 660 nm and another at about 880 nm. The former is about 2.5 times less sensitive than the latter. Wavelength choice provides a cost-effective, dilution-free means to increase sensitivity of molybdenum blue phosphate methods.
(xxii) Interchange of oxidants, such as the use of titanium oxide in UV-assisted automated digestion of TOC and total phosphorus, as long as complete oxidation can be demonstrated.
(xxii) Use of an axially viewed torch with Method 200.7.
At 77 FR 29810, May 18, 2012, § 136.6 was revised to include two paragraphs designated (b)(4)(xxii).
The permittee/laboratory shall use suitable QA/QC procedures when conducting compliance analyses with any part 136 chemical method or an alternative method specified by the permitting authority. These QA/QC procedures are generally included in the analytical method or may be part of the methods compendium for approved part 136 methods from a consensus organization. For example, Standard Methods contains QA/QC procedures in the Part 1000 section of the Standard Methods Compendium. The permittee/laboratory shall follow these QA/QC procedures, as described in the method or methods compendium. If the method lacks QA/QC procedures, the permittee/laboratory has the following options to comply with the QA/QC requirements:
(a) Refer to and follow the QA/QC published in the “equivalent” EPA method for that parameter that has such QA/QC procedures;
(b) Refer to the appropriate QA/QC section(s) of an approved part 136 method from a consensus organization compendium;
(c)(1) Incorporate the following twelve quality control elements, where applicable, into the laboratory's documented standard operating procedure (SOP) for performing compliance analyses when using an approved part 136 method when the method lacks such QA/QC procedures. One or more of the twelve QC elements may not apply to a given method and may be omitted if a written rationale is provided indicating why the element(s) is/are inappropriate for a specific method.
(i) Demonstration of Capability (DOC);
(ii) Method Detection Limit (MDL);
(iii) Laboratory reagent blank (LRB), also referred to as method blank (MB);
(iv) Laboratory fortified blank (LFB), also referred to as a spiked blank, or laboratory control sample (LCS);
(v) Matrix spike (MS) and matrix spike duplicate (MSD), or laboratory fortified matrix (LFM) and LFM duplicate, may be used for suspected matrix interference problems to assess precision;
(vi) Internal standards (for GC/MS analyses), surrogate standards (for organic analysis) or tracers (for radiochemistry);
(vii) Calibration (initial and continuing), also referred to as initial calibration verification (ICV) and continuing calibration verification (CCV);
(viii) Control charts (or other trend analyses of quality control results);
(ix) Corrective action (root cause analysis);
(x) QC acceptance criteria;
(xi) Definitions of preparation and analytical batches that may drive QC frequencies; and
(xii) Minimum frequency for conducting all QC elements.
(2) These twelve quality control elements must be clearly documented in the written standard operating procedure for each analytical method not containing QA/QC procedures, where applicable.
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 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 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 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: 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 °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:
6.3.1Coconut 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, chloromethane, 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
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 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 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
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
8.3.3Compare 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 dealing 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-dichlorobutane 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, 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 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
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 reported with 99% confidence that the value is above zero.
12.2This method is recommended for use in the concentration range from the MDL to 1000×MDL. Direct aqueous injection techniques should be used to measure concentration levels above 1000×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 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 mammalian 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 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.
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 equivalent.
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 standard 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-dichlorobenzene, 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.
6.6.1Place 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. α, α, α,-trifluorotoluene) that encompass the range of the temperature program used in this method. From stock standard solutions prepared as in Section 6.6, 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 mg/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).
9.1The 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 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 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
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.
8.3.2Analyze 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 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 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 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 range pH paper. Samples for acrolein analysis receiving no pH adjustment must be analyzed within 3 days of sampling.
9.3Grab samples must be collected in glass containers having a total volume of at
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 zero.
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.
1.1This 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 range of concentrations found in real samples or should define the working range of the detector.
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
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.
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
8.6.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 may be analyzed to assess the precision of the environmental measurements. When doubt exists over the identification of a peak
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 concentration in 5 to 10 min. At the proper rate of distillation the balls of the column will actively chatter but the chambers will
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 achieved by this column is shown in Figure 2.
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 Means of Electron Capture Gas Chromatography,”
4. ASTM Annual Book of Standards, Part 31, D3694-78. “Standard Practices for Preparation of Sample Containers and for Preservation of Organic Constituents,” American
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 interferences, but unique samples may require additional cleanup approaches to achieve the MDL listed in Table 1.
3.3Some dye plant effluents contain large amounts of components with retention 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—Bioanalytical 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 and 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 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 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,
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 potential to +0.6 V and reanalyze. If the benzidine peak is still obscured by 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 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 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 12.1) 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 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
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
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 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 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 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 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 sensitive.
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) 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.
10.5Add 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-nitrosodiphenylamine 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 nitrosamines:
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 nitrosamines:
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-nitrosodiphenylamine is chromatographed and detected as diphenylamine. Accurate determination depends on removal of diphenylamine 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 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.
12.3Calibrate 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 over the range 0.8 to 55 µg/L.
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 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 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 chromatographic 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 seal.
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%); Toxaphene recovery was demonstrated linear over the range of 10×MDL to 1000×MDL.
14.3This method was tested by 20 laboratories using reagent water, drinking water, surface water, and three industrial
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 activated 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. Table 1 summarizes the recommended operating conditions for the gas chromatograph.
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 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 liquid or gas chromatographic 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 these conditions. The UV detector is recommended for the determination of naphthalene, acenaphthylene, acenapthene, and
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 sample 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 column, 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 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 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 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 × 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 microcoulometric. These detectors have proven effective 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 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. 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
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 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 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,
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 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 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 °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.
6.5.3Stock 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 plastic 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 minimizing 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 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.
9.1Grab 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) 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.
10.6Pour 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 wastewaters 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 Octachlorodibenzo-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., “Interpretation 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 chromatographic/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-bromofluorobenzene (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 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 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 benzo(a)anthracene; and benzo(b)fluoranthene and benzo(k)fluoranthene. The gas chromatographic retention time and mass spectra for these pairs of compounds are not sufficiently 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, α-BHC, β-BHC, δ-BHC, γ-BHC, dibenzo(a,h)anthracene, N-nitrosodimethylamine, 4,4′-DDT, and polychlorinated biphenyls (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 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. Guidelines for the use of alternate column packings 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 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 (
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.
12.4.1.5Rinse 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 (
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).
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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 interferences 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 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 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 minimum.
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, bromomethane, chloroethane, 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 standards used for volatiles analyses are bromochloromethane, 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 records 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 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.
9.1Grab 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 calibration curve given in Figure 5 indicates a concentration of 31.8 µg/L.
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 chromatographically 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, dibenzo(a,h)anthracene, 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 capillary 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 between m/z 441-442 less than 10 percent of the height of the 441 peak), backgound corrected mass spectrum from 50 ng decafluorotriphenylphosphine (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 prepared from materials of known purity and composition. 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
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
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
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 µg/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
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,
(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 (χ
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.
1.1Inductively coupled plasma-atomic emission spectrometry (ICP-AES) is used to determine metals and some nonmetals in solution. This method is a consolidation of existing methods for water, wastewater, and solid wastes.
1.2For reference where this method is approved for use in compliance monitoring programs [e.g., Clean Water Act (NPDES) or Safe Drinking Water Act (SDWA)] consult both the appropriate sections of the Code of Federal Regulation (40 CFR Part 136 Table 1B for NPDES, and Part 141 § 141.23 for drinking water), and the latest
1.3ICP-AES can be used to determine dissolved analytes in aqueous samples after suitable filtration and acid preservation. To reduce potential interferences, dissolved solids should be <0.2% (w/v) (Section 4.2).
1.4With the exception of silver, where this method is approved for the determination of certain metal and metalloid contaminants in drinking water, samples may be analyzed directly by pneumatic nebulization without acid digestion if the sample has been properly preserved with acid and has turbidity of <1 NTU at the time of analysis. This total recoverable determination procedure is referred to as “direct analysis”. However, in the determination of some primary drinking water metal contaminants, preconcentration of the sample may be required prior to analysis in order to meet drinking water acceptance performance criteria (Sections 11.2.2 through 11.2.7).
1.5For the determination of total recoverable analytes in aqueous and solid samples a digestion/extraction is required prior to analysis when the elements are not in solution (e.g., soils, sludges, sediments and aqueous samples that may contain particulate and suspended solids). Aqueous samples containing suspended or particulate material 1% (w/v) should be extracted as a solid type sample.
1.6When determining boron and silica in aqueous samples, only plastic, PTFE or quartz labware should be used from time of sample collection to completion of analysis. For accurate determination of boron in solid samples only quartz or PTFE beakers should be used during acid extraction with immediate transfer of an extract aliquot to a plastic centrifuge tube following dilution of the extract to volume. When possible, borosilicate glass should be avoided to prevent contamination of these analytes.
1.7Silver is only slightly soluble in the presence of chloride unless there is a sufficient chloride concentration to form the soluble chloride complex. Therefore, low recoveries of silver may occur in samples, fortified sample matrices and even fortified blanks if determined as a dissolved analyte or by “direct analysis” where the sample has not been processed using the total recoverable mixed acid digestion. For this reason it is recommended that samples be digested prior to the determination of silver. The total recoverable sample digestion procedure given in this method is suitable for the determination of silver in aqueous samples containing concentrations up to 0.1 mg/L. For the analysis of wastewater samples containing higher concentrations of silver, succeeding smaller volume, well mixed aliquots
1.8The total recoverable sample digestion procedure given in this method will solubilize and hold in solution only minimal concentrations of barium in the presence of free sulfate. For the analysis of barium in samples having varying and unknown concentrations of sulfate, analysis should be completed as soon as possible after sample preparation.
1.9The total recoverable sample digestion procedure given in this method is not suitable for the determination of volatile organo-mercury compounds. However, if digestion is not required (turbidity <1 NTU), the combined concentrations of inorganic and organo-mercury in solution can be determined by “direct analysis” pneumatic nebulization provided the sample solution is adjusted to contain the same mixed acid (HNO
1.10Detection limits and linear ranges for the elements will vary with the wavelength selected, the spectrometer, and the matrices. Table 1 provides estimated instrument detection limits for the listed wavelengths.
1.11Users of the method data should state the data-quality objectives prior to analysis. Users of the method must document and have on file the required initial demonstration performance data described in Section 9.2 prior to using the method for analysis.
2.1An aliquot of a well mixed, homogeneous aqueous or solid sample is accurately weighed or measured for sample processing. For total recoverable analysis of a solid or an aqueous sample containing undissolved material, analytes are first solubilized by gentle refluxing with nitric and hydrochloric acids. After cooling, the sample is made up to volume, is mixed and centrifuged or allowed to settle overnight prior to analysis. For the determination of dissolved analytes in a filtered aqueous sample aliquot, or for the “direct analysis” total recoverable determination of analytes in drinking water where sample turbidity is <1 NTU, the sample is made ready for analysis by the appropriate addition of nitric acid, and then diluted to a predetermined volume and mixed before analysis.
2.2The analysis described in this method involves multielemental determinations by ICP-AES using sequential or simultaneous instruments. The instruments measure characteristic atomic-line emission spectra by optical spectrometry. Samples are nebulized and the resulting aerosol is transported to the plasma torch. Element specific emission spectra are produced by a radio-frequency inductively coupled plasma. The spectra are dispersed by a grating spectrometer, and the intensities of the line spectra are monitored at specific wavelengths by a photosensitive device. Photocurrents from the photosensitive device are processed and controlled by a computer system. A background correction technique is required to compensate for variable background contribution to the determination of the analytes. Background must be measured adjacent to the analyte wavelength during analysis. Various interferences must be considered and addressed appropriately as discussed in Sections 4.0, 7.0, 9.0, 10.0, and 11.0.
3.1Calibration Blank—A volume of reagent water acidified with the same acid matrix as in the calibration standards. The calibration blank is a zero standard and is used to calibrate the ICP instrument (Section 7.10.1).
3.2Calibration Standard (CAL)—A solution prepared from the dilution of stock standard solutions. The CAL solutions are used to calibrate the instrument response with respect to analyte concentration (Section 7.9).
3.3Dissolved Analyte—The concentration of analyte in an aqueous sample that will pass through a 0.45 µm membrane filter assembly prior to sample acidification (Section 11.1).
3.4Field Reagent Blank (FRB)—An aliquot of reagent water or other blank matrix that is placed in a sample container in the laboratory and treated as a sample in all respects, including shipment to the sampling site, exposure to the sampling site conditions, storage, preservation, and all analytical procedures. The purpose of the FRB is to determine if method analytes or other interferences are present in the field environment (Section 8.5).
3.5Instrument Detection Limit (IDL)—The concentration equivalent to the analyte signal which is equal to three times the standard deviation of a series of 10 replicate measurements of the calibration blank signal at the same wavelength (Table 1.).
3.6Instrument Performance Check (IPC) Solution—A solution of method analytes, used to evaluate the performance of the instrument system with respect to a defined set of method criteria (Sections 7.11 and 9.3.4).
3.7Internal Standard—Pure analyte(s) added to a sample, extract, or standard solution in known amount(s) and used to measure the relative responses of other method analytes that are components of the same sample or solution. The internal standard must be an analyte that is not a sample component (Section 11.5).
3.8Laboratory Duplicates (LD1 and LD2)—Two aliquots of the same sample taken in the laboratory and analyzed separately with identical procedures. Analyses of LD1 and LD2 indicate precision associated with laboratory procedures, but not with sample collection, preservation, or storage procedures.
3.9Laboratory Fortified Blank (LFB)—An aliquot of LRB to which known quantities of the method analytes are added in the laboratory. The LFB is analyzed exactly like a sample, and its purpose is to determine whether the methodology is in control and whether the laboratory is capable of making accurate and precise measurements (Sections 7.10.3 and 9.3.2).
3.10Laboratory Fortified Sample Matrix (LFM)—An aliquot of an environmental sample to which known quantities of the method analytes are added in the laboratory. The LFM is analyzed exactly like a sample, and its purpose is to determine whether the sample matrix contributes bias to the analytical results. The background concentrations of the analytes in the sample matrix must be determined in a separate aliquot and the measured values in the LFM corrected for background concentrations (Section 9.4).
3.11Laboratory Reagent Blank (LRB)—An aliquot of reagent water or other blank matrices that are treated exactly as a sample including exposure to all glassware, equipment, solvents, reagents, and internal standards that are used with other samples. The LRB is used to determine if method analytes or other interferences are present in the laboratory environment, reagents, or apparatus (Sections 7.10.2 and 9.3.1).
3.12Linear Dynamic Range (LDR)—The concentration range over which the instrument response to an analyte is linear (Section 9.2.2).
3.13Method Detection Limit (MDL)—The minimum concentration of an analyte that can be identified, measured, and reported with 99% confidence that the analyte concentration is greater than zero (Section 9.2.4 and Table 4.).
3.14Plasma Solution—A solution that is used to determine the optimum height above the work coil for viewing the plasma (Sections 7.15 and 10.2.3).
3.15Quality Control Sample (QCS)—A solution of method analytes of known concentrations which is used to fortify an aliquot of LRB or sample matrix. The QCS is obtained from a source external to the laboratory and different from the source of calibration standards. It is used to check either laboratory or instrument performance (Sections 7.12 and 9.2.3).
3.16Solid Sample—For the purpose of this method, a sample taken from material classified as soil, sediment or sludge.
3.17Spectral Interference Check (SIC) Solution—A solution of selected method analytes of higher concentrations which is used to evaluate the procedural routine for correcting known interelement spectral interferences with respect to a defined set of method criteria (Sections 7.13, 7.14 and 9.3.5).
3.18Standard Addition—The addition of a known amount of analyte to the sample in order to determine the relative response of the detector to an analyte within the sample matrix. The relative response is then used to assess either an operative matrix effect or the sample analyte concentration (Sections 9.5.1 and 11.5).
3.19Stock Standard Solution—A concentrated solution containing one or more method analytes prepared in the laboratory using assayed reference materials or purchased from a reputable commercial source (Section 7.8).
3.20Total Recoverable Analyte—The concentration of analyte determined either by “direct analysis” of an unfiltered acid preserved drinking water sample with turbidity of <1 NTU (Section 11.2.1), or by analysis of the solution extract of a solid sample or an unfiltered aqueous sample following digestion by refluxing with hot dilute mineral acid(s) as specified in the method (Sections 11.2 and 11.3).
3.21Water Sample—For the purpose of this method, a sample taken from one of the following sources: drinking, surface, ground, storm runoff, industrial or domestic wastewater.
4.1Spectral interferences are caused by background emission from continuous or recombination phenomena, stray light from the line emission of high concentration elements, overlap of a spectral line from another element, or unresolved overlap of molecular band spectra.
4.1.1Background emission and stray light can usually be compensated for by subtracting the background emission determined by measurement(s) adjacent to the analyte wavelength peak. Spectral scans of samples or single element solutions in the analyte regions may indicate not only when alternate wavelengths are desirable because of severe spectral interference, but also will show whether the most appropriate estimate of the background emission is provided by an interpolation from measurements on both sides of the wavelength peak or by the measured emission on one side or the other. The location(s) selected for the measurement of background intensity will be determined by
4.1.2Spectral overlaps may be avoided by using an alternate wavelength or can be compensated for by equations that correct for interelement contributions, which involves measuring the interfering elements. Some potential on-line spectral interferences observed for the recommended wavelengths are given in Table 2. When operative and uncorrected, these interferences will produce false-positive determinations and be reported as analyte concentrations. The interferences listed are only those that occur between method analytes. Only interferences of a direct overlap nature that were observed with a single instrument having a working resolution of 0.035 nm are listed. More extensive information on interferant effects at various wavelengths and resolutions is available in Boumans' Tables.
4.1.3When interelement corrections are applied, there is a need to verify their accuracy by analyzing spectral interference check solutions as described in Section 7.13. Interelement corrections will vary for the same emission line among instruments because of differences in resolution, as determined by the grating plus the entrance and exit slit widths, and by the order of dispersion. Interelement corrections will also vary depending upon the choice of background correction points. Selecting a background correction point where an interfering emission line may appear should be avoided when practical. Interelement corrections that constitute a major portion of an emission signal may not yield accurate data. Users should not forget that some samples may contain uncommon elements that could contribute spectral interferences.
4.1.4The interference effects must be evaluated for each individual instrument whether configured as a sequential or simultaneous instrument. For each instrument, intensities will vary not only with optical resolution but also with operating conditions (such as power, viewing height and argon flow rate). When using the recommended wavelengths given in Table 1, the analyst is required to determine and document for each wavelength the effect from the known interferences given in Table 2, and to utilize a computer routine for their automatic correction on all analyses. To determine the appropriate location for off-line background correction, the user must scan the area on either side adjacent to the wavelength and record the apparent emission intensity from all other method analytes. This spectral information must be documented and kept on file. The location selected for background correction must be either free of off-line interelement spectral interference or a computer routine must be used for their automatic correction on all determinations. If a wavelength other than the recommended wavelength is used, the user must determine and document both the on-line and off-line spectral interference effect from all method analytes and provide for their automatic correction on all analyses. Tests to determine the spectral interference must be done using analyte concentrations that will adequately describe the interference. Normally, 100 mg/L single element solutions are sufficient, however, for analytes such as iron that may be found at high concentration a more appropriate test would be to use a concentration near the upper LDR limit. See Section 10.4 for required spectral interference test criteria.
4.1.5When interelement corrections are not used, either on-going SIC solutions (Section 7.14) must be analyzed to verify the absence of interelement spectral interference or a computer software routine must be employed for comparing the determinative data to limits files for notifying the analyst when an interfering element is detected in the sample at a concentration that will produce either an apparent false positive concentration, greater than the analyte IDL, or false negative analyte concentration, less than the 99% lower control limit of the calibration blank. When the interference accounts for 10% or more of the analyte concentration, either an alternate wavelength free of interference or another approved test procedure must be used to complete the analysis. For example, the copper peak at 213.853 nm could be mistaken for the zinc peak at 213.856 nm in solutions with high copper and low zinc concentrations. For this example, a spectral scan in the 213.8 nm region would not reveal the misidentification because a single peak near the zinc location would be observed. The possibility of this misidentification of copper for the zinc peak at 213.856 nm can be identified by measuring the copper at another emission line, e.g., 324.754 nm. Users should be aware that, depending upon the instrumental resolution, alternate wavelengths with adequate sensitivity and freedom from interference may not be available for all matrices. In these circumstances the analyte must be determined using another approved test procedure.
4.2Physical interferences are effects associated with the sample nebulization and transport processes. Changes in viscosity and surface tension can cause significant inaccuracies, especially in samples containing
4.3Chemical interferences include molecular-compound formation, ionization effects, and solute-vaporization effects. Normally, these effects are not significant with the ICP-AES technique. If observed, they can be minimized by careful selection of operating conditions (such as incident power and observation height), by buffering of the sample, by matrix matching, and by standard-addition procedures. Chemical interferences are highly dependent on matrix type and the specific analyte element.
4.4Memory interferences result when analytes in a previous sample contribute to the signals measured in a new sample. Memory effects can result from sample deposition on the uptake tubing to the nebulizer, and from the buildup of sample material in the plasma torch and spray chamber. The site where these effects occur is dependent on the element and can be minimized by flushing the system with a rinse blank between samples (Section 7.10.4). The possibility of memory interferences should be recognized within an analytical run and suitable rinse times should be used to reduce them. The rinse times necessary for a particular element must be estimated prior to analysis. This may be achieved by aspirating a standard containing elements corresponding to either their LDR or a concentration ten times those usually encountered. The aspiration time should be the same as a normal sample analysis period, followed by analysis of the rinse blank at designated intervals. The length of time required to reduce analyte signals to within a factor of two of the method detection limit, should be noted. Until the required rinse time is established, this method requires a rinse period of at least 60 seconds between samples and standards. If a memory interference is suspected, the sample must be re-analyzed after a long rinse period.
5.1The toxicity or carcinogenicity of each reagent used in this method have not been fully established. Each chemical should be regarded as a potential health hazard and exposure to these compounds should be as low as reasonably achievable. Each laboratory is responsible for maintaining a current awareness file of OSHA regulations regarding the safe handling of the chemicals specified in this method.
5.2The acidification of samples containing reactive materials may result in the release of toxic gases, such as cyanides or sulfides. Acidification of samples should be done in a fume hood.
5.3All personnel handling environmental samples known to contain or to have been in contact with human waste should be immunized against known disease causative agents.
5.4The inductively coupled plasma should only be viewed with proper eye protection from the ultraviolet emissions.
5.5It is the responsibility of the user of this method to comply with relevant disposal and waste regulations. For guidance see Sections 14.0 and 15.0.
6.1Inductively coupled plasma emission spectrometer:
6.1.1Computer-controlled emission spectrometer with background-correction capability.
6.1.2Radio-frequency generator compliant with FCC regulations.
6.1.3Argon gas supply—High purity grade (99.99%). When analyses are conducted frequently, liquid argon is more economical and requires less frequent replacement of tanks than compressed argon in conventional cylinders.
6.1.4A variable speed peristaltic pump is required to deliver both standard and sample solutions to the nebulizer.
6.1.5(Optional) Mass flow controllers to regulate the argon flow rates, especially the aerosol transport gas, are highly recommended. Their use will provide more exacting control of reproducible plasma conditions.
6.2Analytical balance, with capability to measure to 0.1 mg, for use in weighing solids, for preparing standards, and for determining dissolved solids in digests or extracts.
6.3A temperature adjustable hot plate capable of maintaining a temperature of 95 °C.
6.4(Optional) A temperature adjustable block digester capable of maintaining a temperature of 95 °C and equipped with 250 mL constricted digestion tubes.
6.5(Optional) A steel cabinet centrifuge with guard bowl, electric timer and brake.
6.6A gravity convection drying oven with thermostatic control capable of maintaining 180 °C ± 5 °C.
6.7(Optional) An air displacement pipetter capable of delivering volumes ranging from 0.1-2500 µL with an assortment of high quality disposable pipet tips.
6.8Mortar and pestle, ceramic or nonmetallic material.
6.9Polypropylene sieve, 5-mesh (4 mm opening).
6.10Labware—For determination of trace levels of elements, contamination and loss are of prime consideration. Potential contamination sources include improperly cleaned laboratory apparatus and general contamination within the laboratory environment from dust, etc. A clean laboratory work area designated for trace element sample handling must be used. Sample containers can introduce positive and negative errors in the determination of trace elements by contributing contaminants through surface desorption or leaching, or depleting element concentrations through adsorption processes. All reusable labware (glass, quartz, polyethylene, PTFE, FEP, etc.) should be sufficiently clean for the task objectives. Several procedures found to provide clean labware include washing with a detergent solution, rinsing with tap water, soaking for four hours or more in 20% (v/v) nitric acid or a mixture of HNO
6.10.1Glassware—Volumetric flasks, graduated cylinders, funnels and centrifuge tubes (glass and/or metal-free plastic).
6.10.2Assorted calibrated pipettes.
6.10.3Conical Phillips beakers (Corning 1080-250 or equivalent), 250 mL with 50 mm watch glasses.
6.10.4Griffin beakers, 250 mL with 75 mm watch glasses and (optional) 75 mm ribbed watch glasses.
6.10.5(Optional) PTFE and/or quartz Griffin beakers, 250 mL with PTFE covers.
6.10.6Evaporating dishes or high-form crucibles, porcelain, 100 mL capacity.
6.10.7Narrow-mouth storage bottles, FEP (fluorinated ethylene propylene) with screw closure, 125 mL to 1 L capacities.
6.10.8One-piece stem FEP wash bottle with screw closure, 125 mL capacity.
7.1Reagents may contain elemental impurities which might affect analytical data. Only high-purity reagents that conform to the American Chemical Society specifications
7.2Hydrochloric acid, concentrated (sp.gr. 1.19)—HCl.
7.2.1Hydrochloric acid (1+1)—Add 500 mL concentrated HCl to 400 mL reagent water and dilute to 1 L.
7.2.2Hydrochloric acid (1+4)—Add 200 mL concentrated HCl to 400 mL reagent water and dilute to 1 L.
7.2.3Hydrochloric acid (1+20)—Add 10 mL concentrated HCl to 200 mL reagent water.
7.3Nitric acid, concentrated (sp.gr. 1.41)—HNO
7.3.1Nitric acid (1+1)—Add 500 mL concentrated HNO
7.3.2Nitric acid (1+2)—Add 100 mL concentrated HNO
7.3.3Nitric acid (1+5)—Add 50 mL concentrated HNO
7.3.4Nitric acid (1+9)—Add 10 mL concentrated HNO
7.4Reagent water. All references to water in this method refer to ASTM Type I grade water.
7.5Ammonium hydroxide, concentrated (sp.gr. 0.902).
7.6Tartaric acid, ACS reagent grade.
7.7Hydrogen peroxide, 50%, stabilized certified reagent grade.
7.8Standard Stock Solutions—Stock standards may be purchased or prepared from ultra-high purity grade chemicals (99.99-99.999% pure). All compounds must be dried for one hour at 105 °C, unless otherwise specified. It is recommended that stock solutions be stored in FEP bottles. Replace stock standards when succeeding dilutions for preparation of calibration standards cannot be verified.
CAUTION: Many of these chemicals are extremely toxic if inhaled or swallowed (Section 5.1). Wash hands thoroughly after handling.
Typical stock solution preparation procedures follow for 1 L quantities, but for the purpose of pollution prevention, the analyst is encouraged to prepare smaller quantities when possible. Concentrations are calculated based upon the weight of the pure element or upon the weight of the compound multiplied
From pure element,
7.8.1Aluminum solution, stock, 1 mL = 1000 µg Al: Dissolve 1.000 g of aluminum metal, weighed accurately to at least four significant figures, in an acid mixture of 4.0 mL of (1+1) HCl and 1 mL of concentrated HNO
7.8.2Antimony solution, stock, 1 mL = 1000 µg Sb: Dissolve 1.000 g of antimony powder, weighed accurately to at least four significant figures, in 20.0 mL (1+1) HNO
7.8.3Arsenic solution, stock, 1 mL = 1000 µg As: Dissolve 1.320 g of As
7.8.4Barium solution, stock, 1 mL = 1000 µg Ba: Dissolve 1.437 g BaCO
7.8.5Beryllium solution, stock, 1 mL = 1000 µg Be:
7.8.6Boron solution, stock, 1 mL = 1000 µg B:
7.8.7Cadmium solution, stock, 1 mL = 1000 µg Cd: Dissolve 1.000 g Cd metal, acid cleaned with (1+9) HNO
7.8.8Calcium solution, stock, 1 mL = 1000 µg Ca: Suspend 2.498 g CaCO
7.8.9Cerium solution, stock, 1 mL = 1000 µg Ce: Slurry 1.228 g CeO
7.8.10Chromium solution, stock, 1 mL = 1000 µg Cr: Dissolve 1.923 g CrO
7.8.11Cobalt solution, stock, 1 mL = 1000 µg Co: Dissolve 1.000 g Co metal, acid cleaned with (1+9) HNO
7.8.12Copper solution, stock, 1 mL = 1000 µg Cu: Dissolve 1.000 g Cu metal, acid cleaned with (1+9) HNO
7.8.13Iron solution, stock, 1 mL = 1000 µg Fe: Dissolve 1.000 g Fe metal, acid cleaned with (1+1) HCl, weighed accurately to four significant figures, in 100 mL (1+1) HCl with heating to effect dissolution. Let solution cool and dilute with reagent water in a 1 L volumetric flask.
7.8.14Lead solution, stock, 1 mL = 1000 µg Pb: Dissolve 1.599 g Pb(NO
7.8.15Lithium solution, stock, 1 mL = 1000 µg Li: Dissolve 5.324 g Li
7.8.16Magnesium solution, stock, 1 mL = 1000 µg Mg: Dissolve 1.000 g cleanly polished Mg ribbon, accurately weighed to at least four significant figures, in slowly added 5.0 mL (1+1) HCl (CAUTION: reaction is vigorous). Add 20.0 mL (1+1) HNO
7.8.17Manganese solution, stock, 1 mL = 1000 µg Mn: Dissolve 1.000 g of manganese metal, weighed accurately to at least four significant figures, in 50 mL (1+1) HNO
7.8.18Mercury solution, stock, 1 mL = 1000 µg Hg:
7.8.19Molybdenum solution, stock, 1 mL = 1000 µg Mo: Dissolve 1.500 g MoO
7.8.20Nickel solution, stock, 1 mL = 1000 µg Ni: Dissolve 1.000 g of nickel metal, weighed accurately to at least four significant figures, in 20.0 mL hot concentrated HNO
7.8.21Phosphorus solution, stock, 1 mL = 1000 µg P: Dissolve 3.745 g NH
7.8.22Potassium solution, stock, 1 mL = 1000 µg K: Dissolve 1.907 g KCl (K fraction = 0.5244) dried at 110 °C, weighed accurately to at least four significant figures, in reagent water, add 20 mL (1+1) HCl and dilute to volume in a 1 L volumetric flask with reagent water.
7.8.23Selenium solution, stock, 1 mL = 1000 µg Se: Dissolve 1.405 g SeO
7.8.24Silica solution, stock, 1 mL = 1000 µg SiO
7.8.25Silver solution, stock, 1 mL = 1000 µg Ag: Dissolve 1.000 g Ag metal, weighed accurately to at least four significant figures, in 80 mL (1+1) HNO
7.8.26Sodium solution, stock, 1 mL = 1000 µg Na: Dissolve 2.542 g NaCl (Na fraction = 0.3934), weighed accurately to at least four significant figures, in reagent water. Add 10.0 mL concentrated HNO
7.8.27Strontium solution, stock, 1 mL = 1000 µg Sr: Dissolve 1.685 g SrCO
7.8.28Thallium solution, stock, 1 mL = 1000 µg Tl: Dissolve 1.303 g TlNO
7.8.29Tin solution, stock, 1 mL = 1000 µg Sn: Dissolve 1.000 g Sn shot, weighed accurately to at least four significant figures, in an acid mixture of 10.0 mL concentrated HCl and 2.0 mL (1+1) HNO
7.8.30Titanium solution, stock, 1 mL = 1000 µg Ti:
7.8.31Vanadium solution, stock, 1 mL = 1000 µg V: Dissolve 1.000 g V metal, acid cleaned with (1+9) HNO
7.8.32Yttrium solution, stock 1 mL = 1000 µg Y: Dissolve 1.270 g Y
7.8.33Zinc solution, stock, 1 mL = 1000 µg Zn: Dissolve 1.000 g Zn metal, acid cleaned with (1+9) HNO
7.9Mixed Calibration Standard Solutions—For the analysis of total recoverable digested samples prepare mixed calibration standard solutions (see Table 3) by combining appropriate volumes of the stock solutions in 500 mL volumetric flasks containing 20 mL (1+1) HNO
Note: If the addition of silver to the recommended mixed-acid calibration standard results in an initial precipitation, add 15 mL of reagent water and warm the flask until the solution clears. For this acid combination, the silver concentration should be limited to 0.5 mg/L.
7.10Blanks—Four types of blanks are required for the analysis. The calibration blank is used in establishing the analytical curve, the laboratory reagent blank is used to assess possible contamination from the sample preparation procedure, the laboratory fortified blank is used to assess routine laboratory performance and a rinse blank is used to flush the instrument uptake system and nebulizer between standards, check solutions, and samples to reduce memory interferences.
7.10.1The calibration blank for aqueous samples and extracts is prepared by acidifying reagent water to the same concentrations of the acids as used for the standards. The calibration blank should be stored in a FEP bottle.
7.10.2The laboratory reagent blank (LRB) must contain all the reagents in the same volumes as used in the processing of the samples. The LRB must be carried through the same entire preparation scheme as the samples including sample digestion, when applicable.
7.10.3The laboratory fortified blank (LFB) is prepared by fortifying an aliquot of the laboratory reagent blank with all analytes to a suitable concentration using the following recommended criteria: Ag 0.1 mg/L, K 5.0 mg/L and all other analytes 0.2 mg/L or a concentration approximately 100 times their respective MDL, whichever is greater. The LFB must be carried through the same entire preparation scheme as the samples including sample digestion, when applicable.
7.10.4The rinse blank is prepared by acidifying reagent water to the same concentrations of acids as used in the calibration blank and stored in a convenient manner.
7.11Instrument Performance Check (IPC) Solution—The IPC solution is used to periodically verify instrument performance during analysis. It should be prepared in the same acid mixture as the calibration standards by combining method analytes at appropriate concentrations. Silver must be limited to <0.5 mg/L; while potassium and phosphorus because of higher MDLs and silica because of potential contamination should be at concentrations of 10 mg/L. For other analytes a concentration of 2 mg/L is recommended. The IPC solution should be prepared from the same standard stock solutions used to prepare the calibration standards and stored in an FEP bottle. Agency programs may specify or request that additional instrument performance check solutions be prepared at specified concentrations in order to meet particular program needs.
7.12Quality Control Sample (QCS)—Analysis of a QCS is required for initial and periodic verification of calibration standards or stock standard solutions in order to verify instrument performance. The QCS must be obtained from an outside source different from the standard stock solutions and prepared in the same acid mixture as the calibration standards. The concentration of the analytes in the QCS solution should be 1 mg/L, except silver, which must be limited to a concentration of 0.5 mg/L for solution stability. The QCS solution should be stored in a FEP bottle and analyzed as needed to meet data-quality needs. A fresh solution should be prepared quarterly or more frequently as needed.
7.13Spectral Interference Check (SIC) Solutions—When interelement corrections are applied, SIC solutions are needed containing
7.13.1SIC solutions containing (a) 300 mg/L Fe; (b) 200 mg/L AL; (c) 50 mg/L Ba; (d) 50 mg/L Be; (e) 50 mg/L Cd; (f) 50 mg/L Ce; (g) 50 mg/L Co; (h) 50 mg/L Cr; (i) 50 mg/L Cu; (j) 50 mg/L Mn; (k) 50 mg/L Mo; (l) 50 mg/L Ni; (m) 50 mg/L Sn; (n) 50 mg/L SiO
Note: If wavelengths other than those recommended in Table 1 are used, other solutions different from those above (a through q) may be required.
7.13.2For interferences from iron and aluminum, only those correction factors (positive or negative) when multiplied by 100 to calculate apparent analyte concentrations that exceed the determined analyte IDL or fall below the lower 3-sigma control limit of the calibration blank need be tested on a daily basis.
7.13.3For the other interfering elements, only those correction factors (positive or negative) when multiplied by 10 to calculate apparent analyte concentrations that exceed the determined analyte IDL or fall below the lower 3-sigma control limit of the calibration blank need be tested on a daily basis.
7.13.4If the correction routine is operating properly, the determined apparent analyte(s) concentration from analysis of each interference solution (a through q) should fall within a specific concentration range bracketing the calibration blank. This concentration range is calculated by multiplying the concentration of the interfering element by the value of the correction factor being tested and dividing by 10. If after subtraction of the calibration blank the apparent analyte concentration is outside (above or below) this range, a change in the correction factor of more than 10% should be suspected. The cause of the change should be determined and corrected and the correction factor should be updated.
Note: The SIC solution should be analyzed more than once to confirm a change has occurred with adequate rinse time between solutions and before subsequent analysis of the calibration blank.
7.13.5If the correction factors tested on a daily basis are found to be within the 10% criteria for five consecutive days, the required verification frequency of those factors in compliance may be extended to a weekly basis. Also, if the nature of the samples analyzed is such (e.g., finished drinking water) that they do not contain concentrations of the interfering elements at the 10 mg/L level, daily verification is not required; however, all interelement spectral correction factors must be verified annually and updated, if necessary.
7.13.6If the instrument does not display negative concentration values, fortify the SIC solutions with the elements of interest at 1 mg/L and test for analyte recoveries that are below 95%. In the absence of measurable analyte, over-correction could go undetected because a negative value could be reported as zero.
7.14For instruments without interelement correction capability or when interelement corrections are not used, SIC solutions (containing similar concentrations of the major components in the samples, e.g., 10 mg/L) can serve to verify the absence of effects at the wavelengths selected. These data must be kept on file with the sample analysis data. If the SIC solution confirms an operative interference that is 10% of the analyte concentration, the analyte must be determined using a wavelength and background correction location free of the interference or by another approved test procedure. Users are advised that high salt concentrations can cause analyte signal suppressions and confuse interference tests.
7.15Plasma Solution—The plasma solution is used for determining the optimum viewing height of the plasma above the work coil prior to using the method (Section 10.2). The solution is prepared by adding a 5 mL aliquot from each of the stock standard solutions of arsenic, lead, selenium, and thallium to a mixture of 20 mL (1+1) nitric acid and 20 mL (1+1) hydrochloric acid and diluting to 500 mL with reagent water. Store in a FEP bottle.
8.1Prior to the collection of an aqueous sample, consideration should be given to the type of data required, (
8.2For the determination of the dissolved elements, the sample must be filtered through a 0.45 µm pore diameter membrane filter at the time of collection or as soon thereafter as practically possible. (Glass or plastic filtering apparatus are recommended
8.3For the determination of total recoverable elements in aqueous samples, samples are not filtered, but acidified with (1+1) nitric acid to pH <2 (normally, 3 mL of (1+1) acid per liter of sample is sufficient for most ambient and drinking water samples). Preservation may be done at the time of collection, however, to avoid the hazards of strong acids in the field, transport restrictions, and possible contamination it is recommended that the samples be returned to the laboratory within two weeks of collection and acid preserved upon receipt in the laboratory. Following acidification, the sample should be mixed, held for 16 hours, and then verified to be pH <2 just prior withdrawing an aliquot for processing or “direct analysis”. If for some reason such as high alkalinity the sample pH is verified to be >2, more acid must be added and the sample held for 16 hours until verified to be pH <2. See Section 8.1.
Note: When the nature of the sample is either unknown or is known to be hazardous, acidification should be done in a fume hood. See Section 5.2.
8.4Solid samples require no preservation prior to analysis other than storage at 4 °C. There is no established holding time limitation for solid samples.
8.5For aqueous samples, a field blank should be prepared and analyzed as required by the data user. Use the same container and acid as used in sample collection.
9.1Each laboratory using this method is required to operate a formal quality control (QC) program. The minimum requirements of this program consist of an initial demonstration of laboratory capability, and the periodic analysis of laboratory reagent blanks, fortified blanks and other laboratory solutions as a continuing check on performance. The laboratory is required to maintain performance records that define the quality of the data thus generated.
9.2Initial Demonstration of Performance (mandatory).
9.2.1The initial demonstration of performance is used to characterize instrument performance (determination of linear dynamic ranges and analysis of quality control samples) and laboratory performance (determination of method detection limits) prior to analyses conducted by this method.
9.2.2Linear dynamic range (LDR)—The upper limit of the LDR must be established for each wavelength utilized. It must be determined from a linear calibration prepared in the normal manner using the established analytical operating procedure for the instrument. The LDR should be determined by analyzing succeedingly higher standard concentrations of the analyte until the observed analyte concentration is no more than 10% below the stated concentration of the standard. Determined LDRs must be documented and kept on file. The LDR which may be used for the analysis of samples should be judged by the analyst from the resulting data. Determined sample analyte concentrations that are greater than 90% of the determined upper LDR limit must be diluted and reanalyzed. The LDRs should be verified annually or whenever, in the judgment of the analyst, a change in analytical performance caused by either a change in instrument hardware or operating conditions would dictate they be redetermined.
9.2.3Quality control sample (QCS)—When beginning the use of this method, on a quarterly basis, after the preparation of stock or calibration standard solutions or as required to meet data-quality needs, verify the calibration standards and acceptable instrument performance with the preparation and analyses of a QCS (Section 7.12). To verify the calibration standards the determined mean concentrations from three analyses of the QCS must be within 5% of the stated values. If the calibration standard cannot be verified, performance of the determinative step of the method is unacceptable. The source of the problem must be identified and corrected before either proceeding on with the initial determination of method detection limits or continuing with on-going analyses.
9.2.4Method detection limit (MDL)—MDLs must be established for all wavelengths utilized, using reagent water (blank) fortified at a concentration of two to three times the estimated instrument detection limit.
Note: If additional confirmation is desired, reanalyze the seven replicate aliquots on two more nonconsecutive days and again calculate the MDL values for each day. An average of the three MDL values for each analyte
The MDLs must be sufficient to detect analytes at the required levels according to compliance monitoring regulation (Section 1.2). MDLs should be determined annually, when a new operator begins work or whenever, in the judgment of the analyst, a change in analytical performance caused by either a change in instrument hardware or operating conditions would dictate they be redetermined.
9.3Assessing Laboratory Performance (mandatory)
9.3.1Laboratory reagent blank (LRB)—The laboratory must analyze at least one LRB (Section 7.10.2) with each batch of 20 or fewer samples of the same matrix. LRB data are used to assess contamination from the laboratory environment. LRB values that exceed the MDL indicate laboratory or reagent contamination should be suspected. When LRB values constitute 10% or more of the analyte level determined for a sample or is 2.2 times the analyte MDL whichever is greater, fresh aliquots of the samples must be prepared and analyzed again for the affected analytes after the source of contamination has been corrected and acceptable LRB values have been obtained.
9.3.2Laboratory fortified blank (LFB)—The laboratory must analyze at least one LFB (Section 7.10.3) with each batch of samples.Calculate accuracy as percent recovery using the following equation:
If the recovery of any analyte falls outside the required control limits of 85-115%, that analyte is judged out of control, and the source of the problem should be identified and resolved before continuing analyses.
9.3.3The laboratory must use LFB analyses data to assess laboratory performance against the required control limits of 85-115% (Section 9.3.2). When sufficient internal performance data become available (usually a minimum of 20-30 analyses), optional control limits can be developed from the mean percent recovery (x) and the standard deviation (S) of the mean percent recovery. These data can be used to establish the upper and lower control limits as follows:
The optional control limits must be equal to or better than the required control limits of 85-115%. After each five to 10 new recovery measurements, new control limits can be calculated using only the most recent 20-30 data points. Also, the standard deviation (S) data should be used to establish an on-going precision statement for the level of concentrations included in the LFB. These data must be kept on file and be available for review.
9.3.4Instrument performance check (IPC) solution—For all determinations the laboratory must analyze the IPC solution (Section 7.11) and a calibration blank immediately following daily calibration, after every 10th sample (or more frequently, if required) and at the end of the sample run. Analysis of the calibration blank should always be < the analyte IDL, but greater than the lower 3-sigma control limit of the calibration blank. Analysis of the IPC solution immediately following calibration must verify that the instrument is within 5% of calibration with a relative standard deviation <3% from replicate integrations 4. Subsequent analyses of the IPC solution must be within 10% of calibration. If the calibration cannot be verified within the specified limits, reanalyze either or both the IPC solution and the calibration blank. If the second analysis of the IPC solution or the calibration blank confirm calibration to be outside the limits, sample analysis must be discontinued, the cause determined, corrected and/or the instrument recalibrated. All samples following the last acceptable IPC solution must be reanalyzed. The analysis data of the calibration blank and IPC solution must be kept on file with the sample analyses data.
9.3.5Spectral interference check (SIC) solution—For all determinations the laboratory must periodically verify the interelement spectral interference correction routine by analyzing SIC solutions. The preparation and required periodic analysis of SIC solutions and test criteria for verifying the interelement interference correction routine are given in Section 7.13. Special cases where on-going verification is required are described in Section 7.14.
9.4Assessing Analyte Recovery and Data Quality.
9.4.1Sample homogeneity and the chemical nature of the sample matrix can affect analyte recovery and the quality of the data. Taking separate aliquots from the sample for replicate and fortified analyses can in some cases assess the effect. Unless otherwise specified by the data user, laboratory or program, the following laboratory fortified matrix (LFM) procedure (Section 9.4.2) is required. Also, other tests such as the analyte addition test (Section 9.5.1) and sample dilution test (Section 9.5.2) can indicate if matrix effects are operative.
9.4.2The laboratory must add a known amount of each analyte to a minimum of 10% of the routine samples. In each case the LFM aliquot must be a duplicate of the aliquot used for sample analysis and for total recoverable determinations added prior to sample preparation. For water samples, the added analyte concentration must be the same as that used in the laboratory fortified blank (Section 7.10.3). For solid samples, however, the concentration added should be expressed as mg/kg and is calculated for a one gram aliquot by multiplying the added analyte concentration (mg/L) in solution by the conversion factor 100 (mg/L × 0.1L/0.001kg = 100, Section 12.5). (For notes on Ag, Ba, and Sn see Sections 1.7 and 1.8.) Over time, samples from all routine sample sources should be fortified.
Note: The concentration of calcium, magnesium, sodium and strontium in environmental waters, along with iron and aluminum in solids can vary greatly and are not necessarily predictable. Fortifying these analytes in routine samples at the same concentration used for the LFB may prove to be of little use in assessing data quality for these analytes. For these analytes sample dilution and reanalysis using the criteria given in Section 9.5.2 is recommended. Also, if specified by the data user, laboratory or program, samples can be fortified at higher concentrations, but even major constituents should be limited to <25 mg/L so as not to alter the sample matrix and affect the analysis.
9.4.3Calculate the percent recovery for each analyte, corrected for background concentrations measured in the unfortified sample, and compare these values to the designated LFM recovery range of 70-130% or a 3-sigma recovery range calculated from the regression equations given in Table 9.
9.4.4If the recovery of any analyte falls outside the designated LFM recovery range, and the laboratory performance for that analyte is shown to be in control (Section 9.3), the recovery problem encountered with the fortified sample is judged to be matrix related, not system related. The data user should be informed that the result for that analyte in the unfortified sample is suspect due to either the heterogeneous nature of the sample or matrix effects and analysis by method of standard addition or the use of an internal standard(s) (Section 11.5) should be considered.
9.4.5Where reference materials are available, they should be analyzed to provide additional performance data. The analysis of reference samples is a valuable tool for demonstrating the ability to perform the method acceptably. Reference materials containing high concentrations of analytes can provide additional information on the performance of the spectral interference correction routine.
9.5Assess the possible need for the method of standard additions (MSA) or internal standard elements by the following tests. Directions for using MSA or internal standard(s) are given in Section 11.5.
9.5.1Analyte addition test: An analyte(s) standard added to a portion of a prepared sample, or its dilution, should be recovered to within 85% to 115% of the known value. The analyte(s) addition should produce a minimum level of 20 times and a maximum
9.5.2Dilution test: If the analyte concentration is sufficiently high (minimally, a factor of 50 above the instrument detection limit in the original solution but <90% of the linear limit), an analysis of a 1 + 4 dilution should agree (after correction for the fivefold dilution) within 10% of the original determination. If not, a chemical or physical interference effect should be suspected and the associated data flagged accordingly. The method of standard additions or the use of an internal-standard element may provide more accurate data for samples failing this test.
10.1Specific wavelengths are listed in Table 1. Other wavelengths may be substituted if they can provide the needed sensitivity and are corrected for spectral interference. However, because of the difference among various makes and models of spectrometers, specific instrument operating conditions cannot be given. The instrument and operating conditions utilized for determination must be capable of providing data of acceptable quality to the program and data user. The analyst should follow the instructions provided by the instrument manufacturer unless other conditions provide similar or better performance for a task. Operating conditions for aqueous solutions usually vary from 1100-1200 watts forward power, 15-16 mm viewing height, 15-19 L/min. argon coolant flow, 0.6-1 L/min. argon aerosol flow, 1-1.8 mL/min. sample pumping rate with a one minute preflush time and measurement time near 1 s per wavelength peak (for sequential instruments) and near 10 s per sample (for simultaneous instruments). Use of the Cu/Mn intensity ratio at 324.754 nm and 257.610 nm (by adjusting the argon aerosol flow) has been recommended as a way to achieve repeatable interference correction factors.
10.2Prior to using this method optimize the plasma operating conditions. The following procedure is recommended for vertically configured plasmas. The purpose of plasma optimization is to provide a maximum signal-to-background ratio for the least sensitive element in the analytical array. The use of a mass flow controller to regulate the nebulizer gas flow rate greatly facilitates the procedure.
10.2.1Ignite the plasma and select an appropriate incident rf power with minimum reflected power. Allow the instrument to become thermally stable before beginning. This usually requires at least 30 to 60 minutes of operation. While aspirating the 1000 µg/mL solution of yttrium (Section 7.8.32), follow the instrument manufacturer's instructions and adjust the aerosol carrier gas flow rate through the nebulizer so a definitive blue emission region of the plasma extends approximately from 5-20 mm above the top of the work coil.
10.2.2After establishing the nebulizer gas flow rate, determine the solution uptake rate of the nebulizer in mL/min. by aspirating a known volume calibration blank for a period of at least three minutes. Divide the spent volume by the aspiration time (in minutes) and record the uptake rate. Set the peristaltic pump to deliver the uptake rate in a steady even flow.
10.2.3After horizontally aligning the plasma and/or optically profiling the spectrometer, use the selected instrument conditions from Sections 10.2.1 and 10.2.2, and aspirate the plasma solution (Section 7.15), containing 10 µg/mL each of As, Pb, Se and Tl. Collect intensity data at the wavelength peak for each analyte at 1 mm intervals from 14-18 mm above the top of the work coil. (This region of the plasma is commonly referred to as the analytical zone.)
10.2.4The instrument operating condition finally selected as being optimum should provide the lowest reliable instrument detection limits and method detection limits. Refer to Tables 1 and 4 for comparison of IDLs and MDLs, respectively.
10.2.5If either the instrument operating conditions, such as incident power and/or nebulizer gas flow rate are changed, or a new torch injector tube having a different orifice i.d. is installed, the plasma and plasma viewing height should be reoptimized.
10.2.6Before daily calibration and after the instrument warmup period, the nebulizer gas flow must be reset to the determined optimized flow. If a mass flow controller is being used, it should be reset to the recorded optimized flow rate. In order to maintain valid spectral interelement correction routines the nebulizer gas flow rate should be the same from day-to-day (<2% change). The change in signal intensity with a change in
10.3Before using the procedure (Section 11.0) to analyze samples, there must be data available documenting initial demonstration of performance. The required data and procedure is described in Section 9.2. This data must be generated using the same instrument operating conditions and calibration routine (Section 11.4) to be used for sample analysis. These documented data must be kept on file and be available for review by the data user.
10.4After completing the initial demonstration of performance, but before analyzing samples, the laboratory must establish and initially verify an interelement spectral interference correction routine to be used during sample analysis. A general description concerning spectral interference and the analytical requirements for background correction and for correction of interelement spectral interference in particular are given in Section 4.1. To determine the appropriate location for background correction and to establish the interelement interference correction routine, repeated spectral scan about the analyte wavelength and repeated analyses of the single element solutions may be required. Criteria for determining an interelement spectral interference is an apparent positive or negative concentration on the analyte that is outside the 3-sigma control limits of the calibration blank for the analyte. (The upper-control limit is the analyte IDL.) Once established, the entire routine must be initially and periodically verified annually, or whenever there is a change in instrument operating conditions (Section 10.2.5). Only a portion of the correction routine must be verified more frequently or on a daily basis. Test criteria and required solutions are described in Section 7.13. Initial and periodic verification data of the routine should be kept on file. Special cases where on-going verification are required is described in Section 7.14.
11.1.1For the determination of dissolved analytes in ground and surface waters, pipet an aliquot (20 mL) of the filtered, acid preserved sample into a 50 mL polypropylene centrifuge tube. Add an appropriate volume of (1 + 1) nitric acid to adjust the acid concentration of the aliquot to approximate a 1% (v/v) nitric acid solution (e.g., add 0.4 mL (1 + 1) HNO
Note: If a precipitate is formed during acidification, transport, or storage, the sample aliquot must be treated using the procedure described in Sections 11.2.2 through 11.2.7 prior to analysis.
11.2.1For the “direct analysis” of total recoverable analytes in drinking water samples containing turbidity <1 NTU, treat an unfiltered acid preserved sample aliquot using the sample preparation procedure described in Section 11.1.1 while making allowance for sample dilution in the data calculation (Section 1.2). For the determination of total recoverable analytes in all other aqueous samples or for preconcentrating drinking water samples prior to analysis follow the procedure given in Sections 11.2.2 through 11.2.7.
11.2.2For the determination of total recoverable analytes in aqueous samples (other than drinking water with <1 NTU turbidity), transfer a 100 mL (1 mL) aliquot from a well mixed, acid preserved sample to a 250 mL Griffin beaker (Sections 1.2, 1.3, 1.6, 1.7, 1.8, and 1.9). (When necessary, smaller sample aliquot volumes may be used.)
Note: If the sample contains
11.2.3Add 2 mL (1+1) nitric acid and 1.0 mL of (1+1) hydrochloric acid to the beaker containing the measured volume of sample. Place the beaker on the hot plate for solution evaporation. The hot plate should be located in a fume hood and previously adjusted to provide evaporation at a temperature of approximately but no higher than 85 °C. (See the following note.) The beaker should be covered with an elevated watch glass or other necessary steps should be taken to prevent sample contamination from the fume hood environment.
Note: For proper heating adjust the temperature control of the hot plate such that an uncovered Griffin beaker containing 50 mL of water placed in the center of the hot plate can be maintained at a temperature approximately but no higher than 85 °C. (Once the beaker is covered with a watch glass the temperature of the water will rise to approximately 95 °C.)
11.2.4Reduce the volume of the sample aliquot to about 20 mL by gentle heating at 85 °C.
11.2.5Cover the lip of the beaker with a watch glass to reduce additional evaporation and gently reflux the sample for 30 minutes. (Slight boiling may occur, but vigorous boiling must be avoided to prevent loss of the HCl-H
11.2.6Allow the beaker to cool. Quantitatively transfer the sample solution to a 50 mL volumetric flask, make to volume with reagent water, stopper and mix.
11.2.7Allow any undissolved material to settle overnight, or centrifuge a portion of the prepared sample until clear. (If after centrifuging or standing overnight the sample contains suspended solids that would clog the nebulizer, a portion of the sample may be filtered for their removal prior to analysis. However, care should be exercised to avoid potential contamination from filtration.) The sample is now ready for analysis. Because the effects of various matrices on the stability of diluted samples cannot be characterized, all analyses should be performed as soon as possible after the completed preparation.
11.3.1For the determination of total recoverable analytes in solid samples, mix the sample thoroughly and transfer a portion (>20 g) to tared weighing dish, weigh the sample and record the wet weight (WW). (For samples with <35% moisture a 20 g portion is sufficient. For samples with moisture >35% a larger aliquot 50-100 g is required.) Dry the sample to a constant weight at 60 °C and record the dry weight (DW) for calculation of percent solids (Section 12.6). (The sample is dried at 60 °C to prevent the loss of mercury and other possible volatile metallic compounds, to facilitate sieving, and to ready the sample for grinding.)
11.3.2To achieve homogeneity, sieve the dried sample using a 5-mesh polypropylene sieve and grind in a mortar and pestle. (The sieve, mortar and pestle should be cleaned between samples.) From the dried, ground material weigh accurately a representative 1.0 ± 0.01 g aliquot (W) of the sample and transfer to a 250 mL Phillips beaker for acid extraction (Sections 1.6, 1.7, 1.8, and 1.9).
11.3.3To the beaker add 4 mL of (1+1) HNO
Note: For proper heating adjust the temperature control of the hot plate such that an uncovered Griffin beaker containing 50 mL of water placed in the center of the hot plate can be maintained at a temperature approximately but no higher than 85 °C. (Once the beaker is covered with a watch glass the temperature of the water will rise to approximately 95 °C.) Also, a block digester capable of maintaining a temperature of 95 °C and equipped with 250 mL constricted volumetric digestion tubes may be substituted for the hot plate and conical beakers in the extraction step.
11.3.4Heat the sample and gently reflux for 30 minutes. Very slight boiling may occur, however vigorous boiling must be avoided to prevent loss of the HCl-H
11.3.5Allow the sample to cool and quantitatively transfer the extract to a 100 mL volumetric flask. Dilute to volume with reagent water, stopper and mix.
11.3.6Allow the sample extract solution to stand overnight to separate insoluble material or centrifuge a portion of the sample solution until clear. (If after centrifuging or standing overnight the extract solution contains suspended solids that would clog the nebulizer, a portion of the extract solution may be filtered for their removal prior to analysis. However, care should be exercised to avoid potential contamination from filtration.) The sample extract is now ready for analysis. Because the effects of various matrices on the stability of diluted samples cannot be characterized, all analyses should be performed as soon as possible after the completed preparation.
11.4.1Prior to daily calibration of the instrument inspect the sample introduction system including the nebulizer, torch, injector tube and uptake tubing for salt deposits, dirt and debris that would restrict solution flow and affect instrument performance. Clean the system when needed or on a daily basis.
11.4.2Configure the instrument system to the selected power and operating conditions as determined in Sections 10.1 and 10.2.
11.4.3The instrument must be allowed to become thermally stable before calibration and analyses. This usually requires at least 30 to 60 minutes of operation. After instrument warmup, complete any required optical profiling or alignment particular to the instrument.
11.4.4For initial and daily operation calibrate the instrument according to the instrument manufacturer's recommended procedures, using mixed calibration standard solutions (Section 7.9) and the calibration blank (Section 7.10.1). A peristaltic pump must be used to introduce all solutions to the nebulizer. To allow equilibrium to be reached in the plasma, aspirate all solutions for 30 seconds after reaching the plasma before beginning integration of the background
11.4.5After completion of the initial requirements of this method (Sections 10.3 and 10.4), samples should be analyzed in the same operational manner used in the calibration routine with the rinse blank also being used between all sample solutions, LFBs, LFMs, and check solutions (Section 7.10.4).
11.4.6During the analysis of samples, the laboratory must comply with the required quality control described in Sections 9.3 and 9.4. Only for the determination of dissolved analytes or the “direct analysis” of drinking water with turbidity of <1 NTU is the sample digestion step of the LRB, LFB, and LFM not required.
11.4.7Determined sample analyte concentrations that are 90% or more of the upper limit of the analyte LDR must be diluted with reagent water that has been acidified in the same manner as calibration blank and reanalyzed (see Section 11.4.8). Also, for the interelement spectral interference correction routines to remain valid during sample analysis, the interferant concentration must not exceed its LDR. If the interferant LDR is exceeded, sample dilution with acidified reagent water and reanalysis is required. In these circumstances analyte detection limits are raised and determination by another approved test procedure that is either more sensitive and/or interference free is recommended.
11.4.8When it is necessary to assess an operative matrix interference (e.g., signal reduction due to high dissolved solids), the tests described in Section 9.5 are recommended.
11.4.9Report data as directed in Section 12.0.
11.5If the method of standard additions (MSA) is used, standards are added at one or more levels to portions of a prepared sample. This technique
For more than one fortified portion of the prepared sample, linear regression analysis can be applied using a computer or calculator program to obtain the concentration of the sample solution. An alternative to using the method of standard additions is use of the internal standard technique by adding one or more elements (not in the samples and verified not to cause an uncorrected interelement spectral interference) at the same concentration (which is sufficient for optimum precision) to the prepared samples (blanks and standards) that are affected the same as the analytes by the sample matrix. Use the ratio of analyte signal to the internal standard signal for calibration and quantitation.
12.1Sample data should be reported in units of mg/L for aqueous samples and mg/kg dry weight for solid samples.
12.2For dissolved aqueous analytes (Section 11.1) report the data generated directly from the instrument with allowance for sample dilution. Do not report analyte concentrations below the IDL.
12.3For total recoverable aqueous analytes (Section 11.2), multiply solution analyte concentrations by the dilution factor 0.5, when 100 mL aliquot is used to produce the 50 mL final solution, and report
12.4For analytes with MDLs <0.01 mg/L, round the data values to the thousandth place and report analyte concentrations up to three significant figures. For analytes with MDLs <0.01 mg/L round the data values to the 100th place and report analyte concentrations up to three significant figures. Extract concentrations for solids data should be rounded in a similar manner before calculations in Section 12.5 are performed.
12.5For total recoverable analytes in solid samples (Section 11.3), round the solution analyte concentrations (mg/L) as instructed in Section 12.4. Report the data up to three significant figures as mg/kg dry-weight basis unless specified otherwise by the program or data user. Calculate theconcentration using the equation below:
Do not report analyte data below the estimated solids MDL or an adjusted MDL because of additional dilutions required to complete the analysis.
12.6To report percent solids in solid samples (Section 11.3)calculate as follows:
Note: If the data user, program or laboratory requires that the reported percent solids be determined by drying at 105 °C, repeat the procedure given in Section 11.3 using a separate portion (>20 g) of the sample and dry to constant weight at 103-105 °C.
12.7The QC data obtained during the analyses provide an indication of the quality of the sample data and should be provided with the sample results.
13.1Listed in Table 4 are typical single laboratory total recoverable MDLs determined for the recommended wavelengths using simultaneous ICP-AES and the operating conditions given in Table 5. The MDLs were determined in reagent blank matrix (best case situation). PTFE beakers were used to avoid boron and silica contamination from glassware with the final dilution to 50 mL completed in polypropylene centrifuged tubes. The listed MDLs for solids are estimates and were calculated from the aqueous MDL determinations.
13.2Data obtained from single laboratory method testing are summarized in Table 6 for five types of water samples consisting of drinking water, surface water, ground water, and two wastewater effluents. The data presented cover all analytes except cerium and titanium. Samples were prepared using the procedure described in Section 11.2. For each matrix, five replicate aliquots were prepared, analyzed and the average of the five determinations used to define the sample background concentration of each analyte. In addition, two pairs of duplicates were fortified at different concentration levels. For each method analyte, the sample background concentration, mean percent recovery, standard deviation of the percent recovery, and relative percent difference between the duplicate fortified samples are listed in Table 6. The variance of the five replicate sample background determinations is included in the calculated standard deviation of the percent recovery when the analyte concentration in the sample was greater than the MDL. The tap and well waters were processed in Teflon and quartz beakers and diluted in polypropylene centrifuged tubes. The nonuse of borosilicate glassware is reflected in the precision and recovery data for boron and silica in those two sample types.
13.3Data obtained from single laboratory method testing are summarized in Table 7 for three solid samples consisting of EPA 884 Hazardous Soil, SRM 1645 River Sediment, and EPA 286 Electroplating Sludge. Samples were prepared using the procedure described in Section 11.3. For each method analyte, the sample background concentration, mean percent recovery of the fortified additions, the standard deviation of the percent recovery,
13.4Performance data for aqueous solutions independent of sample preparation from a multilaboratory study are provided in Table 8.
13.5Listed in Table 9 are regression equations for precision and bias for 25 analytes abstracted from EPA Method Study 27, a multilaboratory validation study of Method 200.7.
14.1Pollution prevention encompasses any technique that reduces or eliminates the quantity or toxicity of waste at the point of generation. Numerous opportunities for pollution prevention exist in laboratory operation. The EPA has established a preferred hierarchy of environmental management techniques that places pollution prevention as the management option of first choice. Whenever feasible, laboratory personnel should use pollution prevention techniques to address their waste generation (e.g., Section 7.8). When wastes cannot be feasibly reduced at the source, the Agency recommends recycling as the next best option.
14.2For information about pollution prevention that may be applicable to laboratories and research institutions, consult “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 NW., Washington, DC 20036, (202) 872-4477.
15.1The Environmental Protection Agency requires that laboratory waste management practices be conducted consistent with all applicable rules and regulations. The Agency urges laboratories to protect the air, water, and land by minimizing and controlling all releases from hoods and bench operations, complying with the letter and spirit of any sewer discharge permits and regulations, and by complying with all solid and hazardous waste regulations, particularly the hazardous waste identification rules and land disposal restrictions. For further information on waste management consult “The Waste Management Manual for Laboratory Personnel”, available from the American Chemical Society at the address listed in the Section 14.2.
Two 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 two selected methods are for Thallium and Zinc. The following precision and recovery statements are presented in this appendix and incorporated into Part 136:
For Thallium, 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 a concentration range of 10.00-252 µg/L
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.
For a concentration range of 0.51-189 µg/L
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 of sewage, treated or untreated, as specified in paragraph (a)(1) of this section, shall be designed and operated to either retain, dispose of, or discharge sewage, and shall be certified by the U.S. Coast Guard. If the device has a discharge, the effluent shall not have a fecal coliform bacterial count of greater than 200 per 100 milliliters, nor suspended solids greater than 150 mg/1.
(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
(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 discharge in all or any part of the waters or portions thereof covered by the State's application, he shall publish notice of such findings together with a notice of proposed rule making, and then shall proceed in accordance with 5 U.S.C. 553. If the Administrator's finding is that applicable water quality standards require a complete prohibition covering a more restricted or more expanded area than that applied for by the State, he shall state the reasons why his finding differs in scope from that requested in the State's application.
(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,
(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
(2)(i) For the marine waters of the State of California, the following vessels are completely prohibited from discharging any sewage (whether treated or not):
(A) A large passenger vessel;
(B) A large oceangoing vessel equipped with a holding tank which has not fully used the holding tank's capacity, or which contains more than
(ii) For purposes of paragraph (b)(2) of this section:
(A) “Marine waters of the State of California” means the territorial sea measured from the baseline as determined in accordance with the Convention on the Territorial Sea and the Contiguous Zone and extending seaward a distance of three miles, and all enclosed bays and estuaries subject to tidal influences from the Oregon border (41.999325 North Latitude, 124.212110 West Longitude, decimal degrees, NAD 1983) to the Mexican border (32.471231 North Latitude, 117.137814 West Longitude, decimal degrees, NAD 1983). A map illustrating these waters can be obtained from EPA or viewed at
(B) A “large passenger vessel” means a passenger vessel, as defined in section 2101(22) of title 46, United States Code, of 300 gross tons or more, as measured under the International Convention on Tonnage Measurement of Ships, 1969, measurement system in 46 U.S.C. 14302, or the regulatory measurement system of 46 U.S.C. 14502 for vessels not measured under 46 U.S.C. 14302, that has berths or overnight accommodations for passengers.
(C) A “large oceangoing vessel” means a private, commercial, government, or military vessel of 300 gross tons or more, as measured under the International Convention on Tonnage Measurement of Ships, 1969, measurement system in 46 U.S.C. 14302, or the regulatory measurement system of 46 U.S.C. 14502 for vessels not measured under 46 U.S.C.14302, that is not a large passenger vessel.
(D) A “holding tank” means a tank specifically designed, constructed, and fitted for the retention of treated or untreated sewage, that has been designated and approved by the ship's flag Administration on the ship's stability plan; a designated ballast tank is not a holding tank for this purpose.
(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
(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.
Nomenclature changes to part 141 appear at 69 FR 18803, Apr. 9, 2004.
For community water systems serving 75,000 or more persons, monitoring must begin 1 year following promulation and the
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.
For
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 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 in the operation or maintenance of the distribution system.
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 trihalomethanes set forth in § 141.12(c) shall take effect 2 years after the date of promulgation 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
(h) Regulations for the analytic methods listed at § 141.23(k)(4) for measuring antimony, beryllium, cyanide, nickel, and thallium are effective August 17, 1992. Regulations for the analytic methods listed at § 141.24(f)(16) for dichloromethane, 1,2,4-trichlorobenzene, and 1,1,2-trichloroethane 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)phthalate, hexachlorobenzene, 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 142.62(b) revisions in Appendix A of subpart O for the consumer confidence rule, and Appendices A and B of subpart Q for the public notification rule are effective for the purpose of compliance on January 23, 2006. However, the consumer confidence rule reporting requirements relating to arsenic listed in § 141.154(b) and (f) are effective for the purpose of compliance on February 22, 2002.
(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 levels for turbidity are applicable to both
(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.
At 54 FR 27527, June 29, 1989, § 141.13 was amended by adding introductory text; however, the amendment could not be incorporated because introductory text already exists.
(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
(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 H must collect at least one sample near the first service connection each day the turbidity level of the source water, measured as specified in § 141.74(b)(2), exceeds 1 NTU. This sample must be analyzed for the presence of total coliforms. When one or more turbidity measurements in any day exceed 1 NTU, the system must collect this coliform sample within 24 hours of the first exceedance, 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. Sample results from this coliform monitoring must be included in determining compliance with the MCL for total coliforms in § 141.63.
(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
(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 a site visit before the end of the next month the system provides water to the public. Although a sanitary survey need not be performed, the site visit must be sufficiently detailed to allow the State to determine whether additional monitoring and/or any corrective action is needed. The State cannot approve an employee of the system to perform this site visit, even if the employee is an agent approved by the State to perform sanitary surveys.
(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
(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 signed by the supervisor of the State official who recommended the decision. The State must make this document available to EPA and the public. The written documentation must state the specific cause of the total coliform-positive sample, and what action the system has taken, or will take, to correct this problem. The State may not invalidate a total coliform-positive sample solely on the grounds that all repeat samples are total coliform-negative.
(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.
(3) Sanitary surveys conducted by the State under the provisions of § 142.16(o)(2) of this chapter may be used to meet the sanitary survey requirements of this section.
(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 or one of the alternative methods listed in appendix A to subpart C of this part.
(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 verification), swab the entire membrane filter surface with a sterile cotton swab and transfer the inoculum to EC medium (do not leave the cotton swab in the EC medium), or inoculate individual total coliform-positive colonies into EC Medium. Gently shake the inoculated tubes of EC medium to insure adequate mixing and incubate in a waterbath at 44.5 ±0.2 °C for 24 ±2 hours. Gas production of any amount in the inner fermentation tube of the EC medium indicates a positive fecal coliform test. The preparation of EC medium is described in Method 9221E (paragraph 1a) in Standard Methods for the Examination of Water and Wastewater, 18th edition (1992), 19th edition (1995), and 20th edition (1998); the cited method in any one of these three editions may be used. Public water systems need only determine the presence or absence of fecal coliforms; a determination of fecal coliform density is not required.
(6) Public water systems must conduct analysis of Escherichia coli in accordance with one of the following analytical methods or one of the alternative methods listed in appendix A to subpart C of this part.
(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
(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)
(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
(ix) Membrane Filter Technique using Chromocult
(x) Colitag
(7) As an option to paragraph (f)(6)(iii) of this section, a system with a total coliform-positive, 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.
For
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 pose a risk to public health, it can reduce the required sampling frequency. The option of reducing the turbidity frequency shall be permitted only in those public water systems that practice disinfection and which maintain an active residual disinfectant in the distribution system, and in those cases where the State has indicated in writing that no unreasonable risk to health existed under the circumstances of this option. Turbidity measurements shall be made as directed in § 141.74(a)(1).
(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 (
(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. Compositing of samples must be done in the laboratory.
(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 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.
(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
(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 provided the State 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 (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, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, selenium and thallium shall be as follows:
(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
(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.
(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.
(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 water system shall return to quarterly monitoring if any one sample is ≥50 percent of the MCL.
(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 averaged. 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, 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.
(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 the alternative methods listed in appendix A to subpart C of this part, 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 certification to conduct analyses for antimony, arsenic, asbestos, barium, beryllium, cadmium, chromium, cyanide, fluoride, mercury, nickel, nitrate, nitrite and selenium and thallium, the laboratory must:
(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]
For
(a)-(d) [Reserved]
(e) Analyses for the contaminants in this section shall be conducted using the methods listed in the following table, or the alternative methods listed in appendix A to subpart C of this part, or their equivalent as determined 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 3334, Washington, DC 20460 (Telephone: 202-566-2426); or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to:
(2) [Reserved]
(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
(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 well, the type of soil, and wellhead protection. Surface water systems must consider watershed protection.
(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 (
(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 speci 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. 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.
(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 (
(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.
(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.
(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, with the exception that no monitoring is required for aldicarb, aldicarb sulfoxide or aldicarb sulfone:
(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 (
(4)
(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 (
(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 the monitoring results in detection of one or more of certain related contaminants (heptachlor and 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
(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. 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.
(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 the system (e.g., fluctuations in concentration due to seasonal use, changes in water source).
(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]
(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.
For
(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 the alternative methods listed in appendix A to subpart C this part, 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 § 141.66(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.
(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.
(a)
(i)
(ii)
(2)
(i) Systems without acceptable historical data, as defined below, must collect four consecutive quarterly samples at all sampling points before December 31, 2007.
(ii)
(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)
(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 (e.g., if a system's sampling point is on a nine year monitoring period, and the sample result is above
(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)
(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
(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 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 (screening level), the State may reduce the frequency of monitoring at that sampling point to every 3 years. Systems must collect the same type of 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 appropriate 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)(i) or (b)(2)(iv) of this section.
(c)
(2) Each public water systems shall monitor at the time designated by the State during each compliance period.
(3)
(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 analytical technique may be employed. An alternate technique shall be accepted only if it is substantially equivalent to the prescribed test in both precision and accuracy as it relates to the determination of compliance with any MCL. The use of the alternate analytical technique shall not decrease the frequency of monitoring required by this part.
(a) For the purpose of determining compliance with § 141.21 through 141.27, 141.30, 141.40, 141.74, 141.89 and 141.402, samples may be considered only if they have been analyzed by a laboratory certified by the State except that measurements of 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
Only the editions stated in the following table are approved.
(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.
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 microbiological analyses and turbidity 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
(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.
(f) Copies of monitoring plans developed pursuant to this part shall be kept for the same period of time as the records of analyses taken under the plan are required to be kept under paragraph (a) of this section, except as specified elsewhere in this part.
(a)
(b)
(1)
(2)
(c)
(1)
(2)
(3)
(i)
(ii)
(iii)
(4)
(5)
(ii)
(6)
(i)
(ii)
(7)
(8)
(d)
(1)
(2)
(e)
(a)
(1)
(2)
(A)
(B)
(C)
(ii)
(A)
(B)
(C)
(3)
(4)
(A)
(B)
(C)
(D)
(E)
(F)
(G)
(H)
(I)
(ii)
(A)
(B)
(C)
(D)
(E)
(F)
(G)
(H)
(5)
(i)
(ii)
(iii)
(A) Validation of laboratory performance. Your laboratory must be capable of quantifying each contaminant listed in Table 1, at or below the MRL specified in column 4 of Table 1, in paragraph (a)(3) of this section. You must ensure that the laboratory completes and has on file and available for your inspection, records of two distinct procedures. First, your laboratory must have conducted an IDC involving replicate analyses at or below the MRL as described in this paragraph. Second, for each day that UCMR analyses are conducted by your laboratory, a validation of its ability to quantify each contaminant, at or below the MRL specified in column 4 of Table 1, in paragraph (a)(3) of this section, following the procedure listed in paragraph (a)(5)(iii)(B) of this section, must be performed. The procedure for initial validation of laboratory performance at or below the MRL is as follows:
(
(
(
(
(
(
(
(
(B) Quality control requirements for validation of laboratory performance at or below the MRL.
(
(
(iv)
(v)
(vi)
(6)
(ii)
(b)
(2)
(i)
(ii)
(c)
(1) The following methods from the U.S. Environmental Protection Agency, Water Docket, EPA/DC, EPA West, Room 3334, 1301 Constitution Ave. NW., Washington, DC 20004.
(i) EPA Method 200.8 “Determination of Trace Elements in Waters and Wastes by Inductively Coupled Plasma—Mass Spectrometry,” Revision 5.4, 1994, available at
(ii) EPA Method 218.7 “Determination of Hexavalent Chromium in Drinking Water by Ion Chromatography with Post-Column Derivatization and UV-Visible Spectroscopic Detection,” Version 1.0, November 2011, EPA 815-R-11-005, available at
(iii) EPA Method 300.1 “Determination of Inorganic Anions in Drinking Water by Ion Chromatography,” Revision 1.0, 1997, available at
(iv) EPA Method 522 “Determination of 1,4-Dioxane in Drinking Water by Solid Phase Extraction (SPE) and Gas Chromatography/Mass Spectrometry (GC/MS) with Selected Ion Monitoring (SIM),” Version 1.0, September 2008, EPA/600/R-08/101, available at
(v) EPA Method 524.3 “Measurement of Purgeable Organic Compounds in Water by Capillary Column Gas Chromatography/Mass Spectrometry,” Version 1.0, June 2009, EPA 815-B-09-009, available at
(vi) EPA Method 537 “Determination of Selected Perfluorinated Alkyl Acids in Drinking Water by Solid Phase Extraction and Liquid Chromatography/Tandem Mass Spectrometry (LC/MS/MS),” Version 1.1, September 2009, EPA/600/R-08/092, available at
(vii) EPA Method 539 “Determination of Hormones in Drinking Water by Solid Phase Extraction (SPE) and Liquid Chromatography Electrospray Ionization Tandem Mass Spectrometry (LC-ESI-MS/MS),” Version 1.0, November 2010, EPA 815-B-10-001, available at
(2) The following methods from “ASTM International,” 100 Barr Harbor Drive, West Conshohocken, PA 19428.
(i) ASTM D5673-10 “Standard Test Method for Elements in Water by Inductively Coupled Plasma-Mass Spectrometry,” approved August 1, 2010. Available for purchase at
(ii) ASTM D6581-08 “Standard Test Methods for Bromate, Bromide, Chlorate, and Chlorite in Drinking Water by Suppressed Ion Chromatography,” approved August 15, 2008. Available for purchase at
(3) The following methods from “Standard Methods for the Examination of Water & Wastewater,” 21st edition (2005), American Public Health Association, 800 I Street NW., Washington, DC 20001-3710.
(i) SM 3125 “Metals by Inductively Coupled Plasma/Mass Spectrometry.”
(ii) SM 4110D “Determination of Anions by Ion Chromatography, Part D, Ion Chromatography Determination of Oxyhalides and Bromide.”
(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 three months. A copy of each notice required to be provided by this paragraph shall be sent to EPA and/or the State within 10 days of its issuance. The supplier of water is not required to notify appropriate local and State public health officials of the sodium levels where the State provides such notices in lieu of the supplier.
(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:
(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 (b) of this section for each month in which it is required to monitor for total coliforms.
(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
(a)
(1)
(2) 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 bromate and chlorite identified in this paragraph (a):
(b) TTHM and HAA5. (1) Subpart L—RAA compliance. (i) Compliance dates. Subpart H systems serving 10,000 or more persons must comply with this paragraph (b)(1) beginning January 1, 2002. Subpart H systems serving fewer than 10,000 persons and systems using only ground water not under the direct influence of surface water must comply with this paragraph (b)(1) beginning January 1, 2004. All systems must comply with these MCLs until the date specified for subpart V compliance in § 141.620(c).
(ii) 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 TTHM and HAA5 identified in this paragraph (b)(1):
(2) Subpart V—LRAA compliance. (i) Compliance dates. The subpart V MCLs for TTHM and HAA5 must be complied with as a locational running annual average at each monitoring location beginning the date specified for subpart V compliance in § 141.620(c).
(ii) 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 TTHM and HAA5 identified in this paragraph (b)(2) for all systems that disinfect their source water:
(iii) 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 TTHM and HAA5 identified in this paragraph (b)(2) for consecutive systems and applies only to the disinfected water that consecutive systems buy or otherwise receive:
(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 National Archives and Records
(e)
(f)
(2) [Reserved]
(g)
(h)
(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
(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)(1) 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
(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.
(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
(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)(1) 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 beginning 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 must comply with paragraph (a)(2)(i) of this section.
(3) The residual disinfectant concentration in the water entering the distribution system, measured as specified in § 141.74 (a)(2) 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)(2) 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)(1), 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)(1) 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)(2) 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)(2) 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)(1), 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)(1) 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)(1) 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 1, 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)(1) and (c)(1).
(c)
(2) The turbidity level of representative samples of a system's filtered
(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 or one of the alternative methods listed in appendix A to subpart C of this part 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 or one of the alternative methods listed in appendix A to subpart C of this part. If approved by the State, residual disinfectant concentrations for free chlorine and combined chlorine also may be measured by using DPD colorimetric test kits. In addition States may approve the use of the ITS free chlorine test strip for the determination of free chlorine. Use of the test strips is described in Method D99-003, “Free Chlorine Species (HOCl
(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 coliforms at the following minimum frequency each week the system serves water to the public:
(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
(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
(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 using slow sand filtration or filtration treatment other than conventional treatment, direct filtration, or diatomaceous earth filtration, the State may reduce the sampling frequency to once per day if it determines that less frequent monitoring is sufficient to indicate effective filtration performance. For systems serving 500 or fewer persons, the State may reduce the turbidity sampling frequency to once per day, regardless of the type of filtration treatment used, if the State determines that less frequent monitoring is sufficient to indicate effective filtration performance.
(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)(1) 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)(1) 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 days after the end of each month the system serves water to the public. Information that must be reported includes:
(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
(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)(1) 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,
(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)(1) 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
(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) [Reserved]
(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 (
(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 from the sample with the lowest concentration to the sample with the highest concentration. Each sampling result shall be assigned a number, ascending by single integers beginning with the number 1 for the sample with the lowest contaminant level. The number assigned to the sample with the highest contaminant level shall be equal to the total number of samples taken.
(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.
(v) For a public water system that has been allowed by the State to collect fewer than five samples in accordance with § 141.86(c), the sample result with the highest concentration is considered the 90th percentile value.
(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 appropriate to ensure optimal corrosion control treatment is maintained.
(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
(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 upcoming long-term change in treatment or addition of a new source as described in that section. The State must review and approve the addition of a new source or long-term change in water treatment before it is implemented by the water system. 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 accordance with the deadlines in paragraph (e) of this section. Any such large system shall adhere to the schedule specified in that paragraph for medium-size systems, with the time periods for completing each step being triggered by the date the system is no longer deemed to have optimized corrosion control under this paragraph.
(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 the end of the monitoring period during which such system exceeds the lead or copper action level.
(ii) For small systems, within 24 months after the end of the monitoring period during which 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)(1) 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
(2) Any water system resuming a lead service line replacement program after the cessation of its lead service line replacement program as allowed by paragraph (f) of this section shall update its inventory of lead service lines to include those sites that were previously determined not to require replacement through the sampling provision under paragraph (c) of this section. The system will then divide the updated number of remaining lead service lines by the number of remaining years in the program to determine the number of lines that must be replaced per year (7 percent lead service line replacement is based on a 15-year replacement program, so, for example, systems resuming lead service line replacement after previously conducting two years of replacement would divide the updated inventory by 13). For those systems that have completed a 15-year lead service line replacement program, the State will determine a schedule for replacing or retesting lines that were previously tested out under the replacement program when the system re-exceeds the action level.
(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 State may allow the water system to provide notice under the previous sentence less than 45 days prior to commencing partial lead service line replacement where such replacement is in conjunction with emergency repairs. In addition, the water system shall inform the resident(s) served by the line that the system will, at the system's expense, collect a sample from each partially-replaced lead service line that is representative of the water in the service line for analysis of lead content, as prescribed under § 141.86(b)(3), within 72 hours after the completion of the partial replacement of the service line. The system shall collect the sample and report the results of the analysis to the owner and the resident(s) served by the line within three business days of receiving the results. Mailed notices post-marked within three business days of receiving the results shall be considered “on time.”
(2) The water system shall provide the information required by paragraph
(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)(2) 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).
All water systems must deliver a consumer notice of lead tap water monitoring results to persons served by the water system at sites that are tested, as specified in paragraph (d) of this section. 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 paragraph (a) of this section in accordance with the requirements in paragraph (b) of this section. Water systems that exceed the lead action level must sample the tap water of any customer who requests it in accordance with paragraph (c) of this section.
(a)
(i) IMPORTANT INFORMATION ABOUT LEAD IN YOUR DRINKING WATER. [INSERT NAME OF WATER SYSTEM] found elevated levels of lead in drinking water in some homes/buildings. Lead can cause serious health problems, especially for pregnant women and young children. Please read this information closely to see what you can do to reduce lead in your drinking water.
(ii)
(iii)
(B) Explain possible sources of lead in drinking water and how lead enters drinking water. Include information on home/building plumbing materials and service lines that may contain lead.
(C) Discuss other important sources of lead exposure in addition to drinking water (e.g., paint).
(iv) Discuss the steps the consumer can take to reduce their exposure to lead in drinking water.
(A) Encourage running the water to flush out the lead.
(B) Explain concerns with using hot water from the tap and specifically caution against the use of hot water for preparing baby formula.
(C) Explain that boiling water does not reduce lead levels.
(D) Discuss other options consumers can take to reduce exposure to lead in drinking water, such as alternative sources or treatment of water.
(E) Suggest that parents have their child's blood tested for lead.
(v) Explain why there are elevated levels of lead in the system's drinking water (if known) and what the water system is doing to reduce the lead levels in homes/buildings in this area.
(vi) For more information, call us at [INSERT YOUR NUMBER] [(IF APPLICABLE), or visit our Web site at [INSERT YOUR WEB SITE HERE]]. For more information on reducing lead exposure around your home/building and the health effects of lead, visit EPA's Web site at
(2)
(i) Tell consumers how to get their water tested.
(ii) Discuss lead in plumbing components and the difference between low lead and lead free.
(b)
(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 conducting public education tasks under this section, must conduct the public education tasks under this section within 60 days after the end of the monitoring period in which the exceedance occurred:
(i) Deliver printed materials meeting the content requirements of paragraph (a) of this section to all bill paying customers.
(ii)(A) Contact customers who are most at risk by delivering education materials that meet the content requirements of paragraph (a) of this section to local public health agencies even if they are not located within the water system's service area, along with an informational notice that encourages distribution to all the organization's potentially affected customers or community water system's users. The water system must contact the local public health agencies directly by phone or in person. The local public health agencies may provide a specific list of additional community based organizations serving target populations, which may include organizations outside the service area of the water system. If such lists are provided, systems must deliver education materials that meet the content requirements of paragraph (a) of this section to all organizations on the provided lists.
(B) Contact customers who are most at risk by delivering materials that meet the content requirements of paragraph (a) of this section to the following organizations listed in 1 through 6 that are located within the water system's service area, along with an informational notice that encourages distribution to all the organization's potentially affected customers or community water system's users:
(
(
(
(
(
(
(C) Make a good faith effort to locate the following organizations within the service area and deliver materials that meet the content requirements of paragraph (a) of this section to them, along with an informational notice that encourages distribution to all potentially affected customers or users. The good faith effort to contact at-risk customers may include requesting a specific contact list of these organizations from the local public health agencies, even if the agencies are not located within the water system's service area:
(
(
(
(iii) No less often than quarterly, provide information on or in each water bill as long as the system exceeds the action level for lead. The message on the water bill must include the following statement exactly as written except for the text in brackets for which the water system must include system-specific information: [INSERT NAME OF WATER SYSTEM] found high levels of lead in drinking water in some homes. Lead can cause serious health problems. For more information please call [INSERT NAME OF WATER SYSTEM] [or visit (INSERT YOUR WEB SITE HERE)]. The message or delivery mechanism can be modified in consultation with the State; specifically, the State may allow a separate mailing of public education materials to customers if the water system cannot place the information on water bills.
(iv) Post material meeting the content requirements of paragraph (a) of this section on the water system's Web site if the system serves a population greater than 100,000.
(v) Submit a press release to newspaper, television and radio stations.
(vi) In addition to paragraphs (b)(2)(i) through (v) of this section, systems must implement at least three activities from one or more categories listed below. The educational content and selection of these activities must be determined in consultation with the State.
(A) Public Service Announcements.
(B) Paid advertisements.
(C) Public Area Information Displays.
(D) E-mails to customers.
(E) Public Meetings.
(F) Household Deliveries.
(G) Targeted Individual Customer Contact.
(H) Direct material distribution to all multi-family homes and institutions.
(I) Other methods approved by the State.
(vii) For systems that are required to conduct monitoring annually or less frequently, the end of the monitoring period is September 30 of the calendar year in which the sampling occurs, or, if the State has established an alternate monitoring period, the last day of that period.
(3) As long as a community water system exceeds the action level, it must repeat the activities pursuant to paragraph (b)(2) of this section as described in paragraphs (b)(3)(i) through (iv) of this section.
(i) A community water system shall repeat the tasks contained in paragraphs (b)(2)(i), (ii) and (vi) of this section every 12 months.
(ii) A community water system shall repeat tasks contained in paragraph (b)(2)(iii) of this section with each billing cycle.
(iii) A community water system serving a population greater than 100,000 shall post and retain material on a publicly accessible Web site pursuant to paragraph (b)(2)(iv) of this section.
(iv) The community water system shall repeat the task in paragraph (b)(2)(v) of this section twice every 12 months on a schedule agreed upon with the State. The State can allow activities in paragraph (b)(2) of this section to extend beyond the 60-day requirement if needed for implementation purposes on a case-by-case basis; however, this extension must be approved in writing by the State in advance of the 60-day deadline.
(4) Within 60 days after the end of the monitoring period in which the exceedance occurred (unless it already is repeating public education tasks pursuant to paragraph (b)(5) of this section), a non-transient non-community water system shall deliver the public education materials specified by paragraph (a) 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.
(iii) For systems that are required to conduct monitoring annually or less frequently, the end of the monitoring period is September 30 of the calendar year in which the sampling occurs, or, if the State has established an alternate monitoring period, the last day of that period.
(5) A non-transient non-community water system shall repeat the tasks contained in paragraph (b)(4) of this section at least once during each calendar year in which the system exceeds the lead action level. The State can allow activities in (b)(4) of this section to extend beyond the 60-day requirement if needed for implementation purposes on a case-by-case basis; however, this extension must be approved in writing by the State in advance of the 60-day deadline.
(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 only the text specified in paragraph (a)(1) of this section in lieu of the text in paragraphs (a)(1) and (a)(2) of this section and to perform the tasks listed in paragraphs (b)(4) and (b)(5) of this section in lieu of the tasks in paragraphs (b)(2) and (b)(3) of this section if:
(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) A community water system serving 3,300 or fewer people may limit certain aspects of their public education programs as follows:
(i) With respect to the requirements of paragraph (b)(2)(vi) of this section, a system serving 3,300 or fewer must implement at least one of the activities listed in that paragraph.
(ii) With respect to the requirements of paragraph (b)(2)(ii) of this section, a system serving 3,300 or fewer people may limit the distribution of the public education materials required under that paragraph to facilities and organizations served by the system that are most likely to be visited regularly by pregnant women and children.
(iii) With respect to the requirements of paragraph (b)(2)(v) of this section, the State may waive this requirement for systems serving 3,300 or fewer persons as long as system distributes notices to every household served by the system.
(c)
(d)
(2)
(3)
(4)
(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 material composition of the service connections that connect a structure to the distribution system; and
(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 to collect first-draw samples after instructing the residents of the sampling procedures specified in this paragraph. To avoid problems of residents handling nitric acid, acidification of first-draw samples may be done up to 14 days after the sample is collected. After acidification to resolubilize the metals, the sample must stand in the original container for the time specified in the approved EPA method before the sample can be analyzed. If a system allows residents to perform sampling, the system may not challenge, based on alleged errors in sample collection, the accuracy of sampling results.
(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(b)(7), 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
(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 meets the lead action level and 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. This sampling shall begin during the calendar year immediately following the end of the second consecutive six-month monitoring period. 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 meets the lead action level and 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. Samples collected once every three years shall be collected no later than every third calendar year. 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
(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 shall conduct the lead and copper tap sampling during the months of June, July, August, or September unless the State has approved a different sampling period in accordance with paragraph (d)(4)(iv)(A) of this section.
(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. This sampling shall begin during the period approved or designated by the State in the calendar year immediately following the end of the second consecutive six-month monitoring period for systems initiating annual monitoring and during the three-year period following the end of the third consecutive calendar year of annual monitoring for systems initiating triennial monitoring.
(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
(B) Any water system subject to the reduced monitoring frequency that fails to meet the lead action level during any four-month monitoring period or 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). This standard tap water sampling shall begin no later than the six-month period beginning January 1 of the calendar year following the lead action level exceedance or water quality parameter excursion. 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 shall notify the State in writing in accordance with § 141.90(a)(3) of any upcoming long-term change in treatment or addition of a new source as described in that section. The State must review and approve the addition of a new source or long-term change in water treatment before it is implemented by the water system. 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
(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 taken at the same locations as the invalidated samples or, if that is not possible, at locations other than those already used for sampling during the monitoring period.
(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) Any water system with a full or partial waiver shall notify the State in writing in accordance with § 141.90(a)(3) of any upcoming long-term change in treatment or addition of a new source, as described in that section. The State must review and approve the addition of a new source or long-term change in water treatment before it is implemented by the water system. The State has the authority to require the system to add or modify waiver conditions (e.g., require recertification that the system is free of lead-containing and/or copper-containing materials, require additional round(s) of monitoring), if it deems such modifications are necessary to address treatment or source water changes at the system.
(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, (e.g., as a result of new construction or repairs), the system shall notify the State in writing no later than 60 days after becoming aware of such a change.
(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, 2000. Thereafter, the waiver shall remain in effect as long as the system meets the continued 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 round of monitoring conducted pursuant to paragraph (g)(2) of this section.
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 (
(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
(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 quality parameters reflecting optimal corrosion control treatment specified by the State under § 141.82(f) during three consecutive years of monitoring may reduce the frequency with which it collects the number of tap samples for applicable water quality parameters specified in this paragraph (e)(1) of this section from every six months to annually. This sampling begins during the calendar year immediately following the end of the monitoring period in which the third consecutive year of six-month monitoring occurs. Any water system that maintains the range of values for the water quality parameters reflecting optimal corrosion control treatment specified by the State under § 141.82(f), during three consecutive years of annual monitoring under this paragraph may reduce the frequency with which it collects the number of tap samples for applicable water quality parameters specified in paragraph (e)(1) of this section from annually to every three years. This sampling begins no later than the third calendar year following the end of the monitoring period in which the third consecutive year of monitoring occurs.
(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). Monitoring conducted every three years shall be done no later than every third calendar year.
(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
(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
(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 be collected as soon as possible after the initial sample was taken (but not to exceed two weeks) at the same sampling point. If a State-required confirmation sample is taken for lead or copper, then the results of the initial and confirmation sample shall be averaged in determining compliance with the State-specified maximum permissible levels. Any sample value below the detection limit shall be considered to be zero. Any value above the detection limit but below the PQL shall either be considered as the measured value or be considered one-half the PQL.
(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. Triennial samples shall be collected every third calendar year.
(ii) A water system using surface water (or a combination of surface and
(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) provided that the samples are collected no later than every ninth calendar year and 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 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.
(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.
(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)(iv).
(iv) Be currently certified by EPA or the State to perform analyses to the specifications described in paragraph (a)(1) 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 the water system requests invalidation pursuant to § 141.86(f)(2);
(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(b)(7), 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
(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) At a time specified by the State, or if no specific time is designated by the State, then as early as possible prior to the addition of a new source or any long-term change in water treatment, 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 submit written documentation to the State describing the change or addition. The State must review and approve the addition of a new source or long-term change in treatment before it is implemented by the water system. Examples of long-term treatment changes include the addition of a new treatment process or modification of an existing treatment process. Examples of modifications include switching secondary disinfectants, switching coagulants (e.g., alum to ferric chloride), and switching corrosion inhibitor products (e.g., orthophosphate to blended phosphate). Long-term changes can include dose changes to existing chemicals if the system is planning long-term changes to its finished water pH or residual inhibitor concentration. Long-term treatment changes would not include chemical dose fluctuations associated with daily raw water quality changes.
(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 and what corrective action, if any, the system plans to remove these materials.
(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
(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) No later than 12 months after the end of a monitoring period in which a system exceeds the lead action level in sampling referred to in § 141.84(a), the system must submit written documentation to the State of the material evaluation conducted as required in § 141.86(a), identify the initial number of lead service lines in its distribution system at the time the system exceeds the lead action level, and provide the system's schedule for annually replacing at least 7 percent of the initial number of lead service lines in its distribution system.
(2) No later than 12 months after the end of a monitoring period in which 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 (e)(1) 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 section shall contain the following information:
(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 the delivery requirements in § 141.85(b); 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.
(3) No later than 3 months following the end of the monitoring period, each system must mail a sample copy of the consumer notification of tap results to the State along with a certification that the notification has been distributed in a manner consistent with the requirements of § 141.85(d).
(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 treatment 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 microbiological 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, 1301 Constitution Avenue, NW., EPA West, Room B102, Washington, DC 20460, or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to:
(b)
(2) Analyses 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 DBP contaminants in §§ 141.64, 141.135, and subparts U and V of this part, the laboratory must:
(i) Analyze Performance Evaluation (PE) samples that are acceptable to EPA or the State at least once during each consecutive 12 month period by each method for which the laboratory desires certification.
(ii) Until March 31, 2007, in these analyses of PE samples, the laboratory must achieve quantitative results within the acceptance limit on a minimum of 80% of the analytes included in each PE sample. The acceptance limit is defined as the 95% confidence interval calculated around the mean of the PE study between a maximum and minimum acceptance limit of ±50% and ±15% of the study mean.
(iii) Beginning April 1, 2007, the laboratory must achieve quantitative results on the PE sample analyses that are within the following acceptance limits:
(iv) Beginning April 1, 2007, report quantitative data for concentrations at least as low as the ones listed in the following table for all DBP samples analyzed for compliance with §§ 141.64, 141.135, and subparts U and V of this part:
(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)
(ii) Ultraviolet Absorption at 254 nm (UV
(5)
(6)
(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 to qualify for reduced monitoring.
(b)
(ii) Systems may reduce monitoring, except as otherwise provided, in accordance with the following table:
(iii)
(iv) Systems on a reduced monitoring schedule may remain on that reduced schedule as long as the average of all samples taken in the year (for systems which must monitor quarterly) or the result of the sample (for systems which must monitor no more frequently than annually) is no more than 0.060 mg/L and 0.045 mg/L for TTHMs and HAA5, respectively. 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 TTHMs and 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 the quarter immediately following the monitoring period in which the system
(v) 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.
(vi) 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)
(B) Beginning April 1, 2009, systems may no longer use the provisions of paragraph (b)(3)(ii)(A) of this section to
(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 for total trihalomethanes, haloacetic acids (five), or bromate; or the MRDL for chlorine or chloramine, 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 § 141.131(d). Systems practicing softening are required to meet the Step 1 TOC reductions in the far-right column (Source water alkalinity >120 mg/L) for the specified source water TOC:
(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 necessary chemicals to maintain the pH between 5.3 and 5.7 in samples until the TOC removal of 0.3 mg/L per 10 mg/L alum added (or equivalant addition of iron coagulant) is reached.
(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, detected means: at or above the levels prescribed by § 141.23(a)(4) for inorganic contaminants, at or above the levels prescribed by § 141.24(f)(7) for the contaminants listed in § 141.61(a), at or above the levels prescribed by § 141.24(h)(18) for the contaminants listed in § 141.61(c), at or above the levels prescribed by § 141.131(b)(2)(iv) for the contaminants or contaminant groups listed in § 141.64, and at or above the levels prescribed by § 141.25(c) for radioactive contaminants.
(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
(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 monitoring location: the highest average of any of the monitoring locations and the range of all monitoring locations expressed in the same units as the MCL. For the MCLs for TTHM and HAA5 in § 141.64(b)(2), systems must include the highest locational running annual average for TTHM and HAA5 and the range of individual sample results for all monitoring locations expressed in the same units as the MCL. If more than one location exceeds the TTHM or HAA5 MCL, the system must include the locational running annual averages for all locations that exceed 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 monitoring locations: the average and range of detection expressed in the same units as the MCL. The system is required to include individual sample results for the IDSE conducted under subpart U of this part when determining the range of TTHM and HAA5 results to be reported in the annual consumer confidence report for the calendar year that the IDSE samples were taken.
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
(e) Information on
(1) If the system has performed any monitoring for
(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
(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
(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.
(6)
(A) The nature of the particular significant deficiency or the source of the fecal contamination (if the source is known) and the date the significant deficiency was identified by the State or the dates of the fecal indicator-positive ground water source samples;
(B) If the fecal contamination in the ground water source has been addressed under § 141.403(a) and the date of such action;
(C) For each significant deficiency or fecal contamination in the ground water source that has not been addressed under § 141.403(a), the State-approved plan and schedule for correction, including interim measures, progress to date, and any interim measures completed; and
(D) If the system receives notice of a fecal indicator-positive ground water source sample that is not invalidated by the State under § 141.402(d), the potential health effects using the health effects language of Appendix A of subpart O.
(ii) If directed by the State, a system with significant deficiencies that have been corrected before the next report is issued must inform its customers of the significant deficiency, how the deficiency was corrected, and the date of correction under paragraph (h)(6)(i) of this section.
(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 risk from infections. These people should seek advice about drinking water from their health care providers.
(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) Every report must include the following lead-specific information:
(1) A short informational statement about lead in drinking water and its effects on children. The statement must include the following information:
(2) A system may write its own educational statement, but only in consultation with the State.
(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.
(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 1, 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
(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
(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
(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)
(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)
(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 this section. Such persons may include those who do not pay water bills or do not have service connection addresses (e.g., house renters, apartment dwellers, university students, nursing home patients, prison inmates, etc.). Other methods may include: Publication in a local newspaper; delivery of multiple copies for distribution by customers that provide their drinking water to others (e.g., apartment building owners or large private employers); posting in public places served by the system or on the Internet; or delivery to community organizations.
(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 (e.g., community centers).
(a)
(b)
(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 (e.g., house renters, apartment dwellers, university students, nursing home patients, prison inmates, etc.). Other methods may include: Publication in a local newspaper; delivery of multiple copies for distribution by customers that provide their drinking water to others (e.g., apartment building owners or large private employers); posting in public places or on the Internet; or delivery to community organizations.
(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 (e.g., community centers).
(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 owner, operator, or designee of the public water system as a source of additional information concerning the notice; and
(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)
(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)
(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.
(a)
(b)
(a)
(b)
(a)
(b)
(c)
(d)
(1) The special notice for repeated failure to conduct monitoring must contain the following language:
We are required to monitor the source of your drinking water for
For more information, please call (name of water system contact) of (name of water system) at (phone number).
(2) The special notice for failure to determine bin classification or mean
We are required to monitor the source of your drinking water for
(3) Each special notice must also include a description of what the system is doing to correct the violation and when the system expects to return to compliance or resolve the situation.
1. Violations and other situations not listed in this table (e.g., 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 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.
11. The arsenic Tier 3 violation MCL citations are effective January 23, 2006. Until then, the citations are § 141.23(a), (l).
12. 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.
13. 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.
14. §§ 141.64(b)(1) 141.132(a)-(b) apply until §§ 141.620-141.630 take effect under the schedule in § 141.620(c).
15. 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.
16. 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.
17. Some water systems must monitor for certain unregulated contaminants listed in § 141.40.
18. 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. . .”
19. In addition to §§ 1415 and 1416 of the Safe Drinking Water Act, 40 CFR 142.307 specifies
20. 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 serious adverse effects on health as a result of short-term exposure. These could include outbreaks not related to treatment deficiencies, as well as situations that have the potential to cause outbreaks, such as failures or significant interruption in water treatment processes, natural disasters that disrupt the water supply or distribution system, chemical spills, or unexpected loading of possible pathogens into the source water.
21. Primacy agencies may place other situations in any tier they believe appropriate, based on threat to public health.
22. Failure to collect three or more samples for
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 2002 Long Term 1 Enhanced Surface Water Treatment Rule. The MCL for the monthly 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 2002 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 1, 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 not necessarily 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. The uranium MCL is effective December 8, 2003 for all community water systems.
17. Picocuries per liter
18. 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 subpart L DBP MCLs and disinfectant maximum residual disinfectant levels (MRDLs) beginning January 1, 2002. All other community and non-transient non-community systems must comply with subpart L DBP MCLs and disinfectant MRDLs beginning January 1, 2004. Subpart H transient non-community systems serving ≥10,000 that use chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2002. All other transient non-community systems that use chlorine dioxide as a disinfectant or oxidant must comply with the chlorine dioxide MRDL beginning January 1, 2004.
19. Community and non-transient non-community systems must comply with subpart V TTHM and HAA5 MCLs of 0.080 mg/L and 0.060 mg/L, respectively (with compliance calculated as a locational running annual average) on the schedule in § 141.620.
20. The MCL for total trihalomethanes is the sum of the concentrations of the individual trihalomethanes.
21. The MCL for haloacetic acids is the sum of the concentrations of the individual haloacetic acids.
22. MRDLG—Maximum residual disinfectant level goal.
23. MRDL—Maximum residual disinfectant level.
(a)
(b)
(c)
(1) Sanitary survey information requirements for all ground water systems as described in § 141.401.
(2) Microbial source water monitoring requirements for ground water systems that do not treat all of their ground water to at least 99.99 percent (4-log) treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer as described in § 141.402.
(3) Treatment technique requirements, described in § 141.403, that apply to ground water systems that have fecally contaminated source waters, as determined by source water monitoring conducted under § 141.402, or that have significant deficiencies that are identified by the State or that are identified by EPA under SDWA section 1445. A ground water system with fecally contaminated source water or with significant deficiencies subject to the treatment technique requirements of this subpart must implement one or more of the following corrective action options: correct all significant deficiencies; provide an alternate source of water; eliminate the source of contamination; or provide treatment that reliably achieves at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer.
(4) Ground water systems that provide at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer are required to conduct compliance monitoring to demonstrate treatment effectiveness, as described in § 141.403(b).
(5) If requested by the State, ground water systems must provide the State with any existing information that will enable the State to perform a hydrogeologic sensitivity assessment. For the purposes of this subpart, “hydrogeologic sensitivity assessment” is a determination of whether ground water systems obtain water from hydrogeologically sensitive settings.
(d)
(a) Ground water systems must provide the State, at the State's request, any existing information that will enable the State to conduct a sanitary survey.
(b) For the purposes of this subpart, a “sanitary survey,” as conducted by the State, includes but is not limited to, an onsite review of the water source(s) (identifying sources of contamination by using results of source water assessments or other relevant information where available), facilities, equipment, operation, maintenance, and monitoring compliance of a public water system to evaluate the adequacy of the system, its sources and operations and the distribution of safe drinking water.
(c) The sanitary survey must include an evaluation of the applicable components listed in paragraphs (c)(1) through (8) of this section:
(1) Source,
(2) Treatment,
(3) Distribution system,
(4) Finished water storage,
(5) Pumps, pump facilities, and controls,
(6) Monitoring, reporting, and data verification,
(7) System management and operation, and
(8) Operator compliance with State requirements.
(a)
(i) The system does not provide at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer for each ground water source; and
(ii) The system is notified that a sample collected under § 141.21(a) is total coliform-positive and the sample is not invalidated under § 141.21(c).
(2)
(i) The State may extend the 24-hour time limit on a case-by-case basis if the system cannot collect the ground water source water sample within 24 hours due to circumstances beyond its control. In the case of an extension, the State must specify how much time the system has to collect the sample.
(ii) If approved by the State, systems with more than one ground water source may meet the requirements of this paragraph (a)(2) by sampling a representative ground water source or sources. If directed by the State, systems must submit for State approval a triggered source water monitoring plan that identifies one or more ground water sources that are representative of each monitoring site in the system's sample siting plan under § 141.21(a) and that the system intends to use for representative sampling under this paragraph.
(iii) A ground water system serving 1,000 people or fewer may use a repeat sample collected from a ground water
(3)
(4)
(ii) In addition to the other requirements of this paragraph (a), a wholesale ground water system must comply with paragraphs (a)(4)(ii)(A) and (a)(4)(ii)(B) of this section.
(A) A wholesale ground water system that receives notice from a consecutive system it serves that a sample collected under § 141.21(a) is total coliform-positive must, within 24 hours of being notified, collect a sample from its ground water source(s) under paragraph (a)(2) of this section and analyze it for a fecal indicator under paragraph (c) of this section.
(B) If the sample collected under paragraph (a)(4)(ii)(A) of this section is fecal indicator-positive, the wholesale ground water system must notify all consecutive systems served by that ground water source of the fecal indicator source water positive within 24 hours of being notified of the ground water source sample monitoring result and must meet the requirements of paragraph (a)(3) of this section.
(5)
(i) The State determines, and documents in writing, that the total coliform-positive sample collected under § 141.21(a) is caused by a distribution system deficiency; or
(ii) The total coliform-positive sample collected under § 141.21(a) is collected at a location that meets State criteria for distribution system conditions that will cause total coliform-positive samples.
(b)
(1) Collection of a total of 12 ground water source samples that represent each month the system provides ground water to the public,
(2) Collection of samples from each well unless the system obtains written State approval to conduct monitoring at one or more wells within the ground water system that are representative of multiple wells used by that system and that draw water from the same hydrogeologic setting,
(3) Collection of a standard sample volume of at least 100 mL for fecal indicator analysis regardless of the fecal indicator or analytical method used,
(4) Analysis of all ground water source samples using one of the analytical methods listed in the in paragraph (c)(2) of this section for the presence of
(5) Collection of ground water source samples at a location prior to any treatment of the ground water source unless the State approves a sampling location after treatment, and
(6) Collection of ground water source samples at the well itself unless the system's configuration does not allow
(c)
(2) A ground water system must analyze all ground water source samples collected under paragraph (a) of this section using one of the analytical methods listed in the following table in paragraph (c)(2) of this section or one of the alternative methods listed in appendix A to subpart C of this part for the presence of
(d)
(i) The system provides the State with written notice from the laboratory that improper sample analysis occurred; or
(ii) The State determines and documents in writing that there is substantial evidence that a fecal indicator-positive ground water source sample is not related to source water quality.
(2) If the State invalidates a fecal indicator-positive ground water source sample, the ground water system must collect another source water sample under paragraph (a) of this section within 24 hours of being notified by the State of its invalidation decision and have it analyzed for the same fecal indicator using the analytical methods in paragraph (c) of this section. The State may extend the 24-hour time limit on a case-by-case basis if the system cannot collect the source water sample within 24 hours due to circumstances beyond its control. In the case of an extension, the State must specify how much time the system has to collect the sample.
(e)
(2) If the system's configuration does not allow for sampling at the well itself, the system may collect a sample at a State-approved location to meet the requirements of paragraph (a) of this section if the sample is representative of the water quality of that well.
(f)
(g)
(h)
(a)
(2) If directed by the State, a ground water system with a ground water source sample collected under § 141.402(a)(2), § 141.402(a)(4), or § 141.402(b) that is fecal indicator-positive must comply with the treatment technique requirements of this section.
(3) When a significant deficiency is identified at a Subpart H public water system that uses both ground water and surface water or ground water under the direct influence of surface water, the system must comply with provisions of this paragraph except in cases where the State determines that the significant deficiency is in a portion of the distribution system that is served solely by surface water or ground water under the direct influence of surface water.
(4) Unless the State directs the ground water system to implement a specific corrective action, the ground water system must consult with the State regarding the appropriate corrective action within 30 days of receiving written notice from the State of a significant deficiency, written notice from a laboratory that a ground water source sample collected under § 141.402(a)(3) was found to be fecal indicator-positive, or direction from the State that a fecal indicator'positive collected under § 141.402(a)(2), § 141.402(a)(4), or § 141.402(b) requires corrective action. For the purposes of this subpart, significant deficiencies
(5) Within 120 days (or earlier if directed by the State) of receiving written notification from the State of a significant deficiency, written notice from a laboratory that a ground water source sample collected under § 141.402(a)(3) was found to be fecal indicator-positive, or direction from the State that a fecal indicator-positive sample collected under § 141.402(a)(2), § 141.402(a)(4), or § 141.402(b) requires corrective action, the ground water system must either:
(i) Have completed corrective action in accordance with applicable State plan review processes or other State guidance or direction, if any, including State-specified interim measures; or
(ii) Be in compliance with a State-approved corrective action plan and schedule subject to the conditions specified in paragraphs (a)(5)(ii)(A) and (a)(5)(ii)(B) of this section.
(A) Any subsequent modifications to a State-approved corrective action plan and schedule must also be approved by the State.
(B) If the State specifies interim measures for protection of the public health pending State approval of the corrective action plan and schedule or pending completion of the corrective action plan, the system must comply with these interim measures as well as with any schedule specified by the State.
(6)
(i) Correct all significant deficiencies;
(ii) Provide an alternate source of water;
(iii) Eliminate the source of contamination; or
(iv) Provide treatment that reliably achieves at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer for the ground water source.
(7)
(ii) In addition to the applicable public notification requirements of § 141.202, a non-community ground water system that receives notice from the State of a significant deficiency must inform the public served by the water system in a manner approved by the State of any significant deficiency that has not been corrected within 12 months of being notified by the State, or earlier if directed by the State. The system must continue to inform the public annually until the significant deficiency is corrected. The information must include:
(A) The nature of the significant deficiency and the date the significant deficiency was identified by the State;
(B) The State-approved plan and schedule for correction of the significant deficiency, including interim measures, progress to date, and any interim measures completed; and
(C) For systems with a large proportion of non-English speaking consumers, as determined by the State, information in the appropriate language(s) regarding the importance of the notice or a telephone number or address where consumers may contact the system to obtain a translated copy
(iii) If directed by the State, a non-community water system with significant deficiencies that have been corrected must inform its customers of the significant deficiencies, how the deficiencies were corrected, and the dates of correction under paragraph (a)(7)(ii) of this section.
(b)
(2)
(i) The system must notify the State in writing that it provides at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer for the ground water source. Notification to the State must include engineering, operational, or other information that the State requests to evaluate the submission.
(ii) The system must conduct compliance monitoring as required under § 141.403(b)(3) of this subpart within 30 days of placing the source in service.
(iii) The system must conduct ground water source monitoring under § 141.402 if the system subsequently discontinues 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer for the ground water source.
(3)
(i)
(B)
(ii)
(A) The membrane has an absolute molecular weight cut-off (MWCO), or an alternate parameter that describes the exclusion characteristics of the membrane, that can reliably achieve at least 4-log removal of viruses;
(B) The membrane process is operated in accordance with State-specified compliance requirements; and
(C) The integrity of the membrane is intact.
(iii)
(A) Monitor the alternative treatment in accordance with all State-specified monitoring requirements; and
(B) Operate the alternative treatment in accordance with all compliance requirements that the State determines to be necessary to achieve at least 4-log treatment of viruses.
(c)
(d) Failure to meet the monitoring requirements of paragraph (b) of this section is a monitoring violation and requires the ground water system to provide public notification under § 141.204.
(a) A ground water system with a significant deficiency is in violation of the treatment technique requirement if, within 120 days (or earlier if directed by the State) of receiving written notice from the State of the significant deficiency, the system:
(1) Does not complete corrective action in accordance with any applicable State plan review processes or other State guidance and direction, including State specified interim actions and measures, or
(2) Is not in compliance with a State-approved corrective action plan and schedule.
(b) Unless the State invalidates a fecal indicator-positive ground water source sample under § 141.402(d), a ground water system is in violation of the treatment technique requirement if, within 120 days (or earlier if directed by the State) of meeting the conditions of § 141.403(a)(1) or § 141.403(a)(2), the system:
(1) Does not complete corrective action in accordance with any applicable State plan review processes or other State guidance and direction, including State-specified interim measures, or
(2) Is not in compliance with a State-approved corrective action plan and schedule.
(c) A ground water system subject to the requirements of § 141.403(b)(3) that fails to maintain at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer for a ground water source is in violation of the treatment technique requirement if the failure is not corrected within four hours of determining the system is not maintaining at least 4-log treatment of viruses before or at the first customer.
(d) Ground water system must give public notification under § 141.203 for the treatment technique violations specified in paragraphs (a), (b) and (c) of this section.
(a)
(1) A ground water system conducting compliance monitoring under § 141.403(b) must notify the State any time the system fails to meet any State-specified requirements including, but not limited to, minimum residual disinfectant concentration, membrane operating criteria or membrane integrity, and alternative treatment operating criteria, if operation in accordance with the criteria or requirements is not restored within four hours. The ground water system must notify the State as soon as possible, but in no case later than the end of the next business day.
(2) After completing any corrective action under § 141.403(a), a ground water system must notify the State within 30 days of completion of the corrective action.
(3) If a ground water system subject to the requirements of § 141.402(a) does not conduct source water monitoring under § 141.402(a)(5)(ii), the system must provide documentation to the State within 30 days of the total coliform positive sample that it met the State criteria.
(b)
(1) Documentation of corrective actions. Documentation shall be kept for a period of not less than ten years.
(2) Documentation of notice to the public as required under § 141.403(a)(7). Documentation shall be kept for a period of not less than three years.
(3) Records of decisions under § 141.402(a)(5)(ii) and records of invalidation of fecal indicator-positive ground water source samples under § 141.402(d). Documentation shall be kept for a period of not less than five years.
(4) For consecutive systems, documentation of notification to the wholesale system(s) of total-coliform positive samples that are not invalidated under § 141.21(c). Documentation shall be kept for a period of not less than five years.
(5) For systems, including wholesale systems, that are required to perform compliance monitoring under § 141.403(b):
(i) Records of the State-specified minimum disinfectant residual. Documentation shall be kept for a period of not less than ten years.
(ii) Records of the lowest daily residual disinfectant concentration and records of the date and duration of any failure to maintain the State-prescribed minimum residual disinfectant concentration for a period of more than four hours. Documentation shall be kept for a period of not less than five years.
(iii) Records of State-specified compliance requirements for membrane filtration and of parameters specified by the State for State-approved alternative treatment and records of the date and duration of any failure to meet the membrane operating, membrane integrity, or alternative treatment operating requirements for more than four hours. Documentation shall
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
(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 1, 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
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. Your State may approve a more representative TTHM and HAA5 data set to determine these levels.
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.
Use the tables in § 141.74(b)(3)(v) to determine the appropriate CT99.9 value. 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
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 in §§ 141.543 and 141.544 and provide the benchmark(s) to your State. Your system may only make a significant disinfection practice change after consulting with the State for approval. Your system must submit the following information to the State as part of the consultation and approval process:
(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 according to § 141.570. The following table describes the required limits for specific filtration technologies.
(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
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.
(a) The requirements of subpart U of this part constitute national primary drinking water regulations. The regulations in this subpart establish monitoring and other requirements for identifying subpart V compliance monitoring locations for determining compliance with maximum contaminant levels for total trihalomethanes (TTHM) and haloacetic acids (five)(HAA5). You must use an Initial Distribution System Evaluation (IDSE) to determine locations with representative high TTHM and HAA5 concentrations throughout your distribution system. IDSEs are used in conjunction with, but separate from, subpart L compliance monitoring, to identify and select subpart V compliance monitoring locations.
(b)
(c)
(2) For the purpose of the schedule in paragraph (c)(1) of this section, the State may determine that the combined distribution system does not include certain consecutive systems based on factors such as receiving water from a wholesale system only on an emergency basis or receiving only a small percentage and small volume of water from a wholesale system. The State may also determine that the combined distribution system does not include certain wholesale systems based on factors such as delivering water to a consecutive system only on an emergency basis or delivering only a small percentage and small volume of water to a consecutive system.
(d) You must conduct standard monitoring that meets the requirements in
(1) You must have taken the full complement of routine TTHM and HAA5 compliance samples required of a system with your population and source water under subpart L of this part (or you must have taken the full complement of reduced TTHM and HAA5 compliance samples required of a system with your population and source water under subpart L if you meet reduced monitoring criteria under subpart L of this part) during the period specified in § 141.603(a) to meet the 40/30 certification criteria in § 141.603. You must have taken TTHM and HAA5 samples under §§ 141.131 and 141.132 to be eligible for the very small system waiver in § 141.604.
(2) If you have not taken the required samples, you must conduct standard monitoring that meets the requirements in § 141.601, or a system specific study that meets the requirements in § 141.602.
(e) You must use only the analytical methods specified in § 141.131, or otherwise approved by EPA for monitoring under this subpart, to demonstrate compliance with the requirements of this subpart.
(f) IDSE results will not be used for the purpose of determining compliance with MCLs in § 141.64.
(a)
(1) Your standard monitoring plan must include a schematic of your distribution system (including distribution system entry points and their sources, and storage facilities), with notes indicating locations and dates of all projected standard monitoring, and all projected subpart L compliance monitoring.
(2) Your standard monitoring plan must include justification of standard monitoring location selection and a summary of data you relied on to justify standard monitoring location selection.
(3) Your standard monitoring plan must specify the population served and system type (subpart H or ground water).
(4) You must retain a complete copy of your standard monitoring plan submitted under this paragraph (a), including any State modification of your standard monitoring plan, for as long as you are required to retain your IDSE report under paragraph (c)(4) of this section.
(b)
(2) You must take samples at locations other than the existing subpart L monitoring locations. Monitoring locations must be distributed throughout the distribution system.
(3) If the number of entry points to the distribution system is fewer than the specified number of entry point monitoring locations, excess entry point samples must be replaced equally at high TTHM and HAA5 locations. If there is an odd extra location number, you must take a sample at a high TTHM location. If the number of entry points to the distribution system is more than the specified number of entry point monitoring locations, you must take samples at entry points to the distribution system having the highest annual water flows.
(4) Your monitoring under this paragraph (b) may not be reduced under the provisions of § 141.29 and the State may not reduce your monitoring using the provisions of § 142.16(m).
(c)
(1) Your IDSE report must include all TTHM and HAA5 analytical results from subpart L compliance monitoring and all standard monitoring conducted during the period of the IDSE as individual analytical results and LRAAs presented in a tabular or spreadsheet format acceptable to the State. If changed from your standard monitoring plan submitted under paragraph (a) of this section, your report must also include a schematic of your distribution system, the population served, and system type (subpart H or ground water).
(2) Your IDSE report must include an explanation of any deviations from your approved standard monitoring plan.
(3) You must recommend and justify subpart V compliance monitoring locations and timing based on the protocol in § 141.605.
(4) You must retain a complete copy of your IDSE report submitted under this section for 10 years after the date that you submitted your report. If the State modifies the subpart V monitoring requirements that you recommended in your IDSE report or if the State approves alternative monitoring locations, you must keep a copy of the State's notification on file for 10 years after the date of the State's notification. You must make the IDSE report and any State notification available for review by the State or the public.
(a)
(1)
(i)
(B) The monitoring locations and frequency must meet the conditions identified in this paragraph (a)(1)(i)(B). Each location must be sampled once during the peak historical month for TTHM levels or HAA5 levels or the month of warmest water temperature for every 12 months of data submitted for that location. Monitoring results must include all subpart L compliance monitoring results plus additional monitoring results as necessary to meet minimum sample requirements.
(ii)
(A) You must report previously collected monitoring results and certify that the reported monitoring results include all compliance and non-compliance results generated during the time period beginning with the first reported result and ending with the most recent subpart L results.
(B) You must certify that the samples were representative of the entire distribution system and that treatment, and distribution system have not changed significantly since the samples were collected.
(C) Your study monitoring plan must include a schematic of your distribution system (including distribution system entry points and their sources, and storage facilities), with notes indicating the locations and dates of all completed or planned system specific study monitoring.
(D) Your system specific study plan must specify the population served and system type (subpart H or ground water).
(E) You must retain a complete copy of your system specific study plan submitted under this paragraph (a)(1), including any State modification of your system specific study plan, for as long as you are required to retain your IDSE report under paragraph (b)(5) of this section.
(F) If you submit previously collected data that fully meet the number of samples required under paragraph (a)(1)(i)(B) of this section and the State rejects some of the data, you must either conduct additional monitoring to replace rejected data on a schedule the
(2)
(i)
(B) The model must represent the criteria listed in paragraphs (a)(2)(i)(B)(1) through (9) of this section.
(1) 75% of pipe volume;
(2) 50% of pipe length;
(3) All pressure zones;
(4) All 12-inch diameter and larger pipes;
(5) All 8-inch and larger pipes that connect pressure zones, influence zones from different sources, storage facilities, major demand areas, pumps, and control valves, or are known or expected to be significant conveyors of water;
(6) All 6-inch and larger pipes that connect remote areas of a distribution system to the main portion of the system;
(7) All storage facilities with standard operations represented in the model; and
(8) All active pump stations with controls represented in the model; and
(9) All active control valves.
(C) The model must be calibrated, or have calibration plans, for the current configuration of the distribution system during the period of high TTHM formation potential. All storage facilities must be evaluated as part of the calibration process. All required calibration must be completed no later than 12 months after plan submission.
(ii)
(A) Tabular or spreadsheet data demonstrating that the model meets requirements in paragraph (a)(2)(i)(B) of this section.
(B) A description of all calibration activities undertaken, and if calibration is complete, a graph of predicted tank levels versus measured tank levels for the storage facility with the highest residence time in each pressure zone, and a time series graph of the residence time at the longest residence time storage facility in the distribution system showing the predictions for the entire simulation period (
(C) Model output showing preliminary 24 hour average residence time predictions throughout the distribution system.
(D) Timing and number of samples representative of the distribution system planned for at least one monitoring period of TTHM and HAA5 dual sample monitoring at a number of locations no less than would be required for the system under standard monitoring in § 141.601 during the historical month of high TTHM. These samples must be taken at locations other than existing subpart L compliance monitoring locations.
(E) Description of how all requirements will be completed no later than 12 months after you submit your system specific study plan.
(F) Schematic of your distribution system (including distribution system entry points and their sources, and storage facilities), with notes indicating the locations and dates of all completed system specific study monitoring (if calibration is complete) and all subpart L compliance monitoring.
(G) Population served and system type (subpart H or ground water).
(H) You must retain a complete copy of your system specific study plan submitted under this paragraph (a)(2), including any State modification of your system specific study plan, for as long as you are required to retain your IDSE report under paragraph (b)(7) of this section.
(iii) If you submit a model that does not fully meet the requirements under paragraph (a)(2) of this section, you must correct the deficiencies and respond to State inquiries concerning the model. If you fail to correct deficiencies or respond to inquiries to the State's satisfaction, you must conduct standard monitoring under § 141.601.
(b)
(1) Your IDSE report must include all TTHM and HAA5 analytical results from subpart L compliance monitoring and all system specific study monitoring conducted during the period of the system specific study presented in a tabular or spreadsheet format acceptable to the State. If changed from your system specific study plan submitted under paragraph (a) of this section, your IDSE report must also include a schematic of your distribution system, the population served, and system type (subpart H or ground water).
(2) If you used the modeling provision under paragraph (a)(2) of this section, you must include final information for the elements described in paragraph (a)(2)(ii) of this section, and a 24-hour time series graph of residence time for each subpart V compliance monitoring location selected.
(3) You must recommend and justify subpart V compliance monitoring locations and timing based on the protocol in § 141.605.
(4) Your IDSE report must include an explanation of any deviations from your approved system specific study plan.
(5) Your IDSE report must include the basis (analytical and modeling results) and justification you used to select the recommended subpart V monitoring locations.
(6) You may submit your IDSE report in lieu of your system specific study plan on the schedule identified in § 141.600(c) for submission of the system specific study plan if you believe that you have the necessary information by the time that the system specific study plan is due. If you elect this approach, your IDSE report must also include all information required under paragraph (a) of this section.
(7) You must retain a complete copy of your IDSE report submitted under this section for 10 years after the date that you submitted your IDSE report. If the State modifies the subpart V monitoring requirements that you recommended in your IDSE report or if the State approves alternative monitoring locations, you must keep a copy of the State's notification on file for 10 years after the date of the State's notification. You must make the IDSE report and any State notification available for review by the State or the public.
(a)
(b)
(2) The State may require you to submit compliance monitoring results, distribution system schematics, and/or recommended subpart V compliance monitoring locations in addition to your certification. If you fail to submit the requested information, the State may require standard monitoring under § 141.601 or a system specific study under § 141.602.
(3) The State may still require standard monitoring under § 141.601 or a system specific study under § 141.602 even if you meet the criteria in paragraph (a) of this section.
(4) You must retain a complete copy of your certification submitted under this section for 10 years after the date that you submitted your certification.
(a) If you serve fewer than 500 people and you have taken TTHM and HAA5 samples under subpart L of this part, you are not required to comply with this subpart unless the State notifies you that you must conduct standard monitoring under § 141.601 or a system specific study under § 141.602.
(b) If you have not taken TTHM and HAA5 samples under subpart L of this part or if the State notifies you that you must comply with this subpart, you must conduct standard monitoring under § 141.601 or a system specific study under § 141.602.
(a) Your IDSE report must include your recommendations and justification for where and during what month(s) TTHM and HAA5 monitoring for subpart V of this part should be conducted. You must base your recommendations on the criteria in paragraphs (b) through (e) of this section.
(b) You must select the number of monitoring locations specified in the table in this paragraph (b). You will use these recommended locations as subpart V routine compliance monitoring locations, unless State requires different or additional locations. You should distribute locations throughout the distribution system to the extent possible.
(c) You must recommend subpart V compliance monitoring locations based on standard monitoring results, system specific study results, and subpart L compliance monitoring results. You must follow the protocol in paragraphs (c)(1) through (c)(8) of this section. If required to monitor at more than eight locations, you must repeat the protocol as necessary. If you do not have existing subpart L compliance monitoring results or if you do not have enough existing subpart L compliance monitoring results, you must repeat the protocol, skipping the provisions of paragraphs (c)(3) and (c)(7) of this section as necessary, until you have identified the required total number of monitoring locations.
(1) Location with the highest TTHM LRAA not previously selected as a subpart V monitoring location.
(2) Location with the highest HAA5 LRAA not previously selected as a subpart V monitoring location.
(3) Existing subpart L average residence time compliance monitoring location (maximum residence time compliance monitoring location for ground water systems) with the highest HAA5 LRAA not previously selected as a subpart V monitoring location.
(4) Location with the highest TTHM LRAA not previously selected as a subpart V monitoring location.
(5) Location with the highest TTHM LRAA not previously selected as a subpart V monitoring location.
(6) Location with the highest HAA5 LRAA not previously selected as a subpart V monitoring location.
(7) Existing subpart L average residence time compliance monitoring location (maximum residence time compliance monitoring location for ground water systems) with the highest TTHM LRAA not previously selected as a subpart V monitoring location.
(8) Location with the highest HAA5 LRAA not previously selected as a subpart V monitoring location.
(d) You may recommend locations other than those specified in paragraph (c) of this section if you include a rationale for selecting other locations. If the State approves the alternate locations, you must monitor at these locations to determine compliance under subpart V of this part.
(e) Your recommended schedule must include subpart V monitoring during the peak historical month for TTHM and HAA5 concentration, unless the State approves another month. Once you have identified the peak historical month, and if you are required to conduct routine monitoring at least quarterly, you must schedule subpart V compliance monitoring at a regular frequency of every 90 days or fewer.
(a)
(b)
(c)
(6) Your monitoring frequency is specified in § 141.621(a)(2).
(i) If you are required to conduct quarterly monitoring, you must begin monitoring in the first full calendar quarter that includes the compliance date in the table in this paragraph (c).
(ii) If you are required to conduct monitoring at a frequency that is less than quarterly, you must begin monitoring in the calendar month recommended in the IDSE report prepared under § 141.601 or § 141.602 or the calendar month identified in the subpart V monitoring plan developed under § 141.622 no later than 12 months after the compliance date in this table.
(7) If you are required to conduct quarterly monitoring, you must make compliance calculations at the end of the fourth calendar quarter that follows the compliance date and at the end of each subsequent quarter (or earlier if the LRAA calculated based on fewer than four quarters of data would cause the MCL to be exceeded regardless of the monitoring results of subsequent quarters). If you are required to conduct monitoring at a frequency that is less than quarterly, you must make compliance calculations beginning with the first compliance sample taken after the compliance date.
(8) For the purpose of the schedule in this paragraph (c), the State may determine that the combined distribution system does not include certain consecutive systems based on factors such as receiving water from a wholesale system only on an emergency basis or receiving only a small percentage and small volume of water from a wholesale system. The State may also determine that the combined distribution system does not include certain wholesale systems based on factors such as delivering water to a consecutive system only on an emergency basis or delivering only a small percentage and small volume of water to a consecutive system.
(d)
(2)
(e)
(a)
(2) You must monitor at no fewer than the number of locations identified in this paragraph (a)(2).
(3) If you are an undisinfected system that begins using a disinfectant other than UV light after the dates in subpart U of this part for complying with the Initial Distribution System Evaluation requirements, you must consult with the State to identify compliance monitoring locations for this subpart. You must then develop a monitoring plan under § 141.622 that includes those monitoring locations.
(b)
(a)(1) You must develop and implement a monitoring plan to be kept on file for State and public review. The monitoring plan must contain the elements in paragraphs (a)(1)(i) through (a)(1)(iv) of this section and be complete no later than the date you conduct your initial monitoring under this subpart.
(i) Monitoring locations;
(ii) Monitoring dates;
(iii) Compliance calculation procedures; and
(iv) Monitoring plans for any other systems in the combined distribution system if the State has reduced monitoring requirements under the State authority in § 142.16(m).
(2) If you were not required to submit an IDSE report under either § 141.601 or § 141.602, and you do not have sufficient subpart L monitoring locations to identify the required number of subpart V compliance monitoring locations indicated in § 141.605(b), you must identify additional locations by alternating selection of locations representing high TTHM levels and high HAA5 levels until the required number of compliance monitoring locations have been identified. You must also provide the rationale for identifying the locations as having high levels of TTHM or HAA5. If you have more subpart L monitoring locations than required for subpart V compliance monitoring in § 141.605(b), you must identify which locations you will use for subpart V compliance monitoring by alternating selection of locations representing high TTHM levels and high HAA5 levels until the required number of subpart V compliance monitoring locations have been identified.
(b) If you are a subpart H system serving > 3,300 people, you must submit a copy of your monitoring plan to the State prior to the date you conduct
(c) You may revise your monitoring plan to reflect changes in treatment, distribution system operations and layout (including new service areas), or other factors that may affect TTHM or HAA5 formation, or for State-approved reasons, after consultation with the State regarding the need for changes and the appropriateness of changes. If you change monitoring locations, you must replace existing compliance monitoring locations with the lowest LRAA with new locations that reflect the current distribution system locations with expected high TTHM or HAA5 levels. The State may also require modifications in your monitoring plan. If you are a subpart H system serving > 3,300 people, you must submit a copy of your modified monitoring plan to the State prior to the date you are required to comply with the revised monitoring plan.
(a) You may reduce monitoring to the level specified in the table in this paragraph (a) any time the LRAA is ≤0.040 mg/L for TTHM and ≤0.030 mg/L for HAA5 at all monitoring locations. You may only use data collected under the provisions of this subpart or subpart L of this part to qualify for reduced monitoring. In addition, the source water annual average TOC level, before any treatment, must be ≤4.0 mg/L at each treatment plant treating surface water or ground water under the direct influence of surface water, based on monitoring conducted under either § 141.132(b)(1)(iii) or § 141.132(d).
(b) You may remain on reduced monitoring as long as the TTHM LRAA ≤0.040 mg/L and the HAA5 LRAA ≤0.030 mg/L at each monitoring location (for systems with quarterly reduced monitoring) or each TTHM sample ≤0.060 mg/L and each HAA5 sample ≤0.045 mg/L (for systems with annual or less frequent monitoring). In addition, the source water annual average TOC level, before any treatment, must be ≤4.0 mg/L at each treatment plant treating surface water or ground water under the direct influence of surface water, based on monitoring conducted under either § 141.132(b)(1)(iii) or § 141.132(d).
(c) If the LRAA based on quarterly monitoring at any monitoring location exceeds either 0.040 mg/L for TTHM or 0.030 mg/L for HAA5 or if the annual (or less frequent) sample at any location exceeds either 0.060 mg/L for TTHM or 0.045 mg/L for HAA5, or if the source water annual average TOC level, before any treatment, >4.0 mg/L at any treatment plant treating surface water or ground water under the direct influence of surface water, you must resume routine monitoring under § 141.621 or begin increased monitoring if § 141.625 applies.
(d) The State may return your system to routine monitoring at the State's discretion.
If you are a consecutive system that does not add a disinfectant but delivers water that has been treated with a primary or residual disinfectant other than ultraviolet light, you must comply with analytical and monitoring requirements for chlorine and chloramines in § 141.131 (c) and § 141.132(c)(1) and the compliance requirements in § 141.133(c)(1) beginning April 1, 2009, unless required earlier by the State, and report monitoring results under § 141.134(c).
(a) If you are required to monitor at a particular location annually or less frequently than annually under § 141.621 or § 141.623, you must increase monitoring to dual sample sets once per quarter (taken every 90 days) at all locations if a TTHM sample is >0.080 mg/L or a HAA5 sample is >0.060 mg/L at any location.
(b) You are in violation of the MCL when the LRAA exceeds the subpart V MCLs in § 141.64(b)(2), calculated based on four consecutive quarters of monitoring (or the LRAA calculated based on fewer than four quarters of data if the MCL would be exceeded regardless of the monitoring results of subsequent quarters). You are in violation of the monitoring requirements for each quarter that a monitoring result would be used in calculating an LRAA if you fail to monitor.
(c) You may return to routine monitoring once you have conducted increased monitoring for at least four
(a) You have exceeded the operational evaluation level at any monitoring location where the sum of the two previous quarters' TTHM results plus twice the current quarter's TTHM result, divided by 4 to determine an average, exceeds 0.080 mg/L, or where the sum of the two previous quarters' HAA5 results plus twice the current quarter's HAA5 result, divided by 4 to determine an average, exceeds 0.060 mg/L.
(b)(1) If you exceed the operational evaluation level, you must conduct an operational evaluation and submit a written report of the evaluation to the State no later than 90 days after being notified of the analytical result that causes you to exceed the operational evaluation level. The written report must be made available to the public upon request.
(2) Your operational evaluation must include an examination of system treatment and distribution operational practices, including storage tank operations, excess storage capacity, distribution system flushing, changes in sources or source water quality, and treatment changes or problems that may contribute to TTHM and HAA5 formation and what steps could be considered to minimize future exceedences.
(i) You may request and the State may allow you to limit the scope of your evaluation if you are able to identify the cause of the operational evaluation level exceedance.
(ii) Your request to limit the scope of the evaluation does not extend the schedule in paragraph (b)(1) of this section for submitting the written report. The State must approve this limited scope of evaluation in writing and you must keep that approval with the completed report.
You may remain on reduced monitoring after the dates identified in § 141.620(c) for compliance with this subpart only if you qualify for a 40/30 certification under § 141.603 or have received a very small system waiver under § 141.604, plus you meet the reduced monitoring criteria in § 141.623(a), and you do not change or add monitoring locations from those used for compliance monitoring under subpart L of this part. If your monitoring locations under this subpart differ from your monitoring locations under subpart L of this part, you may not remain on reduced monitoring after the dates identified in § 141.620(c) for compliance with this subpart.
If you were on increased monitoring under § 141.132(b)(1), you must remain on increased monitoring until you qualify for a return to routine monitoring under § 141.625(c). You must conduct increased monitoring under § 141.625 at the monitoring locations in the monitoring plan developed under § 141.622 beginning at the date identified in § 141.620(c) for compliance with this subpart and remain on increased monitoring until you qualify for a return to routine monitoring under § 141.625(c).
(a)
(i) Number of samples taken during the last quarter.
(ii) Date and results of each sample taken during the last quarter.
(iii) Arithmetic average of quarterly results for the last four quarters for each monitoring location (LRAA), beginning at the end of the fourth calendar quarter that follows the compliance date and at the end of each subsequent quarter. If the LRAA calculated based on fewer than four quarters of data would cause the MCL to be exceeded regardless of the monitoring results of subsequent quarters, you must report this information to the State as part of the first report due following
(iv) Whether, based on § 141.64(b)(2) and this subpart, the MCL was violated at any monitoring location.
(v) Any operational evaluation levels that were exceeded during the quarter and, if so, the location and date, and the calculated TTHM and HAA5 levels.
(2) If you are a subpart H system seeking to qualify for or remain on reduced TTHM/HAA5 monitoring, you must report the following source water TOC information for each treatment plant that treats surface water or ground water under the direct influence of surface water to the State within 10 days of the end of any quarter in which monitoring is required:
(i) The number of source water TOC samples taken each month during last quarter.
(ii) The date and result of each sample taken during last quarter.
(iii) The quarterly average of monthly samples taken during last quarter or the result of the quarterly sample.
(iv) The running annual average (RAA) of quarterly averages from the past four quarters.
(v) Whether the RAA exceeded 4.0 mg/L.
(3) The State may choose to perform calculations and determine whether the MCL was exceeded or the system is eligible for reduced monitoring in lieu of having the system report that information
(b)
(a) The requirements of this subpart W are national primary drinking water regulations. The regulations in this subpart establish or extend treatment technique requirements in lieu of maximum contaminant levels for
(b)
(1) Wholesale systems, as defined in § 141.2, must comply with the requirements of this subpart based on the population of the largest system in the combined distribution system.
(2) The requirements of this subpart for filtered systems apply to systems required by National Primary Drinking Water Regulations to provide filtration treatment, whether or not the system is currently operating a filtration system.
(3) The requirements of this subpart for unfiltered systems apply only to unfiltered systems that timely met and continue to meet the filtration avoidance criteria in subparts H, P, and T of this part, as applicable.
(c)
(1) Systems must conduct an initial and a second round of source water monitoring for each plant that treats a surface water or GWUDI source. This monitoring may include sampling for
(2) Systems that plan to make a significant change to their disinfection practice must develop disinfection profiles and calculate disinfection benchmarks, as described in §§ 141.708 through 141.709.
(3) Filtered systems must determine their
(4) Systems with uncovered finished water storage facilities must comply with the requirements to cover the facility or treat the discharge from the facility as described in § 141.714.
(5) Systems required to provide additional treatment for
(6) Systems must comply with the applicable recordkeeping and reporting requirements described in §§ 141.721 through 141.722.
(7) Systems must address significant deficiencies identified in sanitary surveys performed by EPA as described in § 141.723.
(a)
(1) Filtered systems serving at least 10,000 people must sample their source water for
(2) Unfiltered systems serving at least 10,000 people must sample their source water for
(3)(i) Filtered systems serving fewer than 10,000 people must sample their source water for
(ii) A filtered system serving fewer than 10,000 people may avoid
(4) Filtered systems serving fewer than 10,000 people must sample their source water for
(i) For systems using lake/reservoir sources, the annual mean
(ii) For systems using flowing stream sources, the annual mean
(iii) The system does not conduct
(iv) Systems using ground water under the direct influence of surface water (GWUDI) must comply with the requirements of paragraph (a)(4) of this section based on the
(5) For filtered systems serving fewer than 10,000 people, the State may approve monitoring for an indicator other than
(6) Unfiltered systems serving fewer than 10,000 people must sample their source water for
(7) Systems may sample more frequently than required under this section if the sampling frequency is evenly spaced throughout the monitoring period.
(b)
(c)
(d)
(2) Unfiltered systems are not required to conduct source water monitoring under this subpart if the system will provide a total of at least 3-log
(3) If a system chooses to provide the level of treatment in paragraph (d)(1) or (2) of this section, as applicable, rather than start source water monitoring, the system must notify the State in writing no later than the date the system is otherwise required to submit a sampling schedule for monitoring under § 141.702. Alternatively, a system may choose to stop sampling at any point after it has initiated monitoring if it notifies the State in writing that it will provide this level of treatment. Systems must install and operate technologies to provide this level of treatment by the applicable treatment compliance date in § 141.713.
(e)
(1) Systems must sample their source water only during the months that the plant operates unless the State specifies another monitoring period based on plant operating practices.
(2) Systems with plants that operate less than six months per year and that monitor for
(f)(1)
(2) The requirements of § 141.701(f) apply to subpart H systems that begin operation after the monitoring start date applicable to the system's size under paragraph (c) of this section.
(3) The system must begin a second round of source water monitoring no later than 6 years following initial bin classification under § 141.710 or determination of the mean
(g) Failure to collect any source water sample required under this section in accordance with the sampling schedule, sampling location, analytical method, approved laboratory, and reporting requirements of §§ 141.702 through 141.706 is a monitoring violation.
(h)
(a) Systems required to conduct source water monitoring under § 141.701 must submit a sampling schedule that specifies the calendar dates when the system will collect each required sample.
(1) Systems must submit sampling schedules no later than 3 months prior to the applicable date listed in § 141.701(c) for each round of required monitoring.
(2)(i) Systems serving at least 10,000 people must submit their sampling schedule for the initial round of source water monitoring under § 141.701(a) to EPA electronically at
(ii) If a system is unable to submit the sampling schedule electronically, the system may use an alternative approach for submitting the sampling schedule that EPA approves.
(3) Systems serving fewer than 10,000 people must submit their sampling schedules for the initial round of source water monitoring § 141.701(a) to the State.
(4) Systems must submit sampling schedules for the second round of source water monitoring § 141.701(b) to the State.
(5) If EPA or the State does not respond to a system regarding its sampling schedule, the system must sample at the reported schedule.
(b) Systems must collect samples within two days before or two days after the dates indicated in their sampling schedule (
(1) If an extreme condition or situation exists that may pose danger to the sample collector, or that cannot be avoided and causes the system to be unable to sample in the scheduled five-day period, the system must sample as close to the scheduled date as is feasible unless the State approves an alternative sampling date. The system must submit an explanation for the delayed sampling date to the State concurrent with the shipment of the sample to the laboratory.
(2)(i) If a system is unable to report a valid analytical result for a scheduled sampling date due to equipment failure, loss of or damage to the sample, failure to comply with the analytical method requirements, including the quality control requirements in § 141.704, or the failure of an approved laboratory to analyze the sample, then the system must collect a replacement sample.
(ii) The system must collect the replacement sample not later than 21 days after receiving information that an analytical result cannot be reported for the scheduled date unless the system demonstrates that collecting a replacement sample within this time frame is not feasible or the State approves an alternative resampling date. The system must submit an explanation for the delayed sampling date to the State concurrent with the shipment of the sample to the laboratory.
(c) Systems that fail to meet the criteria of paragraph (b) of this section for any source water sample required under § 141.701 must revise their sampling schedules to add dates for collecting all missed samples. Systems must submit the revised schedule to the State for approval prior to when
(a) Systems required to conduct source water monitoring under § 141.701 must collect samples for each plant that treats a surface water or GWUDI source. Where multiple plants draw water from the same influent, such as the same pipe or intake, the State may approve one set of monitoring results to be used to satisfy the requirements of § 141.701 for all plants.
(b)(1) Systems must collect source water samples prior to chemical treatment, such as coagulants, oxidants and disinfectants, unless the system meets the condition of paragraph (b)(2) of this section.
(2) The State may approve a system to collect a source water sample after chemical treatment. To grant this approval, the State must determine that collecting a sample prior to chemical treatment is not feasible for the system and that the chemical treatment is unlikely to have a significant adverse effect on the analysis of the sample.
(c) Systems that recycle filter backwash water must collect source water samples prior to the point of filter backwash water addition.
(d)
(2) Systems that use bank filtration as pretreatment to a filtration plant must collect source water samples from the well (
(e)
(1) If a sampling tap is available where the sources are combined prior to treatment, systems must collect samples from the tap.
(2) If a sampling tap where the sources are combined prior to treatment is not available, systems must collect samples at each source near the intake on the same day and must follow either paragraph (e)(2)(i) or (ii) of this section for sample analysis.
(i) Systems may composite samples from each source into one sample prior to analysis. The volume of sample from each source must be weighted according to the proportion of the source in the total plant flow at the time the sample is collected.
(ii) Systems may analyze samples from each source separately and calculate a weighted average of the analysis results for each sampling date. The weighted average must be calculated by multiplying the analysis result for each source by the fraction the source contributed to total plant flow at the time the sample was collected and then summing these values.
(f)
(a)
(1) Systems must analyze at least a 10 L sample or a packed pellet volume of at least 2 mL as generated by the methods listed in paragraph (a) of this section. Systems unable to process a 10 L sample must analyze as much sample volume as can be filtered by two filters approved by EPA for the methods listed in paragraph (a) of this section, up to a packed pellet volume of at least 2 mL.
(2)(i) Matrix spike (MS) samples, as required by the methods in paragraph (a) of this section, must be spiked and filtered by a laboratory approved for
(ii) If the volume of the MS sample is greater than 10 L, the system may filter all but 10 L of the MS sample in the field, and ship the filtered sample and the remaining 10 L of source water to the laboratory. In this case, the laboratory must spike the remaining 10 L of water and filter it through the filter used to collect the balance of the sample in the field.
(3) Flow cytometer-counted spiking suspensions must be used for MS samples and ongoing precision and recovery (OPR) samples.
(b)
(1) The time from sample collection to initiation of analysis may not exceed 30 hours unless the system meets the condition of paragraph (b)(2) of this section.
(2) The State may approve on a case-by-case basis the holding of an
(3) Systems must maintain samples between 0 °C and 10 °C during storage and transit to the laboratory.
(c)
(a)
(b)
(c)
(a) Systems must report results from the source water monitoring required under § 141.701 no later than 10 days after the end of the first month following the month when the sample is collected.
(b)(1) All systems serving at least 10,000 people must report the results from the initial source water monitoring required under § 141.701(a) to EPA electronically at
(2) If a system is unable to report monitoring results electronically, the system may use an alternative approach for reporting monitoring results that EPA approves.
(c) Systems serving fewer than 10,000 people must report results from the initial source water monitoring required under § 141.701(a) to the State.
(d) All systems must report results from the second round of source water monitoring required under § 141.701(b) to the State.
(e) Systems must report the applicable information in paragraphs (e)(1) and (2) of this section for the source water monitoring required under § 141.701.
(1) Systems must report the following data elements for each
(i) For matrix spike samples, systems must also report the sample volume spiked and estimated number of oocysts spiked. These data are not required for field samples.
(ii) For samples in which less than 10 L is filtered or less than 100% of the sample volume is examined, systems must also report the number of filters used and the packed pellet volume.
(iii) For samples in which less than 100% of sample volume is examined, systems must also report the volume of resuspended concentrate and volume of this resuspension processed through immunomagnetic separation.
(2) Systems must report the following data elements for each
(a)(1) Systems may comply with the initial source water monitoring requirements of § 141.701(a) by grandfathering sample results collected before the system is required to begin monitoring (
(2) A filtered system may grandfather
(b)
(c)
(1) Laboratories analyzed
(i)
(ii)
(iii)
(iv)
(v)
(vi)
(2) For each
(d)
(e)
(1) The State may approve grandfathering of previously collected data where there are time gaps in the sampling frequency if the system conducts additional monitoring the State specifies to ensure that the data used to comply with the initial source water monitoring requirements of § 141.701(a) are seasonally representative and unbiased.
(2) Systems may grandfather previously collected data where the sampling frequency within each month varied. If the
(f)
(1) Systems must report that they intend to submit previously collected monitoring results for grandfathering. This report must specify the number of previously collected results the system will submit, the dates of the first and last sample, and whether a system will conduct additional source water monitoring to meet the requirements of § 141.701(a). Systems must report this information no later than the date the sampling schedule under § 141.702 is required.
(2) Systems must report previously collected monitoring results for grandfathering, along with the associated documentation listed in paragraphs (f)(2)(i) through (iv) of this section, no later than two months after the applicable date listed in § 141.701(c).
(i) For each sample result, systems must report the applicable data elements in § 141.706.
(ii) Systems must certify that the reported monitoring results include all results the system generated during the time period beginning with the first reported result and ending with the final reported result. This applies to samples that were collected from the sampling location specified for source water monitoring under this subpart, not spiked, and analyzed using
(iii) Systems must certify that the samples were representative of a plant's source water(s) and the source water(s) have not changed. Systems must report a description of the sampling location(s), which must address the position of the sampling location in relation to the system's water source(s) and treatment processes, including points of chemical addition and filter backwash recycle.
(iv) For
(g) If the State determines that a previously collected data set submitted for grandfathering was generated during source water conditions that were not normal for the system, such as a drought, the State may disapprove the data. Alternatively, the State may approve the previously collected data if the system reports additional source water monitoring data, as determined by the State, to ensure that the data set used under § 141.710 or § 141.712 represents average source water conditions for the system.
(h) If a system submits previously collected data that fully meet the number of samples required for initial source water monitoring under § 141.701(a) and some of the data are rejected due to not meeting the requirements of this section, systems must conduct additional monitoring to replace rejected data on a schedule the State approves. Systems are not required to begin this additional monitoring until two months after notification that data have been rejected and additional monitoring is necessary.
(a) Following the completion of initial source water monitoring under § 141.701(a), a system that plans to make a significant change to its disinfection practice, as defined in paragraph (b) of this section, must develop disinfection profiles and calculate disinfection benchmarks for
(1) A completed disinfection profile and disinfection benchmark for
(2) A description of the proposed change in disinfection practice.
(3) An analysis of how the proposed change will affect the current level of disinfection.
(b) Significant changes to disinfection practice are defined as follows:
(1) Changes to the point of disinfection;
(2) Changes to the disinfectant(s) used in the treatment plant;
(3) Changes to the disinfection process; or
(4) Any other modification identified by the State as a significant change to disinfection practice.
(a) Systems required to develop disinfection profiles under § 141.708 must follow the requirements of this section. Systems must monitor at least weekly for a period of 12 consecutive months to determine the total log inactivation for
(b) Systems with a single point of disinfectant application prior to the entrance to the distribution system must conduct the monitoring in paragraphs (b)(1) through (4) of this section. Systems with more than one point of disinfectant application must conduct the monitoring in paragraphs (b)(1) through (4) of this section for each disinfection segment. Systems must monitor the parameters necessary to determine the total inactivation ratio, using analytical methods in § 141.74(a).
(1) For systems using a disinfectant other than UV, the temperature of the disinfected water must be measured at each residual disinfectant concentration sampling point during peak hourly flow or at an alternative location approved by the State.
(2) For systems using chlorine, the pH of the disinfected water must be measured at each chlorine residual disinfectant concentration sampling point during peak hourly flow or at an alternative location approved by the State.
(3) The disinfectant contact time(s) (t) must be determined during peak hourly flow.
(4) The residual disinfectant concentration(s) (C) of the water before or at the first customer and prior to each additional point of disinfectant application must be measured during peak hourly flow.
(c) In lieu of conducting new monitoring under paragraph (b) of this section, systems may elect to meet the requirements of paragraphs (c)(1) or (2) of this section.
(1) Systems that have at least one year of existing data that are substantially equivalent to data collected under the provisions of paragraph (b) of this section may use these data to develop disinfection profiles as specified in this section if the system has neither made a significant change to its treatment practice nor changed sources since the data were collected. Systems may develop disinfection profiles using up to three years of existing data.
(2) Systems may use disinfection profile(s) developed under § 141.172 or §§ 141.530 through 141.536 in lieu of developing a new profile if the system has neither made a significant change to its treatment practice nor changed sources since the profile was developed. Systems that have not developed a virus profile under § 141.172 or §§ 141.530 through 141.536 must develop a virus profile using the same monitoring data on which the
(d) Systems must calculate the total inactivation ratio for
(1) Systems using only one point of disinfectant application may determine the total inactivation ratio for the disinfection segment based on either of the methods in paragraph (d)(1)(i) or (ii) of this section.
(i) Determine one inactivation ratio (CTcalc/CT
(ii) Determine successive CTcalc/CT
(2) Systems using more than one point of disinfectant application before the first customer 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
(3) The system must determine the total logs of inactivation by multiplying the value calculated in paragraph (d)(1) or (d)(2) of this section by 3.0.
(4) Systems must calculate the log of inactivation for viruses using a protocol approved by the State.
(e) Systems must use the procedures specified in paragraphs (e)(1) and (2) of
(1) For each year of profiling data collected and calculated under paragraphs (a) through (d) of this section, systems must determine the lowest mean monthly level of both
(2) The disinfection benchmark is the lowest monthly mean value (for systems with one year of profiling data) or the mean of the lowest monthly mean values (for systems with more than one year of profiling data) of
(a) Following completion of the initial round of source water monitoring required under § 141.701(a), filtered systems must calculate an initial
(b)(1) For systems that collect a total of at least 48 samples, the bin concentration is equal to the arithmetic mean of all sample concentrations.
(2) For systems that collect a total of at least 24 samples, but not more than 47 samples, the bin concentration is equal to the highest arithmetic mean of all sample concentrations in any 12 consecutive months during which
(3) For systems that serve fewer than 10,000 people and monitor for
(4) For systems with plants operating only part of the year that monitor fewer than 12 months per year under § 141.701(e), the bin concentration is equal to the highest arithmetic mean of all sample concentrations during any year of
(5) If the monthly
(c) Filtered systems must determine their initial bin classification from the following table and using the
(d) Following completion of the second round of source water monitoring required under § 141.701(b), filtered systems must recalculate their
(e)(1) Filtered systems must report their initial bin classification under paragraph (c) of this section to the State for approval no later than 6 months after the system is required to complete initial source water monitoring based on the schedule in § 141.701(c).
(2) Systems must report their bin classification under paragraph (d) of this section to the State for approval no later than 6 months after the system is required to complete the second round of source water monitoring based on the schedule in § 141.701(c).
(3) The bin classification report to the State must include a summary of source water monitoring data and the calculation procedure used to determine bin classification.
(f) Failure to comply with the conditions of paragraph (e) of this section is a violation of the treatment technique requirement.
(a) Filtered systems must provide the level of additional treatment for
(b)(1) Filtered systems must use one or more of the treatment and management options listed in § 141.715, termed the microbial toolbox, to comply with the additional
(2) Systems classified in Bin 3 and Bin 4 must achieve at least 1-log of the additional
(c) Failure by a system in any month to achieve treatment credit by meeting criteria in §§ 141.716 through 141.720 for microbial toolbox options that is at least equal to the level of treatment required in paragraph (a) of this section is a violation of the treatment technique requirement.
(d) If the State determines during a sanitary survey or an equivalent source water assessment that after a system completed the monitoring conducted under § 141.701(a) or § 141.701(b), significant changes occurred in the system's watershed that could lead to increased contamination of the source water by
(a)
(2) Following completion of the second round of source water monitoring required under § 141.701(b), unfiltered systems must calculate the arithmetic mean of all
(3) If the monthly
(4) The report to the State of the mean
(5) Failure to comply with the conditions of paragraph (a) of this section is a violation of the treatment technique requirement.
(b)
(1) Unfiltered systems with a mean
(2) Unfiltered systems with a mean
(c)
(1) Systems that use chlorine dioxide or ozone and fail to achieve the
(2) Systems that use UV light and fail to achieve the
(d)
(a) Following initial bin classification under § 141.710(c), filtered systems must provide the level of treatment for
(b) Following initial determination of the mean
(c)
(d) If the bin classification for a filtered system changes following the second round of source water monitoring, as determined under § 141.710(d), the system must provide the level of treatment for
(e) If the mean
(a) Systems using uncovered finished water storage facilities must comply with the conditions of this section.
(b) Systems must notify the State of the use of each uncovered finished water storage facility no later than April 1, 2008.
(c) Systems must meet the conditions of paragraph (c)(1) or (2) of this section for each uncovered finished water storage facility or be in compliance with a State-approved schedule to meet these conditions no later than April 1, 2009.
(1) Systems must cover any uncovered finished water storage facility.
(2) Systems must treat the discharge from the uncovered finished water storage facility to the distribution system to achieve inactivation and/or removal of at least 4-log virus, 3-log
(d) Failure to comply with the requirements of this section is a violation of the treatment technique requirement.
(a)(1) Systems receive the treatment credits listed in the table in paragraph (b) of this section by meeting the conditions for microbial toolbox options described in §§ 141.716 through 141.720. Systems apply these treatment credits to meet the treatment requirements in § 141.711 or § 141.712, as applicable.
(2) Unfiltered systems are eligible for treatment credits for the microbial toolbox options described in § 141.720 only.
(b) The following table summarizes options in the microbial toolbox:
(a)
(1) Systems that intend to apply for the watershed control program credit must notify the State of this intent no later than two years prior to the treatment compliance date applicable to the system in § 141.713.
(2) Systems must submit to the State a proposed watershed control plan no later than one year before the applicable treatment compliance date in § 141.713. The State must approve the watershed control plan for the system to receive watershed control program treatment credit. The watershed control plan must include the elements in paragraphs (a)(2)(i) through (iv) of this section.
(i) Identification of an “area of influence” outside of which the likelihood of
(ii) Identification of both potential and actual sources of
(iii) An analysis of the effectiveness and feasibility of control measures that could reduce
(iv) A statement of goals and specific actions the system will undertake to reduce source water
(3) Systems with existing watershed control programs (
(4) If the State does not respond to a system regarding approval of a watershed control plan submitted under this section and the system meets the other requirements of this section, the watershed control program will be considered approved and 0.5 log
(5) Systems must complete the actions in paragraphs (a)(5)(i) through (iii) of this section to maintain the 0.5-log credit.
(i) Submit an annual watershed control program status report to the State. The annual watershed control program status report must describe the system's implementation of the approved plan and assess the adequacy of the plan to meet its goals. It must explain how the system is addressing any shortcomings in plan implementation, including those previously identified by the State or as the result of the watershed survey conducted under paragraph (a)(5)(ii) of this section. It must also describe any significant changes that have occurred in the watershed since the last watershed sanitary survey. If a system determines during implementation that making a significant change to its approved watershed control program is necessary, the system must notify the State prior to making any such changes. If any change is likely to reduce the level of source water protection, the system must also list in its notification the actions the system will take to mitigate this effect.
(ii) Undergo a watershed sanitary survey every three years for community water systems and every five years for noncommunity water systems and submit the survey report to the State. The survey must be conducted according to State guidelines and by persons the State approves.
(A) The watershed sanitary survey must meet the following criteria: encompass the region identified in the State-approved watershed control plan as the area of influence; assess the implementation of actions to reduce source water
(B) If the State determines that significant changes may have occurred in the watershed since the previous watershed sanitary survey, systems must undergo another watershed sanitary survey by a date the State requires, which may be earlier than the regular date in paragraph (a)(5)(ii) of this section.
(iii) The system must make the watershed control plan, annual status reports, and watershed sanitary survey reports available to the public upon request. These documents must be in a plain language style and include criteria by which to evaluate the success of the program in achieving plan goals. The State may approve systems to withhold from the public portions of the annual status report, watershed control plan, and watershed sanitary survey based on water supply security considerations.
(6) If the State determines that a system is not carrying out the approved watershed control plan, the State may withdraw the watershed control program treatment credit.
(b)
(2) If systems conduct alternative source monitoring under paragraph (b)(1) of this section, systems must also monitor their current plant intake concurrently as described in § 141.701.
(3) Alternative source monitoring under paragraph (b)(1) of this section must meet the requirements for source monitoring to determine bin classification, as described in §§ 141.701 through 141.706. Systems must report the alternative source monitoring results to the State, along with supporting information documenting the operating conditions under which the samples were collected.
(4) If a system determines its bin classification under § 141.710 using alternative source monitoring results that reflect a different intake location or a different procedure for managing the timing or level of withdrawal from the source, the system must relocate the intake or permanently adopt the withdrawal procedure, as applicable, no later than the applicable treatment compliance date in § 141.713.
(a)
(1) The presedimentation basin must be in continuous operation and must treat the entire plant flow taken from a surface water or GWUDI source.
(2) The system must continuously add a coagulant to the presedimentation basin.
(3) The presedimentation basin must achieve the performance criteria in paragraph (3)(i) or (ii) of this section.
(i) Demonstrates at least 0.5-log mean reduction of influent turbidity. This reduction must be determined using daily turbidity measurements in the presedimentation process influent and effluent and must be calculated as follows: log
(ii) Complies with State-approved performance criteria that demonstrate at least 0.5-log mean removal of micron-sized particulate material through the presedimentation process.
(b)
(c)
(1) Wells with a ground water flow path of at least 25 feet receive 0.5-log treatment credit; wells with a ground water flow path of at least 50 feet receive 1.0-log treatment credit. The ground water flow path must be determined as specified in paragraph (c)(4) of this section.
(2) Only wells in granular aquifers are eligible for treatment credit. Granular aquifers are those comprised of sand, clay, silt, rock fragments, pebbles or larger particles, and minor cement. A system must characterize the aquifer at the well site to determine aquifer properties. Systems must extract a core from the aquifer and demonstrate that in at least 90 percent of the core length, grains less than 1.0 mm in diameter constitute at least 10 percent of the core material.
(3) Only horizontal and vertical wells are eligible for treatment credit.
(4) For vertical wells, the ground water flow path is the measured distance from the edge of the surface water body under high flow conditions (determined by the 100 year floodplain elevation boundary or by the floodway, as defined in Federal Emergency Management Agency flood hazard maps) to the well screen. For horizontal wells, the ground water flow path is the measured distance from the bed of the river under normal flow conditions to the closest horizontal well lateral screen.
(5) Systems must monitor each wellhead for turbidity at least once every
(6) Springs and infiltration galleries are not eligible for treatment credit under this section, but are eligible for credit under § 141.718(c).
(7)
(i) The study must follow a State-approved protocol and must involve the collection of data on the removal of
(ii) The study must include sampling both from the production well(s) and from monitoring wells that are screened and located along the shortest flow path between the surface water source and the production well(s).
(a)
(b)
(1) The filtered water turbidity for each individual filter must be less than or equal to 0.15 NTU in at least 95 percent of the measurements recorded each month.
(2) No individual filter may have a measured turbidity greater than 0.3 NTU in two consecutive measurements taken 15 minutes apart.
(3) Any system that has received treatment credit for individual filter performance and fails to meet the requirements of paragraph (b)(1) or (2) of this section during any month does not receive a treatment technique violation under § 141.711(c) if the State determines the following:
(i) The failure was due to unusual and short-term circumstances that could not reasonably be prevented through optimizing treatment plant design, operation, and maintenance.
(ii) The system has experienced no more than two such failures in any calendar year.
(c)
(1) Systems cannot receive the prescribed treatment credit for any toolbox box option in §§ 141.717 through 141.720 if that toolbox option is included in a demonstration of performance study for which treatment credit is awarded under this paragraph.
(2) The demonstration of performance study must follow a State-approved protocol and must demonstrate the level of
(3) Approval by the State must be in writing and may include monitoring and treatment performance criteria that the system must demonstrate and report on an ongoing basis to remain eligible for the treatment credit. The State may designate such criteria where necessary to verify that the conditions under which the demonstration of performance credit was approved are maintained during routine operation.
(a)
(1) The
(2) Challenge testing must be performed on full-scale bag or cartridge filters, and the associated filter housing or pressure vessel, that are identical in material and construction to the filters and housings the system will use for removal of
(3) Challenge testing must be conducted using
(4) The maximum feed water concentration that can be used during a challenge test must be based on the detection limit of the challenge particulate in the filtrate (
(5) Challenge testing must be conducted at the maximum design flow rate for the filter as specified by the manufacturer.
(6) Each filter evaluated must be tested for a duration sufficient to reach 100 percent of the terminal pressure drop, which establishes the maximum pressure drop under which the filter may be used to comply with the requirements of this subpart.
(7) Removal efficiency of a filter must be determined from the results of the challenge test and expressed in terms of log removal values using the following equation:
(8) Each filter tested must be challenged with the challenge particulate during three periods over the filtration cycle: within two hours of start-up of a new filter; when the pressure drop is between 45 and 55 percent of the terminal pressure drop; and at the end of the cycle after the pressure drop has
(9) If fewer than 20 filters are tested, the overall removal efficiency for the filter product line must be set equal to the lowest LRV
(10) If a previously tested filter is modified in a manner that could change the removal efficiency of the filter product line, challenge testing to demonstrate the removal efficiency of the modified filter must be conducted and submitted to the State.
(b)
(i) The removal efficiency demonstrated during challenge testing conducted under the conditions in paragraph (b)(2) of this section.
(ii) The maximum removal efficiency that can be verified through direct integrity testing used with the membrane filtration process under the conditions in paragraph (b)(3) of this section.
(2)
(i) Challenge testing must be conducted on either a full-scale membrane module, identical in material and construction to the membrane modules used in the system's treatment facility, or a smaller-scale membrane module, identical in material and similar in construction to the full-scale module. A module is defined as the smallest component of a membrane unit in which a specific membrane surface area is housed in a device with a filtrate outlet structure.
(ii) Challenge testing must be conducted using
(iii) The maximum feed water concentration that can be used during a challenge test is based on the detection limit of the challenge particulate in the filtrate and must be determined according to the following equation:
(iv) Challenge testing must be conducted under representative hydraulic conditions at the maximum design flux and maximum design process recovery specified by the manufacturer for the membrane module. Flux is defined as the throughput of a pressure driven membrane process expressed as flow per unit of membrane area. Recovery is defined as the volumetric percent of feed water that is converted to filtrate over the course of an operating cycle uninterrupted by events such as chemical cleaning or a solids removal process (
(v) Removal efficiency of a membrane module must be calculated from
(vi) The removal efficiency of a membrane filtration process demonstrated during challenge testing must be expressed as a log removal value (LRV
(vii) The challenge test must establish a quality control release value (QCRV) for a non-destructive performance test that demonstrates the
(viii) If a previously tested membrane is modified in a manner that could change the removal efficiency of the membrane or the applicability of the non-destructive performance test and associated QCRV, additional challenge testing to demonstrate the removal efficiency of, and determine a new QCRV for, the modified membrane must be conducted and submitted to the State.
(3)
(i) The direct integrity test must be independently applied to each membrane unit in service. A membrane unit is defined as a group of membrane modules that share common valving that allows the unit to be isolated from the rest of the system for the purpose of integrity testing or other maintenance.
(ii) The direct integrity method must have a resolution of 3 micrometers or less, where resolution is defined as the size of the smallest integrity breach that contributes to a response from the direct integrity test.
(iii) The direct integrity test must have a sensitivity sufficient to verify the log treatment credit awarded to the membrane filtration process by the State, where sensitivity is defined as the maximum log removal value that can be reliably verified by a direct integrity test. Sensitivity must be determined using the approach in either paragraph (b)(3)(iii)(A) or (B) of this section as applicable to the type of direct integrity test the system uses.
(A) For direct integrity tests that use an applied pressure or vacuum, the direct integrity test sensitivity must be calculated according to the following equation:
(B) For direct integrity tests that use a particulate or molecular marker, the direct integrity test sensitivity must be calculated according to the following equation:
(iv) Systems must establish a control limit within the sensitivity limits of the direct integrity test that is indicative of an integral membrane unit capable of meeting the removal credit awarded by the State.
(v) If the result of a direct integrity test exceeds the control limit established under paragraph (b)(3)(iv) of this section, the system must remove the membrane unit from service. Systems must conduct a direct integrity test to verify any repairs, and may return the membrane unit to service only if the direct integrity test is within the established control limit.
(vi) Systems must conduct direct integrity testing on each membrane unit at a frequency of not less than once each day that the membrane unit is in operation. The State may approve less frequent testing, based on demonstrated process reliability, the use of multiple barriers effective for
(4)
(i) Unless the State approves an alternative parameter, continuous indirect integrity monitoring must include continuous filtrate turbidity monitoring.
(ii) Continuous monitoring must be conducted at a frequency of no less than once every 15 minutes.
(iii) Continuous monitoring must be separately conducted on each membrane unit.
(iv) If indirect integrity monitoring includes turbidity and if the filtrate turbidity readings are above 0.15 NTU for a period greater than 15 minutes (
(v) If indirect integrity monitoring includes a State-approved alternative parameter and if the alternative parameter exceeds a State-approved control limit for a period greater than 15 minutes, direct integrity testing must immediately be performed on the associated membrane units as specified in paragraphs (b)(3)(i) through (v) of this section.
(c)
(d)
(a)
(2) Systems with several disinfection segments in sequence may calculate CT for each segment, where a disinfection segment is defined as a treatment unit process with a measurable disinfectant residual level and a liquid volume. Under this approach, systems must add the
(b)
(2) Systems receive the
(c)
(d)
(1)
(2)
(i) When determining validated operating conditions, systems must account for the following factors: UV absorbance of the water; lamp fouling and aging; measurement uncertainty of on-line sensors; UV dose distributions arising from the velocity profiles through the reactor; failure of UV lamps or other critical system components; and inlet and outlet piping or channel configurations of the UV reactor.
(ii) Validation testing must include the following: Full scale testing of a reactor that conforms uniformly to the UV reactors used by the system and inactivation of a test microorganism whose dose response characteristics have been quantified with a low pressure mercury vapor lamp.
(iii) The State may approve an alternative approach to validation testing.
(3)
(ii) To receive treatment credit for UV light, systems must treat at least 95 percent of the water delivered to the public during each month by UV reactors operating within validated conditions for the required UV dose, as described in paragraphs (d)(1) and (2) of this section. Systems must demonstrate compliance with this condition by the monitoring required under paragraph (d)(3)(i) of this section.
(a) Systems must report sampling schedules under § 141.702 and source water monitoring results under § 141.706
(b) Systems must report the use of uncovered finished water storage facilities to the State as described in § 141.714.
(c) Filtered systems must report their
(d) Unfiltered systems must report their mean source water
(e) Systems must report disinfection profiles and benchmarks to the State as described in §§ 141.708 through 141.709 prior to making a significant change in disinfection practice.
(f) Systems must report to the State in accordance with the following table for any microbial toolbox options used to comply with treatment requirements under § 141.711 or § 141.712. Alternatively, the State may approve a system to certify operation within required parameters for treatment credit rather than reporting monthly operational data for toolbox options.
(a) Systems must keep results from the initial round of source water monitoring under § 141.701(a) and the second round of source water monitoring under § 141.701(b) until 3 years after bin
(b) Systems must keep any notification to the State that they will not conduct source water monitoring due to meeting the criteria of § 141.701(d) for 3 years.
(c) Systems must keep the results of treatment monitoring associated with microbial toolbox options under §§ 141.716 through 141.720 and with uncovered finished water reservoirs under § 141.714, as applicable, for 3 years.
(a) A sanitary survey is an onsite review of the water source (identifying sources of contamination by using results of source water assessments where available), facilities, equipment, operation, maintenance, and monitoring compliance of a PWS to evaluate the adequacy of the PWS, its sources and operations, and the distribution of safe drinking water.
(b) For the purposes of this section, a significant deficiency includes a defect in design, operation, or maintenance, or a failure or malfunction of the sources, treatment, storage, or distribution system that EPA determines to be causing, or has the potential for causing the introduction of contamination into the water delivered to consumers.
(c) For sanitary surveys performed by EPA, systems must respond in writing to significant deficiencies identified in sanitary survey reports 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.
(d) Systems must correct significant deficiencies identified in sanitary survey reports according to the schedule approved by EPA, or if there is no approved schedule, according to the schedule reported under paragraph (c) of this section if such deficiencies are within the control of the system.
(a)
(b)
As used in this subpart, the term:
(a) Each air carrier under this subpart must develop a coliform sampling plan covering each aircraft water system owned or operated by the air carrier that identifies the following:
(1) Coliform sample collection procedures that are consistent with the requirements of § 141.803(a) and (b).
(2) Sample tap location(s) representative of the aircraft water system as specified in § 141.803(b)(2) and (b)(4).
(3) Frequency and number of routine coliform samples to be collected as specified in § 141.803(b)(3).
(4) Frequency of routine disinfection and flushing as specified in the operations and maintenance plan under § 141.804.
(5) Procedures for communicating sample results promptly so that any required actions, including repeat and follow-up sampling, corrective action, and notification of passengers and crew, will be conducted in a timely manner.
(b) Each air carrier must develop a coliform sampling plan for each aircraft with a water system meeting the definition of a public water system by April 19, 2011.
(c) The coliform sampling plan must be included in the Aircraft Water System Operations and Maintenance Plan required in § 141.804. Any subsequent changes to the coliform sampling plan must also be included in the Aircraft Water System Operations and Maintenance Plan required in § 141.804.
(a)
(1) The standard sample volume required for total coliform analysis, regardless of analytical method used, is 100 mL.
(2) Air carriers need determine only the presence or absence of total coliforms and/or
(3) Air carriers must conduct analyses for total coliform and
(4) The time from sample collection to initiation of analysis may not exceed 30 hours. Systems are encouraged but not required to hold samples below 10 °C during transit.
(5) The invalidation of a total coliform sample result can be made only by the Administrator in accordance with § 141.21(c)(1)(i), (ii), or (iii) or by the certified laboratory in accordance with § 141.21(c)(2).
(6)
(b)
(1) Except as provided in paragraph (b)(2) of this section, the air carrier must collect two 100 mL total coliform routine samples at the frequency specified in the sampling plan in § 141.802 and in accordance with paragraph (b)(3) of this section;
(2) The air carrier may collect one 100 mL total coliform routine sample at the frequency specified in the sampling plan in § 141.802 for aircraft with a removable or portable tank that is drained every day of passenger service, and the aircraft has only one tap. Aircraft meeting the requirements of this paragraph do not have to comply with paragraph (b)(4) of this section.
(3) Air carriers must perform routine monitoring for total coliform at a frequency corresponding to the frequency of routine disinfection and flushing as specified in the Table b-1 (Routine Disinfection and Flushing and Routine Sample Frequencies). Air carriers must follow the disinfection and flushing frequency recommended by the aircraft water system manufacturer, when available. Where the aircraft water system manufacturer does not specify a recommended routine disinfection and flushing frequency, the air carrier must choose a frequency from Table b-1 (Routine Disinfection and Flushing and Routine Sample Frequencies):
(4) One sample must be taken from a lavatory and one from a galley; each sample must be analyzed for total coliform. If only one water tap is located in the aircraft water system due to aircraft model type and construction, then a single tap may be used to collect two separate 100 mL samples.
(5) If any routine, repeat, or follow-up coliform sample is total coliform-positive, the air carrier must analyze that total coliform-positive culture medium to determine if
(6) Routine total coliform samples must not be collected within 72 hours after completing routine disinfection and flushing procedures.
(c)
(2)
(i)
(ii)
(iii)
(3)
(i)
(ii)
(iii)
(A) If all repeat samples are total coliform-negative, then the air carrier must maintain the routine monitoring frequency for total coliform as specified in the sampling plan in § 141.802.
(B) If any repeat sample is
(C) If any repeat sample is total coliform-positive and
(d)
(1) Physically disconnecting or shutting off the aircraft water system, where feasible, or otherwise preventing the flow of water through the tap(s);
(2) Providing public notification to passengers and crew in accordance with § 141.805.
(3) Providing alternatives to water from the aircraft water system, such as bottled water for drinking and coffee or tea preparation; antiseptic hand gels or wipes in accordance with 21 CFR part 333—“Topical Anti-microbial Drug Products for Over-the-Counter Human Use” in the galleys and lavatories; and other feasible measures that reduce or eliminate the need to use the aircraft water system during the limited period before public use of the aircraft water system is unrestricted.
(e)
(1) For each aircraft water system, the air carrier must collect a complete set of total coliform follow-up samples consisting of two 100 mL total coliform samples at the same routine sample locations as identified in paragraphs (b)(2) and (b)(4) of this section.
(2) Follow-up samples must be collected prior to providing water to the public for human consumption from the aircraft water system.
(3) If a complete set of follow-up samples is total coliform-negative, the air carrier must return to the routine monitoring frequency for total coliform as specified in the sampling plan required by § 141.802.
(4) If any follow-up sample is
(5) If any follow-up sample is total coliform-positive and
(f)
(g)
(h)
(1) Boarding water from a watering point not in accordance with FDA regulations (21 CFR part 1240 subpart E), or
(2) Boarding water that does not meet NPDWRs applicable to transient non-community water systems (§§ 141.62 and 141.63, as applied to TNCWS),
(3) Boarding water that is otherwise determined to be unsafe due to non-compliance with the procedures specified in § 141.804(b)(6).
(i)
(1) Boarding water from a watering point not in accordance with FDA regulations (21 CFR part 1240, subpart E),
(2) Boarding water that does not meet NPDWRs applicable to transient non-community water systems (§§ 141.62 and 141.63, as applied to TNCWS), or
(3) Boarding water that is otherwise determined to be unsafe due to non-compliance with the procedures specified in § 141.804(b)(6).
(a) Each air carrier must develop and implement an aircraft water system operations and maintenance plan for each aircraft water system that it owns or operates. This plan must be included in a Federal Aviation Administration (FAA)-accepted air carrier operations and maintenance program (14 CFR part 43, 14 CFR part 91, 14 CFR part 121).
(b) Each aircraft water system operations and maintenance plan must include the following:
(1)
(2)
(i) The air carrier must conduct disinfection and flushing of the aircraft water system in accordance with, or is consistent with, the water system manufacturer's recommendations. The air carrier may conduct disinfection and flushing more frequently, but not less frequently, than the manufacturer recommends.
(ii) The operations and maintenance plan must identify the disinfection frequency, type of disinfecting agent, disinfectant concentration to be used, and the disinfectant contact time, and flushing volume or flushing time.
(iii) In cases where a recommended routine disinfection and flushing frequency is not specified by the aircraft water system manufacturer, the air carrier must choose a disinfection and flushing, and corresponding monitoring frequency specified in § 141.803(b)(3).
(3)
(4)
(i) Boarding water procedures;
(ii) Sample collection procedures;
(iii) Disinfection and flushing procedures;
(iv) Public health and safety reasons for the requirements of this subpart.
(5)
(6)
(i) Within the United States, the air carrier must board water from watering points in accordance with Food and Drug Administration (FDA) regulations (21 CFR part 1240, subpart E).
(ii) A description of how the water will be transferred from the watering point to the aircraft in a manner that ensures it will not become contaminated during the transfer.
(iii) A description of how the carrier will ensure that water boarded outside
(iv) A description of emergency procedures that meet the requirements in § 141.803(h) and (i) that must be used in the event that the air carrier becomes aware that water was boarded to operate essential systems, such as toilets, but was boarded from a watering point not in accordance with FDA regulations, does not meet NPDWRs applicable to transient non-community water systems (§§ 141.62 and 141.63, as applied to TNCWSs), or is otherwise unsafe.
(7)
(8)
(c) For existing aircraft, the air carrier must develop the water system operations and maintenance plan required by this section by April 19, 2011;
(d) For new aircraft, the air carrier must develop the operations and maintenance plan required in this section within the first calendar quarter of initial operation of the aircraft.
(e) Any changes to the aircraft water system operations and maintenance plan must be included in the FAA-accepted air carrier operations and maintenance program.
(a) Air carriers must give public notice for each aircraft in all of the following situations:
(1) Public access to the aircraft water system is restricted in response to a routine, repeat or follow-up total coliform-positive or
(2) Failure to perform required routine disinfection and flushing or failure to collect required routine samples in accordance with § 141.803(f);
(3) Failure to collect the required follow-up samples in response to a sample result that is
(4) Failure to collect the required repeat samples or failure to collect the required follow-up samples in response to a sample result that is total coliform-positive and
(5) In accordance with § 141.803(h), the air carrier becomes aware of an
(6) In accordance with § 141.803(i), the air carrier becomes aware of a non-
(7) The Administrator, the carrier, or the crew otherwise determines that notification is necessary to protect public health.
(b)
(2) Must not contain overly technical language or very small print;
(3) Must not be formatted in a way that defeats the purpose of the notice;
(4) Must not contain language that nullifies the purpose of the notice;
(5) Must contain information in the appropriate language(s) regarding the importance of the notice, reflecting a good faith effort to reach the non-English speaking population served, including, where applicable, an easily recognized symbol for non-potable water.
(c) Public notification for paragraph (a)(1) of this section must meet the requirements of paragraph (b) of this section in addition to the following:
(1) Public notification must include a prominently displayed, clear statement in each lavatory indicating that the water is non-potable and should not be
(2) A prominent notice in the galley directed at the crew which includes:
(i) A clear statement that the water is non-potable and should not be used for drinking, food or beverage preparation, hand washing, teeth brushing, or any other consumptive use;
(ii) A description of the violation or situation triggering the notice, including the contaminant(s) of concern;
(iii) When the violation or situation occurred;
(iv) Any potential adverse health effects from the violation or situation, as appropriate, under paragraph (g) of this section;
(v) The population at risk, including sensitive subpopulations particularly vulnerable if exposed to the contaminant in the drinking water;
(vi) What the air carrier is doing to correct the violation or situation; and
(vii) When the air carrier expects to return the system to unrestricted public access.
(3) If passenger access to the water system is physically prevented through disconnecting or shutting off the water, or the flow of water prevented through the tap(s), or if water is supplied only to lavatory toilets, and not to any lavatory or galley taps, then only the notice specified in paragraph (c)(2) of this section is required.
(4) Air carriers must initiate public notification when restriction of public access is initiated in accordance with § 141.803(d) and must continue until the aircraft water system is returned to unrestricted public access.
(d) Public notification for paragraphs (a)(2), (a)(4), and (a)(6) of this section must meet the requirements of paragraph (b) of this section in addition to the following:
(1) Public notification must include a prominently displayed, clear statement in each lavatory indicating that the water is non-potable and should not be used for drinking, food or beverage preparation, hand washing, teeth brushing, or any other consumptive use; and
(2) A prominent notice in the galley directed at the crew which includes:
(i) A clear statement that the water is non-potable and should not be used for drinking, food or beverage preparation, hand washing, teeth brushing, or any other consumptive use;
(ii) A clear statement that it is not known whether the water is contaminated because there was a failure to perform required routine disinfection and flushing; or a failure to perform required monitoring; or water was boarded from a watering point not in accordance with FDA regulations, or that does not meet NPDWRs applicable to transient noncommunity water systems, or that is otherwise determined to be unsafe due to noncompliance with the procedures specified in § 141.804(b)(6);
(iii) When and where the unsafe water was boarded or when the specific monitoring or disinfection and flushing requirement was not met;
(iv) Any potential adverse health effects from exposure to waterborne pathogens that might be in the water, as appropriate, under paragraph (g) of this section;
(v) The population at risk, including sensitive subpopulations particularly vulnerable if exposed to the contaminant in the drinking water; and
(vi) A statement indicating when the system will be disinfected and flushed and returned to unrestricted public access.
(3) If passenger access to the water system is physically prevented through disconnecting or shutting off the water, or the flow of water prevented through the tap(s), or if water is supplied only to lavatory toilets, and not to any lavatory or galley taps, then only the notice specified in paragraph (d)(2) of this section is required.
(4) Air carriers must initiate public notification when restriction of public access is initiated in accordance with § 141.803(d) and must continue until the aircraft water system is returned to unrestricted public access.
(e) Public notification for paragraphs (a)(3) and (a)(5) of this section must meet the requirements of paragraph (b) of this section in addition to the following:
(1) Public notification must include a prominently displayed, clear statement in each lavatory indicating that the
(2) A prominent notice in the galley directed at the crew which includes:
(i) A clear statement that the water is non-potable and should not be used for drinking, food or beverage preparation, hand washing, teeth brushing, or any other consumptive use;
(ii) A clear statement that the water is contaminated and there was a failure to conduct required monitoring; or a clear statement that water is contaminated because water was boarded from a watering point not in accordance with FDA regulations, or that does not meet NPDWRs applicable to transient noncommunity water systems, or that is otherwise determined to be unsafe due to noncompliance with the procedures specified in § 141.804(b)(6);
(iii) A description of the contaminant(s) of concern;
(iv) When and where the unsafe water was boarded or when the specific monitoring requirement was not met;
(v) Any potential adverse health effects from the situation, as appropriate, under paragraph (g) of this section;
(vi) The population at risk, including sensitive subpopulations particularly vulnerable if exposed to the contaminant in the drinking water;
(vii) A statement indicating what the air carrier is doing to correct the situation; and
(viii) When the air carrier expects to return the system to unrestricted public access.
(3) If passenger access to the water system is physically prevented through disconnecting or shutting off the water, or the flow of water prevented through the tap(s), or if water is supplied only to lavatory toilets, and not to any lavatory or galley taps, then only the notice specified in paragraph (e)(2) of this section is required.
(4) Air carriers must initiate public notification when restriction of public access is initiated in accordance with § 141.803(d) and must continue public notification until a complete set of required follow-up samples are total coliform-negative.
(f) Public notification for paragraph (a)(7) of this section must meet the requirements of paragraph (b) of this section in addition to the following:
(1) Notification must be in a form and manner reasonably calculated to reach all passengers and crew while on board the aircraft by using one or more of the following forms of delivery:
(i) Broadcast over public announcement system on aircraft;
(ii) Posting of the notice in conspicuous locations throughout the area served by the water system. These locations would normally be the galleys and in the lavatories of each aircraft requiring posting;
(iii) Hand delivery of the notice to passengers and crew;
(iv) Another delivery method approved in writing by the Administrator.
(2) Air carriers must initiate public notification within 24 hours of being informed by EPA to perform notification and must continue notification for the duration determined by EPA.
(g) In each public notice to the crew, air carriers must use the following standard health effects language that corresponds to the situations in paragraphs (a)(1) through (a)(6) of this section.
(1) Health effects language to be used when public notice is initiated due to the detection of total coliforms only (not
Coliform are bacteria that are naturally present in the environment and are used as an indicator that other, potentially harmful, bacteria may be present. Coliforms were found in [INSERT NUMBER OF SAMPLES DETECTED] samples collected and this is a warning of potential problems. If human pathogens are present, they can cause short-term health effects, such as diarrhea, cramps, nausea, headaches, or other symptoms. They may pose a special health risk for infants, young children, some of the elderly, and people with severely compromised immune systems.
(2) Health effects language to be used when public notice is initiated due to any
(3) Health effects language to be used when public notice is initiated due to a failure to conduct routine monitoring or routine disinfection and flushing in accordance with paragraph (a)(2) of this section; or when there is a failure to conduct repeat or follow-up sampling in accordance with paragraph (a)(4) of this section; or in accordance with paragraph (a)(6) of this section, when the air carrier becomes aware of a non-
Because [REQUIRED MONITORING AND ANALYSIS WAS NOT CONDUCTED], [REQUIRED DISINFECTION AND FLUSHING WAS NOT CONDUCTED] [WATER WAS BOARDED FROM A WATERING POINT NOT IN ACCORDANCE WITH FDA REGULATIONS (21 CR 1240 SUBPART E)], or [OTHER APPROPRIATE EXPLANATION], we cannot be sure of the quality of the drinking water at this time. However, drinking water contaminated with human pathogens can cause short-term health effects, such as diarrhea, cramps, nausea, headaches, or other symptoms. They may pose a special health risk for infants, young children, some of the elderly, and people with severely compromised immune systems.
(4) Health effects language to be used when public notice is initiated due to a failure to conduct required follow-up monitoring in response to a sample result that is
Because required follow-up monitoring and analysis was not conducted after the aircraft water system tested positive for
Water was boarded that is contaminated with
(a) The air carrier must comply with the following requirements regarding reporting of the development of the coliform sampling plan, the operations and maintenance plan, and the disinfection and flushing and coliform sampling frequencies.
(1) The air carrier must report to the Administrator that it has developed the coliform sampling plan required by § 141.802, which covers each existing aircraft water system, as well as report the frequency for routine coliform sampling identified in the coliform sampling plan by April 19, 2011. The air carrier must report to the Administrator that it has developed its operations and maintenance plan required by § 141.804 and report the frequency for routine disinfection and flushing by April 19, 2011;
(2) For each new aircraft meeting the definition of an aircraft water system, which becomes operational after publication of this subpart, the air carrier must report to the Administrator that
(b) The air carrier must report the following information to the Administrator:
(1) A complete inventory of aircraft that are public water systems by April 19, 2011. Inventory information includes, at a minimum, the following:
(i) The unique aircraft identifier number;
(ii) The status (active or inactive) of any aircraft as an aircraft water system as defined in § 141.801;
(iii) The type and location of any supplemental treatment equipment installed on the water system; and
(iv) Whether the aircraft water system can be physically disconnected or shut-off, or the flow of water prevented through the tap(s).
(2) Changes in aircraft inventory no later than 10 days following the calendar month in which the change occurred. Changes in inventory information include, at a minimum, the following:
(i) Change in the unique identifier number for any new aircraft, or any aircraft removed from the carrier's fleet;
(ii) Change in status (active or inactive) of any aircraft as an aircraft water system as defined in § 141.801; and
(iii) Change to the type and location of any supplemental treatment equipment added to or removed from the water system.
(iv) Change to whether the aircraft water system can be physically disconnected or shut-off, or the flow of water prevented through the tap(s).
(3) All sampling results no later than 10 calendar days following the monitoring period in which the sampling occurred. The monitoring period is based on the monitoring frequency identified in the coliform sampling plan required under § 141.802. Routine disinfection and flushing events must be reported no later than 10 calendar days following the disinfection and flushing period in which the disinfection and flushing occurred. The disinfection and flushing period is based on the frequency identified in the operations and maintenance plan required under § 141.804.
(4) All events requiring notification to passengers or crew, or non-routine disinfection and flushing, or non-routine sampling, within 10 days of the event (e.g., notification of positive sample result by laboratory), including information on whether required notification was provided to passengers or crew or both.
(5) Failure to comply with the monitoring or disinfection and flushing requirements of this subpart within 10 calendar days of discovery of the failure.
(6) Changes in disinfection and flushing and coliform sampling frequencies no later than 10 days following the calendar month in which the change occurred. Changes to an aircraft's routine coliform sampling frequency and routine disinfection and flushing frequency must be included in the aircraft water system operation and maintenance plan that is included in the air carrier operations and maintenance program accepted by FAA in accordance with § 141.804.
(c) The air carrier must provide evidence of a self-inspection to the Administrator within 90 days of completion of the self-inspection required under § 141.808(b), including reporting whether all deficiencies were addressed in accordance with § 141.808(c). The air carrier must also report to the Administrator within 90 days that any deficiency identified during a compliance audit conducted in accordance with § 141.808(a) has been addressed. If any deficiency has not been addressed within 90 days of identification of the deficiency, the report must also include a description of the deficiency, an explanation as to why it has not yet been addressed, and a schedule for addressing it as expeditiously as possible.
(d) All information required to be reported to the Administrator under this
(a) The air carrier must keep records of bacteriological analyses for at least 5 years and must include the following information:
(1) The date, time, and place of sampling, and the name of the person who collected the sample;
(2) Identification of the sample as a routine, repeat, follow-up, or other special purpose sample;
(3) Date of the analysis;
(4) Laboratory and person responsible for performing the analysis;
(5) The analytical technique/method used; and
(6) The results of the analysis.
(b) The air carrier must keep records of any disinfection and flushing for at least 5 years and must include the following information:
(1) The date and time of the disinfection and flushing; and
(2) The type of disinfection and flushing (
(c) The air carrier must keep records of a self-inspection for at least 10 years and must include the following information:
(1) The completion date of the self-inspection; and
(2) Copies of any written reports, summaries, or communications related to the self-inspection.
(d) The air carrier must maintain sampling plans and make such plans available for review by the Administrator upon request, including during compliance audits.
(e) The air carrier must maintain aircraft water system operations and maintenance plans in accordance with FAA requirements, and make such plans available for review by the Administrator upon request, including during compliance audits.
(f) The air carrier must keep copies of public notices to passengers and crew issued as required by this subpart for at least 3 years after issuance.
(a) The Administrator may conduct routine compliance audits as deemed necessary in providing regulatory oversight to ensure proper implementation of the requirements in this subpart. Compliance audits may include, but are not limited to:
(1) Bacteriological sampling of aircraft water system;
(2) Reviews and audits of records as they pertain to water system operations and maintenance such as log entries, disinfection and flushing procedures, and sampling results; and
(3) Observation of procedures involving the handling of finished water, watering point selection, boarding of water, operation, disinfection and flushing, and general maintenance and self-inspections of aircraft water system.
(b) Air carriers or their representatives must perform a self-inspection of all water system components for each aircraft water system no less frequently than once every 5 years.
(c) The air carrier must address any deficiency identified during compliance audits or routine self-inspections within 90 days of identification of the deficiency, or where such deficiency is identified during extended or heavy maintenance, before the aircraft is put back into service. This includes any deficiency in the water system's design, construction, operation, maintenance, or administration, as well as any failure or malfunction of any system component that has the potential to cause an unacceptable risk to health or that could affect the reliable delivery of safe drinking water.
(a) Any supplemental drinking water treatment units installed onboard existing or new aircraft must be acceptable to FAA and FDA; and must be installed, operated, and maintained in accordance with the manufacturer's plans and specifications and FAA requirements.
(b) Water supplemental treatment and production equipment must produce water that meets the standards prescribed in this part.
An air carrier is in violation of this subpart when, for any aircraft water system it owns or operates, any of the following occur:
(a) It fails to perform any of the requirements in accordance with § 141.803 or § 141.804.
(b) It has an
(c) It fails to provide notification to passengers and crew in accordance with § 141.805.
(d) It fails to comply with the reporting and recordkeeping requirements of this subpart.
(e) It fails to conduct a self-inspection or address a deficiency in accordance with § 141.808.
(f) It fails to develop a coliform sampling plan in accordance with § 141.802, or fails to have and follow an operations and maintenance plan, which is included in a FAA accepted program in accordance with § 141.804.
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 the Public Health Service Act, as amended by the Safe Drinking Water Act, Public Law 93-523, regulations for the implementation and enforcement of the national primary drinking water regulations contained in part 141 of this chapter.
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
(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 system is in violation of an applicable legal requirement.
(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
(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) Has adopted regulations consistent with 40 CFR part 3—(Electronic reporting) if the state receives electronic documents.
(h) 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 demonstration that any different State regulation is at least as stringent as the comparable regulation contained in part 141.
(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 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 (a) of this section.
(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
(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 certain requirements during the extension period, which may include the following types of activities as determined appropriate by the Administrator on a case-by-case basis:
(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
(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 be retained for not less than one year in the form of actual laboratory reports or in an appropriate summary form.
(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,
(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 for the specified period or 40 years, whichever is less.
(
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(iii) Records of any determination that a public water system supplied by
(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 exceeding 1 NTU near the first service connection as provided in § 141.21(a)(5).
(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
(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.
(8) Any decisions made pursuant to the provisions of 40 CFR part 141, subparts U and V of this part.
(i) IDSE monitoring plans, plus any modifications required by the State, must be kept until replaced by approved IDSE reports.
(ii) IDSE reports and 40/30 certifications, plus any modifications required by the State, must be kept until replaced or revised in their entirety.
(iii) Operational evaluations submitted by a system must be kept for 10 years following submission.
(9) Any decisions made pursuant to the provisions of part 141, subpart W of this chapter.
(i) Results of source water
(ii) The bin classification after the initial and after the second round of source water monitoring for each filtered system, as described in § 141.710 of this chapter.
(iii) Any change in treatment requirements for filtered systems due to watershed assessment during sanitary surveys, as described in § 141.711(d) of this chapter.
(iv) The determination of whether the mean
(v) The treatment processes or control measures that systems use to meet their
(vi) A list of systems required to cover or treat the effluent of an uncovered finished water storage facility, as specified in § 141.714 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
(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 perpetuity or until a more current repeat monitoring determination has been issued.
(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(b)(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(h)(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(h)(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.
(17) Records of the currently applicable or most recent State determination, including all supporting information and an explanation of the technical basis of each decision, made under the following provisions of 40 CFR part 141, subpart S and 40 CFR part 142.
(i) Section 142.16(o)(2)(v). Records of written notices of significant deficiencies.
(ii) Section 141.403(a)(5)(ii) of this chapter. Records of corrective action plans, schedule approvals, and State-specified interim measures.
(iii) Section 142.16(o)(4). Records of confirmations under § 141.403(a) of this chapter that a significant deficiency has been corrected or the fecal contamination in the ground water source has been addressed.
(iv) Section 141.402(a)(5) of this chapter. Records of State determinations and records of ground water system's documentation for not conducting triggered source water monitoring.
(v) Section 141.402(d) of this chapter. Records of invalidations of fecal indicator-positive ground water source samples.
(vi) Section 141.402(a)(2)(ii) of this chapter. Records of State approvals of source water monitoring plans.
(vii) Section 142.16(o)(4)(ii). Records of notices of the minimum residual disinfection concentration (when using chemical disinfection) needed to achieve at least 4-log virus inactivation before or at the first customer.
(viii) Sections 142.16(o)(4)(iv) and 142.16(o)(4)(v) Records of notices of the State-specified monitoring and compliance requirements (when using membrane filtration or alternative treatment) needed to achieve at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log inactivation and removal) before or at the first customer.
(ix) Sections 141.403(b)(1) and 141.403(b)(2) of this chapter. Records of written notices from the ground water system that it provides at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log virus inactivation and removal) before or at the first customer for a ground water source.
(x) Section 142.16(o)(4)(vi). Records of written determinations that the ground water system may discontinue 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log inactivation and removal).
(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.
For
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 under subpart Q of part 141 of this chapter;
(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 installation of treatment as certified under § 141.90(c)(3);
(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 installation 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:
(
(
(
(5)
(6)
(ii) Any change in treatment requirements for these systems due to watershed assessment during sanitary surveys, as described in § 141.711(d) of this chapter.
(iii) The determination of whether the mean
(7)
(ii)
(iii)
(d) The reports submitted pursuant to this section shall be made available by the State to the public for inspection at one or more locations within the State.
For
(a)
(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 unfiltered systems which the State has determined must filter which will be in effect until filtration is installed.
(B) Section 141.72 (a)(4)(ii) and (b)(3)(ii) (determination 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 approval of a program revision must include the information 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)
(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, 141.32, 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):
(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
(4) Sections 141.131(c)(3) and (d) of this chapter (State approval of parties to conduct analyses). Approve parties to conduct pH, bromide, alkalinity, and residual disinfectant concentration measurements. The State's process for approving parties performing water quality measurements for systems subject to 40 CFR part 141, subpart H requirements in paragraph (b)(2)(i)(D) of this section may be used for approving parties measuring water quality parameters for systems subject to subpart L requirements, if the State determines the process is appropriate and applicable.
(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) An application for approval of a State program revision which adopts the requirements specified in §§ 141.11, 141.23, 141.24, 141.32, 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 and 141.24, the State shall describe the procedures and criteria, that it will use to review waiver applications and issue waiver 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 for the inorganic and organic contaminants (
(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 (
(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.
(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
(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 (e.g. geology).
(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)(2) under the national primary drinking water regulations for the inorganic and organic contaminants (
(m)
(n)
(1) Approve an alternative to the
(2) Assess significant changes in the watershed and source water as part of the sanitary survey process and determine appropriate follow-up action for systems, as described in § 141.711(d) of this chapter.
(3) Approve watershed control programs for the 0.5-log treatment credit in the microbial toolbox, as described in § 141.716(a) of this chapter.
(4) Approve protocols for demonstration of performance treatment credits in the microbial toolbox, as allowed under § 141.718(c) of this chapter.
(5) Approve protocols for alternative ozone and chlorine dioxide CT values in the microbial toolbox, as allowed under § 141.720(c) of this chapter.
(6) Approve an alternative approach to UV reactor validation testing in the microbial toolbox, as allowed under § 141.720(d)(2)(iii) of this chapter.
(o)
(1)
(i) The authority contained in statute or regulation to ensure that ground water systems conduct source water
(ii) The authority contained in statute or regulation to ensure that ground water systems take the appropriate corrective actions including interim measures, if necessary, needed to address significant deficiencies.
(iii) The authority contained in statute or regulation to ensure that ground water systems take the appropriate corrective actions, including interim measures if necessary, to address any source water fecal contamination identified during source water monitoring under § 141.402 of this chapter.
(iv) The authority contained in statute or regulation to ensure that ground water systems consult with the State regarding corrective action(s).
(2)
(i) The State must conduct sanitary surveys that address the eight sanitary survey components listed in this section no less frequently than every three years for community water systems, except as provided in paragraph (o)(2)(iii) of this section, and every five years for non-community water systems. The State may conduct more frequent sanitary surveys for any system. The initial sanitary survey for each community water system must be conducted by December 31, 2012, unless the system meets the requirements of paragraph (o)(2)(iii) of this section. The initial sanitary survey for each community water system that meets the requirements of paragraph (o)(2)(iii) of this section and for each non-community water system must be conducted by December 31, 2014. The sanitary survey must include an evaluation of each of the following elements as applicable:
(A) Source,
(B) Treatment,
(C) Distribution system,
(D) Finished water storage,
(E) Pumps, pump facilities, and controls,
(F) Monitoring, reporting, and data verification,
(G) System management and operation, and
(H) Operator compliance with State requirements.
(ii) The State may use a phased review process to meet the requirements of (o)(2)(i) of this section if all the applicable elements of paragraphs (o)(2)(i)(A) through (o)(2)(i)(H) of this section are evaluated within the required interval.
(iii) The State may conduct sanitary surveys once every five years for community water systems if the system either provides at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log inactivation and removal) before or at the first customer for all its ground water sources, or if it has an outstanding performance record, as determined by the State and documented in previous sanitary surveys and has no history of total coliform MCL or monitoring violations under § 141.21 of this chapter since the last sanitary survey. In its primacy application, the State must describe how it will determine whether a community water system has an outstanding performance record.
(iv) The State must define and describe in its primacy application at least one specific significant deficiency in each of the eight sanitary survey elements in paragraphs (o)(2)(i)(A) through (o)(2)(i)(H) of this section. Significant deficiencies include, but are not limited to, defects in design, operation, or maintenance, or a failure or malfunction of the sources, treatment, storage, or distribution system that the State determines to be causing, or have potential for causing, the introduction of contamination into the water delivered to consumers.
(v) As a condition of primacy, the State must provide ground water systems with written notice describing any significant deficiencies no later than 30 days after the State identifies the significant deficiency. The notice may specify corrective actions and deadlines for completion of corrective actions. The State may provide the written notice at the time of the sanitary survey.
(3)
(i) The criteria the State will use under §§ 141.402(a)(2)(i) and 141.402(d)(2) of this chapter for extending the 24-hour time limit for a system to collect a ground water source sample to comply with the source water monitoring requirements.
(ii) The criteria the State will use under §§ 141.402(a)(5)(i) and 141.402(a)(5)(ii) of this chapter to determine whether the cause of the total coliform-positive sample taken under § 141.21(a) of this chapter is directly related to the distribution system.
(iii) The criteria the State will use for determining whether to invalidate a fecal indicator-positive ground water source sample under § 141.402(d)(1)(ii) of this chapter.
(iv) The criteria the State will use to allow source water microbial monitoring at a location after treatment under § 141.402(e)(1) of this chapter.
(4)
(i) The process the State will use to determine that a ground water system achieves at least a 4-log treatment of viruses (using inactivation, removal, or a combination of inactivation and removal) before or at the first customer for a ground water source for systems that are not subject to the source water monitoring requirements of § 141.402(a) of this chapter because the ground water system has informed the State that it provides at least 4-log treatment of viruses.
(ii) The process the State will use to determine the minimum residual disinfectant concentration the system must provide prior to the first customer for systems using chemical disinfection.
(iii) The State-approved alternative technologies that ground water systems may use alone or in combination with other approved technologies to achieve at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of 4-log inactivation and removal) before or at the first customer for a ground water source.
(iv) The monitoring and compliance requirements the State will require for ground water systems treating to at least 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of inactivation and removal) before or at the first customer for State-approved alternative treatment technologies.
(v) The monitoring, compliance and membrane integrity testing requirements the State will require to demonstrate virus removal for ground water systems using membrane filtration technologies.
(vi) The criteria, including public health-based considerations and incorporating on-site investigations and source water monitoring results the State will use to determine if a ground water system may discontinue 4-log treatment of viruses (using inactivation, removal, or a State-approved combination of inactivation and removal) before or at the first customer.
(p)
(1)
(2)
(ii) Section 141.535 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 other means, that the alternative filtration technology, in combination with disinfection treatment that meets the requirements of § 141.72(b) of this chapter, consistently achieves 99.9 percent removal and/or inactivation of
For
(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 (
(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
(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 a draft Rescission Order. The draft order shall:
(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 determination(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
(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 primary enforcement responsibility, variances may be granted by the Administrator pursuant to Subpart E of this part.
(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 with primary enforcement responsibility during the one-year period beginning on such effective date. The Administrator shall conduct such subsequent reviews of exemptions and schedules as he deems necessary to carry out the purposes of this title, but at least one review shall be completed within each 3-year period following the completion of the first review under this paragraph.
(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
(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
(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 subchapter D of this chapter. Such inspection may include inspection, at reasonable times, of records, files, papers, processes, controls and facilities, or testing of any feature of a public water system, including its raw water source.
(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
(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 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 § 142.44.
(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
(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 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 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
(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
(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 is made on behalf of an organization or other entity, the signature of a responsibile 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 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
(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
(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 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 by the system and other relevant information. In no event shall the Administrator require a system to install and/or use a treatment method not described in § 142.60 (a) or (c) to obtain or maintain a variance from the TTHM Rule or in connection with any variance compliance schedule.
(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
(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 by the system and other relevant information.
(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
(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 public water system must develop and put in place a monitoring program that provides reasonable assurances that the bottled water meets all MCLs. The public water system must monitor a representative sample of the bottled water for all contaminants regulated under §§ 141.61 (a) and (c) and 141.62 during the first three-month period that it supplies the bottled water to the public, and annually thereafter. Results of the monitoring program shall be provided to the State annually.
(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 165.110, 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
(3) The public water system must apply effective technology under a State-approved plan. The microbiological 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 heterotrophic 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 in the operation or maintenance of the distribution system.
(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
(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
(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).
(b) [Reserved]
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 which will assume primary enforcement responsibility, including a description of the relationship between owners/operators of the public water systems and the agency.
(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 have primary enforcement responsibility.
(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 (
(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
(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 5 years after the compliance date established in the small system variance to determine whether the public water system continues to meet the eligibility criteria and remains eligible for the small system variance and is complying with the terms and conditions of the small system variance. If the public water system would no longer be eligible for a small system variance, the State or the Administrator must determine whether continuing the variance is in the public interest. If the State or the Administrator finds that continuing the variance is not in the public interest, the variance must be withdrawn.
(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 other documentation supporting the issuance of a variance must be made available to the public after final promulgation.
(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
(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
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 endangerment 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 * * * to assist him in establishing regulations under this title,” and a “right of entry and inspection to determine compliance with this title, including for this purpose, inspection, at reasonable time, or records, files, papers, processes, controls, and facilities * * *.”
(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.
(viii) Subpart H of part 146 sets forth requirements for owners or operators of Class VI 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 dimension, 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
(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)
(f)
(a) The Director may identify (by narrative description, illustrations, maps, or other means) and shall protect as underground sources of drinking water, all aquifers and parts of aquifers which meet the definition of “underground source of drinking water” in § 144.3, except to the extent there is an applicable aquifer exemption under paragraph (b) of this section or an expansion to the areal extent of an existing Class II enhanced oil recovery or enhanced gas recovery aquifer exemption for the exclusive purpose of Class VI injection for geologic sequestration under paragraph (d) of this section. Other than EPA approved aquifer exemption expansions that meet the criteria set forth in § 146.4(d) of this chapter, new aquifer exemptions shall not be issued for Class VI injection wells. 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 § 146.4 of this chapter.
(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. No designation of an expansion to the areal extent of a Class II enhanced oil recovery or enhanced gas recovery aquifer exemption for the exclusive purpose of Class VI injection for geologic sequestration shall be final until approved by the Administrator as a revision to the applicable Federal UIC program under part 147 or as a substantial revision of an approved State UIC program in accordance with § 145.32 of this chapter.
(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
(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 and formation parameters such as permeability and porosity shall be considered by the Director, to the extent such information is available.
(d)
(1) The owner or operator of a Class II enhanced oil recovery or enhanced gas recovery well that requests an expansion of the areal extent of an existing aquifer exemption for the exclusive purpose of Class VI injection for geologic sequestration must define (by narrative description, illustrations, maps, or other means) and describe in geographic and/or geometric terms (such as vertical and lateral limits and gradient) that are clear and definite, all aquifers or parts thereof that are requested to be designated as exempted using the criteria in § 146.4 of this chapter.
(2) In evaluating a request to expand the areal extent of an aquifer exemption of a Class II enhanced oil recovery or enhanced gas recovery well for the purpose of Class VI injection, the Director must determine that the request meets the criteria for exemptions in § 146.4. In making the determination, the Director shall consider:
(i) Current and potential future use of the USDWs to be exempted as drinking water resources;
(ii) The predicted extent of the injected carbon dioxide plume, and any mobilized fluids that may result in degradation of water quality, over the lifetime of the GS project, as informed by computational modeling performed pursuant to § 146.84(c)(1), in order to ensure that the proposed injection operation will not at any time endanger USDWs including non-exempted portions of the injection formation;
(iii) Whether the areal extent of the expanded aquifer exemption is of sufficient size to account for any possible revisions to the computational model during reevaluation of the area of review, pursuant to § 146.84(e); and
(iv) Any information submitted to support a waiver request made by the owner or operator under § 146.95, if appropriate.
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, such as a migration of fluids into a USDW.
(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
(iii) All Class VI program reports shall be consistent with reporting requirements set forth in § 146.91 of this chapter.
(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, III, and VI 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 construction, corrective action, operation, monitoring, or reporting (including closure of the injection well) as are necessary to prevent such movement. In the case of wells authorized by permit, these additional requirements shall be imposed by modifying the permit in accordance with § 144.39, or the permit may be terminated under § 144.40 if cause exists, or appropriate enforcement action may be taken if the permit has been violated. In the case of wells authorized by rule, see §§ 144.21 through 144.24. For EPA administered programs, such enforcement action shall be taken in accordance with appropriate sections of the SDWA.
(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 fluids do not migrate from the injection zone. 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.
(a)
(b)
(c)
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
(d)
The construction, operation or maintenance of any non-experimental Class V geologic sequestration well is prohibited.
(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 other information as is deemed necessary to determine whether the owner or operator has acted or is acting in compliance with Part C of the SDWA or its implementing regulations.
Owners or operators of Class VI wells must obtain a permit. Class VI wells cannot be authorized by rule to inject carbon dioxide.
(a) Owners or operators that are injecting carbon dioxide for the primary purpose of long-term storage into an oil and gas reservoir must apply for and obtain a Class VI geologic sequestration permit when there is an increased risk to USDWs compared to Class II operations. In determining if there is an increased risk to USDWs,
(b) The Director shall determine when there is an increased risk to USDWs compared to Class II operations and a Class VI permit is required. In order to make this determination the Director must consider the following:
(1) Increase in reservoir pressure within the injection zone(s);
(2) Increase in carbon dioxide injection rates;
(3) Decrease in reservoir production rates;
(4) Distance between the injection zone(s) and USDWs;
(5) Suitability of the Class II area of review delineation;
(6) Quality of abandoned well plugs within the area of review;
(7) The owner's or operator's plan for recovery of carbon dioxide at the cessation of injection;
(8) The source and properties of injected carbon dioxide; and
(9) Any additional site-specific factors as determined by the Director.
(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 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; 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
(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 for information within the time period(s) specified by the Director pursuant to paragraph (c) of this section. An owner or operator of a well prohibited from injection under this section shall not resume injection except under a permit issued pursuant to §§ 144.25, 144.31, 144.33 or 144.34.
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) (
(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
(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 years and has met the requirements of paragraphs (c)(2) (A) and (B) of this section] shall notify the Regional Administrator prior to resuming operation of the well.
(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
(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
(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 the movement of injection or formation fluids into an underground source of drinking water.
(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
(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 qualitative analysis and ranges in concentrations of all constituents of injected fluids at least once within the first year of authorization and thereafter whenever the injection fluid is modified to the extent that the initial data are incorrect or incomplete. The owner or operator may request Federal confidentiality as specified in 40 CFR part 2. If the information is proprietary the owner or operator may in lieu of the ranges in concentrations choose to submit maximum concentrations which shall not be exceeded. In such a case the owner or operator shall retain records of the undisclosed concentrations and provide them upon request to the Regional Administrator as part of any enforcement investigation; and
(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 the approval or promulgation of the UIC program, or as required under § 144.14(b) for wells injecting hazardous waste. For EPA administered programs the owner or operator of Class I or III wells shall submit a complete permit application no later than 1 year after the effective date of the program.
(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; and
(5) Other than Class VI wells.
(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 if a permit application has been submitted prior to the expiration of the 90-day period, the Director may extend the temporary permit until final action on the application.
(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 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. UIC permits for Class VI wells shall be issued for the operating life of the facility and the post-injection site care period. The Director shall review each issued Class II, III, and VI 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, or § 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
(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)
(5)
(i) Area of review reevaluations under § 146.84(e)(1) of this chapter;
(ii) Any amendments to the testing and monitoring plan under § 146.90(j) of this chapter;
(iii) Any amendments to the injection well plugging plan under § 146.92(c) of this chapter;
(iv) Any amendments to the post-injection site care and site closure plan under § 146.93(a)(3) of this chapter;
(v) Any amendments to the emergency and remedial response plan under § 146.94(d) of this chapter; or
(vi) A review of monitoring and/or testing results conducted in accordance with permit requirements.
(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
(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).
(h) Amend a Class VI injection well testing and monitoring plan, plugging plan, post-injection site care and site closure plan, or emergency and remedial response plan where the modifications merely clarify or correct the plan, as determined by the Director.
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 reference, a specific citation to these regulations (or the corresponding approved State regulations) 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.
(4) Owners or operators of Class VI wells shall retain records as specified in subpart H of part 146, including §§ 146.84(g), 146.91(f), 146.92(d), 146.93(f), and 146.93(h) of this chapter.
(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 ensure 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 the plan 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. A Class VI permit shall include conditions which meet the requirements set forth in § 146.92 of this chapter. Where the plan meets the requirements of § 146.92 of this chapter, the Director shall incorporate it into the permit as a permit condition. 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, III or VI well lacks mechanical integrity pursuant to § 146.8 or § 146.89 of this chapter for Class VI of this chapter, he/she shall give written notice of his/her 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
(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), paragraphs (a)(7) and (a)(9) of this section, and subpart G of part 146. Permits for owners or operators of Class VI injection wells shall include conditions meeting the requirements of subpart H of part 146. Permits for other wells shall contain the following requirements, when applicable.
(1)
(2) Corrective action as set forth in §§ 144.55, 146.7, and 146.84 of this chapter.
(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 of 40 CFR 136.3 or in appendix III of 40 CFR part 261 or in certain circumstances by other methods that have been approved by the Regional Administrator.
(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), 146.10, and 146.92 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. For Class VI wells, the permittee shall show evidence of such financial responsibility to the Director by the submission of a qualifying instrument (see § 146.85(a) of this chapter), such as a financial statement or other materials acceptable to the Director. The owner or operator of a Class VI well must comply with the financial responsibility requirements set forth in § 146.85 of this chapter.
(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 equipment or methods (including biological monitoring methods when appropriate);
(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 accordance 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 from the options as specified in paragraphs (a) through (f) of this section.
(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 and abandonment cost estimate changes, the owner or operator must compare the new estimate with the trustee's most recent annual valuation of the trust fund. If the value of the fund is less than the amount of the new estimate, the owner or operator, within 60 days after the change in the cost estimate, must either deposit an amount into the fund so that its value after this deposit at least equals the amount of the current plugging and abandonment cost estimate, or obtain other financial assurance as specified in this section to cover the difference.
(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
(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 this section, the following are not required by these requirements:
(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
(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 such assurance from the Regional Administrator.
(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 minimum, provide the insured with the option of renewal at the face amount of the expiring policy. If there is a failure to pay the premium, the insurer may elect to cancel, terminate, or fail to renew the policy by sending notice by certified mail to the owner or operator and the Regional Administrator. Cancellation, termination, or failure to renew may not occur, however, during 120 days beginning with the date of receipt of the notice by both the Regional Administrator and the owner or operator, as evidenced by the return of receipts. Cancellation, termination, or failure to renew may not occur and the policy will remain in full force and effect in the event that on or before the date of expiration:
(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 submit the following items to the Regional Administrator:
(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 Administrator as specified in paragraph (f)(3) of this section. The terms of the corporate guarantee must provide that:
(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
(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
(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 be considered acceptable for meeting the requirements of this subpart. The letter from the State must include, or have attached to it, the following information: the facility's EPA Identification Number, name and address, and the amounts of funds for plugging and abandonment coverage that are guaranteed by the State. The Regional Administrator will notify the owner or operator of his determination regarding the acceptability of the State's guarantee in lieu of mechanisms specified in this subpart. The Regional Administrator may require the owner or operator to submit additional information as is deemed necessary to make this determination. Pending this determination, the owner or operator will be deemed to be in compliance with § 144.63.
(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
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 written 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
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,
(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 to be replaced with the relevant information and the brackets deleted:
[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
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 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 40 CFR 146.04).
(e)
(f)
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 (e.g., transmission and muffler repair shop), or any facility that does any vehicular repair work. Fluids disposed in these wells may contain organic and inorganic chemicals in concentrations that exceed the maximum contaminant levels (MCLs) established by the primary drinking water regulations (see 40 CFR part 141).
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.
(i) States seeking primary enforcement responsibility for Class VI wells must submit a primacy application in accordance with subpart C of this part and meet all requirements of this part. States may apply for primary enforcement responsibility for Class VI wells independently of other injection well classes.
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);
(31) Section 124.17 (a) and (c)—(Response to comments);
(32) Section 144.88—(What are the additional requirements?); and
(33) For states that wish to receive electronic documents, 40 CFR part 3—(Electronic reporting).
(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 that public hearings be held prior to issuing any permit while reducing the amount of advance notice of such a hearing.
(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
(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 any program violation in at least the amount of $2,500 per day. For Class II wells, civil penalties shall be recoverable for any program violation in at least the amount of $1,000 per day.
(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
(a) Any information obtained or used in the administration of a State program shall be available to EPA upon request without restriction. If the information has been submitted to the State under a claim of confidentiality, the State must submit that claim to EPA when providing information under this section. Any information obtained from a State and subject to a claim of confidentiality will be treated in accordance with the regulations in 40 CFR part 2. If EPA obtains from a State information that is not claimed to be confidential, EPA may make that information available to the public without further notice.
(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
(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 to enforce violations of State underground injection control programs, except that, when a State has a fully approved program, EPA will not take enforcement actions without providing prior notice to the State and otherwise complying with section 1423 of SDWA.
(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.
(h) To establish a Federal UIC Class VI program in States not seeking full UIC primary enforcement responsibility approval, pursuant to the SDWA section 1422(c), States shall, by September 6, 2011, submit to the Administrator a new or revised State UIC program complying with §§ 145.22 or 145.32 of this part. Beginning on September 6, 2011 the requirements of subpart H of part 146 of this chapter will be applicable and enforceable by EPA in each State that has not received approval of a new Class VI program application under section 1422 of the Safe Drinking Water Act or a revision of its UIC program under section 1422 of the Safe Drinking Water Act to incorporate subpart H of part 146. Following September 6, 2011, EPA will publish a list of the States where subpart H of part 146 has become applicable.
(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. For Class VI programs, the entire submission can be sent electronically. 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 (
(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. For Class VI programs, the entire submission can be sent electronically. 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. For Class VI programs, submit copies of the current forms in use by the State, if any.
(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 40 CFR part 144. For Class VI programs, a schedule for issuing permits within two years after program approval;
(2) The priorities (according to criteria set forth in § 146.9 of this chapter) 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. For Class VI programs, include the priorities for issuing permits and the number of permits which will be issued during the first two years of program operation;
(3) A description of how the Director will implement the mechanical integrity testing requirements of § 146.8 of this chapter, or, for Class VI wells, the mechanical integrity testing requirements of § 146.89 of this chapter, 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 or 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. For Class VI programs approved before December 10, 2011, a description of the procedure whereby the Director will notify owners or operators of any Class I wells previously permitted for the purpose of geologic sequestration or Class V experimental technology wells no longer being used for experimental purposes
(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. For Class VI programs only, States must incorporate information related to any EPA approved exemptions expanding the areal extent of existing aquifer exemptions for Class II enhanced oil recovery or enhanced gas recovery wells transitioning to Class VI injection for geologic sequestration pursuant to requirements at §§ 146.4(d) and 144.7(d), including a summary of supporting data and the specific location of the aquifer exemption expansions. Other than expansions of the areal extent of Class II enhanced oil recovery or enhanced gas recovery well aquifer exemptions for Class VI injection, new aquifer exemptions shall not be issued for Class VI wells or injection activities;
(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)
(13) For Class VI programs, a description of the procedure whereby the Director must notify, in writing, any States, Tribes, and Territories of any permit applications for geologic sequestration of carbon dioxide wherein the area of review crosses State, Tribal, or Territory boundaries, resulting in the need for trans-boundary coordination related to an injection operation.
(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 the State and by EPA. These may specify the basis on which the Regional Administrator will select facilities or activities within the State for EPA inspection. The Regional Administrator will normally notify the State at least 7 days before any such inspection; and
(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
(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
(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 fails to take corrective action. Such circumstances include the following:
(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 Injection Control program which should include:
(1) A description of the Indian Tribe's previous management experience which may include, the administration of programs and services authorized
(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 § 144.7 of this chapter to be an “exempted aquifer” for Class I-V wells if it meets the criteria in paragraphs (a) through (c) of this section. Class VI wells must meet the criteria under paragraph (d) of this section:
(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.
(d) The areal extent of an aquifer exemption for a Class II enhanced oil recovery or enhanced gas recovery well may be expanded for the exclusive purpose of Class VI injection for geologic sequestration under § 144.7(d) of this chapter if it meets the following criteria:
(1) It does not currently serve as a source of drinking water; and
(2) The total dissolved solids content of the ground water is more than 3,000 mg/l and less than 10,000 mg/l; and
(3) 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, 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 § 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
(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.
(f)
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 into an underground source of drinking water; or
(ii) In the case of an application for an area permit under § 122.39, the project 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
(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
(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 Federal, State, and local regulations and requirements.
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).
(a) Existing Class I municipal disposal wells in specific geographic regions as defined in paragraph (f) of this section may continue to inject without violating the regulatory prohibitions in Parts 144 and 146 of this chapter against the movement of injection or formation fluids into a USDW, provided that such wells meet the requirements of this section, even if the Director determines they have caused or may cause fluid movement into a USDW. Nothing in this section excuses such Class I municipal disposal wells from meeting all other applicable State and Federal requirements including 40 CFR 144.12(a).
(b) For purposes of this section, an existing Class I municipal disposal well is defined as a well for which a complete UIC construction permit application was received by the Director on or before December 22, 2005.
(c) For purposes of this section, the determination that a Class I municipal disposal well has caused or may cause movement of injection or formation fluids into a USDW may be made by the Director based on any relevant data available to him/her, including ground water monitoring data generated pursuant to regulatory requirements governing operation of Class I municipal disposal wells.
(d) In order for a Class I municipal disposal well to qualify for authorization to inject pursuant to paragraph (a) of this section, the Owner/Operator of that well shall:
(1) Develop and implement a pretreatment program that is no less stringent than the requirements of Chapter 62-625, Florida Administrative Code, or have no significant industrial users as defined in that chapter.
(2) Treat the injectate using secondary treatment in a manner that is no less stringent than the requirements of Florida Rule 62-600.420(1)(d), and using high-level disinfection in a manner that is no less stringent than the requirements of Florida Rule 62-600.440(5)(a)-(f), within five years after notification by the Director that the well has caused or may cause fluid movement into a USDW.
(e) Where the Director issued such notice for a well prior to December 22, 2005, in order for that well to qualify for authorization to inject pursuant to paragraph (a) of this section, the Owner/Operator shall:
(1) Develop and implement a pretreatment program that is no less stringent than the requirements of Chapter 62-625, Florida Administrative Code, or have no significant industrial users as defined in that chapter; and
(2) Treat the injectate using secondary treatment in a manner that is no less stringent than the requirements of Florida Rule 62-600.420(1)(d), and using high-level disinfection in a manner that is no less stringent than the requirements of Florida Rule 62-600.440(5)(a)-(f), within five years after December 22, 2005.
(f) Authorization to inject wastewater into existing Class I municipal disposal wells pursuant to this section is limited to Class I municipal disposal wells in Florida in the following counties: Brevard, Broward, Charlotte, Collier, Flagler, Glades, Hendry, Highlands, Hillsborough, Indian River, Lee, Manatee, Martin, Miami-Dade, Monroe, Okeechobee, Orange, Osceola, Palm Beach, Pinellas, St. Johns, St. Lucie, Sarasota, and Volusia.
Prior to commencing injection, any Class I municipal disposal well in one of the counties identified in § 146.15(f) that is not an existing Class I municipal disposal well as defined in § 146.15(b) of this section shall meet all of the requirements for existing wells
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 at the time of drilling and those wells are in compliance with those controls; 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.
(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
(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 of drinking water and the well bore shall be prohibited.
(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
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 wells within the area of review included on the map required under paragraph (a)(2) of this section which penetrate the proposed injection zone or, in the case of Class II wells operating over the fracture pressure of the injection formation, all known wells within the area of review which penetrate formations affected by the increase in pressure. Such data shall include a description of each well's type, construction, date drilled, location, depth, record of plugging and complete, 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. This requirement does not apply to existing Class II wells.
(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
(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 map must show the number or name and location of all existing producing wells, injection wells, abandoned wells, dry holes, public water systems 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 suspected. Only information of public record and pertinent information known to the applicant is required to be included on this map.
(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 and transport can be accurately predicted through the use of models.
(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 compliance no later than 2 years following issuance of the permit and shall require observance of appropriate pressure limitations under paragraph (d)(3) until all other corrective action measures have been implemented.
(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 the casing to the surface, using a minimum of 120% of the calculated annual volume. The Director may require more than 120% when the geology or other circumstances warrant it.
(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 form of diverging holes are not created during drilling; and
(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 assure that the requirements of this part and part 144 are met:
(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 (
(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,
(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
(a) This subpart establishes criteria and standards for underground injection control programs to regulate any Class VI carbon dioxide geologic sequestration injection wells.
(b) This subpart applies to any wells used to inject carbon dioxide specifically for the purpose of geologic sequestration,
(c) This subpart also applies to owners or operators of permit- or rule-authorized Class I, Class II, or Class V experimental carbon dioxide injection projects who seek to apply for a Class VI geologic sequestration permit for their well or wells. Owners or operators seeking to convert existing Class I, Class II, or Class V experimental wells to Class VI geologic sequestration wells must demonstrate to the Director that the wells were engineered and constructed to meet the requirements at § 146.86(a) and ensure protection of USDWs, in lieu of requirements at §§ 146.86(b) and 146.87(a). By December 10, 2011, owners or operators of either Class I wells previously permitted for the purpose of geologic sequestration or Class V experimental technology wells no longer being used for experimental purposes that will continue injection of carbon dioxide for the purpose of GS must apply for a Class VI permit. A converted well must still meet all other requirements under part 146.
(d)
This section sets forth the information which must be considered by the Director in authorizing Class VI wells. For converted Class I, Class II, or Class V experimental 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, and sufficiently identified to be retrieved. In cases where EPA issues the permit, all the information in this section must be submitted to the Regional Administrator.
(a) Prior to the issuance of a permit for the construction of a new Class VI well or the conversion of an existing Class I, Class II, or Class V well to a Class VI well, the owner or operator shall submit, pursuant to § 146.91(e), and the Director shall consider the following:
(1) Information required in § 144.31(e)(1) through (6) of this chapter;
(2) A map showing the injection well for which a permit is sought and the applicable area of review consistent with § 146.84. Within the area of review, the map must show the number or name, and location of all injection wells, producing wells, abandoned wells, plugged wells or dry holes, deep stratigraphic boreholes, State- or EPA-approved subsurface cleanup sites, surface bodies of water, springs, mines (surface and subsurface), quarries, water wells, other pertinent surface features including structures intended for human occupancy, State, Tribal, and Territory boundaries, 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) Information on the geologic structure and hydrogeologic properties of the proposed storage site and overlying formations, including:
(i) Maps and cross sections of the area of review;
(ii) The location, orientation, and properties of known or suspected faults and fractures that may transect the confining zone(s) in the area of review and a determination that they would not interfere with containment;
(iii) Data on the depth, areal extent, thickness, mineralogy, porosity, permeability, and capillary pressure of the injection and confining zone(s); including geology/facies changes based on field data which may include geologic cores, outcrop data, seismic surveys, well logs, and names and lithologic descriptions;
(iv) Geomechanical information on fractures, stress, ductility, rock strength, and in situ fluid pressures within the confining zone(s);
(v) Information on the seismic history including the presence and depth of seismic sources and a determination that the seismicity would not interfere with containment; and
(vi) Geologic and topographic maps and cross sections illustrating regional geology, hydrogeology, and the geologic structure of the local area.
(4) A tabulation of all wells within the area of review which penetrate the injection or confining zone(s). Such data must 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;
(5) Maps and stratigraphic cross sections indicating the general vertical and lateral limits of all USDWs, water wells and springs within the area of review, their positions relative to the injection zone(s), and the direction of water movement, where known;
(6) Baseline geochemical data on subsurface formations, including all USDWs in the area of review;
(7) Proposed operating data for the proposed geologic sequestration site:
(i) Average and maximum daily rate and volume and/or mass and total anticipated volume and/or mass of the carbon dioxide stream;
(ii) Average and maximum injection pressure;
(iii) The source(s) of the carbon dioxide stream; and
(iv) An analysis of the chemical and physical characteristics of the carbon dioxide stream.
(8) Proposed pre-operational formation testing program to obtain an analysis of the chemical and physical characteristics of the injection zone(s) and confining zone(s) and that meets the requirements at § 146.87;
(9) Proposed stimulation program, a description of stimulation fluids to be used and a determination that stimulation will not interfere with containment;
(10) Proposed procedure to outline steps necessary to conduct injection operation;
(11) Schematics or other appropriate drawings of the surface and subsurface construction details of the well;
(12) Injection well construction procedures that meet the requirements of § 146.86;
(13) Proposed area of review and corrective action plan that meets the requirements under § 146.84;
(14) A demonstration, satisfactory to the Director, that the applicant has met the financial responsibility requirements under § 146.85;
(15) Proposed testing and monitoring plan required by § 146.90;
(16) Proposed injection well plugging plan required by § 146.92(b);
(17) Proposed post-injection site care and site closure plan required by § 146.93(a);
(18) At the Director's discretion, a demonstration of an alternative post-injection site care timeframe required by § 146.93(c);
(19) Proposed emergency and remedial response plan required by § 146.94(a);
(20) A list of contacts, submitted to the Director, for those States, Tribes, and Territories identified to be within the area of review of the Class VI project based on information provided in paragraph (a)(2) of this section; and
(21) Any other information requested by the Director.
(b) The Director shall notify, in writing, any States, Tribes, or Territories within the area of review of the Class VI project based on information provided in paragraphs (a)(2) and (a)(20) of this section of the permit application and pursuant to the requirements at § 145.23(f)(13) of this chapter.
(c) Prior to granting approval for the operation of a Class VI well, the Director shall consider the following information:
(1) The final area of review based on modeling, using data obtained during logging and testing of the well and the formation as required by paragraphs
(2) Any relevant updates, based on data obtained during logging and testing of the well and the formation as required by paragraphs (c)(3), (4), (6), (7), and (10) of this section, to the information on the geologic structure and hydrogeologic properties of the proposed storage site and overlying formations, submitted to satisfy the requirements of paragraph (a)(3) of this section;
(3) Information on the compatibility of the carbon dioxide stream with fluids in the injection zone(s) and minerals in both the injection and the confining zone(s), based on the results of the formation testing program, and with the materials used to construct the well;
(4) The results of the formation testing program required at paragraph (a)(8) of this section;
(5) Final injection well construction procedures that meet the requirements of § 146.86;
(6) The status of corrective action on wells in the area of review;
(7) All available logging and testing program data on the well required by § 146.87;
(8) A demonstration of mechanical integrity pursuant to § 146.89;
(9) Any updates to the proposed area of review and corrective action plan, testing and monitoring plan, injection well plugging plan, post-injection site care and site closure plan, or the emergency and remedial response plan submitted under paragraph (a) of this section, which are necessary to address new information collected during logging and testing of the well and the formation as required by all paragraphs of this section, and any updates to the alternative post-injection site care timeframe demonstration submitted under paragraph (a) of this section, which are necessary to address new information collected during the logging and testing of the well and the formation as required by all paragraphs of this section; and
(10) Any other information requested by the Director.
(d) Owners or operators seeking a waiver of the requirement to inject below the lowermost USDW must also refer to § 146.95 and submit a supplemental report, as required at § 146.95(a). The supplemental report is not part of the permit application.
(a) Owners or operators of Class VI wells must demonstrate to the satisfaction of the Director that the wells will be sited in areas with a suitable geologic system. The owners or operators must demonstrate that the geologic system comprises:
(1) An injection zone(s) of sufficient areal extent, thickness, porosity, and permeability to receive the total anticipated volume of the carbon dioxide stream;
(2) Confining zone(s) free of transmissive faults or fractures and of sufficient areal extent and integrity to contain the injected carbon dioxide stream and displaced formation fluids and allow injection at proposed maximum pressures and volumes without initiating or propagating fractures in the confining zone(s).
(b) The Director may require owners or operators of Class VI wells to identify and characterize additional zones that will impede vertical fluid movement, are free of faults and fractures that may interfere with containment, allow for pressure dissipation, and provide additional opportunities for monitoring, mitigation, and remediation.
(a) The area of review is the region surrounding the geologic sequestration project where USDWs may be endangered by the injection activity. The area of review is delineated using computational modeling that accounts for the physical and chemical properties of all phases of the injected carbon dioxide stream and is based on available site characterization, monitoring, and operational data.
(b) The owner or operator of a Class VI well must prepare, maintain, and comply with a plan to delineate the area of review for a proposed geologic sequestration project, periodically reevaluate the delineation, and perform
(1) The method for delineating the area of review that meets the requirements of paragraph (c) of this section, including the model to be used, assumptions that will be made, and the site characterization data on which the model will be based;
(2) A description of:
(i) The minimum fixed frequency, not to exceed five years, at which the owner or operator proposes to reevaluate the area of review;
(ii) The monitoring and operational conditions that would warrant a reevaluation of the area of review prior to the next scheduled reevaluation as determined by the minimum fixed frequency established in paragraph (b)(2)(i) of this section.
(iii) How monitoring and operational data (e.g., injection rate and pressure) will be used to inform an area of review reevaluation; and
(iv) How corrective action will be conducted to meet the requirements of paragraph (d) of this section, including what corrective action will be performed prior to injection and what, if any, portions of the area of review will have corrective action addressed on a phased basis and how the phasing will be determined; how corrective action will be adjusted if there are changes in the area of review; and how site access will be guaranteed for future corrective action.
(c) Owners or operators of Class VI wells must perform the following actions to delineate the area of review and identify all wells that require corrective action:
(1) Predict, using existing site characterization, monitoring and operational data, and computational modeling, the projected lateral and vertical migration of the carbon dioxide plume and formation fluids in the subsurface from the commencement of injection activities until the plume movement ceases, until pressure differentials sufficient to cause the movement of injected fluids or formation fluids into a USDW are no longer present, or until the end of a fixed time period as determined by the Director. The model must:
(i) Be based on detailed geologic data collected to characterize the injection zone(s), confining zone(s) and any additional zones; and anticipated operating data, including injection pressures, rates, and total volumes over the proposed life of the geologic sequestration project;
(ii) Take into account any geologic heterogeneities, other discontinuities, data quality, and their possible impact on model predictions; and
(iii) Consider potential migration through faults, fractures, and artificial penetrations.
(2) Using methods approved by the Director, identify all penetrations, including active and abandoned wells and underground mines, in the area of review that may penetrate the confining zone(s). Provide 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; and
(3) Determine which abandoned wells in the area of review have been plugged in a manner that prevents the movement of carbon dioxide or other fluids that may endanger USDWs, including use of materials compatible with the carbon dioxide stream.
(d) Owners or operators of Class VI wells must perform corrective action on all wells in the area of review that are determined to need corrective action, using methods designed to prevent the movement of fluid into or between USDWs, including use of materials compatible with the carbon dioxide stream, where appropriate.
(e) At the minimum fixed frequency, not to exceed five years, as specified in the area of review and corrective action plan, or when monitoring and operational conditions warrant, owners or operators must:
(1) Reevaluate the area of review in the same manner specified in paragraph (c)(1) of this section;
(2) Identify all wells in the reevaluated area of review that require corrective action in the same manner specified in paragraph (c) of this section;
(3) Perform corrective action on wells requiring corrective action in the reevaluated area of review in the same manner specified in paragraph (d) of this section; and
(4) Submit an amended area of review and corrective action plan or demonstrate to the Director through monitoring data and modeling results that no amendment to the area of review and corrective action plan is needed. Any amendments to the area of review and corrective action plan must be approved by the Director, must be incorporated into the permit, and are subject to the permit modification requirements at § 144.39 or § 144.41 of this chapter, as appropriate.
(f) The emergency and remedial response plan (as required by § 146.94) and the demonstration of financial responsibility (as described by § 146.85) must account for the area of review delineated as specified in paragraph (c)(1) of this section or the most recently evaluated area of review delineated under paragraph (e) of this section, regardless of whether or not corrective action in the area of review is phased.
(g) All modeling inputs and data used to support area of review reevaluations under paragraph (e) of this section shall be retained for 10 years.
(a) The owner or operator must demonstrate and maintain financial responsibility as determined by the Director that meets the following conditions:
(1) The financial responsibility instrument(s) used must be from the following list of qualifying instruments:
(i) Trust Funds.
(ii) Surety Bonds.
(iii) Letter of Credit.
(iv) Insurance.
(v) Self Insurance (
(vi) Escrow Account.
(vii) Any other instrument(s) satisfactory to the Director.
(2) The qualifying instrument(s) must be sufficient to cover the cost of:
(i) Corrective action (that meets the requirements of § 146.84);
(ii) Injection well plugging (that meets the requirements of § 146.92);
(iii) Post injection site care and site closure (that meets the requirements of § 146.93); and
(iv) Emergency and remedial response (that meets the requirements of § 146.94).
(3) The financial responsibility instrument(s) must be sufficient to address endangerment of underground sources of drinking water.
(4) The qualifying financial responsibility instrument(s) must comprise protective conditions of coverage.
(i) Protective conditions of coverage must include at a minimum cancellation, renewal, and continuation provisions, specifications on when the provider becomes liable following a notice of cancellation if there is a failure to renew with a new qualifying financial instrument, and requirements for the provider to meet a minimum rating, minimum capitalization, and ability to pass the bond rating when applicable.
(A)
(B)
(C) Cancellation, termination, or failure to renew may not occur and the financial instrument will remain in full force and effect in the event that on or before the date of expiration: The Director deems the facility abandoned; or the permit is terminated or revoked or a new permit is denied; or closure is ordered by the Director or a U.S. district court or other court of competent jurisdiction; or the owner or operator is named as debtor in a voluntary or involuntary proceeding under Title 11 (Bankruptcy), U.S. Code; or the amount due is paid.
(5) The qualifying financial responsibility instrument(s) must be approved by the Director.
(i) The Director shall consider and approve the financial responsibility demonstration for all the phases of the geologic sequestration project prior to issue a Class VI permit (§ 146.82).
(ii) The owner or operator must provide any updated information related to their financial responsibility instrument(s) on an annual basis and if there are any changes, the Director must evaluate, within a reasonable time, the financial responsibility demonstration to confirm that the instrument(s) used remain adequate for use. The owner or operator must maintain financial responsibility requirements regardless of the status of the Director's review of the financial responsibility demonstration.
(iii) The Director may disapprove the use of a financial instrument if he determines that it is not sufficient to meet the requirements of this section.
(6) The owner or operator may demonstrate financial responsibility by using one or multiple qualifying financial instruments for specific phases of the geologic sequestration project.
(i) In the event that the owner or operator combines more than one instrument for a specific geologic sequestration phase (e.g., well plugging), such combination must be limited to instruments that are not based on financial strength or performance (
(ii) When using a third-party instrument to demonstrate financial responsibility, the owner or operator must provide a proof that the third-party providers either have passed financial strength requirements based on credit ratings; or has met a minimum rating, minimum capitalization, and ability to pass the bond rating when applicable.
(iii) An owner or operator using certain types of third-party instruments must establish a standby trust to enable EPA to be party to the financial responsibility agreement without EPA being the beneficiary of any funds. The standby trust fund must be used along with other financial responsibility instruments (e.g., surety bonds, letters of credit, or escrow accounts) to provide a location to place funds if needed.
(iv) An owner or operator may deposit money to an escrow account to cover financial responsibility requirements; this account must segregate funds sufficient to cover estimated costs for Class VI (geologic sequestration) financial responsibility from other accounts and uses.
(v) An owner or operator or its guarantor may use self insurance to demonstrate financial responsibility for geologic sequestration projects. In order to satisfy this requirement the owner or operator must meet a Tangible Net Worth of an amount approved by the Director, have a Net working capital and tangible net worth each at least six times the sum of the current well plugging, post injection site care and site closure cost, have assets located in the United States amounting to at least 90 percent of total assets or at least six times the sum of the current well plugging, post injection site care and site closure cost, and must
(vi) An owner or operator who is not able to meet corporate financial test criteria may arrange a corporate guarantee by demonstrating that its corporate parent meets the financial test requirements on its behalf. The parent's demonstration that it meets the financial test requirement is insufficient if it has not also guaranteed to fulfill the obligations for the owner or operator.
(vii) An owner or operator may obtain an insurance policy to cover the estimated costs of geologic sequestration activities requiring financial responsibility. This insurance policy must be obtained from a third party provider.
(b) The requirement to maintain adequate financial responsibility and resources is directly enforceable regardless of whether the requirement is a condition of the permit.
(1) The owner or operator must maintain financial responsibility and resources until:
(i) The Director receives and approves the completed post-injection site care and site closure plan; and
(ii) The Director approves site closure.
(2) The owner or operator may be released from a financial instrument in the following circumstances:
(i) The owner or operator has completed the phase of the geologic sequestration project for which the financial instrument was required and has fulfilled all its financial obligations as determined by the Director, including obtaining financial responsibility for the next phase of the GS project, if required; or
(ii) The owner or operator has submitted a replacement financial instrument and received written approval from the Director accepting the new financial instrument and releasing the owner or operator from the previous financial instrument.
(c) The owner or operator must have a detailed written estimate, in current dollars, of the cost of performing corrective action on wells in the area of review, plugging the injection well(s), post-injection site care and site closure, and emergency and remedial response.
(1) The cost estimate must be performed for each phase separately and must be based on the costs to the regulatory agency of hiring a third party to perform the required activities. A third party is a party who is not within the corporate structure of the owner or operator.
(2) During the active life of the geologic sequestration project, the owner or operator must adjust the cost estimate for inflation within 60 days prior to the anniversary date of the establishment of the financial instrument(s) used to comply with paragraph (a) of this section and provide this adjustment to the Director. The owner or operator must also provide to the Director written updates of adjustments to the cost estimate within 60 days of any amendments to the area of review and corrective action plan (§ 146.84), the injection well plugging plan (§ 146.92), the post-injection site care and site closure plan (§ 146.93), and the emergency and remedial response plan (§ 146.94).
(3) The Director must approve any decrease or increase to the initial cost estimate. During the active life of the geologic sequestration project, the owner or operator must revise the cost estimate no later than 60 days after the Director has approved the request to modify the area of review and corrective action plan (§ 146.84), the injection well plugging plan (§ 146.92), the post-injection site care and site closure plan (§ 146.93), and the emergency and response plan (§ 146.94), if the change in the plan increases the cost. If the change to the plans decreases the cost,
(4) Whenever the current cost estimate increases to an amount greater than the face amount of a financial instrument currently in use, 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 cost estimate and submit evidence of such increase to the Director, or obtain other financial responsibility instruments to cover the increase. Whenever the current cost estimate decreases, the face amount of the financial assurance instrument may be reduced to the amount of the current cost estimate only after the owner or operator has received written approval from the Director.
(d) The owner or operator must notify the Director by certified mail of adverse financial conditions such as bankruptcy that may affect the ability to carry out injection well plugging and post-injection site care and site closure.
(1) In the event that the owner or operator or the third party provider of a financial responsibility instrument is going through a bankruptcy, the owner or operator must notify the Director 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 days after commencement of the proceeding.
(2) A guarantor of a corporate guarantee must make such a notification to the Director if he/she is named as debtor, as required under the terms of the corporate guarantee.
(3) An owner or operator who fulfills the requirements of paragraph (a) of this section by obtaining a trust fund, surety bond, letter of credit, escrow account, or insurance policy will be deemed to be without the required financial assurance in the event of bankruptcy of the trustee or issuing institution, or a suspension or revocation of the authority of the trustee institution to act as trustee of the institution issuing the trust fund, surety bond, letter of credit, escrow account, or insurance policy. The owner or operator must establish other financial assurance within 60 days after such an event.
(e) The owner or operator must provide an adjustment of the cost estimate to the Director within 60 days of notification by the Director, if the Director determines during the annual evaluation of the qualifying financial responsibility instrument(s) that the most recent demonstration is no longer adequate to cover the cost of corrective action (as required by § 146.84), injection well plugging (as required by § 146.92), post-injection site care and site closure (as required by § 146.93), and emergency and remedial response (as required by § 146.94).
(f) The Director must approve the use and length of pay-in-periods for trust funds or escrow accounts.
(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 the annulus space between the injection tubing and long string casing.
(b)
(i) Depth to the injection zone(s);
(ii) Injection pressure, external pressure, internal pressure, and axial loading;
(iii) Hole size;
(iv) Size and grade of all casing strings (wall thickness, external diameter, nominal weight, length, joint specification, and construction material);
(v) Corrosiveness of the carbon dioxide stream and formation fluids;
(vi) Down-hole temperatures;
(vii) Lithology of injection and confining zone(s);
(viii) Type or grade of cement and cement additives; and
(ix) Quantity, chemical composition, and temperature of the carbon dioxide stream.
(2) Surface casing must extend through the base of the lowermost USDW and be cemented to the surface through the use of a single or multiple strings of casing and cement.
(3) At least one long string casing, using a sufficient number of centralizers, must extend to the injection zone and must be cemented by circulating cement to the surface in one or more stages.
(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 does not allow fluid movement behind the well bore.
(5) Cement and cement additives must be compatible with the carbon dioxide stream and formation fluids and of sufficient quality and quantity to maintain integrity over the design life of the geologic sequestration project. The integrity and location of the cement shall be verified using technology capable of evaluating cement quality radially and identifying the location of channels to ensure that USDWs are not endangered.
(c)
(2) All owners or operators of Class VI wells must inject fluids through tubing with a packer set at a depth opposite a cemented interval at the location approved by the Director.
(3) In order for the Director to determine and specify requirements for tubing and packer, the owner or operator must submit the following information:
(i) Depth of setting;
(ii) Characteristics of the carbon dioxide stream (chemical content, corrosiveness, temperature, and density) and formation fluids;
(iii) Maximum proposed injection pressure;
(iv) Maximum proposed annular pressure;
(v) Proposed injection rate (intermittent or continuous) and volume and/or mass of the carbon dioxide stream;
(vi) Size of tubing and casing; and
(vii) Tubing tensile, burst, and collapse strengths.
(a) During the drilling and construction of a Class VI injection well, the owner or operator must run appropriate logs, surveys and tests to determine or verify the depth, thickness, porosity, permeability, and lithology of, and the salinity of any formation fluids in all relevant geologic formations to ensure conformance with the injection well construction requirements under § 146.86 and to establish accurate baseline data against which future measurements may be compared. The owner or operator must submit to the Director a descriptive report prepared by a knowledgeable log analyst that includes an interpretation of the results of such logs and tests. At a minimum, such logs and tests must include:
(1) Deviation checks during drilling on all holes constructed by drilling a pilot hole which is enlarged by reaming or another method. Such checks must be at sufficiently frequent intervals to determine the location of the borehole and to ensure that vertical avenues for
(2) Before and upon installation of the surface casing:
(i) Resistivity, spontaneous potential, and caliper logs before the casing is installed; and
(ii) A cement bond and variable density log to evaluate cement quality radially, and a temperature log after the casing is set and cemented.
(3) Before and upon installation of the long string casing:
(i) Resistivity, spontaneous potential, porosity, caliper, gamma ray, fracture finder logs, and any other logs the Director requires for the given geology before the casing is installed; and
(ii) A cement bond and variable density log, and a temperature log after the casing is set and cemented.
(4) A series of tests designed to demonstrate the internal and external mechanical integrity of injection wells, which may include:
(i) A pressure test with liquid or gas;
(ii) A tracer survey such as oxygen-activation logging;
(iii) A temperature or noise log;
(iv) A casing inspection log; and
(5) Any alternative methods that provide equivalent or better information and that are required by and/or approved of by the Director.
(b) The owner or operator must take whole cores or sidewall cores of the injection zone and confining system and formation fluid samples from the injection zone(s), and must submit to the Director a detailed report prepared by a log analyst that includes: Well log analyses (including well logs), core analyses, and formation fluid sample information. The Director may accept information on 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 owner or operator must record the fluid temperature, pH, conductivity, reservoir pressure, and static fluid level of the injection zone(s).
(d) At a minimum, the owner or operator must determine or calculate the following information concerning the injection and confining zone(s):
(1) Fracture pressure;
(2) Other physical and chemical characteristics of the injection and confining zone(s); and
(3) Physical and chemical characteristics of the formation fluids in the injection zone(s).
(e) Upon completion, but prior to operation, the owner or operator must conduct the following tests to verify hydrogeologic characteristics of the injection zone(s):
(1) A pressure fall-off test; and,
(2) A pump test; or
(3) Injectivity tests.
(f) The owner or operator must provide the Director with the opportunity to witness all logging and testing by this subpart. The owner or operator must submit a schedule of such activities to the Director 30 days prior to conducting the first test and submit any changes to the schedule 30 days prior to the next scheduled test.
(a) Except during stimulation, the owner or operator must ensure that injection pressure does not exceed 90 percent of the fracture pressure of the injection zone(s) so as to ensure that the injection does not initiate new fractures or propagate existing fractures in the injection zone(s). In no case may injection pressure initiate fractures in the confining zone(s) or cause the movement of injection or formation fluids that endangers a USDW. Pursuant to requirements at § 146.82(a)(9), all stimulation programs must be approved by the Director as part of the permit application and incorporated into the permit.
(b) Injection between the outermost casing protecting USDWs and the well bore is prohibited.
(c) The owner or operator must fill the annulus between the tubing and the long string casing with a non-corrosive fluid approved by the Director. The owner or operator must maintain on the annulus a pressure that exceeds the operating injection pressure, unless the Director determines that such requirement might harm the integrity of the well or endanger USDWs.
(d) Other than during periods of well workover (maintenance) approved by the Director in which the sealed tubing-casing annulus is disassembled for maintenance or corrective procedures, the owner or operator must maintain mechanical integrity of the injection well at all times.
(e) The owner or operator must install and use:
(1) Continuous recording devices to monitor: The injection pressure; the rate, volume and/or mass, and temperature of the carbon dioxide stream; and the pressure on the annulus between the tubing and the long string casing and annulus fluid volume; and
(2) Alarms and automatic surface shut-off systems or, at the discretion of the Director, down-hole shut-off systems (e.g., automatic shut-off, check valves) for onshore wells or, other mechanical devices that provide equivalent protection; and
(3) Alarms and automatic down-hole shut-off systems for wells located offshore but within State territorial waters, designed to alert the operator and shut-in the well when operating parameters such as annulus pressure, injection rate, or other parameters diverge beyond permitted ranges and/or gradients specified in the permit.
(f) If a shutdown (
(1) Immediately cease injection;
(2) Take all steps reasonably necessary to determine whether there may have been a release of the injected carbon dioxide stream or formation fluids into any unauthorized zone;
(3) Notify the Director within 24 hours;
(4) Restore and demonstrate mechanical integrity to the satisfaction of the Director prior to resuming injection; and
(5) Notify the Director when injection can be expected to resume.
(a) A Class VI 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 a USDW through channels adjacent to the injection well bore.
(b) To evaluate the absence of significant leaks under paragraph (a)(1) of this section, owners or operators must, following an initial annulus pressure test, continuously monitor injection pressure, rate, injected volumes; pressure on the annulus between tubing and long-string casing; and annulus fluid volume as specified in § 146.88 (e);
(c) At least once per year, the owner or operator must use one of the following methods to determine the absence of significant fluid movement under paragraph (a)(2) of this section:
(1) An approved tracer survey such as an oxygen-activation log; or
(2) A temperature or noise log.
(d) If required by the Director, at a frequency specified in the testing and monitoring plan required at § 146.90, the owner or operator must run a casing inspection log to determine the presence or absence of corrosion in the long-string casing.
(e) The Director may require any other test to evaluate mechanical integrity under paragraphs (a)(1) or (a)(2) of this section. Also, the Director may allow the use of a test to demonstrate mechanical integrity other than those listed above with the written approval of the Administrator. To obtain approval for a new mechanical integrity test, the Director must submit a written request to the Administrator setting forth the proposed test and all technical data supporting its use. The Administrator may approve the request if he or she determines that it will reliably demonstrate the mechanical integrity of wells for which its use is proposed. Any alternate method approved by the Administrator will be published in the
(f) 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 must 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/she shall include a description of the test(s) and the method(s) used. In making his/her evaluation, the Director must review monitoring and other test data submitted since the previous evaluation.
(g) The Director may require additional or alternative tests if the results presented by the owner or operator under paragraphs (a) through (d) of this section are not satisfactory to the Director to demonstrate that there is no significant leak in the casing, tubing, or packer, or to demonstrate that there is no significant movement of fluid into a USDW resulting from the injection activity as stated in paragraphs (a)(1) and (2) of this section.
The owner or operator of a Class VI well must prepare, maintain, and comply with a testing and monitoring plan to verify that the geologic sequestration project is operating as permitted and is not endangering USDWs. The requirement to maintain and implement an approved plan is directly enforceable regardless of whether the requirement is a condition of the permit. The testing and monitoring plan must be submitted with the permit application, for Director approval, and must include a description of how the owner or operator will meet the requirements of this section, including accessing sites for all necessary monitoring and testing during the life of the project. Testing and monitoring associated with geologic sequestration projects must, at a minimum, include:
(a) Analysis of the carbon dioxide stream with sufficient frequency to yield data representative of its chemical and physical characteristics;
(b) Installation and use, except during well workovers as defined in § 146.88(d), of continuous recording devices to monitor injection pressure, rate, and volume; the pressure on the annulus between the tubing and the long string casing; and the annulus fluid volume added;
(c) Corrosion monitoring of the well materials for loss of mass, thickness, cracking, pitting, and other signs of corrosion, which must be performed on a quarterly basis to ensure that the well components meet the minimum standards for material strength and performance set forth in § 146.86(b), by:
(1) Analyzing coupons of the well construction materials placed in contact with the carbon dioxide stream; or
(2) Routing the carbon dioxide stream through a loop constructed with the material used in the well and inspecting the materials in the loop; or
(3) Using an alternative method approved by the Director;
(d) Periodic monitoring of the ground water quality and geochemical changes above the confining zone(s) that may be a result of carbon dioxide movement through the confining zone(s) or additional identified zones including:
(1) The location and number of monitoring wells based on specific information about the geologic sequestration project, including injection rate and volume, geology, the presence of artificial penetrations, and other factors; and
(2) The monitoring frequency and spatial distribution of monitoring wells based on baseline geochemical data that has been collected under § 146.82(a)(6) and on any modeling results in the area of review evaluation required by § 146.84(c).
(e) A demonstration of external mechanical integrity pursuant to § 146.89(c) at least once per year until the injection well is plugged; and, if required by the Director, a casing inspection log pursuant to requirements at § 146.89(d) at a frequency established in the testing and monitoring plan;
(f) A pressure fall-off test at least once every five years unless more frequent testing is required by the Director based on site-specific information;
(g) Testing and monitoring to track the extent of the carbon dioxide plume and the presence or absence of elevated pressure (e.g., the pressure front) by using:
(1) Direct methods in the injection zone(s); and,
(2) Indirect methods (e.g., seismic, electrical, gravity, or electromagnetic surveys and/or down-hole carbon dioxide detection tools), unless the Director determines, based on site-specific geology, that such methods are not appropriate;
(h) The Director may require surface air monitoring and/or soil gas monitoring to detect movement of carbon dioxide that could endanger a USDW.
(1) Design of Class VI surface air and/or soil gas monitoring must be based on potential risks to USDWs within the area of review;
(2) The monitoring frequency and spatial distribution of surface air monitoring and/or soil gas monitoring must be decided using baseline data, and the monitoring plan must describe how the proposed monitoring will yield useful information on the area of review delineation and/or compliance with standards under § 144.12 of this chapter;
(3) If an owner or operator demonstrates that monitoring employed under §§ 98.440 to 98.449 of this chapter (Clean Air Act, 42 U.S.C. 7401
(i) Any additional monitoring, as required by the Director, necessary to support, upgrade, and improve computational modeling of the area of review evaluation required under § 146.84(c) and to determine compliance with standards under § 144.12 of this chapter;
(j) The owner or operator shall periodically review the testing and monitoring plan to incorporate monitoring data collected under this subpart, operational data collected under § 146.88, and the most recent area of review reevaluation performed under § 146.84(e). In no case shall the owner or operator review the testing and monitoring plan less often than once every five years. Based on this review, the owner or operator shall submit an amended testing and monitoring plan or demonstrate to the Director that no amendment to the testing and monitoring plan is needed. Any amendments to the testing and monitoring plan must be approved by the Director, must be incorporated into the permit, and are subject to the permit modification requirements at § 144.39 or § 144.41 of this chapter, as appropriate. Amended plans or demonstrations shall be submitted to the Director as follows:
(1) Within one year of an area of review reevaluation;
(2) Following any significant changes to the facility, such as addition of monitoring wells or newly permitted injection wells within the area of review, on a schedule determined by the Director; or
(3) When required by the Director.
(k) A quality assurance and surveillance plan for all testing and monitoring requirements.
The owner or operator must, at a minimum, provide, as specified in paragraph (e) of this section, the following reports to the Director, for each permitted Class VI well:
(a) Semi-annual reports containing:
(1) Any changes to the physical, chemical, and other relevant characteristics of the carbon dioxide stream from the proposed operating data;
(2) Monthly average, maximum, and minimum values for injection pressure, flow rate and volume, and annular pressure;
(3) A description of any event that exceeds operating parameters for annulus pressure or injection pressure specified in the permit;
(4) A description of any event which triggers a shut-off device required pursuant to § 146.88(e) and the response taken;
(5) The monthly volume and/or mass of the carbon dioxide stream injected over the reporting period and the volume injected cumulatively over the life of the project;
(6) Monthly annulus fluid volume added; and
(7) The results of monitoring prescribed under § 146.90.
(b) Report, within 30 days, the results of:
(1) Periodic tests of mechanical integrity;
(2) Any well workover; and,
(3) Any other test of the injection well conducted by the permittee if required by the Director.
(c) Report, within 24 hours:
(1) Any evidence that the injected carbon dioxide stream or associated pressure front may cause an endangerment to a USDW;
(2) Any noncompliance with a permit condition, or malfunction of the injection system, which may cause fluid migration into or between USDWs;
(3) Any triggering of a shut-off system (
(4) Any failure to maintain mechanical integrity; or.
(5) Pursuant to compliance with the requirement at § 146.90(h) for surface air/soil gas monitoring or other monitoring technologies, if required by the Director, any release of carbon dioxide to the atmosphere or biosphere.
(d) Owners or operators must notify the Director in writing 30 days in advance of:
(1) Any planned well workover;
(2) Any planned stimulation activities, other than stimulation for formation testing conducted under § 146.82; and
(3) Any other planned test of the injection well conducted by the permittee.
(e) Regardless of whether a State has primary enforcement responsibility, owners or operators must submit all required reports, submittals, and notifications under subpart H of this part to EPA in an electronic format approved by EPA.
(f) Records shall be retained by the owner or operator as follows:
(1) All data collected under § 146.82 for Class VI permit applications shall be retained throughout the life of the geologic sequestration project and for 10 years following site closure.
(2) Data on the nature and composition of all injected fluids collected pursuant to § 146.90(a) shall be retained until 10 years after site closure. The Director may require the owner or operator to deliver the records to the Director at the conclusion of the retention period.
(3) Monitoring data collected pursuant to § 146.90(b) through (i) shall be retained for 10 years after it is collected.
(4) Well plugging reports, post-injection site care data, including, if appropriate, data and information used to develop the demonstration of the alternative post-injection site care timeframe, and the site closure report collected pursuant to requirements at §§ 146.93(f) and (h) shall be retained for 10 years following site closure.
(5) The Director has authority to require the owner or operator to retain any records required in this subpart for longer than 10 years after site closure.
(a) Prior to the well plugging, the owner or operator must flush each Class VI injection well with a buffer fluid, determine bottomhole reservoir pressure, and perform a final external mechanical integrity test.
(b)
(1) Appropriate tests or measures for determining bottomhole reservoir pressure;
(2) Appropriate testing methods to ensure external mechanical integrity as specified in § 146.89;
(3) The type and number of plugs to be used;
(4) The placement of each plug, including the elevation of the top and bottom of each plug;
(5) The type, grade, and quantity of material to be used in plugging. The material must be compatible with the carbon dioxide stream; and
(6) The method of placement of the plugs.
(c)
(d)
(a) The owner or operator of a Class VI well must prepare, maintain, and comply with a plan for post-injection site care and site closure that meets the requirements of paragraph (a)(2) of this section and is acceptable to the Director. The requirement to maintain and implement an approved plan is directly enforceable regardless of whether the requirement is a condition of the permit.
(1) The owner or operator must submit the post-injection site care and site closure plan as a part of the permit application to be approved by the Director.
(2) The post-injection site care and site closure plan must include the following information:
(i) The pressure differential between pre-injection and predicted post-injection pressures in the injection zone(s);
(ii) The predicted position of the carbon dioxide plume and associated pressure front at site closure as demonstrated in the area of review evaluation required under § 146.84(c)(1);
(iii) A description of post-injection monitoring location, methods, and proposed frequency;
(iv) A proposed schedule for submitting post-injection site care monitoring results to the Director pursuant to § 146.91(e); and,
(v) The duration of the post-injection site care timeframe and, if approved by the Director, the demonstration of the alternative post-injection site care timeframe that ensures non-endangerment of USDWs.
(3) Upon cessation of injection, owners or operators of Class VI wells must either submit an amended post-injection site care and site closure plan or demonstrate to the Director through monitoring data and modeling results that no amendment to the plan is needed. Any amendments to the post-injection site care and site closure plan must be approved by the Director, be incorporated into the permit, and are subject to the permit modification requirements at § 144.39 or § 144.41 of this chapter, as appropriate.
(4) At any time during the life of the geologic sequestration project, the owner or operator may modify and resubmit the post-injection site care and site closure plan for the Director's approval within 30 days of such change.
(b) The owner or operator shall monitor the site following the cessation of injection to show the position of the carbon dioxide plume and pressure front and demonstrate that USDWs are not being endangered.
(1) Following the cessation of injection, the owner or operator shall continue to conduct monitoring as specified in the Director-approved post-injection site care and site closure plan for at least 50 years or for the duration of the alternative timeframe approved by the Director pursuant to requirements in paragraph (c) of this section, unless he/she makes a demonstration under (b)(2) of this section. The monitoring must continue until the geologic sequestration project no longer poses an endangerment to USDWs and the demonstration under (b)(2) of this section is submitted and approved by the Director.
(2) If the owner or operator can demonstrate to the satisfaction of the Director before 50 years or prior to the end of the approved alternative timeframe based on monitoring and other site-specific data, that the geologic sequestration project no longer poses an endangerment to USDWs, the Director may approve an amendment to the post-injection site care and site closure
(3) Prior to authorization for site closure, the owner or operator must submit to the Director for review and approval a demonstration, based on monitoring and other site-specific data, that no additional monitoring is needed to ensure that the geologic sequestration project does not pose an endangerment to USDWs.
(4) If the demonstration in paragraph (b)(3) of this section cannot be made (
(c)
(1) A demonstration of an alternative post-injection site care timeframe must include consideration and documentation of:
(i) The results of computational modeling performed pursuant to delineation of the area of review under § 146.84;
(ii) The predicted timeframe for pressure decline within the injection zone, and any other zones, such that formation fluids may not be forced into any USDWs; and/or the timeframe for pressure decline to pre-injection pressures;
(iii) The predicted rate of carbon dioxide plume migration within the injection zone, and the predicted timeframe for the cessation of migration;
(iv) A description of the site-specific processes that will result in carbon dioxide trapping including immobilization by capillary trapping, dissolution, and mineralization at the site;
(v) The predicted rate of carbon dioxide trapping in the immobile capillary phase, dissolved phase, and/or mineral phase;
(vi) The results of laboratory analyses, research studies, and/or field or site-specific studies to verify the information required in paragraphs (iv) and (v) of this section;
(vii) A characterization of the confining zone(s) including a demonstration that it is free of transmissive faults, fractures, and micro-fractures and of appropriate thickness, permeability, and integrity to impede fluid (e.g., carbon dioxide, formation fluids) movement;
(viii) The presence of potential conduits for fluid movement including planned injection wells and project monitoring wells associated with the proposed geologic sequestration project or any other projects in proximity to the predicted/modeled, final extent of the carbon dioxide plume and area of elevated pressure;
(ix) A description of the well construction and an assessment of the quality of plugs of all abandoned wells within the area of review;
(x) The distance between the injection zone and the nearest USDWs above and/or below the injection zone; and
(xi) Any additional site-specific factors required by the Director.
(2) Information submitted to support the demonstration in paragraph (c)(1) of this section must meet the following criteria:
(i) All analyses and tests performed to support the demonstration must be accurate, reproducible, and performed in accordance with the established quality assurance standards;
(ii) Estimation techniques must be appropriate and EPA-certified test protocols must be used where available;
(iii) Predictive models must be appropriate and tailored to the site conditions, composition of the carbon dioxide stream and injection and site conditions over the life of the geologic sequestration project;
(iv) Predictive models must be calibrated using existing information (e.g., at Class I, Class II, or Class V experimental technology well sites) where sufficient data are available;
(v) Reasonably conservative values and modeling assumptions must be used and disclosed to the Director whenever values are estimated on the basis of known, historical information instead of site-specific measurements;
(vi) An analysis must be performed to identify and assess aspects of the alternative post-injection site care timeframe demonstration that contribute significantly to uncertainty. The owner or operator must conduct sensitivity analyses to determine the effect that significant uncertainty may contribute to the modeling demonstration.
(vii) An approved quality assurance and quality control plan must address all aspects of the demonstration; and,
(viii) Any additional criteria required by the Director.
(d)
(e) After the Director has authorized site closure, the owner or operator must plug all monitoring wells in a manner which will not allow movement of injection or formation fluids that endangers a USDW.
(f) The owner or operator must submit a site closure report to the Director within 90 days of site closure, which must thereafter be retained at a location designated by the Director for 10 years. The report must include:
(1) Documentation of appropriate injection and monitoring well plugging as specified in § 146.92 and paragraph (e) of this section. The owner or operator must provide a copy of a survey plat which has been submitted to the local zoning authority designated by the Director. The plat must indicate the location of the injection well relative to permanently surveyed benchmarks. The owner or operator must also submit a copy of the plat to the Regional Administrator of the appropriate EPA Regional Office;
(2) Documentation of appropriate notification and information to such State, local and Tribal authorities that have authority over drilling activities to enable such State, local, and Tribal authorities to impose appropriate conditions on subsequent drilling activities that may penetrate the injection and confining zone(s); and
(3) Records reflecting the nature, composition, and volume of the carbon dioxide stream.
(g) Each owner or operator of a Class VI injection well must record a notation on the deed to the facility property or any other document that 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 sequester carbon dioxide;
(2) The name of the State agency, local authority, and/or Tribe with which the survey plat was filed, as well as the address of the Environmental Protection Agency Regional Office to which it was submitted; and
(3) The volume of fluid injected, the injection zone or zones into which it was injected, and the period over which injection occurred.
(h) The owner or operator must retain for 10 years following site closure, records collected during the post-injection site care period. The owner or operator must deliver the records to the Director at the conclusion of the retention period, and the records must thereafter be retained at a location designated by the Director for that purpose.
(a) As part of the permit application, the owner or operator must provide the
(b) If the owner or operator obtains evidence that the injected carbon dioxide stream and associated pressure front may cause an endangerment to a USDW, the owner or operator must:
(1) Immediately cease injection;
(2) Take all steps reasonably necessary to identify and characterize any release;
(3) Notify the Director within 24 hours; and
(4) Implement the emergency and remedial response plan approved by the Director.
(c) The Director may allow the operator to resume injection prior to remediation if the owner or operator demonstrates that the injection operation will not endanger USDWs.
(d) The owner or operator shall periodically review the emergency and remedial response plan developed under paragraph (a) of this section. In no case shall the owner or operator review the emergency and remedial response plan less often than once every five years. Based on this review, the owner or operator shall submit an amended emergency and remedial response plan or demonstrate to the Director that no amendment to the emergency and remedial response plan is needed. Any amendments to the emergency and remedial response plan must be approved by the Director, must be incorporated into the permit, and are subject to the permit modification requirements at § 144.39 or § 144.41 of this chapter, as appropriate. Amended plans or demonstrations shall be submitted to the Director as follows:
(1) Within one year of an area of review reevaluation;
(2) Following any significant changes to the facility, such as addition of injection or monitoring wells, on a schedule determined by the Director; or
(3) When required by the Director.
This section sets forth information which an owner or operator seeking a waiver of the Class VI injection depth requirements must submit to the Director; information the Director must consider in consultation with all affected Public Water System Supervision Directors; the procedure for Director—Regional Administrator communication and waiver issuance; and the additional requirements that apply to owners or operators of Class VI wells granted a waiver of the injection depth requirements.
(a) In seeking a waiver of the requirement to inject below the lowermost USDW, the owner or operator must submit a supplemental report concurrent with permit application. The supplemental report must include the following,
(1) A demonstration that the injection zone(s) is/are laterally continuous, is not a USDW, and is not hydraulically connected to USDWs; does not outcrop; has adequate injectivity, volume, and sufficient porosity to safely contain the injected carbon dioxide and formation fluids; and has appropriate geochemistry.
(2) A demonstration that the injection zone(s) is/are bounded by laterally continuous, impermeable confining units above and below the injection zone(s) adequate to prevent fluid movement and pressure buildup outside of the injection zone(s); and that the confining unit(s) is/are free of transmissive faults and fractures. The report shall further characterize the regional fracture properties and contain a demonstration that such fractures will not interfere with injection, serve as conduits, or endanger USDWs.
(3) A demonstration, using computational modeling, that USDWs above and below the injection zone will not be endangered as a result of fluid movement. This modeling should be conducted in conjunction with the area of review determination, as described in § 146.84, and is subject to requirements, as described in § 146.84(c), and periodic reevaluation, as described in § 146.84(e).
(4) A demonstration that well design and construction, in conjunction with the waiver, will ensure isolation of the injectate in lieu of requirements at 146.86(a)(1) and will meet well construction requirements in paragraph (f) of this section.
(5) A description of how the monitoring and testing and any additional plans will be tailored to the geologic sequestration project to ensure protection of USDWs above and below the injection zone(s), if a waiver is granted.
(6) Information on the location of all the public water supplies affected, reasonably likely to be affected, or served by USDWs in the area of review.
(7) Any other information requested by the Director to inform the Regional Administrator's decision to issue a waiver.
(b) To inform the Regional Administrator's decision on whether to grant a waiver of the injection depth requirements at §§ 144.6 of this chapter, 146.5(f), and 146.86(a)(1), the Director must submit, to the Regional Administrator, documentation of the following:
(1) An evaluation of the following information as it relates to siting, construction, and operation of a geologic sequestration project with a waiver:
(i) The integrity of the upper and lower confining units;
(ii) The suitability of the injection zone(s) (e.g., lateral continuity; lack of transmissive faults and fractures; knowledge of current or planned artificial penetrations into the injection zone(s) or formations below the injection zone);
(iii) The potential capacity of the geologic formation(s) to sequester carbon dioxide, accounting for the availability of alternative injection sites;
(iv) All other site characterization data, the proposed emergency and remedial response plan, and a demonstration of financial responsibility;
(v) Community needs, demands, and supply from drinking water resources;
(vi) Planned needs, potential and/or future use of USDWs and non-USDWs in the area;
(vii) Planned or permitted water, hydrocarbon, or mineral resource exploitation potential of the proposed injection formation(s) and other formations both above and below the injection zone to determine if there are any plans to drill through the formation to access resources in or beneath the proposed injection zone(s)/formation(s);
(viii) The proposed plan for securing alternative resources or treating USDW formation waters in the event of contamination related to the Class VI injection activity; and,
(ix) Any other applicable considerations or information requested by the Director.
(2) Consultation with the Public Water System Supervision Directors of all States and Tribes having jurisdiction over lands within the area of review of a well for which a waiver is sought.
(3) Any written waiver-related information submitted by the Public Water System Supervision Director(s) to the (UIC) Director.
(c) Pursuant to requirements at § 124.10 of this chapter and concurrent with the Class VI permit application notice process, the Director shall give public notice that a waiver application has been submitted. The notice shall clearly state:
(1) The depth of the proposed injection zone(s);
(2) The location of the injection well(s);
(3) The name and depth of all USDWs within the area of review;
(4) A map of the area of review;
(5) The names of any public water supplies affected, reasonably likely to be affected, or served by USDWs in the area of review; and,
(6) The results of UIC-Public Water System Supervision consultation required under paragraph (b)(2) of this section.
(d) Following public notice, the Director shall provide all information received through the waiver application process to the Regional Administrator. Based on the information provided, the Regional Administrator shall provide written concurrence or non-concurrence regarding waiver issuance.
(1) If the Regional Administrator determines that additional information is required to support a decision, the Director shall provide the information. At his or her discretion, the Regional Administrator may require that public
(2) In no case shall a Director of a State-approved program issue a waiver without receipt of written concurrence from the Regional Administrator.
(e) If a waiver is issued, within 30 days of waiver issuance, EPA shall post the following information on the Office of Water's Web site:
(1) The depth of the proposed injection zone(s);
(2) The location of the injection well(s);
(3) The name and depth of all USDWs within the area of review;
(4) A map of the area of review;
(5) The names of any public water supplies affected, reasonably likely to be affected, or served by USDWs in the area of review; and
(6) The date of waiver issuance.
(f) Upon receipt of a waiver of the requirement to inject below the lowermost USDW for geologic sequestration, the owner or operator of the Class VI well must comply with:
(1) All requirements at §§ 146.84, 146.85, 146.87, 146.88, 146.89, 146.91, 146.92, and 146.94;
(2) All requirements at § 146.86 with the following modified requirements:
(i) The owner or operator must ensure that Class VI wells with a waiver are constructed and completed to prevent movement of fluids into any unauthorized zones including USDWs, in lieu of requirements at § 146.86(a)(1).
(ii) The casing and cementing program must be designed to prevent the movement of fluids into any unauthorized zones including USDWs in lieu of requirements at § 146.86(b)(1).
(iii) The surface casing must extend through the base of the nearest USDW directly above the injection zone and be cemented to the surface; or, at the Director's discretion, another formation above the injection zone and below the nearest USDW above the injection zone.
(3) All requirements at § 146.90 with the following modified requirements:
(i) The owner or operator shall monitor the groundwater quality, geochemical changes, and pressure in the first USDWs immediately above and below the injection zone(s); and in any other formations at the discretion of the Director.
(ii) Testing and monitoring to track the extent of the carbon dioxide plume and the presence or absence of elevated pressure (e.g., the pressure front) by using direct methods to monitor for pressure changes in the injection zone(s); and, indirect methods (e.g., seismic, electrical, gravity, or electromagnetic surveys and/or down-hole carbon dioxide detection tools), unless the Director determines, based on site-specific geology, that such methods are not appropriate.
(4) All requirements at § 146.93 with the following, modified post-injection site care monitoring requirements:
(i) The owner or operator shall monitor the groundwater quality, geochemical changes and pressure in the first USDWs immediately above and below the injection zone; and in any other formations at the discretion of the Director.
(ii) Testing and monitoring to track the extent of the carbon dioxide plume and the presence or absence of elevated pressure (e.g., the pressure front) by using direct methods in the injection zone(s); and indirect methods (e.g., seismic, electrical, gravity, or electromagnetic surveys and/or down-hole carbon dioxide detection tools), unless the Director determines based on site-specific geology, that such methods are not appropriate;
(5) Any additional requirements requested by the Director designed to ensure protection of USDWs above and below the injection zone(s).
42 U.S.C. 300h
Nomenclature changes to part 147 appear at 69 FR 18803, Apr. 9, 2004.
(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, including any Indian country geographically located within those States, territories, and possessions.
(b) The applicable UIC programs set forth in this part may be State-administered programs approved by EPA, Tribally-administered programs approved by EPA, or Federally-administered programs promulgated by EPA. In some cases, the applicable UIC program for a particular area may consist of a State-administered or Tribally-administered program applicable to some classes of wells and a Federally-administered program applicable to other classes of wells. Approval of a State or Tribal program is based upon a determination by the Administrator that the program meets the requirements of section 1422 or section 1425 of the SDWA, any other applicable provisions of this subpart, and the applicable provisions of 40 CFR parts 124, 144, 145 and 146. A Federally-administered program is promulgated in those instances where the State or Tribe has not submitted any program for approval or where the submitted program does not meet the minimum Federal statutory and regulatory requirements.
(c) In the case of each State or Tribal program approved by EPA pursuant to section 1422 of the SDWA, the relevant subpart describes the major elements
(d) In the case of any program promulgated under section 1422 for a State or Tribe that is to be administered by EPA, the relevant State or Tribal subpart makes applicable the provisions of 40 CFR parts 124, 144, 146, and 148, and any other additional requirements pertinent to the specific State or Tribal program.
(e) Regulatory provisions incorporated by reference (in the case of approved State or Tribal 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) Class VI well owners or operators must comply with § 146.91(e) notwithstanding any State program approvals.
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 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 22-22-1 through 22-22-14 (1980 and Supp. 1983);
(2) Regulations, Policies and Procedures of the Alabama Water Improvement Commission, Title I (Regulations) (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
(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) 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 and the Arkansas Oil and Gas Commission, signed by the EPA Regional Administrator on May 25, 1982.
(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
(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
(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 Connecticut 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, Chapter 28-5 (1982) (Decisions Determining 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
(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
(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 approval 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 Program; Part 705, Procedures for Permit Issuance and Part 730, Underground Injection Control Operating Requirements as amended by IPCB Order No. R-83039 on December 15, 1983.
(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.
(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
(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 tests and pilot projects in order to determine the feasibility of proposed enhanced recovery projects) (June 20, 1985, effective July 1, 1985).
(4) (i) Statewide Order adopting rules and regulations pertaining to the use of salt dome cavities (
(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
(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) of this section, as needed to protect USDWs.
(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:
(2) Montana Code annotated, 1995, Title 82, Chapter 10:
(3) Montana Code annotated, 1995, Title 82, Chapter 11:
(b) The regulatory provisions include: Administrative Rules of Montana Board of Oil and Gas Conservation, Chapter 22, revised March 1996:
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 application or as supplements thereto.
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
(a)
Copies may be inspected at the Environmental Protection Agency, Region IX, 215 Fremont Street, San Francisco, California 99105, or at the National Archives and Records Administration (NARA). For information on the availability of this material at NARA, call 202-741-6030, or go to:
(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
(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
(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 EPA Regional Administrator on June 16, 1983, as amended September 7, 1989.
(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,
(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
(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
(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 provisions of §§ 144.7(b) and 146.4 of this chapter for Class II enhanced recovery injection activities only.
(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
(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
(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
(a)
(1) Pollution Control Act, S.C. Code Ann. Sections 48-1-10, 48-1-90, 48-1-100, 48-1-110 (Law. Co-op. 1976 and Supp. 1983).
(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
(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.
The UIC program for Class I, III, IV, and V wells in the State of Texas, except for those wells on Indian lands, Class III brine mining wells, and certain Class V wells, is the program administered by the Texas Commission on Environmental Quality approved by EPA pursuant to section 1422 of the Safe Drinking Water Act (SDWA). Notice of the original approval for Class I, III, IV, and V wells was published in the
(a)
(1) Texas Statutory and Regulatory Requirements Applicable to the Underground Injection Control Program for Class I, III, IV, and V Wells, except for Class III Brine Mining Wells, March 2002.
(2) Texas Statutory and Regulatory Requirements Applicable to the Underground Injection Control Program for Class III Brine Mining Wells, March 2002.
(b)
(1)
(ii) Vernon's Texas Codes Annotated, Water Code, Chapters 5, 7, 26, and 32, Health and Safety Code Section 361, Government Code (ORA) Chapter 552 and Government Code (APA) Chapter 2001.
(2)
(ii) Vernon's Texas Codes Annotated, Government Code Title 10, Chapters 2001, 552, and 311.
(iii) General Rules of Practice and Procedure before the Railroad Commission of Texas.
(c)
(2)
(d)
(2)
(e)
(2)
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 plug and abandon the well according to the approved plan and schedule.
(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
(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 (June 1983 and Wyoming Statutes Annotated, July 1990 Supp.).
(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 dissected 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
(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
(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 production operations, unless those waters would be classified as a hazardous waste at the time of injection;
(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
(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 (
(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 (
(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,
(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 (
(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)
(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 (
(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 (
(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,
(b) The topographic map (or other map if a topographic map is unavailable) required by § 144.31(e)(7) of this chapter, shall extend two miles from Class II wells, and 2
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.
The UIC program for Class II injection wells on all lands within the exterior boundaries of the Fort Peck Indian Reservation is the program administered by the Assiniboine and Sioux (Fort Peck) Tribes approved by EPA pursuant to section 1425 of the SDWA. Notice of this approval was published in the
(a)
(b)
(c)
(d)
The UIC program for Class II injection wells located: Within the exterior
(a)
(b)
(c)
(2) “Statement of the Attorney General of the Navajo Nation Regarding the Regulatory Authority and Jurisdiction of the Navajo Nation with Respect To Its Underground Injection Control Program”, July 3, 2002.
(3) “Supplemental Statement of the Navajo Nation Attorney General Regarding the Regulatory Authority and Jurisdiction of the Navajo Nation to Operate an Underground Injection Control Program under the Safe Drinking Water Act”, October 11, 2006.
(d)
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 (nonwastewaters) and the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste numbers K001, K015 (wastewaters), K016 (at concentrations greater than or equal to 1%), K018, K019, K020, K021 (nonwastewaters generated by the process described in the waste listing description and disposed after August 17, 1988, and not generated in the course of treating wastewater forms of these wastes), K022 (nonwastewaters), K024, K030, K036 (nonwastewaters generated by the process described in the waste listing description and disposed after August 17, 1988, and not generated in the course of treating wastewater forms of these wastes), K037, K044, K045, nonexplosive K046 (nonwastewaters), K047, K048, K060 (nonwastewaters generated by the process described in the waste listing description and disposed after August 17, 1988, and not generated in the course of treating wastewater forms of these wastes), K061 (nonwastewaters), noncalcium sulfate K069 (nonwastewaters generated by the process described in the waste listing description and disposed after August 17, 1988, and not generated in the course of treating wastewater forms of these wastes), K086 solvent washes, K087, K099, K101 (all wastewaters and less than 1% total arsenic nonwastewaters), K102 (all wastewaters and less than 1% total arsenic nonwastewaters), and K103 are prohibited from underground injection.
(b) Effective June 8, 1989, the waste specified in 40 CFR 261.32 as EPA Hazardous Waste number K036 (wastewaters); 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 (wastewaters) and F019; the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Numbers K004, K008, K015 (nonwastewaters), K017, K021 (wastewaters), K022 (wastewaters), K031, K035, K046 (reactive nonwastewaters and all wastewaters), K060 (wastewaters), K061 (wastewaters), K069 (calcium sulfate nonwastewaters and all wastewaters), K073, K083, K084, K085, K086 (all but solvent washes), K101 (high arsenic nonwastewaters), K102 (high arsenic nonwastewaters), 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,
(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 (nonwastewaters) and K013 (nonwastewaters) 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 (wastewaters), K013 (wastewaters), 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 (nonwastewaters generated by the process described in the waste listing description and disposed after August 17, 1988, and not generated in the course of treating wastewater 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 (nonwastewaters), K010, K027, K028, K029 (nonwastewaters), K038, K039, K040, K043, K095 (nonwastewaters), K096 (nonwastewaters), 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 wastewaters and nonwastewaters. Effective December 8, 1989, F011 (nonwastewaters) and F012 (nonwastewaters) are prohibited pursuant to the treatment standards specified in §§ 268.41 and 268.43 applicable to F011 and F012 wastewaters and nonwastewaters.
(d) Effective August 8, 1990, the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Number K025 (wastewaters), K029 (wastewaters), K041, K042, K095 (wastewaters), K096 (wastewaters), 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,
(e) Effective June 8, 1991, the waste specified in 40 CFR 261.32 as EPA Hazardous Waste number K009 (wastewaters) 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 (nonwastewaters generated by the process described in the waste listing description and disposed after August 17, 1988, and not generated in the course of treating wastewater 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 (nonwastewaters), K007 (nonwastewaters), 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 (nonwastewaters); the wastes specified in 40 CFR 261.32 as EPA Hazardous Waste Numbers K002, K003, K005 (wastewaters), K006, K007 (wastewaters), K026, K032, K033, K034, and K100 (wastewaters); 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 (wastewaters), 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 (wastewaters); the wastes identified in 40 CFR 261.22, 261.23 or 261.24 as hazardous based on a characteristic alone, designated as D002 (wastewaters and nonwastewaters), D003 (wastewaters and nonwastewaters), D007 (wastewaters and nonwastewaters), and D009 (nonwastewaters) 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 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 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) Effective August 23, 2005, the waste specified in 40 CFR 261.32 as EPA Hazardous Waste Number K181 is prohibited from underground injection.
(m) The requirements of paragraphs (a) through (l) 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 hazardous because of attenuation, transformation, or immobilization of hazardous constituents within the injection zone by hydrolysis, 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 ascertained the condition of all wells within the injection well's area of review (as specified in § 146.63) that penetrate the injection zone or the confining zone by use of a protocol acceptable to the Director that meets the substantive 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
(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 additional restricted waste or wastes or to modify any conditions placed on the exemption by the Director. The Director shall reissue the petition if the petitioner complies with the requirements 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 Class I hazardous waste injection well, the Director shall review any petition filed pursuant to § 148.20 and require a new demonstration if information shows that the basis for granting the exemption may no longer be valid.
(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, in the petitioner's judgment, the action was inadequate.
(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 section should be coordinated, if possible, with other Federal public hearings held pursuant to applicable laws and regulations. Any such hearing shall be conducted by the Regional Administrator or designee in an informal, orderly and expeditious manner. Where appropriate, limits may be placed upon the time allowed for oral statements, and statements may be required to be submitted in writing. The record will be held open for further public comment for seven (7) days following the close of the public hearing.
(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
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.
Table of CFR Titles and Chapters
Alphabetical List of Agencies Appearing in the CFR
List of CFR Sections Affected
All changes in this volume of the Code of Federal Regulations that 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.