United States Solid Waste and EPASW-846.3-3a Environmental Protection Emergency Response March 1999 Agency (5305W) www.epa.gov/osw Test Methods for Evaluating Solid Waste: Physical/ Chemical Methods; Third Edition; Final Update III-A Printed on paper that contains at lest 20 percent postconsumer fiber ------- ------- FINAL UPDATE IIIA Cover Sheet THIS PACKET CONTMNS NEW AND REVISED MATERIAL FOR INCLUSION IN: TEST METHODS FOR EVALUATING SOLID WASTE PHYSICAL/CHEMICAL METHODS (SW-846) THIRD EDITION Contents: 1. Cover sheet. (What you are currently reading) 2. Instructions. Read this section! It explains how Update IIIA relates to the rest of your SW-846. 3. Update IPA Table of Contents. The Table of Contents (dated April 1998) lists all of the methods [Third Edition, Updates I, II, IIA, IIB, III, and IIIA) in the order of appearance in the manual. 4. Revised Chapter Five 5. Referral to Office of Water Method 1664. as replacement to Method 9070 i , . . . . . - 5. Method 9071B ------- ------- :[NSTRUCTIONS SW-846, a methods manual, is a "living" document that changes when new data and advances in analytical techniques are incorporated! into the manual as new or revised methods. To date, the Agency has formally issued Final Updates I, II, IIA, IBB, and III. This package contains Final Update III A. For specific and important information regarding this update, please read the section below entitled "About Final Update IHA." These instructions describe how to get your basic manual up-to-date and what to do with your Final Update IIIA package. Additional updates will be released by the Agency hi the future. New instructions, to supersede these, will be included with each of those new update releases. A number of SW-846 update packages have been released to the public since the original Third Edition was released. The dates and labels on these packages can be confusing. In general, final updates should always be incorporated into SW-846 in chronological order (e.g. Update I should be incorporated before Update II). The following definitions are provided to you as a guide: New subscribers are defined as individuals who have recently (6-8 weeks) placed an order with the GPO and have received new copies of the 4 (four) volume set of the Third 'Edition, a copy of Final Update I, a copy of Final Update n/BLA, a copy of Final Update HE, a copy of Final Update III, a copy of Draft Update IVA, and a copy of Final Update IIIA. Previous subscribers are defined as individuals that have received copies of the Third Edition and other SW-846 Updates (including proposed Updates) hi the past and have just received their Final Update IIIA package in the mail. Instructions - 1 Final Update IIIA April 1998 ------- A?f»TTT FTNAT TTPTWTK TTTA As of Update m to SW-846, the two SW-846 methods for determination of oil and grease were Method 9070 for waters and aqueous wastes, and Method 9071A for solid and semi-solid materials such as soil, sediment, and sludge. Method 9070 was virtually identical to Office of Water methods for determination of oil and grease; and Method 9071 A employed drying of the sample with magnesium sulfate and using Soxhlet extraction for the determination. Both methods used l,l,2-tricnloro-l,2,2-trifluoroethane (CFC-113; Freon-113) as the extraction solvent in the testing of samples for oil and grease levels. The Agency recently published a final rule in the Federal Register which finalized Office of Water Method 1664, Revision A, and SW-846 Method 9071B and withdrew previously approved methods (including certain Office of Water methods and SW-846 Method 9070) for the determination of oil and grease and non-polar material (NPM) in EPA's wastewater and hazardous waste programs. These changes were made as a part of EPA's effort to reduce dependency on the use of chlorofluorocarbons (CFCs) in order to protect Earth's ozone layer and to meet the CFC phaseout agreed to in the Montreal Protocol and required by the Clean Air Act Amendments of 1990. Method 1664 now uses normal hexane (n-hexane) as the extraction solvent in place of l,l,2-trichloro-l,2,2-trifluoroethane (CFC-113; Freon-113), a Class 1 CFC. As part of that final rule, SW-846 was amended to delete Method 9070 and to include revised Method 9071B as Final Update mA to the manual. Specifically, Method 9071B addresses the use of n-hexane instead of CFC-113 as the extraction solvent, in a manner consistent with the use of n-hexane in Method 1664. In addition, in place of Method 9070, which used CFC-1 13 as the extraction solvent in the testing of waters and aqueous wastes, the Agency incorporated by reference Method 1664 in the RCRA regulations. As part of Final Update mA, SW-846 refers the regulated community to Method 1664 for testing previously conducted using Method 9070. The' publication number for Method 1664 is EPA-821-R-98-002. Final Update IKA has been issued by the EPA's Office of Solid Waste and contains documents which have been promulgated for inclusion in the SW-846. methods manual. The Final Update mA package includes one revised method (Method 9071B), one revised chapter (Chapter Five), a page to replace Method 9070, and a revised Table of Contents. Method 9070 needs to be removed from the manual when Final Update mA is incorporated. FTNAL TTPDATE TTIA- The following is a brief summary of what new subscribers and previous subscribers should do upon receipt of the Update IDA package: j NEW SUBSCRIBERS - If you are a new subscriber, you should perform the following tasks before addressing your new Update DIA: Instructions - 2 Final Update ------- • Place the original Third Edition of SW-846 (September 1986) in the properly labeled four 3-ring notebooks according to the instructions in Final Update III. • Incorporate Final Update I (July 1992) into the manual according to the instructions in Final Update m. • Incorporate Final Updates H (September 1994) and HA (August 1993) into the manual according to the instructions in Final Update HI. • Incorporate Final Update HE (January 1995) into the manual according to the instructions in Final Update m. • Incorporate Final Update El (December 1996) into the manual according to its instructions. • Either incorporate Draft Update IVA in the manual (without removing any white pages), or keep the colored draft update in a separate binder of your choice. Finally, incorporate Final Update IQA. Final Update IIIA is printed on white paper and has the date of "April 1998" in the lower right hand corner of each page. This package contains revised material for SW-846, specifically a revised Table of Contents, Chapter Five, and Method 9071B. In addition, it contains a page that should be used to replace Method 9070. Remove Method 9070 from the manual. This method has been deleted from SW-846 as part of Final Update IIIA. Then, use the Table of Contents dated April 1998 to determine the correct location for each document in the Final Update IDA package.' PREVIOUS SUBSCRIBERS - If you are a previous subscriber, it is important to establish exactly what is currently contained in your manual before addressing Final Update IIIA. If your manual is properly updated, the ONLY white pages in the document should be dated September '1986 (Third Edition), July 1992 (Final Update I), August 1993 (Final Update IIA), September 1994 (Final Update JJ), January 1995 ([Final Update IIB), and December 1996 (Final Update III). Remove (and recycle or archive) any white pages from your manual that have any other dates. There may also be colored pages (e.g., pink pages for Proposed Update III) inserted in the manual. Remove all yellow, blue, green, or pink pages from the manual. These colored pages represent proposed versions of methods and chapters that have since been finalized. (Some individuals may chose to,keep their copies of colored versions in separate binders.) You may keep your Draft Update IVA pages in the manual if you wish -- that update has not yet been finalized. Follow the last paragraph in the instructions for new subscribers to determine how to incorporate Final Update IIIA. The table below can be used as an aide to determine what should be in your manual. Instructions - 3 Final Update IIIA April 1998 ------- UPDATE HISTORY OF SW-846 The table below can be used as an aid to understanding the update history of SW-846, Third Edition. Finalized updates are printed in bold and underlined. Package Third Edition Proposed Update I Final Update I (Released by accident) Proposed Update n (Released by accident) Final Update I Proposed Update n Proposed Update HA (Method 4010, available from EPA by request.) Final Update TTA (Method 4010, included with Final Update H.) Final Update II Final Update ITB* Proposed Update HI Final Undate ITT Draft Update IVA FJnaLUodate niA** Date September 1986 December 1987 November 1990 November 1990 July 1992 November 1992 October 1992 August 1993 September 1994 January 1995 January 1995 December 1996 January 1998 April 1998 Paper Color White Green White Blue White Yellow White White White White Pink White Salmon White Status of Package Finalized (Promulgated) Obsolete Obsolete! Never formally finalized. Obsolete! Never formally proposed. Finalized (Promulgated) Obsolete Obsolete Finalized (Promulgated) Finalized (Promulgated) Finalized (Promulgated) Proposed Finalize*] (Promulgated) Draft Finalized (Promulgated) * Contains only a revised Table of Contents, a revised Chapter Six,, and revised Methods 9040B and 9045C ** Contains only a revised Table of Contents, a revised Chapter Five, a page to replace Method 9070, and revised Method 9071B. Instructions - 4 Final Update fflA April 1998 ------- ASSISTANCE After reading these instructions, if you need help due to difficulties understanding the status of the package, need assistance in obtaining Method 1664, or have technical questions regarding the methods, you may telephone the Methods Information Communication Exchange (MICE) at 703-821-4690 or send an E-mail to: mice@lan828.ehsg.saic.com. If you have questions concerning your SW-846 U.S. Government Printing Office (GPO) subscription, you should telephone the GPO at 202-512-1806. If you did not purchase your SW- 846 from the GPO, the GPO will not be able to help you. SW-846 AVAILABILITY ON CD-ROM A CD-ROM version (Version 2.0) of Test Methods for Evaluating Solid Waste, Physical/Chemical Methods (SW-846) has been developed by EPA in cooperation with the National Technical Information Service (NTTS). On a single disc, it includes all text and figures found in the final version of SW-846 as updated by Updates I, n, HA, HB, and ffl. (It does not include Final Update HIA. This update may be included in a future revision to the CD.) It can be used for word searching (e.g, analytes, keywords); and to cut and paste or export text and diagrams to update or develop laboratory standard operating procedures (SOPs). To order by phone, call NTIS at (800) 553-6847 and request order number PB97-501928GEI for a single user copy, PB97- 502512GEI for a 5-user LAN copy, or PB97-502520GEI for unlimited users. To receive information by fax from NTIS about this CD-ROM, call (703) 365-0759 and enter publication number code 8698. A CD-ROM version of Draft Update TV on CD-ROM is planned for the future. To place an early order by phone, call NTIS at (800) 553-6847 and request order number PB97-501936GEI (single user), PB97-502538GEI (5-user LAN), or PB97-502546GEI (unlimited users).. Instructions - 5 Final Update HIA April 1998 ------- ------- TABLE OF CONTENTS VOLUME ONE SECTION A DISCLAIMER ABSTRACT TABLE OF CONTENTS METHOD INDEX AND CONVERSION TABLE PREFACE ACKNOWLEDGEMENTS PART I METHODS FOR ANALYTES AND PROPERTIES CHAPTER ONE - QUALITY CONTROL j 1.0 Introduction 2.0 QA Project Plan 3.0 Field Operations 4.0 Laboratory Operations 5.0 Definitions 6.0 References CHAPTER TWO - CHOOSING THE CORRECT PROCEDURE 2.1 Purpose 2.2 Required Information 2.3 Implementing the Guidance ' - ' 2.4 Characteristics 2.5 Ground Water ', 2.6 References CHAPTER THREE - INORGANIC ANALYTES 3.1 Sampling Considerations 3.2 Sample Preparation Methods Method 3005A: Acid Digestion of Waters for Total Recoverable or Dissolved Metals for Analysis by FLAA or ICP Spectroscopy Method 301OA: Acid Digestion of Aqueous Samples and Extracts for Total Metals for Analysis by FLAA or ICP Spectroscopy Method 3015: Microwave Assisted Acid Digestion of Aqueous Samples and Extracts CONTENTS - 1 Revision 5 April 1998 ------- Method 3020A: Method 3031: Method 3040A: Method 3050B: Method 3051: Method 3052: Method 3060A: Acid Digestion of Aqueous Samples and Extracts for Total Metals for Analysis by GFAA Spectroscopy Acid Digestion of Oils for Metals Analysis by Atomic Absorption or ICP Spectrometry Dissolution Procedure for Oils, Greases, or Waxes Acid Digestion of Sediments, Sludges, and Soils Microwave Assisted Acid Digestion of Sediments, Sludges, Soils, and Oils Microwave Assisted Acid Digestion of Siliceous and Organically Based Matrices Alkaline Digestion for Hexavalent Chromium 3.3 Methods for Determination of Inorganic Analytes ... i • '''",'' '• ! ' • ! Method 601 OB: Inductively Coupled Plasma-Atomic Emission Spectrometry Method 6020: Inductively Coupled Plasma-Mass Spectrometry Method 7000A: Atomic Absorption Methods Method 7020: Aluminum (Atomic Absorption, Direct Aspiration) Method 7040: Antimony (Atomic Absorption, Direct Aspiration) Method 7041: Antimony (Atomic Absorption, Furnace Technique) Method 7060A: Arsenic (Atomic Absorption, Furnace Technique) Method 7061A: Arsenic (Atomic Absorption, Gaseous Hydride) Method 7062: Antimony and Arsenic (Atomic Absorption, Borohyclride Reduction) Method 7063: Arsenic in Aqueous Samples and Extracts by Anodic Stripping Voltammetry (ASV) Method 7080A: Barium (Atomic Absorption, Direct Aspiration) Method 7Q81: Barium (Atomic Absorption, Furnace Technique) Method 7090: Beryllium (Atomic Absorption, Direct Aspiration) Method 7091: Beryllium (Atomic Absorption, Furnace Technique) Method 7130: Cadmium (Atomic Absorption, Direct Aspiration) Method" 7131 A: Cadmium (Atomic Absorption, Furnace Technique) Method 7140: Calcium (Atomic Absorption, Direct Aspiration) Method 7190: Chromium (Atomic Absorption, Direct Aspiration) Method 7191: Chromium (Atomic Absorption, Furnace Technique) Method 7195: Chromium, Hexavalent (Coprecipltation) Mejhod 7196A: Chromium, Hexavalent (Colorimetric) Method 7197: Chromium, Hexavalent (Chelatiori/Extraction) Method 7198: Chromium, Hexavalent (Differential Pulse Polarography) Method 7199: Determination of Hexavalent Chromium in Drinking Water, ; Groundwater and Industrial Wastewater Effluents by Ion Chromatography Method 7200: Cobalt (Atomic Absorption, Direct Aspiration) Method 7201: Cobalt (Atomic Absorption, Furnace Technique) Method 7210: Copper (Atomic Absorption, Direct Aspiration) Method 7211: Copper (Atomic Absorption, Furnace Technique) Method 7380: Iron (Atomic Absorption, Direct Aspiration) Method 7381: Iron (Atomic Absorption, Furnace Technique) Method 7420: Lead (Atomic Absorption, Direct Aspiration) Method 7421: Lead (Atomic Absorption, Furnace Technique) Method 7430: Lithium (Atomic Absorption, Direct Aspiration) CONTENTS - 2 Revision 5 April 1998 ------- Method 7450: Method 7460: Method 7461: Method 7470A: Method 7471A: Method 7472: Method Method Method Method Method Method Method Method Method Method Method Method Method Method Method Method Method Method Method Method Method 7480: 7481: 7520: 7521: 7550: 7580: 7610: 7740: 7741A: 7742: 7760A: 7761: 7770: 7780: 7840: 7841: 7870: 7910: 7911: 7950: 7951: Magnesium (Atomic Absorption, Direct Aspiration) Manganese (Atomic Absorption, Direct Aspiration) Manganese (Atomic Absorption, Furnace Technique) Mercury in Liquid Waste (Manual Cold-Vapor Technique) Mercury in Solid or Semisolid Waste (Manual Cold-Vapor Technique) Mercury in Aqueous Samples and Extracts by Anodic Stripping Voltammetry (ASV) Molybdenum (Atomic Absorption, Direct Aspiration) Molybdenum (Atomic Absorption, Furnace Technique) Nickel (Atomic Absorption, Direct Aspiration) Nickel (Atomic Absorption, Furnace Method) Osmium (Atomic Absorption, Direct Aspiration) White Phosphorus (P4) ; by Solvent Extraction and Gas Chromatography Potassium (Atomic Absorption, Direct Aspiration) Selenium (Atomic Absorption, Furnace Technique) Selenium (Atomic Absorption, Gaseous Hydride) Selenium (Atomic Absorption, Borohydride Reduction) Silver (Atomic Absorption, Direct Aspiration) Silver (Atomic Absorption, Furnace Technique) Sodium (Atomic Absorption, Direct Aspiration) Strontium (Atomic Absorption, Direct Aspiration) Thallium (Atomic Absorption, Direct Aspiration) Thallium (Atomic Absorption, Furnace Technique) fin (Atomic Absorption, Direct Aspiration) Vanadium (Atomic Absorption, Direct Aspiration) Vanadium (Atomic Absorption, Furnace Technique) Zinc (Atomic Absorption, Direct Aspiration) Zinc (Atomic Absorption, Furnace Technique) APPENDIX - COMPANY REFERENCES NQTE: A suffix of "A" in the method number indicates revision one (the method has been revised once). A suffix of "B" in the method number indicates revision two (the method has been revised twice). A suffix of "C" in the method number indicates revision three (the method has been revised three times). In order to properly document the method used for analysis, the entire method number including the suffix letter designation (e.g., A, B, or C) must be identified by the analyst. A method reference found within the RCRA regulations and the text of SW-846 methods and chapters refers to the latest promulgated revision of the method, even though the method number does not include the appropriate letter suffix. CONTENTS - 3 Revision 5 April 1998 ------- VOLUME ONE SECTION B DISCLAIMER ABSTRACT TABLE OF CONTENTS METHOD INPEX AND CONVERSION TABLE PREFACE ACKNOWLEDGEMENTS CHAPTER ONE. REPRINTED - QUALITY CONTROL 1.0 Introduction 2.0 QA Project Plan 3.0 Field Operations 4.0 Laboratory Operations 5.0 Definitions \ 6.0 References CHAPTER FOUR - ORGANIC ANALYTES 4.1 Sampling Considerations 4.2 Sample Preparation Methods | j 'I, 4.2.1 Extractions and Preparations Method 3500B: Organic Extraction and Sample Preparation Method 351OC: Separatory Funnel Liquid-Liquid Extraction Method 3520C: Continuous Liquid-Liquid Extraction Method 3535: Solid-Phase Extraction (SPE) Method 3540C: Soxhlet Extraction Method 3541: Automated Soxhlet Extraction Method 3542: Extraction of Semivolatile Analytes Collected Using Method 0010 (Modified Method 5 Sampling train) Method 3545: Pressurized F-luid Extraction (PFE) Method 3550B: Ultrasonic Extraction Method 3560: Supercritical Fluid Extraction of Total Recoverable Petroleum Hydrocarbons Method 3561: Supercritical Fluid Extraction of Polynuclear Aromatic Hydrocarbons MethodI 3580A: Waste Dilution Method 3585: Waste Dilution for Volatile Organics Method 5000: Sample Preparation for Volatile Organic Compounds Method 5021: Volatile Organic Compounds in Soils and Other Solid Matrices Using Equilibrium Headspace Analysis Method 5030B: Purge-and-Trap for Aqueous Samples CONTENTS-4 Revisions April 1998 ------- Method 5031: Method 5032: Method 5035: Method 5041A: Volatile, Nonpurgeable, Water-Soluble Compounds by Azeotropjc Distillation Volatile Organic Compounds by Vacuum Distillation Closed-System Purge-and-Trap and Extraction for Volatile Organics in Soil and Waste Samples Analysis for Desorption of St>rbent Cartridges from Volatile Organic Sampling Train (VQST) 4.2.2 Cleanup Method 3600C: Cleanup Method 361 OB: Alumina Cleanup Method 3611B: Alumina Column Cleanup and Separation of Petroleum Wastes Method 3620B: Florisil Cleanup Method 3630C: Silica Gel Cleanup Method 3640A: Gel-Permeation Cleanup ; Method 3650B: Acid-Base Partition Cleanup Method 3660B: Sulfur Cleanup ; Method 3665A: Sulfuric Acid/Permanganate ;Cleanup 4.3 Determination of Organic Analytes 4.3.1 Gas Chromatographic Methods Method 8000B: Method 8011: Method 801 SB: Method 8021B: Method 8031: Method 8032A: Method 8033: Method 8041: Method 8061A: by Method Method Method Method Method Method Method 8070A: 8081A: 8082: 8091: 8100: 8111: 8121: Method 8131: Method 8141 A: Method 8151 A: Determinative Chromatographic Separations 1,2-Dibromoethane and ] 1,2-Dibromo-3-chloropropane Microextraction and Gas Chromatography Nonhalogenated Organics Using GC/FID Aromatic and Halogenated Volatiles by Gas Chromatography Using Pholtoionization and/or Electrolytic Conductivity Detectors Acrylonitrile by Gas Chromatography Acrylamide by Gas Chromatography Acetonitrile by Gas Chromatography with Nitrogen-Phosphorus Detection Phenols by Gas Chromatography Phthalate Esters by Gas Chromatography with Electron Capture Detection (GC/ECD) Nitrosamines by Gas Chromatography Organochlorine Pesticides by Gas Chromatography Polychlorinated Biphenyls (PCBs) by Gas Chromatography Nitroaromatics and Cyclic Ketones by Gas Chromatography Polynuclear Aromatic Hydrocarbons Haloethers by Gas Chromatography Chlorinated Hydrocarbons by Gas Chromatography: Capillary Column Technique Aniline and Selected Derivatives by Gas Chromatography Organophosphorus Compounds by Gas Chromatography: Capillary Column Technique Chlorinated Herbicides by GC Using Methylation Penllafluorobenzylation Derivatization or CONTENTS - 5 Revision 5 April 1998 ------- 4.3.2 Gas Chromatographic/Mass Spectroscopic Methods Method 8260B: Volatile Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS) Method 8270C: Semivolatile Organic Compounds by Gas Chromatography/Mass Spectrometry (GC/MS) Method 8275A: Semivolatile Organic Compounds (PAHs and PCBs) in Soils/Sludges and Solid Wastes Using Thermal Extraction/Gas Chromatography/Mass Spectrometry (TE/GC/MS) Method 8280A: The Analysis of Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzofurans by High Resolution Gas Chromatography/Low Resolution Mass Spectrometry (HRGC/LRMS) Method 8290: Polychlorinated Dibenzodioxins (PCDDs) and Polychlorinated Dibenzofurans (PCDFs) by High-Resolution Gas Chromatography/High-Resolution Mass Spectrometry (HRGC/HRMS) Attachment A: Procedures for the Collection, Handling, Analysis, and Reporting of Wipe Tests Performed within the Laboratory 4.3.3 High Performance Liquid Chromatographic Methods Method 8310: Polynudear Aromatic Hydrocarbons Method 8315A: Determination of Carbonyl Compounds by High Performance Liquid Chromatography (HPLC) Appendix A: Recrystallization of 2,4-Dinitrophenylhydrazine (DNPH) Method 8316: Acrylamide, Acrylonitrile and Acrolein by High Performance Liquid Chromatography (HPLC) Method 8318: N-Methylcarbamates by High Performance Liquid Chromatography (HPLC) Method 8321A: Solvent Extractable Nonvolatile Compounds by High Performance Liquid Chromatography/Thermospray/Mass Spectrometry (HPLC/TS/MS) or Ultraviolet (UV) Detection Method 8325: Solvent Extractable Nonvolatile Compounds by High Performance Liquid Chromatography/Pariicle Beam/Mass Spectrometry (HPLC/PB/MS) Method 8330: Nitroaromatics and Nitramines by High Performance Liquid Chromatography (HPLC) Method 8331: Tetrazene by Reverse Phase High Performance Liquid Chromatography (HPLC) Method 8332: Nitroglycerine by High Performance Liquid Chromatography 4.3,4 Infrared Methods Method 8410: Gas Chromatography/Fourier Transform Infrared (GC/FT-IR) Spectrometry for Semivolatile Organics: Capillary Column Method 8430: Analysis of Bis(2-chloroethyl) Ether and Hydrolysis Products by Direct Aqueous Injection GC/FT-IR Method 8440: Total Recoverable Petroleum Hydrocarbons by Infrared Spectrophotometry CONTENTS-6 Revisions April 1998 ------- 4.3.5 Miscellaneous Spectrometric Methods Method 8520: Continuous Measurement of Formaldehyde in Ambient Air 4.4 Immunoassay Methods i Method 4000: Immunoassay Method 401OA: Screening for Pentachlorophenol by Immunoassay Method 4015: Screening for 2,4-Dichlorophenoxyacetic Acid by Immunoassay Method 4020: Screening for Polychlorinated Biphenyls by Immunoassay Method 4030: Soil Screening for Petroleum Hydrocarbons by Immunoassay Method 4035: Soil Screening for Polynuclear Aromatic Hydrocarbons by Immunoassay Method 4040: Soil Screening for Toxaphene by Immunoassay Method 4041: Soil Screening for Chlordane by Immunoassay Method 4042: Soil Screening for DDT by Immunoassay Method 4050: TNT Explosives in Soil by Immunoassay Method 4051: Hexahydro-I.S.S-trinitro-I.S.S-triazine (RDX) in Soil by .Immunoassay 4.5 Miscellaneous Screening Methods Method 3810: Headspace Method 3820: Hexadecane Extraction and Screening of Purgeable Organics Method 8515: Colorimetric Screening Method for Trinitrotoluene (TNT) in Soil Method 9078: Screening Test Method for Polychlorinated Biphenyls in Sorl Method 9079: Screening Test Method for Poiychlorinated Biphenyls in Transformer Oil APPENDIX - COMPANY REFERENCES NOTE: A suffix of "A" in the method number indicates revision one (the method has been revised once). A suffix of "B" in the method number indicates revision two (the method has been revised twice). A suffix of "C" in the method number indicates revision three (the method has been revised three times). In order to properly document the method used for analysis, the entire method number including the suffix letter designation (e.g.,, A, B, or C) must be identified by the analyst. A method reference found within.the RCRA regulations and the text of SW-846 methods and chapters refers to the latest promulgated revision of the method, even though the method number does not include the appropriate letter suffix. CONTENTS - 7 Revision 5 April 1998 ------- VOLUME ONE SECTION C DISCLAIMER ABSTRACT TABLE OF CONTENTS METHOD INDEX AND CONVERSION TABLE PREFACE CHAPTER ONE. REPRINTED - QUALITY CONTROL 1.0 Introduction 2.0 QA Project Plan 3.0 Field Operations 4.0 Laboratory Operations 5.0 Definitions 6.0 References CHAPTER FIVE - MISCELLANEOUS TEST METHODS Method 5050: Method 901 OB: Method 9012A: Method 9013: Method 9014: Method 9020B: Method 9021: Method 9022: Method 9023: Method 9030B: Method 9031: Method 9034: Method 9035: Method 9036: Method 9038: Method 9056: Method 9057: Method 9060: Method 9065: Method 9066: Method 9067: Method 9070: Method9071B: Bomb Preparation Method for Solid Waste Total and Amenable Cyanide: Distillation Total and Amenable Cyanide (Automated Colorimetric, with Off-Line Distillation) Cyanide Extraction Procedure for Solids and Oils Titrimetric and Manual Spectrophotometric Determinative Methods for Cyanide Total Organic Halides (TOX) Purgeable Organic Halides (POX) Total Organic Halides (TOX) by Neutron Activation Analysis Extractable Organic Halides (EOX) in Solids Acid-Soluble and Acid-Insoluble Sulfides: Distillation Extractable Sulfides Titrimetric Procedure for Acid-Soluble and Acid-Insoluble Sulfides Sulfate (Colorimetric, Automated, Chlorari ilate) Sulfate (Colorimetric, Automated, Methylthymol Blue, AA II) Sulfate (Turbidimetric) Determination of Inorganic Anions by Ion Chromatography Determination of Chloride from HCI/CI2 Emission Sampling Train (Methods 0050 and 0051) by Anion Chromatography Total Organic Carbon Phenolics (Spectrophotometric, Manual 4-AAP with Distillation) Phenolics (Colorimetric, Automated 4-AAP with Distillation) Phenolics (Spectrophotometric, MBTH with Distillation) See Method 1664, Publication No. EPA-821-R-98-002 n-Hexane Extractable Material (HEM) for Sludge, Sediment, and Solid Samples CONTENTS - 8 Revision 5 April 1998 ------- Method 9075: Method 9076: Method 9077: Method A: Method B: Method C: Method 9131: Method 9132: Method 9210: Method 9211: Method 9212: Method 9213: Method 9214: Method 9215: Method 9250: Method 9251: Method 9253: Method 9320: Test Method for Total Chlorine in New and Used Petroleum Products by X-Ray Fluorescence Spectrometry (XRF) Test Method for Total Chlorine in New and Used Petroleum Products by Oxidative Combustion and Microcoulometry Test Methods for Total Chlorine in New and Used Petroleum Products (Field Test Kit Methods) Fixed End Point Test Kit Method Reverse Titration Quantitative End Point Test Kit Method Direct Titration Quantitative End Point Test Kit Method Total Coliform: Multiple Tube Fermentation Technique Total Coliform: Membrane-Filter Technique Potentiometric Determination of Nitrate in Aqueous Samples with Ion- Selective Electrode Potentiometric Determination of Bromide in Aqueous Samples with Ion-Selective Electrode Potentiometric Determination of Chloride in Aqueous Samples with Ion-Selective Electrode Potentiometric Determination of Cyanide in Aqueous Samples and Distillates with Ion-Selective Electrode Potentiometric Determination of Fluoride in Aqueous Samples with Ion-Selective Electrode Potentiometric Determination of Sulfide in Aqueous Samples and Distillates with Ion-Selective Electrode Chloride (Colorimetric, Automated Ferricyanide AAI) Chloride (Colorimetric, Automated Ferricyanide AAI I) Chloride (Titrimetric, Silver Nitrate) Radium-228 CHAPTER SIX - PROPERTIES Method 1030: Method 1120: Method 1312: Method 1320: Method 1330A: Method 9041 A: Method 9045C: Method 9050A: Method 9080: Method 9081: Method 9090A: Method 9095A: Method 9096: Appendix A: Method 9100: Method 9310: Method 9315: Ignitability of Solids Dermal Corrosion Synthetic Precipitation Leaching Procedure Multiple Extraction Procedure Extraction Procedure for Oily Wastes pH Paper Method Soil and Waste pH Specific Conductance ; Cation-Exchange Capacity of Soils (Ammonium Acetate) Cation-Exchange Capacity of Soils (Sodium Acetate) Compatibility Test for Wastes and Membrane Liners Paint Filter Liquids Test Liquid Release Test (LRT) Procedure Liquid Release Test Pre-Test Saturated Hydraulic Conductivity, Saturated Leachate Conductivity, and Intrinsic Permeability Gross Alpha and Gross Beta Alpha-Emitting Radium Isotopes CONTENTS - 9 Revision 5 April 1998 ------- PART II CHARACTERISTICS CHAPTER SEVEN - CHARACTERISTICS INTRODUCTION AND REGULATORY DEFINITIONS 7.1 Ignitability 7.2 Corrosivity 7.3 Reactivity Test Method to Determine Hydrogen Cyanide Released from Wastes Test Method to Determine Hydrogen Sulfide Released from Wastes 7.4 Toxicity Characteristic Leaching Procedure CHAPTER EIGHT- METHODS FOR DETERMINING CHARACTERISTICS 8.1 Ignitability Method 1010: Pensky-Martens Closed-Cup Method for Determining Ignitability Method 1020A: Setaflash Closed-Cup Method for Determining Ignitability 8.2 Corrosivity Method 9040B: pH Electrometric Measurement Method 1110: Corrosivity Toward Steel 8.3 Reactivity 8.4 Toxicity Method 1310A: Extraction Procedure (EP) Toxicity Test Method and Structural Integrity Test Method 1311: Toxicity Characteristic Leaching Procedure : APPENDIX - COMPANY REFERENCES MOTE: A suffix of "A" in the method number indicates revision one (the method has been revised once). A suffix of "B" in the method number indicates revision two (the method has been revised twice). A suffix of "C" in the method number indicates revision three (the method has been revised three times). In order to properly document the method used for analysis, the entire method number including the suffix letter designation (e.g., A, B, or C) must be identified by the analyst. A method reference found within the RCRA regulations and the text of SW-846 methods and chapters refers to the latest promulgated revision of the method, even though the method number does not include the appropriate letter suffix. CONTENTS - 10 Revision 5 April 1998 ------- VOLUME TWO DISCLAIMER ABSTRACT TABLE OF CONTENTS METHOD INDEX AND CONVERSION TABLE PREFACE CHAPTER ONE, REPRINTED - QUALITY CONTROL 1.0 Introduction 2.0 QA Project Plan 3.0 Field Operations 4.0 Laboratory Operations 5.0 Definitions 6.0 References PART III SAMPLING CHAPTER NINE - SAMPL INin PLAN 9.1 Design and Development 9.2 Implementation CHAPTER TEN - SAMPLING METHODS Method 0010: Appendix A: Appendix B: Method 0011: Method 0020: Method 0023A: Method 0030: Method 0031: Method 0040: Method 0050: Method 0051: Method 0060: Method 0061: Method 0100: Modified Method 5 Sampling Train Preparation of XAD-2 Sorbent Resin Total Chromatographable Organic Material Analysis Sampling for Selected Aldehyde and Ketone Emissions from Stationary Sources Source Assessment Sampling System (SASS) Sampling Method for Polychlorinated Dibenzo-p-Dioxins and Polychlorinated Dibenzo.furan Emissions from Stationary Sources Volatile Organic Sampling Train Sampling Method for Volatile Organic Compounds (SMVOC) Sampling of Principal Organic Hazardous Constituents from Combustion Sources Using Tedlar® Bags Isokinetic HCI/CI2 Emission Sampling Train Midget Impinger HCI/CI2 Emission Sampling Train Determination of Metals in Stack Emissions Determination of Hexavalent Chromium Emissions from Stationary Sources Sampling for Formaldehyde and Other Carbonyl Compounds in Indoor Air CONTENTS - 11 Revision 5 April 1998 ------- PART IV MONITORING CHAPTER ELEVEN - GROUND WATER MONITORING 11.1 Background and Objectives 11.2 Relationship to the Regulations and to Other Documents 11.3 Revisions and Additions 11.4 Acceptable Designs and Practices 11.5 Unacceptable Designs and Practices CHAPTER TWELVE - LAND TREATMENT MONITORING 12.1 Background 12.2 Treatment Zone 12.3 Regulatory Definition 12.4 Monitoring and Sampling Strategy 12.5 Analysis 12.6 References and Bibliography CHAPTER THIRTEEN - INCINERATION 13.1 Introduction 13.2 Regulatory Definition 13.3 Waste Characterization Strategy 13.4 Stack-Gas Effluent Characterization Strategy 13.5 Additional Effluent Characterization Strategy 13.6 Selection of Specific Sampling and Analysis Methods 13.7 References APPENDIX- COMPANY REFERENCES NOTE: A suffix of "A" in the method number indicates revision one (the method has been revised once). A suffix of "B" in the method number indicates revision two (the method has been revised twice). A suffix of "C" in the method number indicates revision three (the method has been revised three times). In order to properly document the method used for analysis, the entire method number including the suffix letter designation (e.g., A, B, or C) must be identified by the analyst. A method reference found within the RCRA regulations and the text of SW-846 methods and chapters refers to the latest promulgated revision of the method, even though the method number does not include the appropriate letter suffix. CONTENTS-12 Revision 5 April 1998 ------- CHAPTER FIVE MISCELLANEOUS TEST METHODS Prior to employing the methods in this chapter, analysts are advised to consult the disclaimer statement at the front of this manual and the information in Chapter Two for guidance on the allowed flexibility in the choice of apparatus, reagents, and supplies. In addition, unless specified in a regulation, the use of SW-846 methods is not mandatory in response to Federal testing requirements. The information contained in each procedure is provided by EPA as guidance to be used by the analyst and the regulated community in making judgements necessary to meet the data quality objectives or needs for the intended use of the data. The following methods are found in Chapter Five: Method 5050: Method 9010B: Method 9012A: Method 9013: Method 9014: Method Method Method Method Method Method Method 9020B: 9021: 9022: 9023: 9030B: 9031: 9034: Method 9035: Method 9036: Method 9038: Method 9056: Method 9057: Method 9060: Method 9065: Method 9066: Method 9067: Method 9070: Method 9071B: Method 9075: Method 9076: Bomb Preparation Method for Solid Waste Total and Amenable Cyanide: Distillation Total and Amenable Cyanide (Automated Colorimetric, with Off-line Distillation) Cyanide Extraction Procedure for Solids and Oils Titrimetric and Manual Spectrophotometric Determinative Methods for Cyanide Total Organic Halicles (TOX) Purgeable Organic Halides (POX) Total Organic Halicles (TOX) by Neutron Activation Analysis Extractable Organic Halides (EOX) in Solids Acid-Soluble and Acid-Insoluble Sulfides: Distillation Extractable Sulfides Titrimetric Procedure for AcidrSoluble and Acid-Insoluble Sulfides . Sulfate (Colorimetric, Automated, Chloranilate) Sulfate (Colorimetric, Automated, Methylthymol Blue, AA II) Sulfate (Turbidimetric) Determination of Inorganic Anions by Ion Chromatography Determination of Chloride from HCI/CI2 Emission Sampling Train (Methods 0050 and 0051) by Anion Chromatography Total Organic Carbon Phenolics (Spectrophotometric, Manual 4-AAP with Distillation) : Phenolics (Colorimetric, Automated 4-AAP with Distillation) Phenolics (Spectrophotometric, MBTH with Distillation) See Method 1664, Publication No. EPA-821-R-98-002 n-Hexane Extractable Material (HEM) for Sludge, Sediment, and Solid Samples Test Method for Total Chlorine in New and Used Petroleum Products by X-Ray Fluorescence Spectrometry (XRF) Test Method for Total Chlorine in New and Used Petroleum Products by Oxidative Combustion and Microcoulometry FIVE - 1 Revision 3 April 1998 ------- Method 9077: Method A: Method B: Method C: Method 9131: Method 9132: Method 9210: Method 9211: Method 9212: Method 9213: Method 9214: Method 9215: Method 9250: Method 9251: Method 9253: Method 9320: Test Methods for Total Chlorine in New and Used Petroleum Products (Field Test Kit Methods) Fixed End Point Test Kit Method Reverse Titration Quantitative End Point Test Kit Method Direct Titration Quantitative End Point Test Kit Method Total Coliform: Multiple Tube Fermentation Technique Total Coliform: Membrane-Filter Technique Potentiometric Determination of Nitrate in Aqueous Samples with Ion-Selective Electrode Potentiometric Determination of Bromide in Aqueous Samples with Ion-Selective Electrode Potentiometric Determination of Chloride in Aqueous Samples with Ion-Selective Electrode Potentiometric Determination of Cyanide in Aqueous Samples and Distillates with Ion-Selective Electrode Potentiometric Determination of Fluoride in Aqueous Samples with Ion-Selective Electrode Potentiometric Determination of Sulfide in Aqueous Samples and Distillates with Ion-Selective Electrode Chloride (Colorimetric, Automated Ferricyanide AAI) Chloride (Colorimetric, Automated Feirricyanide AAI I) Chloride (titrimetric, Silver Nitrate) Radium-228 FIVE - 2 Revision 3 April 1998 ------- METHOD 9070 See Method 1664, Publication No. EPA-821-R-98-002. Referral to Method 1664 April 1998 ------- ------- METHOD 9071B n-HEXANE EXTRACTABLE MATERIAL. fHEM^ FOR SLUDGE. SEDIMENT. AND SOLID SAMPLES 1.0 SCOPE AND APPLICATION , • • ; 1.1 Method 9071 may be used to quantify low concentrations of oil and grease in soil, sediments, sludges, and other solid materials amenable to chemical drying and solvent extraction with n-hexane. "Oil and grease" is a conventional pollutant under 40 CFR 401.16 and generally refers to substances, including biological lipids and mineral hydrocarbons, that have similar physical characteristics and common solubility in an organic extracting solvent. As such, oil and grease is an operationally defined parameter, and the results will depend entirely on the extracting solvent and method of extraction. Method 9071 employs n-hexane as the extraction solvent with Soxhlet extraction and the results of this method are appropriately termed "n-hexane extractable material (HEM)." Section 1.2 lists the type of materials that may be extracted by this method. In the context of this method, "HEM" is used throughout this method and for operational purposes, may be considered synonymous with "oil and grease" within the limitations discussed below. 1.2 Specifically, Method 9071 is suitable for extracting relatively non-volatile hydrocarbons, vegetable oils, animal fats, waxes, soaps, greases, biological lipids, and related materials. 1.3 Method 9071 is not recommended for measuring materials that volatilize at temperatures below 85°C. Petroleum fuels from gasoline through #2 fuel oil may be partially lost during the solvent removal process. 1.4 Some crude oils and heavy fuel oils may contain materials that are not soluble in n-hexane, and recovery of these materials may be low. ; 2.0 SUMMARY OF METHOD 2.1 A representative portion of wet (as received) waste is acidified with concentrated HCI and chemically dried with magnesium sulfate or sodium sulfate. Magnesium sulfate monohydrate is used to dry acidified sludges as it will combine with 75% of its own weight in water in forming MgSO4 • 7H2O. Anhydrous sodium sulfate is used to dry soil and sediment samples. 2.2 After drying, the HEM is extracted with n-hexane using a Soxhlet apparatus. The n-hexane extract is then distilled from the extract and the HEM is desiccated and weighed. 2.3 When necessary, a separate sample portion is evaluated for percent solids, and the dry weight fraction may be used to calculate the dry-weight HEM concentration of the soil, sediment, or waste. 3.0 DEFINITIONS ' ; 3.1 n-Hexane extractable material (HEM, oil and grease): Material that is extracted from a sample using n-hexane and determined by this method. This material includes relatively non- volatile hydrocarbons, vegetable oils, animal fats, waxes, soaps, greases, and related matter. 3:2 Refer to Chapter One for additional definitions. , 9071B-1 : Revision 2 : April 1998 ------- 4.0 INTERFERENCES 4.1 This method is entirely empirical, and duplicate results having a high degree of precision can be obtained only by strict adherence to all details. The rate of cycling and time of extraction in the Soxhlet apparatus must be consistent and length of time required for drying and cooling extracted materials must be the same in order to generate consistent results. It is important that the procedures be performed as directed due to the varying solubilities of the different greases and heavy mineral oils. 4.2 Solvents, reagents, glassware, and other sample-processing hardware may yield artifacts that could affect the results. All solvents and reagents used in the analysis should be demonstrated to be free from interferences by processing a method blank with each analytical batch. Specific selection of reagents, solvent washes, or purification of solvents may be required. Use of plastic measuring devices, and/or plastic tubing attachments must be avoided. 4.3 Glassware should be cleaned by washing with hot tap water with detergent, rinsing with tap water and reagent water, and rinsing with solvent. Glassware may also be baked at 200-250 °C for 1 hour. Boiling flasks that are used to contain the extracted residues may be dried in an oven at 105-115°C and stored in a desiccator until used. Depending on the project DQOs, strict adherence to the washing and handling procedures cited above may not be necessary as long as the laboratory can demonstrate that alternative cleaning procedures yield acceptable method performance and meet method blank acceptance criteria. 4.4 A gradual increase in weight may result due to the absorption of oxygen; a gradual loss of weight may result due to volatilization. Extracted residues should be maintained in a desiccator during cooling and prior to weighing. Extracted residues should be weighed as soon as possible after cooling. 4.5 The presence of non-oily extractable substance such as sulfur compounds, organic dyes, and chlorophyll, may result in a positive bias. For the purpose of this method, all materials extracted and retained during this procedure'are defined as HEM. 5.0 SAFETY 5.1 The toxicity or carcinogenicity of each reagent used in this method has not been * precisely determined; however, each chemical should be treated as a potential health hazard. Exposure to these chemicals should be reduced to the lowest possible level. It is suggested that the laboratory perform personal hygiene monitoring of each analyst that uses this method. This monitoring should be performed using Occupational Safety and Health Administration (OSHA) or National Institute of Occupational Safety and Health (NIOSH) approved personal hygiene monitoring methods. Results of this monitoring should be made available to the analyst. 5.2 n-Hexane has been shown to have increased neurotoxic effects over other hexanes and some other solvents. OSHA has proposed a time-weighted average (TWA) of 50 parts-per- million (ppm); NIOSH concurs that an 8-hour TWA/permissible exposure limit (PEL) of 50 ppm is appropriate for n-hexane; and the American Conference of Governmental Industrial Hygienists (ACGIH) has published a threshold limit value (TLV) of 50 ppm for n-hexanel Inhalation of n-hexane should be minimized by performing all operations with n-hexane in a explosion-proof hood or well- ventilated area. 9071B-2 Revision 2 April 1998 ------- 5.3 n-Hexane has a flash point of -23 °C (-9°F), has explosive limits in air in the range of 1 to 7 percent, and poses a serious fire risk when heated or exposed to flame. n-Hexane can react vigorously with oxidizing materials. The laboratory should include procedures in its operations that address the safe handling of n-hexane. 5.4 Unknown samples may contain high concentrations of volatile toxic compounds. Sample containers should be opened in a hood and handled with gloves to prevent exposure. 5.5 This method does not address all safety issues associated with its use. The laboratory is responsible for maintaining a safe work environment and 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 be available to all personnel involved in these analyses. 6.0 EQUIPMENT AND SUPPLIES 6.1 Soxhlet extraction apparatus. 6.2 Heating mantle - explosion-proof, with temperature control. 6.3 Boiling flask - 125-mL or appropriate size. 6.4 Analytical balance - capable of weighing 0.1 mg. 6,5 Vacuum pump, or other vacuum source. 6.6 Paper extraction thimble for Soxhlet apparatus. ; 6.7 Glass wool or small glass beads to fill thimble. 6.8 Grease-free, non-absorbent cotton - To remove possible interferences, each batch of cotton should be washed with n-hexane. Solvent washing may not be necessary if the laboratory can demonstrate that the unwashed cxrtton does not affect the performance of the method or that the concentration of HEM in the sample is so high that low contaminant concentration is insignificant. 6.9 Beakers-100-150-mL. 6.10 pH paper. 6.11 Porcelain mortar and pestle. '. 6.12 Extraction flask - 150-ml. or appropriate size. 6.13 Waterbath or steam bath-explosion-proof - capable of maintaining a temperature of at least 85°C. 6.14 Distilling apparatus - For removing n-hexane from extract. 6.14.1 Distilling head-Claisen (VWR Scientific No 26339-005, or equivalent), includes Claisen-type connecting tube and condenser. 9071B-3 ' Revision 2 April 1998 ------- 6.14.2 Distillation adapter (used to attach distilling head and to the waste collection flask for recovery of solvent). 6.14.3 Distillate collection flask (attached to the distilling adaptor for collection of the distilled solvent). 6.14.4 Ice bath or recirculating chiller (to aid in the condensation and collection of the distilled solvent). 1 ' i . '' 6.15 Desiccator - Cabinet or jar type, capable of holding boiling flasiks during cooling and storage. 6.16 Tongs - for handling the boiling flasks. 6.17 Glass fiber filter paper - Whatman No. 40 or equivalent. " 6.18 Boiling chips - Silicon carbide or fluoropolymer. 1 ! 7.0 REAGENTS 7.1 Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all reagents shall conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society, where such specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficiently high purity to permit its use without lessening the accuracy of the determination. " •, • i ' ' 7.2 Reagent water. All references to water in this method refer to reagent water, as defined in Chapter One. 7.3 Concentrated hydrochloric acid (HCI). 7.4 Magnesium sulfate monohydrate. Prepare MgSO4 • H2O by spreading a thin layer in a dish and drying in an oven at 150°C overnight. Store in a tightly sealed glass container until used. I. • " I :,l I , , 7.5 Sodium sulfate, granular, anhydrous (Na2SO4). Purify by heating at 400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with methylene chloride. If the sodium sulfate 5s precleaned with methylene chloride, a method blank must be analyzed, demonstrating that there is no interference from the sodium sulfate. Store in a tightly sealed glass container until used. . . i -r !• • 7.6 n-Hexane. Purity of 85%, 99.0% minimum saturated C6 isomers, residue less than 1 mg/L Boiling point, 69° C. 7.7 Hexadecane(CH3(CH2)14CH3)/stearic acid (CH3(CH2)16COOH). 1:1 spiking solution. Prepare in acetone at a concentration of 2 mg/mL each. Weigh 200 ± 2 mg of stearic acid and 200 ± 2 mg hexadecane into a 100 ml_ volumetric flask and fill to the mark with acetone. The total concentration of this stock is 4000 mg/L (ppm) HEM. This standard may be used for spiking samples and preparing laboratory control samples. Store in a glass container with a fluoropolymer-lined cap at room temperature. Shield from light. Note: The spiking solution may require warming for complete dissolution of stearic acid. 9071B-4 Revision 2 April 1998 !,, JAl'ii" ------- 8.0 SAMPLE COLLECTION, PRESERVATION, AND STORAGE 8.1 A minimum of 100 grams of sample should be collected using a metal spatula, spoon, or equivalent device. Samples should be collected into a pre-cleaned wide-mouth glass container fitted with a TFE-lined screw cap. i 8.2 When practical (i.e., when the sample matrix allows the complete mixing of sample and acid such as with a pourable sludge or sediment), the sample should be preserved to a pH < 2 by adding 1 mL of concentrated HCI per 100 gram of sample and cooled to 4 ± 2 °C. If acidification is not practical (as with a dry soil), the addition of the HCI is not required and the sample should be cooled to 4 ± 2 °C. The laboratory must be notified so that the sample can be acidified prior to analysis. 8.3 A holding time has not been established for HEM in solids, but it is recommended that the sample be analyzed as soon as possible. 9.0 QUALITY CONTROL 9.1 Each 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 the analysis of spiked samples as a continuing check on performance. The laboratory is required to maintain performance records to define the quality of data that is generated. 9.2 Employ a minimum, of one method blank per analytical batch or twenty samples, whichever is more frequent, to verify that all reagents, solvents, and equipment are contamination free. Prepare the method blank from 5 g of inert matrix such as pre-deaned sand or similar material, and carry it through the analytical process. 9.3 Run one matrix duplicate and matrix spike sample every twenty samples or analytical batch, whichever is more frequent. Matrix duplicates and spikes are brought through the whole sample preparation and analytical process. 9.4 The performance of the method should be evaluated by the use of a Laboratory Control Sample (LCS). The LCS is prepared by spiking an inert matrix (as pre-cleaned sand or similar material) with an appropriate volume of spiking solution (Sec. 7.7) and carrying it through the analytical process. . : 10.0 CALIBRATION AND STANDARDIZATION 10.1 Calibrate the analytical balance at 2 mg and 1000 mg using class "S" weights. 10.2 Calibration shall be within ± 10% (i.e., ± 0,2 mg) at 2 mg and ± 0.5 % (i.e., ± 5 mg) at 1000 mg. If values are not within these limits, recalibrate the: balance. 9071B-5 Revision 2 April 1998 ------- 11.6 PROCEDURE 11.1 Determination of Sample Dry Weight Fraction - , . . • • „ , i 11.1.1 When it is necessary to report the HEM on a dry weight basis, determine the ' dry weight fraction using a separate aliquot of sample, as discussed below. The aliquot used for this determination cannot be used to evaluate HEM. 11.1.2 Weigh 5-10 gram (± 0.01 gram) of the sample into pre-weighed crucible. Determine the weight of the wet sample by subtracting the weight of the crucible. 11.1.3 Place the crucible with the wet sample in an oven overnight at 105°C. Remove crucible from oven and place in a desiccator to cool. Weigh. Determine dry weight of sample by subtracting the weight of the crucible. Determine the dry weight fraction of the sample as follows: NOTE: The drying oven should be contained in a hood or vented. Significant laboratory contamination may result from a heavily contaminated hazardous waste sample. i • u*«. « g of dry sample dry weight fraction = M -* -~L— g of sample 11.2 Sample Preparation. 11.2.1 Sludge/Waste Samples 11.2.1.1 Weigh out 20 ± 0.5 grams of wet sample into a 150-mL beaker. 11.2.1.2 If the sample has not been acidified, acidify to a pH <; 2 with approximately 0.3 ml_ concentrated HCI. 11.2.1.3 Add 25 grams Mg2SO4 • H2O (Sec. 7.4) and stir to a smooth paste. 11.2.1.4 Spread paste on sides of beaker to facilitate evaporation. Let stand about 15-30 min or until material is solidified. : i I . ' 11.2.1.5 Remove solids and grind to fine powder in a mortar. 11.2.1.6 Add the powder to the paper extraction thimble. 11.2.1.7 Wipe beaker and mortar with pieces of filter paper moistened with n-hexane and add to thimble. 11.2.1.8 Fill thimble with glass wool (or glass beads). 9071B - 6 Revision 2 April 1998 ------- 11.2.2 Sediment/Soil Samples 11.2.2.1 Decant and discard any water layer on a sediment sample. Mix sample thoroughly, especially composited samples. Discard any foreign objects such as sticks, leaves, and rocks. 11.2.2.2 Blend 10 grams of the sample with 10 grams of anhydrous sodium sulfate (Sec. 7.5) as described in Section 11.2.1. Transfer homogenized paste to an extraction thimble and cover with glass wool or glass beads. The extraction thimble must drain freely for the duration of the extraction period. 11.3 Extraction 11.3.1 Set-up the Soxhlet apparatus containing the extraction thimble and sample and attach a 125-mL boiling flask containing 90 mL of n-hexane. Add boiling chips. Adjust the heating control on the heating mantle so that a cycling rate of 20 cycles/h is obtained. Extract for a period of 4 hrs. 11.3.2 Tare a clean 250-mL or appropriate sized boiling flask as follows: 11.3.2.1 Dry the flask in an oven at 105-115°C for a minimum of 2 h. 11.3.2.2 Remove from the oven and immediately transfer to a desiccator to cool at room temperature. 11.3.2.3 When cool, remove from the desiccator with tongs and weigh immediately on a calibrated balance. 11.3.3 At the end of the 4 h extraction period, filter the extract through grease-free cotton, into the pre-weighed boiling flask (Sec. 11.3.2). Use gloves to avoid adding fingerprints to the flask. 11.3.4 Rinse flask and cotton with n-hexane and add to the 250-mL boiling flask. NOTE: If the extract is clear and no suspended particles are present, the filtration Step may be omitted. 11.3.5 Connect the boiling flask to the distilling head apparatus and distill the solvent by immersing the lower half of the flask in a water bath or a steam bath. A heating mantle may also be used. Adjust the temperature of the heating device to complete the distillation in less than 30 minutes. Collect the solvent for reuse or appropriate disposal. 11.3.6 When the distillation is complete, remove the distilling head. Immediately remove the flask from the heat source and wipe the outside to remove excess moisture and fingerprints. To remove solvent vapor, sweep out the flask for 15 sec with air by inserting a glass tube that is connected to a vacuum source. 11.3.7 Cool the boiling flask in a desiccator for 30 min and weigh. Determine the gain in weight of the boiling flask by subtracting the weight of the boiling flask (Sec. 11.3.2) from the final boiling flask weight. 9071B - 7 Revision 2 April 1998 ------- 12.0 DATA ANALYSIS AND CALCULATIONS Calculate the concentration of HEM in the sample as follows: ,._.. ... . ... gam in weight of flask(mg) X 1000 HEM (mg/kg wet weight) = *- . * . —\.., . weight of wet solid (g) NOTE: If it is necessary to report the results on a dry weight basis, divide the result obtained above by the dry weight fraction calculated in Sec. 11.1.3. Report the results as mg/kg HEM dry weight. If it is necessary to report the results as a percentage of the wet or dry weight, divide the wet-weight concentration or dry weight concentration by 10,000 and report the result as % HEM wet or dry weight. i i . •• . • 13.0 METHOD PERFORMANCE In a preliminary study designed to find a suitable replacement for F:reon-113, three EPA contract laboratories evaluated a total of 28 solid samples derived from various industrial and commercial processes for oil and grease. This study evaluated a total of six solvents, including n- hexane, to determine which of the alternative solvents produced results most closely with that of Freon-113. In tfiis study, each waste was Soxhlet-extractecl in triplicate using Freon-113 and each of the alternative solvents. Based on the overall results, n-hexane was judged to be the best alternative solvent. The data provided in Table i compare the results for Freon-113 and n-hexane for each waste. For a complete discussion of this study, refer to reference 1 in Section 16.0. 14.0 POLLUTION PREVENTION 14.1 Pollution prevention encompasses any technique that reduces or eliminates the quantity and/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. When wastes cannot be feasibly reduced at the source, the Agency recommends recycling as the next best option. 14.2 For 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 St., N.W. Washington, D.C. 20036, (202) 872-4477. 15.0 WASTE MANAGEMENT „• !| • '• | The Environmental Protection Agency requires that laboratory waste management practices be conducted consistent with all applicable Federal, state and local 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 i 9071B - 8 Revision 2 April 1998 ------- 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 Sec. 14.2. 16.0 REFERENCES , : 1. Preliminary Report of EPA Efforts to Replace Freon for the Determination of Oil and Grease, United States Environmental Protection Agency, Office of Water, EPA-821-93-009. June 1993. 2. Method 1664, Revision A: n-Hexane Extractable Material (HEM; Oil and Grease) and Silica Gel Treated N-Hexane Extractable Material (SGT-HEM) by Extraction and Gravimetry. 17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA The pages to follow contain Table 1, and a flow diagram of the method procedure. 9071B-9 Revision 2 April 1998 ------- TABLE 1 SOXHLET EXTRACTION OF SOLIDS USING FREON-113 AND N-HEXANE All concentrations in mg/kg Facility/ Process Paper Mill POTW Leather Tannery POTW Petroleum Refinery Industrial Laundry Fish Oil Plant Coke Plant Wood Preserving Plant Drilling Fluid Supplier Contam. Soils Poultry Plant Rolling Mill Mayonnaise •Plant Seafood Plant Waste Stream Dewatered Sludge Sewage Sludge Dewatered Sludge Digested Sludge API Separator Sludge DAF Sludge Oily Sludge Waste Activated Sludge Solid Waste Used drilling mud kerosene Contaminated Soil Waste Activated Sludge Dewatered Scale Oily Sludge Waste Sludge Solvent: Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Rep No. 1 11000 6600 98000 110000 11000 21000 130000 54000 320000 240000 310000 290000 890000 440000 8300 14000 150000 140000 1300 1300 2000 2500 38000 5900 11000 14000 880000 590000 64000 34000 9071 B- Rep No. 2 5300 2400 81000 86000 12000 15000 97000 76000 350000 320000 310000 360000 1000000 530000 8000 19000 140000 130000 1600 1200 1400 3200 11000 11000 14000 14000 850000 780000 31000 10 Rep No. 3 7900 11000 81000 80000 12000 19000 66000 48000 250000 240000 240000 180000 770000 460000 18000 15000 140000 130000 1300 1600 1900 2600 40000 46000 17000 16000 780000 520000 53000 27000 Mean Concen- tration 8000 6600 87000 91000 42000 18000 98000 59000 310000 270000 290000 280000 890000 480000 11000 16000 140000 130000 1400 1400 1700 2800 30000 21000 14000 15000 840000 630000 58000 31000 ! Standard Deviation 2762 4203 9940 13281 732 3201 33028 14516 53257 43822 41717 90819 131249 46318 5505 2732 3512 6557 .157 201 352 410 16263 21795 2884 983 50521 132020 7526 3867 Revision 2 April 1998 ------- TABLE 1 (CONTINUED) ; Facility/ Process Seafood Plant Poultry Plant Railroad Yard Can Manufact Plant Soup Plant Oily Water Treatment Plant Can Manufact Plant Can Manufact Plant Drum Handling Facility Polymer Plant Restaurant Leather Tannery Waste Stream Oily Sludge DAF Sludge Oily Sludge Filter Cake DAF Sludge Oily Sludge Oily Sludge Filter Cake Oily Sludge Dewatered Sludge Vegetable Oil Waste Waste Sludge Solvent: Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Freon Hexane Source: Reference 1 Rep No. 1 400000 400000 670000 530000 870000 850000 62000 69000 600000 580000 76000 77000 94000 80000 290000 290000 1200000 990000 13000 8400 760000 1100000 180000 240000 9071 B- Rep No. 2 410000 390000 600000 530000 920000 840000 62000 64000 590000 520000 75000 60000 88000, 90000 290000 290000 1100000 1000000 12000 6900 610000 980000 220000 270000 11 Rep No. 3 430000 390000 570000 530000 870000 830000 60000 66000 610000 600000 70000 79000 94000 83000 300000 290000 1200000 980000 8200 9100 780000 980000 190000 210000 Mean Concen- tration 410000 400000 610000 530000 890000 840000 61000 66000 600000 570000 74000 72000 92000 85000 290000 290000 1200000 1000000 11000 8100 720000 1000000 190000 240000 Standard Deviation 16371 7095 49549 2449 27906 6884 976 2615 10066 40361 3215 107-13 3291 4992 6217 .2029 57735 27319 2524 1122 92060 80064 22140 31177 Revision 2 April 1998 ------- METHOD 9071B n-HEXANE EXTRACTABLE MATERIAL fHEM^ FOR SLUDGE SEDIMENT. AND SOLID SAMPLES 11.1 Determine dry weight fraction of sample. 11.2.1.1 Weigh a sample of wet sludge and place in beaker. 11.2.1.2 Acidify to pH <2. 11.2 Is sample sludge or sediment/ soil? 11.2.2.1 Decant water; mix sample; discard foreign objects. 11.2.2.2 Blend with sodium sulfate; add to extraction thimble. 11.2.1.3 Add magnesium sulfate monohydrate and stir. B 11.2.1.5 Remove and grind solids to a fine powder. 9071 B- 12 Revision 2 April 1998 ------- METHOD 9071B n-HEXANE EXTRACTABLE MATERIAL. (HEM) FOR SLUDGE. (Continued) SEDIMENT. AND SOLID SAMPLES B 11.2.1.6 Add powder to paper extraction thimble. 11.2.1.7 Wipe beaker and mortar; add to thimble. 11.2.1.8 Fill thimble with glass wool. 11.3.1 Extract in Soxhlet apparatus for 4 hours. 11.3.3 Filter extract into boiling flask. 11.3.4 Rinse flask with solvent. 11.3.5 Evaporate and collect solvent for reuse. 11.3.6 Remove solvent vapor. 11.3.7 Cool and weigh boiling flask. 12.0 Calculate concentration of HEM Stop 9071 B- 13 Revision 2 April 1998 ------- ------- |