METHOD STATUS TABLE
SW-846, THIRD EDITION, UPDATES I, II, AND IIA
September 1994
Use this table as a reference guide to identify the
promulgation status of SW-846 methods.
The methods in this table are listed sequentially by
number.
This table should not be used as a Table of Contents for
SW-846. Refer to the Table of Contents found in Final
Update II (dated September 1994} for the order in which
the methods appear in SW-846.
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INSTRUCTIONS
SW-846 is a "living" document that changes when new data and advances in
analytical techniques are incorporated into the manual as new or revised
methods. Periodically, the Agency issues these methods as updates to the
manual. To date, the Agency has issued Final Updates I, II, and IIA. These
instructions include directions on getting the basic manual up-to-date and
incorporating Final Updates II and IIA into your SW-846. The Agency will
release additional proposed and final updates in the future. New instructions,
to supersede these, will be included with each of those updates. However, in
general, final updates should always be incorporated into SW-846 in
chronological order (e.g. Update I should be incorporated before Update II).
If you have any difficulty with these directions, you may telephone the Methods
Information Communication Exchange (MICE) at 703-821-4789 for help. If
you have questions concerning your SW-846 U.S. Government Printing Office
(GPO) subscription, you should telephone the GPO at 202-512-2303. If you
did not purchase your SW-846 from the GPO, the GPO will not be able to help
you.
FINAL UPDATE IIA; Final Update IIA contains only one method, Method
4010, dated August 1993. This method was promulgated on January 4, 1994
(59 FR 458). It should be inserted into the manual according to the location
specified in the Final Update II Table of Contents (dated September 1994).
FINAL UPDATE II: Final Update II has been promulgated and is now
officially part of SW-846. These instructions for insertion of Final Update II
are divided into two (2) sections: Section A • Instructions for New Subscribers
and Section B - Instructions for Previous Subscribers.
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, and a copy of Final Updates II and IIA.
Previous subscribers are defined as individuals that have received copies of the Third
Edition and other SW-846 Updates (including proposed Updates) in the past and have
just received their Final Update II and IIA package in the mail.
Update II and IIA Instructions - 1 Final
-------
Please use the following instructions for new subscribers or previous
subscribers in sequence to piece together your new SW-846 manual.
A. INSTRUCTIONS FOR NEW SUBSCRIBERS
i. If you have not already done so, open the packages that contain the Third Edition of
SW-846, The Third Edition should include 4 (four) volumes of material (i.e. Volumes
IA, IB, 1C, and II) and will be dated "September 1986" in the lower right hand corner
of each page. Four 3-ring binders (one binder for each volume) and a set of tabs
should also be included. You should place each volume of material in the
appropriately labeled 3-ring binder and insert the tabs. Check the Table of Contents
(dated September 1986) if you have any questions about the order of the methods or
about which volume the methods should be inserted into.
You will be missing some methods from the Third Edition since any Third Edition
September1986 material, that was superseded by Final Update I July 1992 material.
has already been removed from vour copy of the Third Edition.
ii. If you have not already done so, open the package that contains Final Update I. Final
Update I should be a single package printed on white paper with the date "July 1992"
in the lower right hand corner of each page. This package contains new methods and
revised methods. In order to have a complete SW-846 manual, you should insert the
new and revised July 1992 material using the Table of Contents (dated July 1992) at
the front of Final Update I to identify the correct location for each chapter and
method.
Since you are a new subscriber to SW-846, you need not be concerned about the
removal or replacement of the previous version of Update I, as discussed in item (A)
of the Final Update I instructions. Again, any Third Edition September 1986 material.
that was superseded by Final Update I July 1992 material has already been removed
from your copy of the Third Edition. For example, your copy of the Third Edition does
not contain a copy of the September 1986 version of Chapter One because it was
superseded by the July 1992 revision of Chapter One contained in your Final Update
I package.
Final Update I also includes copies of September 1986 "replacement methods" which
are included with your copy of Final Update I and are discussed in item (E) in the
Final Update I instructions. You should not insert the replacement methods? The
replacement methods were sent to subscribers before final Update II was released.
Update II and IIA Instructions - 2 Final
-------
The Disclaimer and Chapter One at the front of Update I should also be photocopied
3 times and inserted at the front of volumes IB, 1C, and II in order to complete the
manual.
Note: Update I does not contain any changes to Volume II other than the
insertion of the Disclaimer and Chapter One, Also, some methods will have an
"A" after the method number. The "A" methods have been revised once.
iii. Finally, open the package labeled Final Updates II and HA. Final Updates II and IIA
should be a single package printed on white paper. Update II has the date "September
1994" in the lower right hand corner of each page. Update IIA (Method 4010) has the
date "August 1993" in the lower right hand corner of each page. This package contains
new methods and revised methods. In order to have a complete SW-846 manual, you
should insert the new methods and use the revised September 1994 methods to replace
older Third Edition and Final Update I methods that are out of date. Use the Table
of Contents (September 1994) at the front of Final Update II to identify the correct
location for each chapter and method.
The Abstract and Table of Contents at the front of Final Update II should also be
photocopied 3 times and inserted at the front of volumes IB, 1C, and II in order to
complete the manual.
Please Note:
• Update II does not contain any changes to Volume II other than the insertion of
the Abstract and Table of Contents.
• Some methods will have an "A" or a "B" after the method number. The "A"
methods have been revised once. The "B" methods have been revised twice.
• Methods 5100, 5110, and 9200A were included in the Proposed Update II
(November 1992) package but are not included in the Final Update II (September
1994) package. The final Federal Register Rule for Update II explains why these
methods were not finalized (promulgated).
Update II and IIA Instructions - 3 Final
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B. INSTRUCTIONS FOR PREVIOUS SUBSCRIBERS
i. Background Information: A number of SW-846 update packages have been released
to the public since the original Third Edition was released. The number and labels on
these packages can be confusing. The following table titled "A Brief History of the
SW-846 Third Edition and Updates" has been provided as an aid. Currently finalized
(promulgated) methods have been printed in bold. An individual or organization that
has held an SW-846 GPO subscription for several years may have received copies of
any or all of the following documents:
A BRIEF HISTORY OF THE SW-846 THIRD EDITION AND UPDATES
Package
Third Edition
Proposed Update 1
Final Update I
(Accidently Released)
Proposed Update II
(Accidently Released)
Final Update I
Proposed Update II
Proposed Update IIA"
(Available by request only.)
Final Update IIA' (Included
wir ". il Update II.)
Final update II
Date Listed on Methods
September 1986
December 1987
November 1990
November 1990
July 1992
November 1992
October 1992
August 1993
September 1994
Color of Paper
White
Green
White
Blue
White
Yellow
White
White
White
Status of Package
Finalized (Promulgated)
Obsolete
Obsolete! Never formally
finalized.
Obsolete! Never formally
proposed.
Finalized (Promulgated)
Obsolete
Obsolete
Finalized (Promulgated)
Finalized (Promulgated)
" Contains only Method 4010.
ii. In order to begin updating the manual it is important to establish exactly what is
currently contained in the manual that you have. If the manual has been properly
updated, the ONLY white pages in the document should be dat.v September 1986
(Third Edition) and July 1992 (Final Update I). Remove and discard (or archive) any
white pages from your manual that have any date other than September 1986 and July
1992.
There may also be yellow pages dated September 1992 (Proposed Update II) inserted
in the manual. Remove and discard all yellow pages or other colored pages (green or
blue) from the manual. Some individuals may have chosen to keep their copy of
Proposed Update II in a separate binder and removal will not be necessary.
Update fl and IIA
Instructions - 4
Final
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iii. Open the package labeled Final Updates II and IIA. Final Updates II and IIA should
be a single package printed on white paper. Update II has the date "September 1994"
in the lower right hand corner of each page. Update IIA (Method 4010) has the date
"August 1993" in the lower right hand corner of each page. This package contains new
methods and revised methods. In order to have a complete SW-846 manual, you
should insert the new methods and use the revised September 1994 methods to replace
older Third Edition and Final Update I methods that are out of date. Use the Table
of Contents (September 1994) at the front of Final Update II to identify the correct
location for each chapter and method.
The Abstract and Table of Contents at the front of Final Update II should also be
photocopied 3 times and inserted at the front of volumes IB, 1C, and II in order to
complete the manual.
Please Note:
• Update II does not contain any changes to Volume II other than the insertion of
the Abstract and Table of Contents,
• Some methods will have an "A" or a "B" after the method number. The "A"
methods have been revised once. The "B" methods have been revised twice.
• Methods 5100, 5110, and 9200A were included in the Proposed Update II
(November 1992) package but are not included in the Final Update II (September
1994) package. The final Federal Register Rule for Update II explains why these
methods were not finalized (promulgated).
Update II and IIA Instructions - 5 Final
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ABSTRACT
Test Methods for Evaluating Solid Waste, Physical/Chemical Methods (SW-846)
provides test procedures and guidance which are recommended for use in conducting
the evaluations and measurements needed to comply with the Resource Conservation
and Recovery Act (RCRA), Public Law 94-580, as amended. These methods are
approved by the U.S. Environmental Protection Agency for obtaining data to
satisfy the requirements of 40 CFR Parts 122 through 270 promulgated under RCRA,
as amended. This manual presents the state-of-the-art in routine analytical
tested adapted for the RCRA program. It contains procedures for field and
laboratory quality control, sampling, determining hazardous constituents in
wastes, determining the hazardous characteristics of wastes (toxicity,
ignitability, reactivity, and corrosivity), and for determining physical
properties of wastes. It also contains guidance on how to select appropriate
methods.
Several of the hazardous waste regulations under Subtitle C of RCRA require
that specific testing methods described in SW-846 be employed for certain
applications. Refer to 40 Code of Federal Regulations (CFR), Parts 260 through
270, for those specific requirements. Any reliable analytical method may be used
to meet other requirements under Subtitle C of RCRA.
ABSTRACT - 1 Revision 2
September 1994
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TABLE OF CONTENTS
VOLUME ONE
SECTION A
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS
PART I HETHODS FOR ANALYTES AND PROPERTIES
CHAPTER ONE - 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 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 - METALLIC 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 Flame Atomic Absorption
(FLAA) or Inductively Coupled Plasma (ICP) Spectroscopy
Method 3010A; Acid Digestion of Aqueous Samples and Extracts for Total
Metals for Analysis by Flame Atomic Absorption (FLAA) or
Inductively Coupled Plasma (ICP) Spectroscopy
Method 3015: Microwave Assisted Acid Digestion of Aqueous Samples ind
Extracts
CONTENTS - 1 Revision 2
September 1994
-------
Method 3020A:
Method 3040:
Method 3050A:
Method 3051:
Acid Digestion of Aqueous Samples and Extracts for Total
Metals for Analysis by Graphite Furnace Atomic
Absorption (6FAA) Spectroscopy
Dissolution Procedure for Oils, Greases, or Waxes
Acid Digestion of Sediments, Sludges, and Soils
Microwave Assisted Acid Digestion of Sediments, Sludges,
Soils, and Oils
3.3 Methods for Determination of Metals
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
6010A:
6020:
7000A:
7020:
7040:
7041:
7060A:
7061A:
7062:
7080A:
7081:
7090:
7091:
7130:
7131A:
7140:
7190:
7191:
7195:
7196A:
7197:
7198:
7200:
7201:
7210:
7211:
7380:
7381:
7420:
7421:
7430:
7450:
7460:
7461:
7470A:
7471A:
Method 7480:
Method 7481:
Method 7520:
Method 7550:
'• ^thod 7610:
Chod 7740:
Inductively Coupled PIasma-Atomic Emission Spectroscopy
Inductively Coupled Plasma - Mass Spectrometry
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)
Antimony (AA, Furnace Technique)
Arsenic (AA, Furnace Technique)
Arsenic (AA, Gaseous Hydride)
Antimony and Arsenic (AA, Borohydride Reduction)
Barium (AA, Direct Aspiration)
Barium (AA, Furnace Technique)
Beryl!iui (AA, Direct Aspiration)
Beryl!iui (AA, Furnace Technique)
Cadmium (AA, Direct Aspiration)
Cadmium (AA, Furnace Technique)
Calcium (AA, Direct Aspiration)
Chromium (AA, Direct Aspiration)
Chromium (AA, Furnace Technique)
Chromium, Hexavalent (Coprecipitation)
Chromium, Hexavalent (Colorimetric)
Chromium, Hexavalent (Che!at ion/Extract ion)
Chromium, Hexavalent (Differential Pulse Polarography)
Cobalt (AA, Direct Aspiration)
Cobalt (AA, Furnace Technique)
Copper (AA, Direct Aspiration)
Copper (AA, Furnace Technique)
Iron (AA, Direct Aspiration)
Iron (AA, Furnace Technique)
Lead (AA, Direct Aspiration)
Lead (AA, Furnace Technique)
Lithium (AA, Direct Aspiration)
Magnesium (AA, Direct Aspiration)
Manganese (AA, Direct Aspiration)
Manganese (AA, Furnace Technique)
Mercury in Liquid Waste (Manual Cold-Vapor Technique)
Mercury in Solid or Semisolid Waste (Manual Cold-Vapor
Technique)
Molybdenum (AA, Direct Aspiration)
Molybdenum (AA, Furnace Technique)
Nickel (AA, Direct Aspiration)
Osmium (AA, Direct Aspiration)
Potassium (AA, Direct Aspiration)
Selenium (AA, Furnace Technique)
CONTENTS - 2
Revision 2
September 1994
-------
Method 7741A: Selenium (AA, Gaseous Hydride)
Method 7742: Selenium (AA, Borohydride Reduction)
Method 7760A: Silver (AA, Direct Aspiration)
Method 7761: Silver (AA, Furnace Technique)
Method 7770: Sodium (AA, Direct Aspiration)
Method 7780; Strontium (AA, Direct Aspiration)
Method 7840: Thallium (AA, Direct Aspiration)
Method 7841: Thallium (AA, Furnace Technique)
Method 7870: Tin (AA, Direct Aspiration)
Method 7910: Vanadium (AA, Direct Aspiration)
Method 7911: Vanadium (AA, Furnace Technique)
Method 7950: Zinc (AA, Direct Aspiration)
Method 7951: Zinc (AA, Furnace Technique)
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). In
order to properly document the method used for analysis, the entire
method number including the suffix letter designation (e.g., A or B)
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 2
September 1994
-------
VOLUME ONE
SECTION 8
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
HETHOD INDEX 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
4.2.1 Extractions and Preparations
Method 3500A: Organic Extraction and Sample Preparation
Method 3510B: Separatory Funnel Liquid-Liquid Extraction
Method 3520B: Continuous Liquid-Liquid Extraction
Method 3540B: Soxhlet Extraction
Method 3S41: Automated Soxhlet Extraction
Method 3550A: Ultrasonic Extraction
Method 3580A; Haste Dilution
Method 5030A: Purge-and-Trap
Method 5040A: Analysis of Sorbent Cartridges from Volatile Organic
Sampling Train (VOST): Gas Chromatography/Mass
Spectrometry Technique
Method 5041: Protocol for Analysis of Sorbent Cartridges from
Volatile Organic Sampling Train (VOST): Wide-bore
Capillary Column Technique
Method 5100: Determination of the Volatile Organic Concentration of
Waste Samples
Method 5110: Determination of Organic Phase Vapor Pressure in Waste
Samples
4.2.2 Cleanup
Method 3600B: Cleanup
Method 3610A: Alumina Column Cleanup
CONTENTS - 4 Revision 2
September 1994
-------
Method 3611A:
Method
Method
Method
Method
Method
Method
3620A;
3630B;
3640A:
3650A:
3660A:
3665:
Alumina Column
Petroleum Wastes
Florisil Column Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Acid/Permanganate Cleanup
Cleanup and Separation of
4.3 Determination of Organic Analytes
4.3.1
Gas Chromatographic Methods
Method 8000A:
Method 801OB:
Method 8011:
Method 8015A:
Method 8020A:
Method 8021A:
Method 8030A:
Method 8031:
Method 8032:
Method 8040A:
Method 8060:
Method 8061:
Method 8070:
Method 8080A:
Method 8081:
Method 8090:
Method 8100:
Method 8110:
Method 8120A:
Method 8121:
Method 8140:
Method 8141A;
Method 8150B:
Method 8151:
Gas Chromatography
Halogenated Volatile Organics by Gas Chromatography
1,2-Dibromoethane and l»2-Dibromo-3-chloropropane by
Microextraction and Gas Chromatography
Nonhalogenated Volatile Organics by Gas Chromatography
Aromatic Volatile Organics by Gas Chromatography
Halogenated Volatiles by Gas Chromatography Using
Photoionization and Electrolytic Conductivity Detectors
in Series: Capillary Column Technique
Acrolein and Acrylonitrile by Gas Chromitography
Acrylonitrile by Gas Chromatography
Acrylamide by Gas Chromatography
Phenols by Gas Chromatography
Phthalate Esters
Phthalate Esters by Capillary Gas Chromatography with
Electron Capture Detection (GC/ECD)
Nitrosamines by Gas Chromatography
Organochlorine Pesticides and Polychlorinated Biphenyls
by Gas Chromatography
Organochlorine Pesticides and PCBs as Aroclors by Gas
Chromatography: Capillary Column Technique
Nitroaromatics and Cyclic Ketones
Polynuclear Aromatic Hydrocirbons
Haloethers by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography:
Capillary Column Technique
Organophosphorus Pesticides
Organophosphorus Compounds by Gas Chromatography:
Capillary Column Technique
Chlorinated Herbicides by Gas Chromatography
Chlorinated Herbicides by GC Using Methylation or
PentafluorobenzylationDerivatization: Capillary Column
Technique
CONTENTS - 5
Revision 2
September 1994
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4.3.2
Gas Chromatographic/Mass Spectroscopic Methods
Method 8240B:
Method 8250A:
Method 8260A:
Method 8270B:
Method 8280:
Appendix A:
Appendix B:
Method 8290:
Appendix A:
Gas
Volatile Organic Compounds by Gas Chromatography/Mass
Spectrometry (GC/MS)
Semivolatile Organic Compounds by
Chromatograph. 'Mass Spectroraetry (GC/MS)
Volatile Organic Compounds by Gas Chroraatography/Mass
Spectrometry (GC/MS): Capillary Column Technique
Semivolatile Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS): Capillary
Column Technique
The Analysis of Polychlorinated Dibenzo-p-Dioxins
Polychlorinated Dibenzofurans
Signal-to-No1se Determination Methods
Recommended Safety and Handling Procedures
PCDDs/PCDFs
Polychlorinated Dibenzodioxins (PCDDs)
Polychlorinated Dibenzofurans (PCDFs) by High-Resolution
Gas Chromatography/High-Resolution Mass Spectroraetry
(HRGC/HRMS)
Procedures for the Collection, Handling,
Analysis, and Reporting of Wipe Tests Performed
within the Laboratory
and
for
and
4.3.3
Method 8310:
Method 8315:
Appendix A:
Method 8316:
Method 8318:
Method 8321:
Method 8330:
Method 8331:
High Performance Liquid Chromatographic Methods
Polynuclear Aromatic Hydrocarbons
Determination of Carbonyl Compounds by High Performance
Liquid Chromatography (HPLC)
Recrystallization of 2,4-Dinitrophenylhydrazine
(DNPH)
Acrylamide, Acrylonitrile and Acrolein by High
Performance Liquid Chromatography (HPLC)
N-Methylcarbamates by High Performance Liquid
Chromatography (HPLC)
Solvent Extractable Non-Volatile Compounds by High
Performance Liquid Chromatography/Thermospray/Mass
Spectrometry (HPLC/TSP/MS) or Ultraviolet (UV) Detection
Nitroaromatics and Nitramines by High Performance Liquid
Chromatography (HPLC)
Tetrazene by Reverse Phase High Performance Liquid
Chromatography (HPLC)
4.3.4
Method 8410:
Fourier Transform Infrared Methods
Gas Chromatography/Fourier Transform Infrared (GC/FT-IR)
Spectrometry for Semi volatile Organics: Capillary
Column
CONTENTS - 6
Revision 2
September 1994
-------
4.4 Miscellaneous Screening Methods
Method 3810: Headspace
Method 3820: Hexadecane Extraction and Screening of Purgeable
Organics
Method 4010: Screening for Pentachlorophenol by Immunoassay
Method 8275: Thermal Chromatography/Mass Spectrometry (TC/MS) for
Screening Semi volatile Organic Compounds
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). In
order to properly document the method used for analysis, the entire
method number including the suffixletterdesignation (e.g., A or B)
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 2
September 1994
-------
VOLUME ONE
SECTION C
UV)
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 SOSO: Bomb Preparation Method for Solid Waste
Method 9010A: Total and Amenable Cyanide (Colorimetric, Manual)
Method 9012: Total and Amenable Cyanide (Colorimetric, Automated
Method 9013: Cyanide Extraction Procedure for Solids and Oils
Method 9020B: Total Organic Hal ides (TOX)
Method 9021: Purgeable Organic Hal ides (POX)
Method 9022: Total Organic Hal ides (TOX) by Neutron Activation
Analysis
Acid-Soluble and Acid-Insoluble Sulfides
Extractable Sulfides
Sulfate (Colorimetric, Automated,
Sulfate (Colorimetric, Automated,
II)
Method 9038: Sulfate (Turbidimetric)
Method 90S6: Determination of Inorganic Anions by Ion Chromatography
Method 9060: Total Organic Carbon
Method 906S: Phenolics (Spectrophotometric,
Distillation)
Phenolics (Col orimetric, Automated
Distillation)
Method 9067: Phenolics (Spectrophotometric, MBTH with Distillation)
Method 9070: Total Recoverable Oil & Grease (Gravimetric, Separatory
Funnel Extraction)
Method 9071A: Oil and firease Extraction Method for Sludge and Sediment
Samples
Method 9075: Test Method for Total Chlorine in New and Used Petroleum
Products by X-Ray Fluore-cence Spectrometry (XRF)
Method 9076: Test Method for Total Ch -ine in New and Used Petroleum
Products by Oxidative Combustion and Microcoulometry
Method 9030A:
Method 9031:
Method 903S:
Method 9036:
Method 9066:
Chioranilate)
Methylthymol Blue, AA
Manual 4-AAP with
4-AAP with
CONTENTS - 8
Revision 2
September 1994
-------
Method 9077:
Method A:
Method B:
Method C:
Method 9131;
Method 9132:
Method 9200;
Method 9250:
Method 9251:
Method 9252A:
Method 9253:
Method 9320:
CHAPTER SIX -- PROPERTIES
Method 1312:
Method 1320:
Method 1330A:
Method 9040A:
Method 9041A:
Method 90451:
Method 9050:
Method 9080:
Method 9081:
Method 9090A:
Method 9095:
Method 9096:
Appendix A:
Method 9100:
Method 9310:
Method 9315:
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
Nitrate
Chloride (Colorimetric, Automated Ferricyanide AAI)
Chloride (Colorimetric, Automated Ferricyanide AAII)
Chloride (Titrimetric, Mercuric Nitrate)
Chloride (Titrimetric, Silver Nitrate)
Radium-228
Synthetic Precipitation Leaching Procedure
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Electrometric Measurement
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 Herabrane Liners
Paint Filter Liquids Test
Liquid Release Test (LRT) Procedure
LRT Pre-Test
Saturated Hydraulic Conductivity, Saturated Leachate
Conductivity, and Intrinsic Permeability
Gross Alpha and Gross Beta
Alpha-Emitting Radium Isotopes
PART II CHARACTERISTICS
CHAPTER SEVEN -- 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
CONTENTS - 9
Revision 2
September 1994
-------
CHAPTER EIGHT -- METHODS FOR DETERMININGCHARACTERISTICS
8.1 Ignitability
Method 1010:
Method 1020A;
8.2 Corrosivity
Method 1110:
8.3
8.4
Pensky-Martens Closed-Cup Method for Determining
Ignilability
Setaflash Closed-Cup Method for Determining Ignitability
Corrosivity Toward Steel
Reactivity
Toxicity
Method 1310A:
Method 1311:
APPENDIX — COMPANY REFERENCES
Extraction Procedure (EP) Toxicity Test Method and
Structural Integrity Test
Toxicity Characteristic Leaching Procedure
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). In
order to properly document the method used for analysis, the entire
method number including the suffix letter designation (e.g., A or B)
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 2
September 1994
-------
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 -- SAMPLING PLAN
9.1 Design and Development
9.2 Implementation
CHAPTER TEN - SAMPLING HETHODS
Method 0010: Modified Method 5 Sampling Train
Appendix A: Preparation of XAD-2 Sorbent Resin
Appendix B; Total Chromatographable Organic Material Analysis
Method 0020; Source Assessment Sampling System (SASS)
Method 0030: Volatile Organic Sampling Train
PART IV MONITORING
CHAPTER ELEVEN -- GROUND MATER 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
CONTENTS - 11 Revision 2
September 1994
-------
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). In
order to properly document the method used for analysis, the entire
method number including the suffix 1 etter designation (e.g.f A or B)
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 2
September 1994
-------
-------
SH-846 METHOD STATUS TABLE
September 1994
NETH NO.
THIRD ED
DATED
9/86
0010
0020
0030
1010
1020
1110
1310
"
NETH NO.
FINAL
UPDATE I
DATED
7/92
"
** *"•
"** ™"
1020A
"
1310A
1311
NETH NO.
FINAL
UPDT. II
DATED
9/94
"
*•> mt
* "
"
"
1312
METHOD TITLE
Modified Method 5
Sampling Train
Source Assessment
Sampling System
(SASS)
Volatile Organic
Sampling Train
Pensky-Mirtens
Closed-Cup Method
for Determining
Ignitability
Setaflash Closed-Cup
Method for
Determining
Igni lability
Corrosivity Toward
Steel
Extraction Procedure
(EP) Toxicity Test
Method and
Structural Integrity
Test
Toxicity
Characteristic
Leaching Procedure
Synthetic
Precipitation
Leaching Procedure
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol I!
Chap 10
Vol II
Chap 10
Vol II
Chap 10
Vol 1C
Chap 8
Sec 8.1
Vol 1C
Chap 8
Sec 8.1
Vol 1C
Chap 8
Sec 8.2
Vol 1C
Chap 8
Sec 8.4
Vol 1C
Chap 8
Sec 8.4
Vol 1C
Chap 6
CURRENT
PROMUL-
GATED
METHOD
0010
Rev 0
9/86
0020
Rev 0
9/86
0030
Rev 0
9/86
1010
Rev 0
9/86
1020A
Rev 1
7/92
1110
Rev 0
9/86
1310A
Rev 1
7/92
1311
Rev 0
7/92
1312
Rev 0
9/94
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH MO.
THIRD ED
DATED
9/86
1320
1330
3005
3010
"" ""
3020
3040
3050
HETH NO.
FINAL
UPDATE I
DATED
7/92
"
1330A
3005A
3010A
4* -m
3020A
"" ""
3050A
METH NO.
FINAL
UPDT. II
DATED
9/94
"
"
3015
""" """
METHOD TITLE
Multiple Extraction
Procedure
Extraction Procedure
for Oily Wastes
Acid Digestion of
Waters for Total
Recoverable or
Dissolved Metals for
Analysis by FLAA or
ICP Spectroscopy
Acid Digestion of
Aqueous Samples and
Extracts for Total
Metals for Analysis
by FLAA or ICP
Spectroscopy
Microwave Assisted
Acid Digestion of
Aqueous Samples and
Extracts
Acid Digestion of
Aqueous Samples and
Extracts for Total
Metals for Analysis
by GFAA Spectroscopy
Dissolution
Procedure for Oils,
Greases, or Waxes
Acid Digestion of
Sediments, Sludges,
and Soils
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
Vol IA
Chap 3
Sec 3.2
CURRENT
PROMUL-
GATED
METHOD
1320
Rev 0
9/86
1330A
Rev 1
7/92
3005A
Rev 1
7/92
3010A
Rev 1
7/92
3015
Rev 0
9/94
3020A
Rev 1
7/92
3040
Rev 0
9/86
3050A
Rev 1
7/92
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
«K -m
3500
3510
3520
3540
** «
3550
3580
3600
METH NO.
FINAL
UPDATE I
DATED
7/92
** mm
3500A
3510A
3520A
3540A
*~ """
"
3580A
3600A
NETH NO.
FINAL
UPDT. II
DATED
9/94
3051
— »
3510B
3520B
3540B
3541
3550A
3600B
METHOD TITLE
Microwave Assisted
Acid Digestion of
Sediments, Sludges,
Soils, and Oils
Organic Extraction
and Sample
Preparation
Separatory Funnel
Liquid-Liquid
Extraction
Continuous Liquid-
Liquid Extraction
Soxhlet Extraction
Automated Soxhlet
Extraction
Ultrasonic Extrac-
tion
Waste Dilution
Cleanup
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.2
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4.2.2
CURRENT
PROMUL-
GATED
METHOD
3051
Rev 0
9/94
3500A
Rev 1
J7/92
3510B
Rev 2
9/94
3520B
Rev 2
9/94
3540B
Rev 2
9/94
3541
Rev 0
9/94
3550A
Rev 1
9/94
3580A
Rev 1
7/92
3600B
Rev 2
9/94
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
3610
3611
3620
3630
3640
3650
3660
«* *»
3810
METH NO.
FINAL
UPDATE I
DATED
7/92
3610A
361 1A
3620A
3630A
'"" '"*
3650A
3660A
METH NO.
FINAL
UPDT. II
DATED
9/94
«* «•>,
"" "™
•H *•>
3630B
3640A
™* ""
*. *.
3665
METHOD TITLE
Alumina Column
Cleanup
Alumina Column
Cleanup and
Separation of
Petrol eui Wastes
Florisil Column
Cleanup
Silica Gel Cleanup
Gel -Permeation
Cleanup
Acid-Base Partition
Cleanup
Sulfur Cleanup
Sulfuric
Acid/Permanganate
Cleanup
Headspace
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec
4.2.2
Vol IB
Chap 4
Sec 4.4
CURRENT
PROMUL-
GATED
METHOD
3610A
Rev 1
7/92
3611A
Rev 1
7/92
3620A
Rev 1
7/92
3630B
Rev 2
9/94
3640A
Rev 1
9/94
3650A
Rev 1
7/92
3660A
Rev 1
7/92
3665
Rev 0
9/94
3810
Rev 0
9/86
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETH NO.
THIRD ED
DATED
9/86
3820
5030
5040
«. i.
6010
NETH NO.
FINAL
UPDATI I
DATED
7/9Z
"
5030A
™" ™
601 OA
NETH NO.
FINAL
UPDT. II
DATED
9/94
"
4010
(Update
IIA,
dated
8/93)
*• **
5040A
5041
5050
"
NETHOD TITLE
Hexadecane
Extraction and
Screening of
Purgeable Organics
Screening for
Pentachl orophenol
by Immunoassay
Purge-and-Trap
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST): Gas
Ch romat ography/Has s
Spectrometry
Technique
Protocol for
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST) : Wide -bore
Capillary Column
Technique
Bomb Preparation
Hethod for Solid
Waste
Inductively Coupled
Plasma-Atomic
Emission
Spectroscopy
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec
4.2.1
Vol IB
Chap 4
Sec
4,2.1
Vol IB
Chap 4
Sec
4.2.1
Vol 1C
Chap 5
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
3820
Rev 0
9/86
4010
Rev 0
8/93
503 OA
Rev 1
7/92
5040A
Rev 1
9/94
5041
Rev 0
9/94
5050
Rev 0
9/94
6010A
Rev 1
7/92
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
"
7000
7020
7040
7041
7060
7061
<•* «•
7080
METH NO.
FINAL
UPDATE I
DATED
7/92
"
7000A
•H w.
W —
"™ ~"
"
7061A
«. «~
HETH NO.
FINAL
UPDT. II
DATED
9/94
6020
"
mm mm
— ~
"" ""
7060A
"
7062
7080A
METHOD TITLE
Inductively Coupled
Plasma - Mass
Spectrometry
Atomic Absorption
Methods
Aluminum (Atomic
Absorption, Direct
Aspiration)
Antimony (Atomic
Absorption, Direct
Aspiration)
Antimony (Atomic
Absorption, Furnace
Technique)
Arsenic (Atomic
Absorption, Furnace
Technique)
Arsenic (Atomic
Absorption, Gaseous
Hydride)
Antimony and Arsenic
(Atomic Absorption,
Borohydride
Reduction)
Barium (Atomic
Absorption, Direct
Aspiration)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
6020
Rev 0
9/94
7000A
Rev 1
7/92
7020
Rev 0
9/86
7040
Rev 0
9/86
7041
Rev 0
9/86
7060A
Rev 1
9/94
7061A
Rev 1
7/92
7062
Rev 0
9/94
7080A
Rev 1
9/94
-------
SH-846 METHOD STATUS TABLE (9/94), COKTINUED
KETH NO.
THIRD ED
DATED
9/86
"
7090
7091
7130
7131
7140
7190
7191
7195
HETH NO.
FINAL
UPDATE I
DATED
7/92
7081
"M "*
*" — •
*" *"
*"" """
**. _
™" ""
"™ ""*
"
HETH NO.
FINAL
UPDT. II
DATED
9/94
•m mm
•mm —
<** «••
"* ""
7131A
**• """
_ «
*"" ™*
METHOD TITLE
Barium (Atomic
Absorption, Furnace
Technique)
Beryllium {Atomic
Absorption, Direct
Aspiration)
Beryllium {Atomic
Absorption, Furnace
Technique)
Cadmium (Atomic
Absorption, Direct
Aspiration)
Cadmium (Atomic
Absorption, Furnace
Technique)
Calcium (Atomic
Absorption, Direct
Aspiration)
Chromium (Atomic
Absorption, Direct
Aspiration)
Chromium (Atomic
Absorption, Furnace
Technique)
Chromium, Hexavalent
(Coprecipitation)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3,3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3,3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7081
Rev 0
7/92
7090
Rev 0
9/86
7091
Rev 0
9/86
7130
Rev 0
9/86
7131A
Rev 1
9/94
7140
Rev 0
9/86
7190
Rev 0
9/86
7191
Rev 0
9/86
7195
Rev 0
9/86
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7196
7197
7198
7200
7201
7210
""" *"
7380
METH NO.
FINAL
UPDATE I
DATED
7/92
7196A
** ""
"
"
7211
mm «•
7381
HETH NO.
FINAL
UPDT, II
DATED
S/94
-— -»
*" *"
"
"
•* w
** *"
"
"*° "™"
"
METHOD TITLE
Chromium, Hexavalent
(Colorimetric)
Chromium, Hexavalent
(Chel at ion/Extrac-
tion)
Chromium, Hexavalent
(Differential Pulse
Polarography)
Cobalt (Atonic
Absorption, Direct
Aspiration)
Cobalt (Atonic
Absorption, Furnace
Technique)
Copper (Atomic
Absorption, Direct
Aspiration)
Copper (Atonic
Absorption, Furnace
Technique)
Iron (Atomic
Absorption, Direct
Aspiration)
Iron (Atomic
Absorption, Furnace
Technique)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7196A
Rev 1
7/92
7197
Rev 0
9/86
7198
Rev 0
9/86
7200
Rev 0
9/86
7201
Rev 0
9/86
7210
Rev 0
9/86
7211
Rev 0
7/92
7380
Rev 0
9/86
7381
Rev 0
7/92
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
7420
7421
™" "~
7450
7460
7470
7471
7480
HETH NO.
FINAL
UPDATE I
DATED
7/92
_ _•
•" **
7430
*" "**
»_ «
7461
™" ™"
""" "°*
"
METH NO.
FINAL
UPDT. II
DATED
9/94
** ™"
"" **
*"" **
_ _.
"
7470A
7471A
"
NETHOD TITLE
Lead {Atomic
Absorption, Direct
Aspiration)
Lead (Atomic
Absorption, Furnace
Technique)
Lithium (Atomic
Absorption, Direct
Aspiration)
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
Semi sol id Waste
(Manual Cold- Vapor
Technique)
Molybdenum (Atomic
Absorption, Direct
Aspiration)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3,3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7420
Rev 0
9/86
7421
Rev 0
9/86
7430
Rev 0
7/92
7450
Rev 0
9/86
7460
Rev 0
9/86
7461
Rev 0
7/92
7470A
Rev 1
9/94
7471A
Rev 1
9/94
7480
Rev 0
9/86
-------
SM-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO*
THIRD ED
DATED
9/86
7481
7520
7550
7610
7740
7741
«. —
7760
™ "
METH NO.
FINAL
UPDATE I
DATED
7/92
m* HP
"" "~
_ —
*" "
~ "•
H* «*•
7760A
7761
METH NO.
FINAL
UPDT. II
DATED
9/94
"
~" *"
™* "°*
*** "*"
<•» <•»
7741A
7742
"
^ ^
METHOD TITLE
Molybdenum {Atomic
Absorption, Furnace
Technique)
Nickel (Atomic
Absorption, Direct
Aspiration)
Osmium (Atomic
Absorption, Direct
Aspiration)
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)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol 1A
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7481
Rev 0
9/86
7520
Rev 0
9/86
7550
Rev 0
9/86
7610
Rev 0
9/86
7740
Rev 0
9/86
7741A
Rev 1
9/94
7742
Rev 0
9/94
7760A
Rev 1
7/92
7761
Rev 0
7/92
10
-------
SW-846 METHOD STATUS TABLE (9/94)t CONTINUED
HETH NO.
THIRD ED
DATED
9/86
7770
*** ***
7840
7841
7870
7910
7911
7950
"
HETH NO.
FINAL
UPDATE I
DATED
7/92
"
7780
** **•
"
"" ""
** *"*
7951
HETH NO.
FINAL
UPDT. II
DATED
9/94
™ —
™" ""*
** **•
"
*"* *"
"
METHOD TITLE
Sodium (Atomic
Absorption, Direct
Aspiration)
Strontium (Atomic
Absorption, Direct
Aspiration)
Thallium (Atomic
Absorption, Direct
Aspiration)
Thallium (Atomic
Absorption, Furnace
Technique)
Tin (Atomic
Absorption, Direct
Aspiration)
Vanadium (Atomic
Absorption, Direct
Aspiration)
Vanadium (Atomic
Absorption, Furnace
Technique)
Zinc (Atomic
Absorption, Direct
Aspiration)
Zinc (Atomic
Absorption, Furnace
Technique)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IA
Chap 3
Sec 3,3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
Vol IA
Chap 3
Sec 3.3
CURRENT
PROMUL-
GATED
METHOD
7770
Rev 0
9/86
7780
Rev 0
7/92
7840
Rev 0
9/86
7841
Rev 0
9/86
7870
Rev 0
9/86
7910
Rev 0
9/86
7911
Rev 0
9/86
7950
Rev 0
9/86
7951
Rev 0
7/92
11
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8000
8010
8015
8020
8030
METH NO.
FINAL
UPDATE I
DATED
7/92
8000A
8010A
8011
801 5A
mm, mm.
8021
8030A
METH NO.
FINAL
UPDT. II
DATED
9/94
** "*
8010B
8020A
8021A
"
8031
METHOD TITLE
Gas Chromatography
Halogenated Volatile
Organics by Gas
Chromatography
1 , 2-Di bromoethane
and l,2-Dibr0mo-3-
chloropropane by
Microextraction and
Gas Chroraatography
Nonhal ogenated
Volatile Organics by
Gas Chromatography
Aromatic Volatile
Organics by Gas
Chromatography
Halogenated
Volatiles by Gas
Chromatography Using
Photoionization and
Electrolytic
Conductivity
Detectors in Series:
Capillary Column
Technique
Acrolein and
Acrylonitrile by Gas
Chromatography
Acrylonitrile by Gas
Chromatography
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3,1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8000A
Rev 1
7/92
8010B
Rev 2
9/94
8011
Rev 0
7/92
8015A
Rev 1
7/92
8020A
Rev 1
9/94
8021A
Rev 1
9/94
8030A
Rev 1
7/92
8031
Rev 0
9/94
12
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
~ ™
8040
8060
» •*
8080
8090
METH NO.
FINAL
UPDATE I
DATED
7/92
~ —
8040A
«* «*
8070
~ ~
HETH NO.
FINAL
UPDT. II
DATED
9/94
8032
"
"
8061
"
8080A
8081
METHOD TITLE
Acryl amide by Gas
Chromatography
Phenols by Gas
Chromatography
Phthalate Esters
Phthalate Esters by
Capillary Gas
Chromatography with
Electron Capture
Detection (6C/ECD)
Nitros amines by Gas
Chromatography
Organochlorine Pes-
ticides and
Polychlorinated
Biphenyls by Gas
Chromatography
Organochlorine
Pesticides and PCBs
as Aroclors by Gas
Chromatography:
Capillary Column
Technique
Nitroaromatics and
Cyclic Ketones
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3,1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4,3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8032
Rev 0
9/94
8040A
Rev 1
7/92
8060
Rev 0
9/86
8061
Rev 0
9/94
8070
Rev 0
7/92
8080A
Rev 1
9/94
8081
Rev 0
9/94
8090
Rev 0
9/86
13
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8100
"" ""
8120
8140
8150
NETH NO.
FINAL
UPDATE I
DATED
7/92
*"* *"*
8110
w <«*
™ ™
8141
81 BOA
HETH NO.
FINAL
UPDT. II
DATED
9/94
"* """
"
8120A
8121
~* ™
8141A
81506
8151
METHOD TITLE
Polynuclear Aromatic
Hydrocarbons
Haloethers by Gas
Chroiatography
Chlorinated
Hydrocarbons by Gas
Chromatography
Chlorinated
Hydrocarbons by Gas
Chromatography:
Capillary Column
Technique
Organophosphorus
Pesticides
Organophosphorus
Compounds by Gas
Chromatography:
Capillary Column
Technique
Chlorinated
Herbicides by Gas
Chromatography
Chlorinated
Herbicides by GC
Using Methyl at ion or
Ptntaf 1 uorobenzyl -
atlon Derivati-
zation: Capillary
Column Technique
SN-S46
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4,3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
Vol IB
Chap 4
Sec
4.3.1
CURRENT
PROMUL-
GATED
METHOD
8100
Rev 0
9/86
8110
Rev 0
7/92
8120A
Rev 1
9/94
8121
Rev 0
9/94
8140
Rev 0
9/86
8141A
Rev 1
9/94
8150B
Rev 2
9/94
8151
Rev 0
9/94
14
-------
SH-646 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8240
8250
8270
8280
HETH NO.
FINAL
UPDATE I
DATED
7/92
8240A
8260
8270A
METH NO.
FINAL
UPDT. II
DATED
9/94
8240B
8250A
8260A
8270B
8275
METHOD TITLE
Volatile Organic
Compounds by Gas
Chromatography/Mass
Spectrometry {GC/MS)
Semi volatile Organic
Compounds
by Gas
Chromatography/Mass
Spectroraetry { GC/MS }
Volatile Organic
Compounds by Gas
Chromatography/Mass
Spectroraetry
(GC/MS): Capillary
Column Technique
Serai volatile Organic
Compounds by Gas
Chroraatography/Mass
Spectroraetry
(GC/MS): Capillary
Column Technique
Thermal
Chromatography/Mass
Spectrometry (TC/MS)
for Screening
Serai volatile Organic
Compounds
The Analysis of
Polychlorinated
Dibenzo-p-Dioxins
and Polychlorinated
Dibenzofurans
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec 4.4
Vol IB
Chap 4
Sec
4.3.2
CURRENT
PROMUL-
GATED
METHOD
8240B
Rev 2
9/94
8250A
Rev 1
9/94
8260A
Rev 1
9/94
8270B
Rev 2
9/94
8275
Rev 0
9/94
8280
Rev 0
9/86
15
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
NETHNO.
THIRD ED
DATED
9/86
8310
"
METH NO.
FINAL
UPDATE I
DATED
7/92
«* «*
METH NO.
FINAL
UPDT, II
DATED
9/94
8290
mm
8315
8316
8318
METHOD TITLE
Polychlorinated
Dibenzod toxins
(PCDDs) and
Polyehlorinated
Dibenzofurans
(PCDFs) by High-
Resolution Gas
Chromatography/HI gh-
Resolution Mass
Spectrometry
(HRGC/HRMS)
Polynuclear Aromatic
Hydrocarbons
Determination of
Carbonyl Compounds
by High Performance
Liquid
Chromatography
(HPLC)
Acryl amide,
Acrylonitrile and
Acrolein by High
Performance Liquid
Chrotnatography
(HPLC)
N-Methyl carbamates
by High Performance
Liquid Chroma-
tography (HPLC)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.2
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
CURRENT
PROMUL-
GATED
METHOD
8290
Rev 0
9/94
8310
Rev 0
9/86
8315
Rev 0
9/94
8316
Rev 0
9/94
8318
Rev 0
9/94
16
-------
SH-846 METHOD STATUS TABLE (9/94)f CONTINUED
HETH NO.
THIRD ED
DATED
9/86
9010
9012
METH NO.
FINAL
UPDATE I
DATED
7/92
9010A
HETH NO.
FINAL
UPDT. II
DATED
9/94
8321
8330
8331
8410
"
METHOD TITLE
Solvent Extractable
Non-Volatile
Compounds by High
Performance Liquid
Chromatography/Ther-
mo spray/Mass
Spectrometry
(HPLC/TSP/MS) or
Ultraviolet (UV)
Detection
Nitroaromatics and
Nitramines by High
Performance Liquid
Chroraatography
(HPLC)
Tetrazene by Reverse
Phase High
Performance Liquid
Chromatography
(HPLC)
Gas Chroroa-
tography/Fouri er
Transform Infrared
(EC/FT- IR) Spec-
trometry for
Semi volatile
Organ ics: Capillary
Column
Total and Amenable
Cyanide
(Colorimetric,
Manual)
Total and Amenable
Cyanide
(Colorimetric,
Automated UV)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.3
Vol IB
Chap 4
Sec
4.3.4
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
8321
Rev 0
9/94
8330
Rev 0
9/94
8331
Rev 0
9/94
8410
Rev 0
9/94
9010A
Rev 1
7/92
9012
Rev 0
9/86
17
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
«H *»
9020
mm w
9022
9030
"* ™*
9035
9036
9038
METH NO.
FINAL
UPDATE I
DATED
7/92
9013
9020A
9021
9030A
9031
•V K
METH NO.
FINAL
UPDT. II
DATED
9/94
*"" *"
9020B
•» *»
"
_ _
~ ~
« »
METHOD TITLE
Cyanide Extraction
Procedure for Solids
and Oils
Total Organic
Hal ides (TOX)
Purgeable Organic
Hal ides (POX)
Total Organic
Hal ides (TOX) by
Neutron Activation
Analysis
Acid-Soluble and
Acid- Insoluble
Sul fides
Extractable Syl fides
Sul fate
{Colorimetric,
Automated ,
Chi orani late)
Sul fate
(Colorimetric,
Automated,
Methyl thymol Blue,
AA II)
Sul fate
(Turbidimetric)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
9013
Rev 0
7/92
9020B
Rev 2
9/94
9021
Rev 0
7/92
9022
Rev 0
9/86
9030A
Rev 1
7/92
9031
Rev 0
7/92
9035
Rev 0
9/86
9036
Rev 0
9/86
9038
Rev 0
9/86
18
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9040
9041
9045
9050
_ „. ,
9060
9065
9066
9067
METH NO.
FINAL
UPDATE I
DATED
7/92
"
9041A
9045A
"
un *
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH HO.
THIRD ED
DATED
9/86
9070
9071
9080
9081
METH NO.
FINAL
UPDATE I
DATED
7/§2
"
"
METH NO.
FINAL
UPDT. II
DATED
9/§4
9071A
9075
9076
9077
"
"
METHOD TITLE
Total Recoverable
Oil & Grease
(Gravimetric,
Separatory Funnel
Extraction)
Oil and Grease
Extraction Method
for Sludge and
Sediment
Sampl es
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 Oxi dative
Combustion and
MicrocouTometry
Test Methods for
Total Chlorine in
New and Used
Petroleum Products
(Field Test Kit
Methods)
Cit ion -Exchange
Capacity of Soils
(tenon i urn Acetate)
Cat ion -Exchange
Capacity of Soils
(Sodium Acetate)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 6
Vol 1C
Chap 6
CURRENT
PROMUL-
GATED
METHOD
9070
t
Rev 0
9/86
9071A
Rev 1
9/94
9075
Rev 0
9/94
9076
Rev 0
9/94
9077
Rev 0
9/94
9080
Rev 0
9/86
9081
Rev 0
9/86
20
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9090
9095
~ ™
9100
9131
9132
9200
9250
9251
METH NO.
FINAL
UPDATE I
DATED
7/92
9090A
— —
mm —
_ <•
™* "™*
"" "
* *°
METH NO.
FINAL
UPDT. II
DATED
9/94
"
"* "™
9096
~ ~
"
_ — .
*** """
METHOD TITLE
Compatibility Test
for Wastes and
Membrane Liners
Paint Filter Liquids
Test
Liquid Release Test
(LRT) Procedure
Saturated Hydraulic
Conductivity,
Saturated Leachate
Conductivity, and
Intrinsic
Permeability
Total Col i form:
Multiple Tube
Fermentation
Technique
Total Col i form:
Membrane Filter
Technique
Nitrate
Chloride
(Colorimetric,
Automated
Ferri cyanide AAI)
Chloride
(Coloriraetrie,
Automated
Ferri cyanide AAI I)
SH-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 5
.Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 5
CURRENT
PROMUL-
GATED
METHOD
9090A
Rev 1
7/92
9095
Rev 0
9/86
9096
Rev 0
9/94
9100
Rev 0
9/86
9131
Rev 0
9/86
9132
Rev 0
9/86
9200
Rev 0
9/86
9250
Rev 0
9/86
9251
Rev 0
9/86
21
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9252
™" "*
9310
9315
9320
HCN Test
Method
H2S Test
Method
KETH NO.
FINAL
UPDATE I
DATED
7/92
_ M
*" ""
*** **
** —
_ ^,
HCN Test
Method
H2S Test
Method
HETH NO.
FINAL
UPDT. II
DATED
9/94
9252A
9253
*"* **"
mm «•
*"" ""
HCN Test
Method
H2S Test
Method
METHOD TITLE
Chloride
(Titrimetric,
Mercuric Nitrate)
Chloride
(Titrimetric, Silver
Nitrate)
Gross Alpha and
Gross Beta
Alpha- Emitting
Radium Isotopes
Radium- 2 28
Test Method to
Determine Hydrogen
Cyanide Released
from Wastes
Test Method to
Determine Hydrogen
Sulfide Released
from Wastes
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 5
Vol 1C
Chap 5
Vol 1C
Chap 6
Vol 1C
Chap 6
Vol 1C
Chap 5
Vol 1C
Chap 7
Sec 7.3
Vol 1C
Chap 7
Sec 7.3
CURRENT
PROMUL-
GATED
METHOD
9252A
Rev 1
9/94
9213
Rev 0
9/94
9310
Rev 0
9/86
9315
Rev 0
9/86
9320
Rev 0
9/86
Guidance
Method
Only
Guidance
Method
Only
22
\
-------
PREFACE AND OVERVIEW
PURPOSE OF THE MANUAL
Test Methods for Evaluating Solid Waste (SW-846) 1s Intended to provide a
unified, up-to-date source of Information on sampling and analysis related to
compliance with RCRA regulations. It brings together Into one reference all
sampling and testing methodology approved by the Office of Solid Waste for use
1n Implementing the RCRA regulatory program. The manual provides methodology
for collecting and testing representative samples of waste and other materials
to be monitored. Aspects of sampling and testing covered 1n SW-846 include
quality control, sampling plan development and Implementation, analysis of
Inorganic and organic constituents, the estimation of Intrinsic physical
properties, and the appraisal of waste characteristics.
The procedures described 1n this manual are meant to be comprehensive and
detailed, coupled with the realization that the problems encountered 1n
sampling and analytical situations require a certain amount of flexibility.
The solutions to these problems will depend, in part, on the skill, training,
and experience of the analyst. For some situations, it 1s possible to use
this manual 1n rote fashion. In other situations, 1t will require a
combination of technical abilities, using the manual as guidance rather than
in a step-by-step, word-by-word fashion. Although this puts an extra burden
on the user, 1t 1s unavoidable because of the variety of sampling and
analytical conditions found with hazardous wastes.
ORGANIZATION AND FORMAT
This manual 1s divided into two volumes. Volume I focuses on laboratory
activities and 1s divided for convenience Into three sections. Volume IA
deals with quality control, selection of appropriate test methods, and
analytical methods for metallic species. Volume IB consists of methods for
organic analytes. Volume 1C includes a variety of test methods for
miscellaneous analytes and properties for use 1n evaluating the waste
characteristics. Volume II deals with sample acquisition and includes quality
control, sampling plan design and implementation, and field sampling methods.
Included for the convenience of sampling personnel are discusssions of the
ground water, land treatment, and Incineration monitoring regulations.
Volume I begins with an overview of the quality control precedures to be
imposed upon the sampling and analytical methods. The quality control chapter
(Chapter One) and the methods chapters are Interdependent. The analytical
procedures cannot be used without a thorough understanding of the quality
control requirements and the means to implement them. This understanding can
be achieved only be reviewing Chapter One and the analytical methods together.
It is expected that Individual laboratories, using SW-846 as the reference
PREFACE - 1
Revision
Date September 1986
-------
source, will select appropriate methods and develop a standard operating'
procedure (SOP) to be followed by the laboratory. The SOP should Incorporate
the pertinent Information from this manual adopted to the specific needs and
circumstances of the Individual laboratory as well as to the materials to be
evaluated.
The method selection chapter (Chapter Two) presents a comprehensive
discussion of the application of these methods to various matrices in the
determination of groups of analytes or specific analytes. It aids the chemist
1n constructing the correct analytical method from the array of procedures
which may cover the matrix/analyte/concentration combination of interests.
The section discusses the objective of the testing program and Its
relationship to the choice of an analytical method. Flow charts are presented
along with tables to guide in the selection of the correct analytical
procedures to form the appropriate method.
The analytical methods are separated Into distinct procedures describing
specific, independent analytical operations. These Include extraction,
digestion, cleanup, and determination. This format allows Unking of the
various steps 1n the analysis according to: the type of sample (e.g., water,
soil, sludge, still bottom),' analytes(s) of interest; needed sensitivity; and
available analytical instrumentation. The chapters describing Miscellaneous
Test Methods and Properties, however, give complete methods which are not
amenable to such segmentation to form discrete procedures.
The Introductory material at the beginning of each section containing
analytical procedures presents information on sample handling and
preservation, safety, and sample preparation.
Part II of Volume I (Chapters Seven and Eight) describes the
characteristics of a waste. Sections following the regulatory descriptions
contain the methods used to determine if the waste 1s hazardous because it
exhibits a particular characteristic.
Volume II gives background Information on statistical and nonstatistical
aspects of sampling. It also presents practical sampling techniques
appropriate for situations presenting a variety of physical conditions.
A discussion of the regulatory requirements with respect to several
monitoring categories is also given 1n this volume. These include ground
water monitoring, land treatment, and incineration. The purpose of this
guidance 1s to orient the user to the objective of the analysis, and to assist
In developing data quality objectives, sampling plans, and laboratory SOP's.
Significant interferences, or other problems, may be encountered with
certain samples. In these situations, the analyst 1s advised to contact the
Chief, Methods Section (WH-562B) Technical Assessment Branch, Office of Solid
Waste, US EPA, Washington, DC 20460 (202-382-4761) for assistance. The
manual 1s Intended to serve all those with a need to evaluate solid waste.
Your comments, corrections, suggestions, and questions concerning any material
contained in, or omitted from, this manual will be gratefully appreciated.
Please direct your comments to the above address.
PREFACE - 2
Revision 0
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
Method Number,
Third Edition
0010
0020
0030
1010
1020
1110
1310
1320
1330
3005
3010
3020
3040
3050
3500
3510
3520
3540
3550
3580
3600
3610
3611
3620
3630
3640
3650
3660
3810
3820
5030
5040
6010
7000
7020
Chapter Number,
Third Edition
Ten
Ten
Ten
Eight (8.1)
Eight (8.1)
Eight (8.2)
Eight (8.4)
Six
Six
Three
Three
Three
Three
Three
Four (4.2.1)
Method Number,
Current Revision
(4.2.1)
.2.1)
Four (4.2.2)
Four (4.2.2
Four (4.2.2
Four (4.2.2
Four (4.2.2)
Four (4.2.2)
Four (4.2.2)
Four (4.2.2)
Four (4.4)
Four (4.4)
Four (4,
Four (4,
Three
Three
Three
*ll
.1)
Second Edition
0010
0020
0030
1010
1020
1110
1310
1320
1330
3005
3010
3020
3040
3050
None (new method)
3510
3520
3540
3550
None (new method)
None (new method)
None (new method)
3570
None (new method)
None (new method)
None (new method)
None (new method)
None (new method)
5020
None (new method)
5030
3720
6010
7000
7020
Number
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 1
Revision 0
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
(Continued)
Method Number,
Third Edition
Chapter Number,
Third Edition
Method Number,
Second Edition
Current Revision
Number
7040
7041
7060
7061
7080
7090
7091
7130
7131
7140
7190
7191
7195
7196
7197
7198
7200
7201
7210
7380
7420
7421
7450
7460
7470
7471
7480
7481
7520
7550
7610
7740
7741
7760
7770
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
7040
7041
7060
7061
7080
7090
7091
7130
7131
7140
7190
7191
7195
7196
7197
7198
7200
7201
7210
7380
7420
7421
7450
7460
7470
7471
7480
7481
7520
7550
7610
7740
7741
7760
7770
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 2
Revision p
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
(Continued)
Method Number,
Third Edition
7840
7841
7870
7910
7911
7950
8000
8010
8015
8020
8030
8040
8060
8080
8090
8100
8120
8140
8150
8240
8250
8270
8280
8310
9010
9020
9022
9030
9035
9036
9038
9040
9041
9045
9050
ChapterNumber,
Third Edition
Three
Three
Three
Three
Three
Three
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Method Number,
Current Revision
Four
Four
Four
(4.3
4.3
4.3
.1)
.1)
Four (4.3.1
Four (4.3.2)
Four (4
Four (4
Four (4
Four (4
Five
Five
Five
Five
Five
Five
Five
Six
Six
Six
Six
.3.2)
.3.2)
.3.2)
.3.3)
Second Edition
7840
7841
7870
7910
7911
7950
None (new method)
8010
8015
8020
8030
8040
8060
8080
8090
8100
8120
8140
8150
8240
8250
8270
None (new method)
8310
9010
9020
9022
9030
9035
9036
9038
9040
9041
9045
9050
Number
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 3
Revision 0
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
(Continued)
Method Number,
Third Edition
Chapter Number,
Third Edition
Method Number,
Second Edition
Current Revision
9060 Five
,9065 Five
-9066 Five
9067 Five
9070 Five
9071 Five
9080 Six
9081 Six
9090 Six
9095 Six
9100 Six
9131 Five
9132 Five
9200 Five
9250 Five
9251 Five
9252 Five
9310 Six
9315 Six
9320 Five
HCN Test Method Seven
H2S Test Method Seven
9060
9065
9066
9067
9070
9071
9080
9081
9090
9095
9100
9131
9132
9200
9250
9251
9252
9310
9315
9320
HCN Test Method
H2S Test Method
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 4
Revision 0_
Date September
1986
-------
CHAPTER ONE
TABLE OF CONTENTS
Section
1.0
2.0
3.0
INTRODUCTION
QA PROJECT PLAN
2.1 DATA QUALITY OBJECTIVES
2.2 PROJECT OBJECTIVES . .
2.3 SAMPLE COLLECTION , . . . .
2.4 ANALYSIS AND TESTING
2.5 QUALITY CONTROL . . .
2.6 PROJECT DOCUMENTATION .........
2.7 ORGANIZATION PERFORMING FIELD OR LABORATORY
OPERATIONS . .
2.7.1 Performance Evaluation
2.7.2 Internal Assessment by QA Function
2.7.3 External Assessment .
2.7.4 On-Site Evaluation
2.7.4.1 Field Activities
2.7.4.2 Laboratory Activities
2.7.5 QA Reports .......
FIELD OPERATIONS
3.1 FIELD LOGISTICS
3.2 EQUIPMENT/INSTRUMENTATION
3.3 OPERATING PROCEDURES
3.3.1 Sample Management ........
3.3.2 Reagent/Standard Preparation . .
3.3.3 Decontamination
3.3.4 Sample Collection
3.3.5 Field Measurements .
3.3.6 Equipment Calibration And Maintenance . . . .
3.3.7 Corrective Action .
3.3.8 Data Reduction and Validation ........
3.3.9 Reporting
3.3.10 Records Management ...
3.3.11 Waste Disposal .
3.4 FIELD QA AND QC REQUIREMENTS
3.4.1 Control Samples
3.4.2 Acceptance Criteria
3.4.3 Deviations . .
3.4.4 Corrective Action . .
3.4.5 Data Handling ....
3.5 QUALITY ASSURANCE REVIEW
3.6 FIELD RECORDS
Paae
.... 1
.... 1
.... 2
.... 2
.... 3
.... 3
.... 3
.... 3
.... 4
.... 5
.... 5
.... 5
.... 5
.... 5
.... 6
.... 7
.... 8
.... 8
.... 9
.... 9
.... 9
.... 9
.... 9
.... 10
.... 10
.... 10
.... 10
.... 11
.... 11
.... 11
.... 11
.... 11
.... 11
.... 12
.... 12
.... 12
.... 12
.... 13
.... 13
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TABLE OF CONTENTS
(continued)
Section Page
4.0 LABORATORY OPERATIONS 14
4.1 FACILITIES 14
4.2 EQUIPMENT/INSTRUMENTATION .................. 15
4.3 OPERATING PROCEDURES 15
4.3.1 Sample Management 16
4.3.2 Reagent/Standard Preparation 16
4.3.3 General Laboratory Techniques 16
4.3.4 Test Methods 16
4.3.1 Equipment Calibration and Maintenance 17
4.3.6 QC 17
4.3.7 Corrective Action 17
4.3.8 Data Reduction and Validation 18
4.3.9 Reporting . 18
4.3.10 Records Management 18
4.3.11 Waste Disposal 18
4.4 LABORATORY QA AND QC PROCEDURES . 18
4.4.1 Method Proficiency 18
4.4.2 Control Limits 19
4.4.3 Laboratory Control Procedures . . 19
4.4.4 Deviations 20
4.4.5 Corrective Action 20
4.4.6 Data Handling 20
4.5 QUALITY ASSURANCE REVIEW . 21
4.6 LABORATORY RECORDS 21
5.0 DEFINITIONS 23
6.0 REFERENCES . ......... 29
INDEX 30
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CHAPTER ONE
QUALITY CONTROL
1.0 INTRODUCTION
It is the goal of the U.S. Environmental Protection Agency's (EPA's)
quality assurance (QA) program to ensure that all data be scientifically valid,
defensible, and of known precision and accuracy. The data should be of
sufficient known quality to withstand scientific and legal challenge relative to
the use for which the data are obtained. The QA program is management's tool for
achieving this goal.
For RCRA analyses, the recommended minimum requirements for a QA program
and the associated quality control (QC) procedures are provided in this chapter.
The data acquired from QC procedures are used to estimate the quality of
analytical data, to determine the need for corrective action in response to
identified deficiencies, and to interpret results after corrective action
procedures are implemented. Method-specific QC procedures are incorporated in
the individual methods since they are not applied universally.
A total program to generate data of acceptable quality should include both
a QA component, which encompasses the management procedures and controls, as well
as an operational day-to-day QC component. This chapter defines fundamental
elements of such a data collection program. Data collection efforts involve:
1. design of a project plan to achieve the data quality objectives
(DQOs);
2. implementation of the project plan; and
3. assessment of the data to determine if the DQOs are met.
The project plan may be a sampling and analysis plan or a waste analysis plan if
it covers the QA/QC goals of the Chapter, or it may be a Quality Assurance
Project Plan as described later in this chapter.
This chapter identifies the minimal QC components that should be used in
the performance of sampling and analyses, including the QC information which
should be documented. Guidance is provided to construct QA programs for field
and laboratory work conducted in support of the RCRA program.
2.0 QA PROJECT PLAN
It is recommended that all projects which generate environment-related data
in support of RCRA have a QA Project Plan (QAPjP) or equivalent. In some
instances, a sampling and analysis plan or a waste analysis plan may be
equivalent if it covers all of the QA/QC goals outlined in this chapter. In
addition, a separate QAPjP need not be prepared for routine analyses or
activities where the procedures to be followed are described in a Standard
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Operating Procedures manual or similar document and include the elements of a
QAPjP. These documents should be available and referenced in the documentation
and/or records for the analysis activities. The term "QAPjP" in this chapter
refers to any of these QA/QC documents.
The QAPjP should detail the QA/QC goals and protocols for a specific data
collection activity. The QAPjP sets forth a plan for sampling and analysis
activities that will generate data of a quality commensurate with their intended
use. QAPjP elements should include a description of the project and its
objectives; a statement of the DQOs of the project; identification of those in-
volved in the data collection and their responsibilities and authorities;
reference to (or inclusion of) the specific sample collection and analysis
procedures that will be followed for all aspects of the project; enumeration of
QC procedures to be followed; and descriptions of all project documentation.
Additional elements should be included in the QAPjP if needed to address all
quality related aspects of the data collection project. Elements should be
omitted only when they are inappropriate for the project or when absence of those
elements will not affect the quality of data obtained for the project (see
reference 1).
The role and importance of DQOs and project documentation are discussed
below in Sections 2.1 through 2,6. Management and organization play a critical
role In determining the effectiveness of a QA/QC program and ensuring that all
required procedures are followed. Section 2.7 discusses the elements of an
organization's QA program that have been found to ensure an effective program.
Field operations and laboratory operations (along with applicable QC procedures)
are discussed in Sections 3 and 4, respectively.
2.1 DATA QUALITY OBJECTIVES
Data quality objectives (DQOs) for the data collection activity describe
the overall level of uncertainty that a decision-maker is willing to accept in
results derived from environmental data. This uncertainty is used to specify the
quality of the measurement data required, usually in terms of objectives for
precision, bias, representativeness, comparability and completeness. The DQOs
should be defined prior to the initiation of the field and laboratory work. The
field and laboratory organizations performing the work should be aware of the
DQOs so that their personnel may make informed decisions during the course of the
project to attain those DQOs. Hore detailed information on DQOs is available
from the U.S. EPA Quality Assurance Management Staff (QAMS) (see references 2 and
4).
2.2 PROJECT OBJECTIVES
A statement of the project objectives and how the objectives are to be
attained should be concisely stated and sufficiently detailed to permit clear
understanding by all parties involved in the data collection effort. This
includes a statement of what problem is to be solved and the information required
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41
in the process. It also includes appropriate statements of the DQOs (i.e., the
acceptable level of uncertainty in the information).
2.3 SAMPLE COLLECTION
Sampling procedures, locations, equipment, and sample preservation and
handling requirements should be specified in the QAPjP. Further details on
quality assurance procedures for field operations are described in Section 3 of
this chapter. The OSW is developing policies and procedures for sampling In a
planned revision of Chapter Nine of this manual. Specific procedures for
groundwater sampling are provided in Chapter Eleven of this manual.
2.4 ANALYSIS AND TESTING
Analytes and properties of concern, analytical and testing procedures to
be employed, required detection limits, and requirements for precision and bias
should be specified. All applicable regulatory requirements and the project DQOs
should be considered when developing the specifications. Further details on the
procedures for analytical operations are described in Section 4 of this chapter.
2.5 QUALITY CONTROL
The quality assurance program should address both field and laboratory
activities. Quality control procedures should be specified for estimating the
precision and bias of the data. Recommended minimum requirements for QC samples
have been established by EPA and should be met in order to satisfy recommended
minimum criteria for acceptable data quality. Further details on procedures for
field and laboratory operations are described in Sections 3 and 4, respectively,
of this chapter.
2.6 PROJECT DOCUMENTATION
Documents should be prepared and maintained in conjunction with the data
collection effort. Project documentation should be sufficient to allow review
of all aspects of the work being performed. The QAPjP discussed in Sections 3
and 4 is one important document that should be maintained.
The length of storage time for project records should comply with
regulatory requirements, organizational policy, or project requirements,
whichever is more stringent. It is recommended that documentation be stored for
three years from submission of the project final report.
Documentation should be secured in a facility that adequately
addresses/minimizes its deterioration for the length of time that it is to be
retained. A system allowing for the expedient retrieval of information should
exist.
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Access to archived information should be controlled to maintain the
integrity of the data. Procedures should be developed to identify those
individuals with access to the data.
2.7 ORGANIZATION PERFORMING FIELD OR LABORATORY OPERATIONS
Proper design and structure of the organization facilitates effective and
efficient transfer of information and helps to prevent important procedures from
being overlooked.
The organizational structure, functional responsibilities, levels of
authority, job descriptions, and lines of communication for all project
activities should be established and documented. One person may cover more than
one organizational function. Each project participant should have a clear
understanding of his or her duties and responsibilities and the relationship of
those responsibilities to the overall data collection effort.
The management of each organization participating in a project involving
data collection activities should establish that organization's operational and
QA policies. This information should be documented in the QAPjP. The management
should ensure that (1) the appropriate methodologies are followed as documented
in the QAPjPs; (2) personnel clearly understand their duties and
responsibilities; (3) each staff member has access to appropriate project
documents; (4) any deviations from the QAPjP are communicated to the project
management and documented; and (5) communication occurs between the field,
laboratory, and project management, as specified in the QAPjP. In addition, each
organization should ensure that their activities do not increase the risk to
humans or the environment at or about the project location. Certain projects may
require specific policies or a Health and Safety Plan to provide this assurance.
The management of the participating field or laboratory organization should
establish personnel qualifications and training requirements for the project.
Each person participating in the project should have the education, training,
technical knowledge, and experience, or a combination thereof, to enable that
individual to perform assigned functions. Training should be provided for each
staff member as necessary to perform their functions properly. Personnel
qualifications should be documented in terms of education, experience, and
training, and periodically reviewed to ensure adequacy to current
responsibilities.
Each participating field organization or laboratory organization should
have a designated QA function (i.e., a team or individual trained in QA) to
monitor operations to ensure that the equipment, personnel, activities,
procedures, and documentation conform with the QAPjP. To the extent possible,
the QA monitoring function should be entirely separate from, and independent of,
personnel engaged in the work being monitored. The QA function should be
responsible for the QA review.
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2.7.1 Performance Eva!nation
Performance evaluation studies are used to measure the performance of the
laboratory on unknown samples. Performance evaluation samples are typically
submitted to the laboratory as blind samples by an independent outside source.
The results are compared to predetermined acceptance limits. Performance
evaluation samples can also be submitted to the laboratory as part of the QA
function during internal assessment of laboratory performance. Records of all
performance evaluation studies should be maintained by the laboratory. Problems
identified through participation in performance evaluation studies should be
immediately investigated and corrected.
2.7.2 Internal Assessment by QA Function
Personnel performing field and laboratory activities are responsible for
continually monitoring Individual compliance with the QAPjP. The QA function
should review procedures, results and calculations to determine compliance with
the QAPjP. The results of this internal assessment should be reported to
management with requirements for a plan to correct observed deficiencies.
2.7.3 External Assessment
The field and laboratory activities may be reviewed by personnel external
to the organization. Such an assessment is an extremely valuable method for
identifying overlooked problems. The results of the external assessment should
be submitted to management with requirements for a plan to correct observed
deficiencies.
2.7.4 On-Site Evaluation
On-site evaluations may be conducted as part of both internal and external
assessments. The focus of an on-site evaluation is to evaluate the degree of
conformance of project activities with the applicable QAPjP. On-site evaluations
may include, but are not limited to, a complete review of facilities, staff,
training, instrumentation, procedures, methods, sample collection, analyses, QA
policies and procedures related to the generation of environmental data. Records
of each evaluation should include the date of the evaluation, location, the areas
reviewed, the person performing the evaluation, findings and problems, and
actions recommended and taken to resolve problems. Any problems identified that
are likely to affect data integrity should be brought immediately to the
attention of management.
2.7.4.1 Field Activities
The review of field activities should be conducted by one or more persons
knowledgeable in the activities being reviewed and include evaluating, at a
minimum, the following subjects:
Completeness ofField Reports -- This review determines whether all
requirements for field activities in the QAPjP have been fulfilled, that
complete records exist for each field activity, and that the procedures
ONE - 5 Revision 1
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specified in the QAPjP have been implemented. Emphasis on field
documentation will help assure sample integrity and sufficient technical
information to recreate each field event. The results of this
completeness check should be documented, and environmental data affected
by incomplete records should be identified.
Identification of Valid Samples -- This review involves interpretation and
evaluation of the field records to detect problems affecting the repre-
sentativeness of environmental samples. Examples of items that might
indicate potentially invalid samples include improper well development,
improperly screened wells, instability of pH or conductivity, and collec-
tion of volatiles near internal combustion engines. The field records
should be evaluated against the QAPjP and SOPs. The reviewer should docu-
ment the sample validity and identify the environmental data associated
with any poor or incorrect field work.
Correlation of Field Test Data -- This review involves comparing any
available results of field measurements obtained by more than one method.
For example, surface geophysical methods should correlate with direct
methods of site geologic characterization such as lithologic logs
constructed during drilling operations.
Identification ofAnomalous Field Test Data -- This review identifies any
anomalous field test data. For example, a water temperature for one well
that is 5 degrees higher than any other well temperature in the same
aquifer should be noted. The reviewer should evaluate the impact of
anomalous field measurement results on the associated environmental data.
Validationof Field Analyses -- This review validates and documents all
data from field analysis that are generated in situ or from a mobile
laboratory as specified in Section 2.7.4.2. The reviewer should document
whether the QC checks meet the acceptance criteria, and whether corrective
actions were taken for any analysis performed when acceptance criteria
were exceeded.
2.7.4.2 Laboratory Activities
The review of laboratory data should be conducted by one or more persons
knowledgeable in laboratory activities and include evaluating, at a minimum, the
following subjects:
Completeness of Laboratory Records -- This review determines whether: (1)
all samples and analyses required by the QAPjP have been processed, (2)
complete records exist for each analysis and the associated QC samples,
and that (3) the procedures specified in the QAPjP have been implemented.
The results of the completeness check should be documented, and
environmental data affected by incomplete records should be identified.
Evaluation of Data with Respect to Detection and Quantitation Limits --
This review compares analytical results to required quantitation limits.
Reviewers should document instances where detection or quantitation limits
ONE - 6 Revision 1
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exceed regulatory limits, action levels, or target concentrations
specified in the QAPjP.
Evaluation of Data withRespect to Control Limits -- This review compares
the results of QC and calibration check samples to control criteria.
Corrective action should be implemented for data not within control
limits. The reviewer should check that corrective action reports, and the
results of reanalysis, are available. The review should determine
whether samples associated with out-of-control QC data are identified in
a written record of the data review, and whether an assessment of the
utility of such analytical results is recorded.
Review of Holding Time Data -- This review compares sample holding times
to those required by the QAPjP, and notes all deviations.
Review of Performance Evaluation (PE) Results -- PE study results can be
helpful in evaluating the impact of out-of-control conditions. This review
documents any recurring trends or problems evident in PE studies and
evaluates their effect on environmental data.
Correlation of Laboratory Data -- This review determines whether the
results of data obtained from related laboratory tests, e.g., Purgeable
Organic Hal ides (POX) and Volatile Organics, are documented, and whether
the significance of any differences is discussed in the reports.
2.7.5 QA Reports
There should be periodic reporting of pertinent QA/QC information to the
project management to allow assessment of the overall effectiveness of the QA
program. There are three major types of QA reports to project management:
Periodic Report on Key QA Activities -- Provides summary of key QA activi-
ties during the period, stressing measures that are being taken to improve
data quality; describes significant quality problems observed and
corrective actions taken; reports information regarding any changes in
certification/accreditation status; describes involvement in resolution of
quality issues with clients or agencies; reports any QA organizational
changes; and provides notice of the distribution of revised documents
controlled by the QA organization (i.e., procedures).
Report on Measurement Quality Indicators -- Includes the assessment of QC
data gathered over the period, the frequency of analyses repeated due to
unacceptable QC performance, and, if possible, the reason for the unac-
ceptable performance and corrective action taken.
Reports on QA Assessments -- Includes the results of the assessments and
the plan for correcting identified deficiencies; submitted immediately
following any internal or external on-site evaluation or upon receipt of
the results of any performance evaluation studies.
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3.0 FIELD OPERATIONS
The field operations should be conducted In such a way as to provide
reliable Information that meets the DQOs. To achieve this, certain minimal
policies and procedures should be implemented. The OSW is considering revisions
of Chapter Nine and Eleven of this manual. Supplemental information and guidance
is available 1n the RCRA Ground-Water Honltoring Technical Enforcement Guidance
Document (TEGD) (Reference 3). The project documentation should contain the
information specified below.
3.1 FIELD LOGISTICS
The QAPjP should describe the type(s) of field operations to be performed
and the appropriate area(s) in which to perform the work. The QAPjP should
address ventilation, protection from extreme weather and temperatures, access to
stable power, and provision for water and gases of required purity.
Whenever practical, the sampling site facilities should be examined prior
to the start of work to ensure that all required items are available. The actual
area of sampling should be examined to ensure that trucks, drilling equipment,
and personnel have adequate access to the site.
The determination as to whether sample shipping is necessary should be made
during planning for the project. This need is established by evaluating the
analyses to be performed, sample holding times, and location of the site and the
laboratory. Shipping or transporting of samples to a laboratory should be done
within a timeframe such that recommended holding times are met.
Samples should be packaged, labelled, preserved (e.g., preservative added,
iced, etc.), and documented in an area which is free of contamination and
provides for secure storage. The level of custody and whether sample storage is
needed should be addressed in the QAPjP.
Storage areas for solvents, reagents, standards, and reference materials
should be adequate to preserve their identity, concentration, purity, and
stability prior to use.
Decontamination of sampling equipment may be performed at the location
where sampling occurs, prior to going to the sampling site, or in designated
areas near the sampling site. Project documentation should specify where and how
this work is accomplished. If decontamination is to be done at the site, water
and solvents of appropriate purity should be available. The method of
accomplishing decontamination, including the required materials, solvents, and
water purity should be specified.
During the sampling process and during on-site or jm situ analyses, waste
materials are sometimes generated. The method for storage and disposal of these
waste materials that complies with applicable local, state and Federal
regulations should be specified. Adequate facilities should be provided for the
collection and storage of all wastes, and these facilities should be operated so
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as to minimize environmental contamination. Waste storage and disposal
facilities should comply with applicable federal, state, and local regulations.
The location of long-term and short-term storage for field records, and the
measures to ensure the integrity of the data should be specified.
3.2 EQUIPMENT/INSTRUMENTATION
The equipment, instrumentation, and supplies at the sampling site should
be specified and should be appropriate to accomplish the activities planned. The
equipment and instrumentation should meet the requirements of specifications,
methods, and procedures as specified in the QAPjP.
3.3 OPERATING PROCEDURES
The QAPjP should describe or make reference to all field activities that
may affect data quality. For routinely performed activities, standard operating
procedures (SOPs) are often prepared to ensure consistency and to save time and
effort in preparing QAPjPs. Any deviation from an established procedure during
a data collection activity should be documented. The procedures should be
available for the indicated activities, and should include, at a minimum, the
information described below.
3.3.1 Sample Management
The numbering and labeling system, chain-of-custody procedures, and how the
samples are to be tracked from collection to shipment or receipt by the
laboratory should be specified. Sample management procedures should also specify
the holding times, volumes of sample required by the laboratory, required
preservatives, and shipping requirements.
3.3.2 Reagent/StandardPreparation
The procedures describing how to prepare standards and reagents should be
specified. Information concerning specific grades of materials used in reagent
and standard preparation, appropriate glassware and containers for preparation
and storage, and labeling and record keeping for stocks and dilutions should be
included.
3.3.3 Decontanii nation
The procedures describing decontamination of field equipment before and
during the sample collection process should be specified. These procedures
should include cleaning materials used, the order of washing and rinsing with the
cleaning materials, requirements for protecting or covering cleaned equipment,
and procedures for disposing of cleaning materials.
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3.3.4 Sample Collection
The procedures describing how the sampling operations are actually
performed in the field should be specified. A simple reference to standard
methods is not sufficient, unless a procedure is performed exactly as described
in the published method. Methods from source documents published by the EPA,
American Society for Testing and Materials, U.S. Department of the Interior,
National Water Well Association, American Petroleum Institute, or other
recognized organizations with appropriate expertise should be used, if possible.
The procedures for sample collection should include at least the following:
• Applicability of the procedure,
» Equipment required,
• Detailed description of procedures to be followed in collecting the
samples,
• Common problems encountered and corrective actions to be followed, and
* Precautions to be taken.
3.3.5 Field Measurements
The procedures describing all methods used in the field to determine a
chemical or physical parameter should be described in detail. The procedures
should address criteria from Section 4, as appropriate.
3-3.6 Equipment Callbration And Maintenance
The procedures describing how to ensure that field equipment and
instrumentation are in working order should be specified. These describe
calibration procedures and schedules, maintenance procedures and schedules,
maintenance logs, and service arrangements for equipment. Calibration and
maintenance of field equipment and instrumentation should be in accordance with
manufacturers' specifications or applicable test specifications and should be
documented.
3.3.7 Corrective Action
The procedures describing how to identify and correct deficiencies in the
sample collection process should be specified. These should include specific
steps to take in correcting deficiencies such as performing additional
decontamination of equipment, resampling, or additional training of field
personnel. The procedures should specify that each corrective action should be
documented with a description of the deficiency and the corrective action taken,
and should include the person(s) responsible for implementing the corrective
action.
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3.3.8 Data Reduction and Validation
The procedures describing how to compute results from field measurements
and to review and validate these data should be specified. They should Include
all formulas used to calculate results and procedures used to Independently
verify that field measurement results are correct.
3.3.9 Reporting
The procedures describing the process for reporting the results of field
activities should be specified.
3.3.10 Records Management
The procedures describing the means for generating, controlling, and
archiving project-specific records and field operations records should be
specified. These procedures should detail record generation and control and the
requirements for record retention, including type, time, security, and retrieval
and disposal authorities.
Project-specifI.e. recordj relate to field work performed for a project.
These records may Include correspondence, chain-of-custody records, field
notes, all reports issued as a result of the work, and procedures used.
Fieldopjerat1ons records document overall field operations and may include
equipment performance and maintenance logs, personnel files, general field
procedures, and corrective action reports.
3.3.11 Waste Disposal
The procedures describing the methods for disposal of waste materials
resulting from field operations should be specified.
3.4 FIELD QA AND QC REQUIREMENTS
The QAPjP should describe how the following elements of the field QC
program will be implemented.
3.4.1 Control Samples
Control samples are QC samples that are introduced into a process to
monitor the performance of the system. Control samples, which may include blanks
(e.g., trip, equipment, and laboratory), duplicates, spikes, analytical
standards, and reference materials, can be used in different phases of the data
collection process beginning with sampling and continuing through transportation,
storage, and analysis.
Each day of sampling, at least one field duplicate and one equipment
rinsate should be collected for each matrix sampled. If this frequency is not
appropriate for the sampling equipment and method, then the appropriate changes
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should be clearly identified in the QAPjP. When samples are collected for
volatile organic analysis, a trip blank is also recommended for each day that
samples are collected. In addition, for each sampling batch (20 samples of one
matrix type), enough volume should be collected for at least one sample so as to
allow the laboratory to prepare one matrix spike and either one matrix duplicate
or one matrix spike duplicate for each analytical method employed. This means
that the following control samples are recommended:
•Field duplicate (one per day per matrix type)
•Equipment rinsate (one per day per matrix type)
•Trip blank (one per day, volatile organics only)
•Matrix spike (one per batch [20 samples of each matrix type])
•Matrix duplicate or matrix spike duplicate (one per batch)
Additional control samples may be necessary in order to assure data quality to
meet the project-specific DQOs. "
3.4.2 Acceptance Criteria
Procedures should be in place for establishing acceptance criteria for
field activities described in the QAPjP. Acceptance criteria may be qualitative
or quantitative. Field events or data that fall outside of established
acceptance criteria may indicate a problem with the sampling process that should
be investigated.
3.4.3 Deviations
All deviations from plan should be documented as to the extent of, and
reason for, the deviation. Any activity not performed in accordance with
procedures or QAPjPs is considered a deviation from plan. Deviations from plan
may or may not affect data quality.
3.4.4 CorrectiveAction
Errors, deficiencies, deviations, certain field events, or data that fall
outside established acceptance criteria should be investigated. In some in-
stances, corrective action may be needed to resolve the problem and restore
proper functioning to the system. The investigation of the problem and any
subsequent corrective action taken should be documented.
3.4.5 Data Handling
All field measurement data should be reduced according to protocols
described or referenced in the QAPjP. Computer programs used for data reduction
should be validated before use and verified on a regular basis. All information
used in the calculations should be recorded to enable reconstruction of the final
result at a later date.
Data should be reported in accordance with the requirements of the end-user
as described in the QAPjP.
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3.5 QUALITY ASSURANCE REVIEW
The QA Review consists of Internal and external assessments to ensure that
QA/QC procedures are in use and to ensure that field staff conform to these
procedures. QA review should be conducted as deemed appropriate and necessary.
3.6 FIELD RECORDS
Records provide the direct evidence and support for the necessary technical
interpretations, judgments, and discussions concerning project activities. These
records, particularly those that are anticipated to be used as evidentiary data,
should directly support current or ongoing technical studies and activities and
should provide the historical evidence needed for later reviews and analyses.
Records should be legible, identifiable, and retrievable and protected against
damage, deterioration, or loss. The discussion in this section (3.6) outlines
recommended procedures for record keeping. Organizations which conduct field
sampling should develop appropriate record keeping procedures which satisfy
relevant technical and legal requirements.
Field records generally consist of bound field notebooks with prenumbered
pages, sample collection forms, personnel qualification and training forms,
sample location maps, equipment maintenance and calibration forms, chain-of-
custody forms, sample analysis request forms, and field change request forms.
All records should be written in indelible ink.
Procedures for reviewing, approving, and revising field records should be
clearly defined, with the lines of authority included. It is recommended that
all documentation errors should be corrected by drawing a single line through the
error so it remains legible and should be initialed by the responsible
individual, along with the date of change. The correction should be written
adjacent to the error.
Records should include (but are not limited to) the following:
Calibration Records & Traceability of Standards/Reagents -- Calibration is
a reproducible reference point to which all sample measurements can be
correlated. A sound calibration program should include provisions for
documentation of frequency, conditions, standards, and records reflecting
the calibration history of a measurement system. The accuracy of the
calibration standards is important because all data will be 1n reference
to the standards used. A program for verifying and documenting the
accuracy of all working standards against primary grade standards should
be routinely followed.
Sample Collection --To ensure maximum utility of the sampling effort and
resulting data, documentation of the sampling protocol, as performed in
the field, is essential. It is recommended that sample collection records
contain, at a minimum, the names of persons conducting the activity,
sample number, sample location, equipment used, climatic conditions,
documentation of adherence to protocol, and unusual observations. The
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actual sample collection record is usually one of the following: a bound
field notebook with prenumbered pages, a pre-printed form, or digitized
information on a computer tape or disc.
Chain-of-Custody Records -- The chain-of-custody involving the possession
of samples from the time they are obtained until they are disposed or
shipped off-site should be documented as specified in the QAPjP and should
include the following information: (1) the project name; (2) signatures
of samplers; (3) the sample number, date and time of collection, and grab
or composite sample designation; (4) signatures of individuals Involved 1n
sample transfer; and (5) if applicable, the air bill or other shipping
number.
Maps and Drawings -- Project planning documents and reports often contain
maps. The maps are used to document the location of sample collection
points and monitoring wells and as a means of presenting environmental
data. Information used to prepare maps and drawings is normally obtained
through field surveys, property surveys, surveys of monitoring wells,
aerial photography or photogrammetric mapping. The final, approved maps
and/or drawings should have a revision number and date and should be sub-
ject to the same controls as other project records.
QC Samples -- Documentation for generation of QC samples, such as trip and
equipment rinsate blanks, duplicate samples, and any field spikes should
be maintained.
Deviations -- All deviations from procedural documents and the QAPjP
should be recorded in the site logbook.
Reports -- A copy of any report issued and any supporting documentation
should be retained.
4.0 LABORATORY OPERATIONS
The laboratory should conduct its operations in such a way as to provide
reliable information. To achieve this, certain minimal policies and procedures
should be implemented.
4.1 FACILITIES
The QAPjP should address all facility-related issues that may impact
project data quality. Each laboratory should be of suitable size and
construction to facilitate the proper conduct of the analyses. Adequate bench
space or working area per analyst should be provided. The space requirement per
analyst depends on the equipment or apparatus that is being utilized, the number
of samples that the analyst is expected to handle at any one time, and the number
of operations that are to be performed concurrently by a single analyst. Other
issues to be considered include, but are not limited to, ventilation, lighting,
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control of dust and drafts, protection from extreme temperatures, and access to
a source of stable power.
Laboratories should be designed so that there is adequate separation of
functions to ensure that no laboratory activity has an adverse effect on the
analyses. The laboratory may require specialized facilities such as a perchloric
acid hood or glovebox.
Separate space for laboratory operations and appropriate ancillary support
should be provided, as needed, for the performance of routine and specialized
procedures.
As necessary to ensure secure storage and prevent contamination or
misidentification, there should be adequate facilities for receipt and storage
of samples. The level of custody required and any special requirements for
storage such as refrigeration should be described in planning documents.
Storage areas for reagents, solvents, standards, and reference materials
should be adequate to preserve their identity, concentration, purity, and
stability.
Adequate facilities should be provided for the collection and storage of
all wastes, and these facilities should be operated so as to minimize environ-
mental contamination. Waste storage and disposal facilities should comply with
applicable federal, state, and local regulations.
The location of long-term and short-term storage of laboratory records and
the measures to ensure the integrity of the data should be specified.
4.2 EQUIPMENT/INSTRUMENTATION
Equipment and instrumentation should meet the requirements and specifica-
tions of the specific test methods and other procedures as specified in the
QAPjP. The laboratory should maintain an equipment/instrument description list
that includes the manufacturer, model number, year of purchase, accessories, and
any modifications, updates, or upgrades that have been made.
4.3 OPERATING PROCEDURES
The QAPjP should describe or make reference to all laboratory activities
that may affect data quality. For routinely performed activities, SOPs are often
prepared to ensure consistency and to save time and effort in preparing QAPjPs.
Any deviation from an established procedure during a data collection activity
should be documented. It is recommended that procedures be available for the
indicated activities, and include, at a minimum, the information described
below.
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4.3.1 Sample Management
The procedures describing the receipt, handling, scheduling, and storage
of samples should be specified.
Sample Receipt and Handling -- These procedures describe the precautions
to be used in opening sample shipment containers and how to verify that
chain-of-custody has been maintained, examine samples for damage, check
for proper preservatives and temperature, and log samples into the
laboratory sample streams.
Sample Scheduling -- These procedures describe the sample scheduling in
the laboratory and includes procedures used to ensure that holding time
requirements are met.
Sample Storage -- These procedures describe the storage conditions for all
samples, verification and documentation of daily storage temperature, and
how to ensure that custody of the samples is maintained while in the
laboratory.
4,3.2 Reagent/Standard Preparati on
The procedures describing how to prepare standards and reagents should be
specified. Information concerning specific grades of materials used in reagent
and standard preparation, appropriate glassware and containers for preparation
and storage, and labeling and recordkeeping for stocks and dilutions should be
included.
4.3.3 General Laboratory Techniques
The procedures describing all essentials of laboratory operations that are
not addressed elsewhere should be specified. These techniques should include,
but are not limited to, glassware cleaning procedures, operation of analytical
balances, pipetting techniques, and use of volumetric glassware.
4.3.4 Test Methods
Procedures for test methods describing how the analyses are actually
performed in the laboratory should be specified. A simple reference to standard
methods is not sufficient, unless the analysis is performed exactly as described
in the published method. Whenever methods from SW-846 are not appropriate,
recognized methods from source documents published by the EPA, American Public
Health Association (APHA), American Society for Testing and Materials (ASTM), the
National Institute for Occupational Safety and Health (NIOSH), or other
recognized organizations with appropriate expertise should be used, if possible.
The documentation of the actual laboratory procedures for analytical methods
should include the following:
Sample Preparation and Analysis Procedures -- These include applicable
holding time, extraction, digestion, or preparation steps as appropriate
to the method; procedures for determining the appropriate dilution to
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analyze; and any other information required to perform the analysis
accurately and consistently.
Instrument Standardization -- This includes coneentration(s) and frequency
of analysis of calibration standards, linear range of the method, and
calibration acceptance criteria.
Sample Data -- This includes recording requirements and documentation in-
cluding sample identification number, analyst, data verification, date of
analysis and verification, and computational method(s).
Precision and Bias -- This includes all analytes for which the method is
applicable and the conditions for use of this information.
Detection and Reporting Limits -- This includes all analytes in the
method.
Test-Specific QC -- This describes QC activities applicable to the
specific test and references any applicable QC procedures.
4.3.5 Equipment Calibration and Maintenance
The procedures describing how to ensure that laboratory equipment and
instrumentation are in working order should be specified. These procedures
include calibration procedures and schedules, maintenance procedures and
schedules, maintenance logs, service arrangements for all equipment, and spare
parts available in-house. Calibration and maintenance of laboratory equipment
and instrumentation should be in accordance with manufacturers' specifications
or applicable test specifications and should be documented.
4.3.6 flC
The type, purpose, and frequency of QC samples to be analyzed in the
laboratory and the acceptance criteria should be specified. Information should
include the applicability of the QC sample to the analytical process, the
statistical treatment of the data, and the responsibility of laboratory staff and
management in generating and using the data. Further details on development of
project-specific QC protocols are described in Section 4.4.
4.3.7 Corrective Action
The procedures describing how to identify and correct deficiencies in the
analytical process should be specified. These should include specific steps to
take in correcting the deficiencies such as preparation of new standards and
reagents, recalibration and restandardization of equipment, reanalysis of
samples, or additional training of laboratory personnel in methods and
procedures. The procedures should specify that each corrective action should be
documented with a description of the deficiency and the corrective action taken,
and should include the person(s) responsible for implementing the corrective
action.
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4.3.8 Data Reduction and Validation
The procedures describing how to review and validate the data should be
specified. They should include procedures for computing and interpreting the
results from QC samples, and independent procedures to verify that the analytical
results are reported correctly. In addition, routine procedures used to monitor
precision and bias, including evaluations of reagent, equipment rinsate, and trip
blanks, calibration standards, control samples, duplicate and matrix spike
samples, and surrogate recovery, should be detailed in the procedures. More
detailed validation procedures should be performed when required in the contract
or QAPjP.
4.3.9 Reporting
The procedures describing the process for reporting the analytical results
should be specified.
4.3.10 Records Management
The procedures describing the means for generating, controlling, and
archiving laboratory records should be specified. The procedures should detail
record generation and control, and the requirements for record retention, includ-
ing type, time, security, and retrieval and disposal authorities.
Project-specific records may include correspondence, chain-of-custody
records, request for analysis, calibration data records, raw and finished
analytical and QC data, data reports, and procedures used.
Laboratory operations records may include laboratory notebooks, instrument
performance logs and maintenance logs in bound notebooks with prenumbered
pages; laboratory benchsheets; software documentation; control charts;
reference material certification; personnel files; laboratory procedures;
and corrective action reports.
*
4.3.11 Waste Disposal
The procedures describing the methods for disposal of chemicals including
standard and reagent solutions, process waste, and samples should be specified.
4.4 LABORATORY QA AND QC PROCEDURES
The QAPjP should describe how the following required elements of the
laboratory QC program are to be implemented.
4.4.1 Method Profi ci ency
Procedures should be in place for demonstrating proficiency with each
analytical method routinely used in the laboratory. These should include
procedures for demonstrating the precision and bias of the method as performed
by the laboratory and procedures for determining the method detection limit
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(MDL). All terminology, procedures and frequency of determinations associated
with the laboratory's establishment of the HDL and the reporting limit should be
well-defined and well-documented. Documented precision, bias, and HDL
information should be maintained for all methods performed in the laboratory.
4.4.2 Control Limits
Procedures should be in place for establishing and updating control limits
for analysis. Control limits should be established to evaluate laboratory
precision and bias based on the analysis of control samples. Typically, control
limits for bias are based on the historical mean recovery plus or minus three
standard deviation units, and control limits for precision range from zero (no
difference between duplicate control samples) to the historical mean relative
percent difference plus three standard deviation units. Procedures should be in
place for monitoring historical performance and should include graphical (control
charts) and/or tabular presentations of the data.
4.4.3 Laboratory Control Procedures
Procedures should be in place for demonstrating that the laboratory is in
control during each data collection activity. Analytical data generated with
laboratory control samples that fall within prescribed limits are judged to be
generated while the laboratory was in control. Data generated with laboratory
control samples that fall outside the established control limits are judged to
be generated during an "out-of-control" situation. These data are considered
suspect and should be repeated or reported with qualifiers.
Laboratory Control Samples -- Laboratory control samples should be
analyzed for each analytical method when appropriate for the method. A
laboratory control sample consists of either a control matrix spiked with
analytes representative of the target analytes or a certified reference
material.
Laboratory control sample(s) should be analyzed with each batch of samples
processed to verify that the precision and bias of the analytical process
are within control limits. The results of the laboratory control
sample(s) are compared to control limits established for both precision
and bias to determine usability of the data.
Method Blank -- When appropriate for the method, a method blank should be
analyzed with each batch of samples processed to assess contamination
levels in the laboratory. Guidelines should be in place for accepting or
rejecting data based on the level of contamination in the blank.
Procedures should be in place for documenting the effect of the matrix on
method performance. When appropriate for the method, there should be at least
one matrix spike and either one matrix duplicate or one matrix spike duplicate
per analytical batch. Additional control samples may be necessary to assure data
quality to meet the project-specific DQOs.
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Matrix-Specific Bias -- Procedures should be in place for determining the
bias of the method due to the matrix. These procedures should include
preparation and analysis of matrix spikes, selection and use of surrogates
for organic methods, and the method of standard additions for metal and
inorganic methods. When the concentration of the analyte in the sample is
greater than 0.1%, no spike is necessary.
Matrix-Specific Precision -- Procedures should be in place for determining
the precision of the method for a specific matrix. These procedures
should include analysis of matrix duplicates and/or matrix spike
duplicates. The frequency of use of these techniques should be based on
the DQO for the data collection activity.
Matrix-Specific Detection Limit -- Procedures should be 1n place for
determining the HDL for a specific matrix type (e.g., wastewater treatment
sludge, contaminated soil, etc).
4.4.4 Deviations
Any activity not performed in accordance with laboratory procedures or
QAPjPs is considered a deviation from plan. All deviations from plan should be
documented as to the extent of, and reason for, the deviation.
4.4.5 Corrective Action
Errors, deficiencies, deviations, or laboratory events or data that fall
outside of established acceptance criteria should be investigated. In some
instances, corrective action may be needed to resolve the problem and restore
proper functioning to the analytical system. The investigation of the problem
and any subsequent corrective action taken should be documented.
4.4.6 Data Hand!ing
Data resulting from the analyses of samples should be reduced according to
protocols described in the laboratory procedures. Computer programs used for
data reduction should be validated before use and verified on a regular basis.
All information used in the calculations (e.g., raw data, calibration files,
tuning records, results of standard additions, interference check results, and
blank- or background-correction protocols) should be recorded in order to enable
reconstruction of the final result at a later date. Information on the
preparation of the sample (e.g., weight or volume of sample used, percent dry
weight for solids, extract volume, dilution factor used) should also be
maintained in order to enable reconstruction of the final result at a later date.
All data should be reviewed by a second analyst or supervisor according to
laboratory procedures to ensure that calculations are correct and to detect
transcription errors. Spot checks should be performed on computer calculations
to verify program validity. Errors detected in the review process should be
referred to the analyst(s) for corrective action. Data should be reported in
accordance with the requirements of the end-user. It is recommended that the
supporting documentation include at a minimum:
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* Laboratory name and address.
• Sample information (including unique sample Identification, sample
collection date and time, date of sample receipt, and date(s) of sample
preparation and analysis).
* Analytical results reported with an appropriate number of significant
figures.
• Detection limits that reflect dilutions, interferences, or correction for
equivalent dry weight.
• Method reference,
• Appropriate QC results (correlation with sample batch should be traceable
and documented).
« Data qualifiers with appropriate references and narrative on the quality
of the results.
4.5 QUALITY ASSURANCE REVIEW
The QA review consists of internal and external assessments to ensure that
QA/QC procedures are in use and to ensure that laboratory staff conform to these
procedures. QA review should be conducted as deemed appropriate and necessary.
4.6 LABORATORY RECORDS
Records provide the direct evidence and support for the necessary technical
interpretations, judgements, and discussions concerning project activities.
These records, particularly those that are anticipated to be used as evidentiary
data, should directly support technical studies and activities, and provide the
historical evidence needed for later reviews and analyses. Records should be
legible, identifiable, and retrievable, and protected against damage,
deterioration, or loss. The discussion in this section (4.6) outlines
recommended procedures for record keeping. Organizations which conduct field
sampling should develop appropriate record keeping procedures which satisfy
relevant technical and legal requirements.
Laboratory records generally consist of bound notebooks with prenumbered
pages, personnel qualification and training forms, equipment maintenance and
calibration forms, chain-of-custody forms, sample analysis request forms, and
analytical change request forms. All records should be written in indelible ink.
Procedures for reviewing, approving, and revising laboratory records should
be clearly defined, with the lines of authority included. Any documentation
errors should be corrected by drawing a single line through the error so that it
remains legible and should be initialed by the responsible individual, along with
the date of change. The correction is written adjacent to the error.
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Strip-chart recorder printouts should be signed by the person who performed
the instrumental analysis. If corrections need to be made in computerized data,
a system parallel to the corrections for handwritten data should be in place.
Records of sample management should be available to permit the re-creation
of an analytical event for review in the case of an audit or investigation of a
dubious result.
Laboratory records should include, at least, the following:
Operating Procedures -- Procedures should be available to those performing
the task outlined. Any revisions to laboratory procedures should be
written, dated, and distributed to all affected individuals to ensure
implementation of changes. Areas covered by operating procedures are
given in Sections 3.3 and 4.3.
Quality Assurance Plans -- The QAPjP should be on file.
Equipment Maintenance Documentation -- A history of the maintenance record
of each system serves as an indication of the adequacy of maintenance
schedules and parts inventory. As appropriate, the maintenance guidelines
of the equipment manufacturer should be followed. When maintenance is
necessary, it should be documented in either standard forms or in
logbooks. Maintenance procedures should be clearly defined and written
for each measurement system and required support equipment.
Proficiency -- Proficiency information on all compounds reported should be
maintained and should include (1) precision; (2) bias; (3) method detec-
tion limits; (4) spike recovery, where applicable; (5) surrogate recovery,
where applicable; (6) checks on reagent purity, where applicable; and
(7) checks on glassware cleanliness, where applicable.
Calibration Records & Traceability of Standards/Reagents -- Calibration is
a reproducible reference point to which all sample measurements can be
correlated. A sound calibration program should include provisions for
documenting frequency, conditions, standards, and records reflecting the
calibration history of a measurement system. The accuracy of the
calibration standards is important because all data will be in reference
to the standards used. A program for verifying and documenting the
accuracy and traceability of all working standards against appropriate
primary grade standards or the highest quality standards available should
be routinely followed.
Sample Management --All required records pertaining to sample management
should be maintained and updated regularly. These include chain-of-
custody forms, sample receipt forms, and sample disposition records.
Original Data -- The raw data and calculated results for all samples
should be maintained in laboratory notebooks, logs, benchsheets, files or
other sample tracking or data entry forms. Instrumental output should be
stored in a computer file or a hardcopy report.
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QCData -- The raw data and calculated results for all QC and field
samples and standards should be maintained in the manner described in the
preceding paragraph. Documentation should allow correlation of sample
results with associated QC data. Documentation should also include the
source and lot numbers of standards for traceability. QC samples include,
but are not limited to, control samples, method blanks, matrix spikes, and
matrix spike duplicates.
Correspondence -- Project correspondence can provide evidence supporting
technical interpretations. Correspondence pertinent to the project should
be kept and placed in the project files.
Deviations -- All deviations from procedural and planning documents should
be recorded in laboratory notebooks. Deviations from QAPjPs should be
reviewed and approved by the authorized personnel who performed the
original technical review or by their designees.
Final Report -- A copy of any report issued and any supporting documenta-
tion should be retained.
5.0 DEFINITIONS
The following terms are defined for use in this document:
ACCURACY The closeness of agreement between an observed value and
an accepted reference value. When applied to a set of
observed values, accuracy will be a combination of a
random component and of a common systematic error (or
bias) component.
BATCH: A group of samples which behave similarly with respect to
the sampling or the testing procedures being employed and
which are processed as a unit (see Section 3.4.1 for field
samples and Section 4.4.3 for laboratory samples). For QC
purposes, if the number of samples in a group is greater
than 20, then each group of 20 samples or less will all be
handled as a separate batch.
BIAS: The deviation due to matrix effects of the measured value
(x, - xj from a known spiked amount. Bias can be assessed
by comparing a measured value to an accepted reference
value in a sample of known concentration or by determining
the recovery of a known amount of contaminant spiked into
a sample (matrix spike). Thus, the bias (B) due to matrix
effects based on a matrix spike is calculated as:
B - (x. - xu ) - K
where:
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BLANK:
CONTROL SAMPLE:
DATA QUALITY
OBJECTIVES {DQOs}
DATA VALIDATION:
DUPLICATE:
EQUIPMENT BLANK:
EQUIPMENT RINSATE:
ESTIMATED
QUANTITATION
LIMIT (EQL):
x. - measured value for spiked sample,
xu - measured value for unspiked sample, and
K * known value of the spike in the sample.
Using the following equation yields the percent recovery
(XR).
%R
100 (x. - xu)/
see Equipment Rinsate, Method Blank, Trip Blank.
A QC sample introduced into a process to monitor the
performance of the system.
A statement of the overall level of uncertainty that a
decision-maker is willing to accept in results derived
from environmental data (see reference 2, EPA/QAMS, July
16, 1986). This is qualitatively distinct from quality
measurements such as precision, bias, and detection limit.
The process of evaluating the available data against the
project DQOs to make sure that the objectives are met.
Data validation may be very
depending on project DQOs. The
will include analytical results,
data, and may also include field
rigorous, or cursory,
available data reviewed
field QC data and lab QC
records.
see Matrix Duplicate,
Duplicate.
see Equipment Rinsate.
Field Duplicate, Matrix Spike
A sample of analyte-free media which has been used to
rinse the sampling equipment. It is collected after
completion of decontamination and prior to sampling. This
blank is useful in documenting adequate decontamination of
sampling equipment.
The lowest concentration that can be reliably achieved
within specified limits of precision and accuracy during
routine laboratory operating conditions. The EQL is
generally 5 to 10 times the MDL. However, it may be
nominally chosen within these guidelines to simplify data
reporting. For many analytes the EQL analyte
concentration is selected as the lowest non-zero standard
in the calibration curve. Sample EQLs are highly matrix-
dependent. The EQLs in SW-846 are provided for guidance
and may not always be achievable.
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FIELD DUPLICATES:
LABORATORY CONTROL
SAMPLE:
MATRIX:
MATRIX DUPLICATE:
MATRIX SPIKE:
MATRIX SPIKE
DUPLICATES:
METHOD BLANK:
METHOD DETECTION
LIMIT (MDL):
Independent samples which are collected as close as
possible to the same point in space and time. They are
two separate samples taken from the same source, stored in
separate containers, and analyzed independently. These
duplicates are useful in documenting the precision of the
sampling process.
A known matrix spiked with compound(s) representative of
the target analytes. This is used to document laboratory
performance.
The component or substrate (e.g., surface water, drinking
water) which contains the analyte of interest.
An intralaboratory split sample which is used to document
the precision of a method in a given sample matrix.
An aliquot of sample spiked with a known concentration of
target analyte(s). The spiking occurs prior to sample
preparation and analysis. A matrix spike is used to
document the bias of a method in a given sample matrix.
Intralaboratory split samples spiked with identical
concentrations of target analyte(s). The spiking occurs
prior to sample preparation and analysis. They are used
to document the precision and bias of a method in a given
sample matrix.
An analyte-free matrix to which all reagents are added 1n
the same volumes or proportions as used in sample
processing. The method blank should be carried through
the complete sample preparation and analytical procedure.
The method blank is used to document contamination
resulting from the analytical process.
For a method blank to be acceptable for use with the
accompanying samples, the concentration in the blank of
any analyte of concern should not be higher than the
highest of either:
(l)The method detection limit, or
(2)Five percent of the regulatory limit for that analyte,
or
(3)Five percent of the measured concentration in the
sample.
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
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analysis of a sample in a given matrix type containing
the analyte.
For operational purposes, when it is necessary to
determine the MDL in the matrix, the MDL should be
determined by multiplying the appropriate one-sided 99% t-
statistic by the standard deviation obtained from a
minimum of three analyses of a matrix spike containing the
analyte of Interest at a concentration three to five times
the estimated MDL, where the t-statistic is obtained from
standard references or the table below.
No. of samples; t-statistic
3 6.96
4 4.54
5 3.75
6 3.36
7 3.14
8 3.00
9 2.90
10 2.82
Estimate the MDL as follows:
Obtain the concentration value that corresponds to:
a) an instrument signal/noise ratio within the range of
2.5 to 5.0, or
b) the region of the standard curve where there is a
significant change in sensitivity (i.e., a break in the
slope of the standard curve).
Determine the variance (S2) for each analyte as follows:
where xt - the ith measurement of the variable x
and x = the average value of x;
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ORGANIC-FREE
REAGENT WATER:
PRECISION:
Determine the standard deviation (s) for each analyte as
f ol1ows;
s . (S8)"2
Determine the MDL for each analyte as follows:
MDL
"Cn-1, a « .99)'
where t(nw1 w, is the one-sided t-statistic appropriate
for the number" of samples used to determine (s)» at the 99
percent level.
For volatiles, all references to water in the methods
refer to water in which an interferant is not observed at
the method detection limit of the compounds of interest.
Organic-free reagent water can be generated by passing tap
water through a carbon filter bed containing about 1 pound
of activated carbon. A water purification system may be
used to generate organic-free deionized water.
Organic-free reagent water may also be prepared by boiling
water for 15 minutes and, subsequently, while maintaining
the temperature at 90*C» bubbling a contaminant-free inert
gas through the water for 1 hour.
For semivolatiles and nonvolatiles, all references to
water in the methods refer to water in which an
interferant is not observed at the method detection limit
of the compounds of interest. Organic-free reagent water
can be generated by passing tap water through a carbon
filter bed containing about 1 pound of activated carbon.
A water purification system may be used to generate
organic-free deionized water.
The agreement among a set of replicate measurements
without assumption of knowledge of the true value.
Precision is estimated by means of duplicate/replicate
analyses. These samples should contain concentrations of
analyte above the MDL, and may involve the use of matrix
spikes. The most commonly used estimates of precision are
the relative standard deviation (RSD) or the coefficient
of variation (CV),
RSD - CV - 100 S/x,
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PROJECT:
QUALITY ASSURANCE
PROJECT PLAN
(QAPjP):
RCRA:
REAGENT BLANK:
REAGENT GRADE:
REAGENT WATER:
REFERENCE MATERIAL:
SPLIT SAMPLES:
STANDARD ADDITION:
STANDARD CURVE:
where:
x - the arithmetic mean of the xf measurements, and S -
variance; and the relative percent difference (RPD) when
only two samples are available.
RPD - 100 [(x, - x2)/{(Xl + x2)/2}].
Single or multiple data collection activities that are
related through the same planning sequence.
An orderly assemblage of detailed procedures designed to
produce data of sufficient quality to meet the data
quality objectives for a specific data collection
activity.
The Resource Conservation and Recovery Act.
See Method Blank.
Analytical reagent (AR) grade, ACS reagent grade, and
reagent grade are synonymous terms for reagents which
conform to the current specifications of the Committee on
Analytical Reagents of the American Chemical Society.
Water that has been generated by any method which would
achieve the performance specifications for ASTM Type II
water. For organic analyses, see the definition of
organic-free reagent water.
A material containing known quantities of target analytes
in solution or in a homogeneous matrix. It is used to
document the bias of the analytical process.
Aliquots of sample taken from the same container and
analyzed independently. In cases where aliquots of
samples are impossible to obtain, field duplicate samples
should be taken for the matrix duplicate analysis. These
are usually taken after mixing or compositing and are used
to document intra- or interlaboratory precision.
The practice of adding a known amount of an analyte to a
sample immediately prior to analysis. It is typically
used to evaluate interferences.
A plot of concentrations of known analyte standards versus
the instrument response to the analyte. Calibration
standards are prepared by successively diluting a standard
solution to produce working standards which cover the
working range of the instrument. Standards should be
prepared at the frequency specified in the appropriate
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section. The calibration standards should be prepared
using the same type of acid or solvent and at the same
concentration as will result in the samples following
sample preparation. This is applicable to organic and
inorganic chemical analyses.
SURROGATE: An organic compound which is similar to the target
analyte(s) in chemical composition and behavior in the
analytical process, but which is not normally found in
environmental samples.
TRIP BLANK: A sample of analyte-free media taken from the laboratory
to the sampling site and returned to the laboratory
unopened. A trip blank is used to document contamination
attributable to shipping and field handling procedures.
This type of blank is useful in documenting contamination
of volatile organics samples.
6.0 REFERENCES
1. Interim Guidelines and Specifications for Preparing Quality Assurance
Project Plans, QAMS-005/80, December 29, 1980, Office of Monitoring Systems
and Quality Assurance, ORD, U.S. EPA, Washington, DC 20460.
2. Development of Data Quality Objectives, Description of Stages I and II, July
16, 1986, Quality Assurance Management Staff, ORD, U.S. EPA, Washington, DC
20460.
3. RCRA Ground-Water Monitoring Technical Enforcement Guidance Document,
September, 1986, Office of Waste Programs Enforcement. OSWER, U.S. EPA,
Washington, DC, 20460.
4, DQO Training Software, Version 6.5, December, 1988, Quality Assurance
Management Staff, ORD, U.S. EPA, Washington, DC 20460.
5. Preparing Perfect Project Plans, EPA/600/9-89/087, October 1989, Risk
Reduction Engineering Laboratory (Guy Simes), Cincinnati OH.
6. ASTM Method D 1129-77, Specification for Reagent Water. 1991 Annual Book
of ASTM Standards. Volume 11.01 Water and Environmental Technology.
7. Generation of Environmental Data Related to Waste Management Activities
(Draft). February 1989. ASTM.
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INDEX
Accuracy 1, 13, 22, 23", 24
Batch 12, 19, 21, 23"
Bias 2, 3, 17-20, 22, 23"-25, 28
Blank 11, 12, 14, 18-20, 23', 24, 25, 28, 29
Equipment Rinsate 11, 12, 14, 18, 24*
Method Blank 19, 24, 25", 28
Reagent Blank 28"
Trip Blank 12, 18, 24, 29"
Chain-of-Custody 9, 11, 13, 14, 18, 21, 22
Control Chart 18, 19
Control Sample 11, 12, 18, 19, 23, 24"
Data Quality Objectives (DQO) 1-3, 8, 12, 19, 20, 24", 28
Decision-maker 2, 24
Duplicate 11, 12, 14, 18-20, 23, 24*, 25, 27, 28
Field Duplicate 11, 12, 24, 25", 28
Matrix Duplicate 12, 19, 20, 24, 25", 28
Matrix Spike Duplicate 12, 19, 20, 23, 24, 25"
Equipment Blank 11, 24"
Equipment Rinsate 11, 12, 14, 18, 24*
Estimated Quantitation Limit (EQL) 24"
Field Duplicate 12, 24, 25", 28
Laboratory Control Sample 19, 25"
Matrix 11, 12, 18-20, 23-25", 26-28
Matrix Duplicate 12, 19, 20, 24, 25*, 28
Matrix Spike 12, 18-20, 23, 25", 26, 27
Matrix Spike Duplicate 12, 19, 20, 23, 24, 25"
Method Blank 19, 24, 25", 28
Method Detection Limit (MDL) 18-20, 22, 24, 25"-27
Organic-Free Reagent Water 27", 28
Precision 1-3, 17-20, 22, 24, 25, 27", 28
Project 1-5, 7, 8, 11-14, 17-19, 21, 23, 24, 28"
Quality Assurance Project Plan (QAPjP) 1-9, 11, 12, 14, 15, 18, 20, 22, 23, 28*
RCRA 1, 8, 28"
Reagent Blank 28"
Reagent Grade 28'
Reagent Water 27, 28"
Reference Material 8, 11, 15, 18, 19, 28"
Split Samples 25, 28'
Standard Addition 20, 28"
Standard Curve 26, 28"
Surrogate 18, 20, 22, 29"
Trip Blank 12, 18, 24, 29*
Definition of term.
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CHAPTER TWO
CHOOSING THE CORRECT PROCEDURE
2.1 PURPOSE
This chapter aids the analyst in choosing the appropriate methods for
samples, based upon sample matrix and the analytes to be determined.
2.1.1 Trace Analysis vs. .MacrganaTy_s_1s
The methods presented in SW-846 were designed through sample sizing and
concentration procedures to address the problem of "trace" analyses (<1000 ppm),
and have been developed for an optimized working range. These methods are also
applicable to "minor" (1000 ppm - 10,000 ppn) and "major" (>10,000 ppm) analyses,
as well as to "trace" analyses, through use of appropriate sample preparation
techniques that result in analyte concentration within that optimized range. Such
sample preparation techniques include:
1) adjustment of size of sample prepared for analysis,
2) adjustment of injection volumes,
3) dilution or concentration of sample,
4) elimination of concentration steps prescribed for "trace" analyses,
5) direct injection (of samples to be analyzed for volatile constituents).
The performance data presented in each of these methods were generated from
"trace" analyses, and may not be applicable to "minor" and "major" analyses.
Generally, extraction efficiency improves as concentration increases.
CAUTION: Care should be taken when analyzing samples for trace analyses
subsequent to analysis of concentrated samples due to the
possibility of contamination.
2.1.2 Choice of Apparatus and Preparation of Reagents
Since many types and sizes of glassware and supplies are commercially
available, and since it is possible to prepare reagents and standards in many
different ways, those specified in these methods may be replaced by any similar
types as long as this substitution does not affect the overall quality of the
analyses.
2.2 REQUIRED INFORMATION
In order to choose the correct combination of methods to form the
appropriate analytical procedure, some basic information is required.
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2.2.1 Physical Statefs) of Sample
The phase characteristics of the sample must be known. There are several
general categories of phases in which the sample may be categorized:
Aqueous Oil and Organic Liquid
Sludges Solids
Multiphase Samples EP and TCLP Extracts
Ground Water
2.2.2 Analvtes
Analytes are divided into classes based on the determinative methods which
are used to identify and quantify them. Table 2-1 lists the organic analytes of
SW-846 methods, Table 2-2 lists the analytes that may be prepared using Method
3650, and Table 2-3 lists the analytes that are collected from stack gas
effluents using VOST methodology. Tables 2-4 through 2-31 list the target
analytes of each organic determinative method. Some of the analytes appear on
wore than one table, as they may be determined using any of several methods.
Table 2-32 indicates which methods are applicable to inorganic target analytes.
2.2.3 Detection Limits Required
Regulations may require a specific sensitivity or detection limit for an
analysis, as in the determination of analytes for the Toxicity Characteristic
(TC) or for delisting petitions. Drinking water detection limits, for those
specific organic and metallic analytes covered by the National Interim Primary
Drinking Water Standards, are desired in the analysis of ground water.
2.2.4 Analytical Objective
Knowledge of the analytical objective will be useful in the choice of
aliquoting procedures and in the selection of a determinative method. This is
especially true when the sample has more than one phase. Knowledge of the
analytical objective may not be possible or desirable at all management levels,
but that information should be transmitted to the analytical laboratory
management to ensure that the correct techniques are being applied to the
analytical effort.
2.2.5 Detection and Monitoring
The strategy for detection of compounds in environmental or process samples
may be contrasted with the strategy for monitoring samples. Detection samples
define initial conditions. When there is little information available about the
composition of the sample source, e.g., a well or process stream, mass spectral
identification of organic analytes leads to fewer false positive results. Thus,
the most practical form of detection for organic analytes, given the analytical
requirements, is mass spectral identification. The choice of technique for
metals is governed by the detection limit requirements and potential
interferents.
Monitoring samples, on the other hand, are analyzed to confirm existing and
on-going conditions, tracking the presence or absence of constituents in an
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environmental or process matrix. In well defined and stable analytical
conditions and matrices less compound-specific detection modes may be used.
2.2.6 Sample Containers, Preservations, and HoldingTimes
Appropriate sample containers, sample preservation techniques, and sample
holding times for aqueous matrices are listed in Table 2-33, near the end of this
chapter. Similar information may be found in Table 3-1 of Chapter Three
(inorganic analytes) and Table 4-1 of Chapter Four (organic analytes). Samples
must be extracted/analyzed within the specified holding times for the results to
be considered reflective of total concentrations. Analytical data generated
outside of the specified holding times must be considered to be minimum values
only. Such data may be used to demonstrate that a waste is hazardous where it
shows the concentration of a constituent to be above the regulatory threshold but
cannot be used to demonstrate that a waste is not hazardous.
2.3 IMPLEMENTING THE GUIDANCE
The choice of the appropriate sequence of methods depends on the
information required and on the experience of the analyst. Figure 2-1 summarizes
the organic analysis options available. Appropriate selection is confirmed by
the quality control results. The use of the recommended procedures, whether they
are approved or mandatory, does not release the analyst from demonstrating the
correct execution of the method.
2-3.1 Extraction andSample Preparation Procedures
Methods for preparing organic analytes are shown in Table 2-34. Method
3500 and associated methods should be consulted for further details on preparing
the sample for analysis.
2.3.1.1 AqueousSamples
The choice of a preparative method depends on the sample. Methods
3510 and 3520 may be used for extraction of the semivolatile organic
compounds. Method 3510, a separatory funnel extraction, is appropriate
for samples which will not form a persistent emulsion interphase between
the sample and the extraction solvent. The formation of an emulsion that
cannot be broken up by mechanical techniques will prevent proper
extraction of the sample. Method 3520, a liquid-liquid continuous
extraction, may be used for any aqueous sample; this method will minimize
emulsion formation.
2.3.1.1.1 Basic or Neutral Extraction of Semivolatiles
The solvent extract obtained by performing either Method 3510
or 3520 at a neutral or basic pH will contain the compounds of
interest. Refer to Table 1 in the extraction methods (3510 and/or
3120} for guidance on the pH requirements for extraction prior to
analysis.
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2-3.1.1.2 Acidic ExtractionofPhenolsandAcids
The extract obtained by performing either Method 3510 or 3520
at a pH less than or equal to 2 will contain the phenols and acid
extractables.
2.3.1.2 Solid Samples
Soxhlet (Methods 3540 and 3541} and ultrasonic (Method 3550}
extractions are used with solid samples. Consolidated samples should be
ground finely enough to pass through a 1 mm sieve. In limited
applications, waste dilution (Method 3580} may be used if the entire
sample is soluble in the specified solvent.
Methods 35401 and 3541 and 3550 are neutral-pH extraction techniques
and therefore, depending on the analysis requirements, acid-base partition
cleanup (Method 3650} may be necessary. Method 3650 will only be needed
if chromatographic interferences are severe enough to prevent detection of
the analytes of interest. This separation will be most important if a GC
method is chosen for analysis of the sample. If GC/MS is used, the ion
selectivity of the technique may compensate for chromatographic
interferences.
2.3.1.3 Oils and Organic Liquids
Method 3580, waste dilution, may be used and the resultant sample
analyzed directly by GC or GC/MS. To avoid overloading the analytical
detection system, care must be exercised to ensure that proper dilutions
are made. Method 3580 gives guidance on performing waste dilutions.
To remove interferences, Method 3611 may be performed on an oil
sample directly, without prior sample preparation.
Method 3650 is the only other preparative procedure for oils and
other organic liquids. This procedure Is a back extraction into an
aqueous phase. It is generally introduced as a cleanup procedure for
extracts rather than as a preparative procedure. Oils generally have a
high concentration of semivolatile compounds and, therefore, preparation
by Method 3650 should be done on a relatively small aliquot of the sample.
Generally, extraction of 1 ml of oil will be sufficient to obtain a
saturated aqueous phase and avoid emulsions.
2.3.1.4 Sludge Samples
There 1s no set ratio of liquid to solid which enables the anajyst
to determine which of the three extraction methods cited is the most
appropriate. If the sludge is an organic sludge (solid material and
organic liquid, as opposed to an aqueous sludge}, the sample should be
handled as a multiphase sample.
Determining the appropriate methods for analysis of sludges is
complicated because of the lack of precise definition of sludges with
respect to the relative percent of liquid and solid components. They may
be classified into three categories but with appreciable overlap.
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2.3.1.4.1 Liquids
Use of Method 3510 or Method 3520 may be applicable to sludges
that behave like and have the consistency of aqueous liquids.
Ultrasonic extraction (Method 3550) and Soxhlet (Method 3540)
procedures will, most likely, be ineffective because of the
overwhelming presence of the liquid aqueous phase.
2.3.1.4.2 Solids
Soxhlet (Methods 3540 and 3541) and ultrasonic extraction
(Method 3550) will be more effective when applied to sludge samples
that resemble solids. Samples may be dried or centrifuged to form
solid materials for subsequent determination of semi volatile
compounds.
Using Method 3650, Acid-Base Partition Cleanup, on the extract
may be necessary, depending on whether chromatographic interferences
prevent determination of the analytes of interest.
2.3.1.4.3 Emulsions
Attempts should be made to break up and separate the phases of
an emulsion. Several techniques are effective in breaking emulsions
or separating the phases of emulsions.
1. Freezing/thawing: Certain emulsions will separate if exposed to
temperatures below 0°C.
2. Salting out: Addition of a salt to make the aqueous phase of an
emulsion too polar to support a less polar phase promotes
separation.
.3. Centrifugation: Centrifugal force may separate emulsion
components by density.
4. Addition of water or ethanol: Emulsion polymers may be
destabilized when a preponderance of the aqueous phase is added.
If techniques for breaking emulsions fail, use Method 3520.
If the emulsion can be broken, the different phases (aqueous, solid,
or organic liquid) may then be analyzed separately.
2.3.1.5 Multiphase Samples
Choice of the procedure for aliquoting multiphase samples is very
dependent on the objective of the analysis. With a sample in which some
of the phases tend to separate rapidly, the percent weight or volume of
each phase should be calculated and each phase should be individually
analyzed for the required analytes.
An alternate approach is to obtain a homogeneous sample and attempt
a single analysis on the combination of phases. This approach will give
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no information on the abundance of the analytes in the Individual phases
otr r than what can be implied by solubility.
A third alternative is to select phases of interest and to analyze
only those selected phases. This tactic must be consistent with the
sampling/analysis objectives or it will yield insufficient information for
the time and resources expended. The phases selected should be compared
with Figure 2-1 and Tables 2-34 through 2-36 for further guidance.
2.3.2 Cleanup Procedures
Each category in Table 2-35, Cleanup of Organic Analyte Extracts,
corresponds to one of the possible determinative methods available in the manual,
Cleanups employed are determined by the analytes of interest within the extract.
However, the necessity of performing cleanup may also depend upon the matrix from
which the extract was developed. Cleanup of a sample may be done exactly as
listructed in the cleanup method for some of the analytes. There are some
instances when cleanup using one of the methods may only proceed after the
procedure is modified to optimize recovery and separation. Several cleanup
techniques may be possible for each analyte category. The information provided
is not meant to imply that any or all of these methods must be used for the
analysis to be acceptable. Extracts with components which interfere with
spectral or chromatographic determinations are expected to be subjected to
cleanup procedures.
The analyst's discretion must determine the necessity for cleanup
procedures, as there are no clear cut criteria for indicating their use. Method
3600 and associated methods should be consulted for further details on extract
cleanup.
2.3.3 Determinative Procedures
The determinative methods for organic analytes have been divided into three
categories, shown in Table 2-36: gas chromatography/mass spectrometry (GC/MS);
specific detection methods, i.e., gas chromatography (GC); and high performance
liquid chromatography (HPLC). This division is intended to help an analyst
choose which determinative method will apply. Under each analyte column, SH-846
method numbers have been indicated, if appropriate, for the determination of the
analyte. A blank has been left if no chromatographic determinative method is
available.
Generally, the MS procedures are more specific but less sensitive than the
appropriate gas chromatographic/specific detection method.
Method 8000 gives a general description of the technique of gas
chromatography. This method should be consulted prior to application of any of
the gas chromatographic methods.
Methods 8080 and 8081, for organochlorine pesticides and polychlorinated
biphenyls, Methods 8140 and 8141, for organophosphorus pesticides, and Me'thods
8150 and 8151, for chlorinated herbicides, are preferred over GC/MS because of
the combination of selectivity and sensitivity of the flame photometric,
nitrogen-phosphorus, and electron capture detectors.
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Methods 8240 and 8260 are both GC/HS methods for volatile analytes. Method
8240 uses a packed column whereas Method 8260 employs a capillary column. Better
chromatographic separation of the volatile compounds may be obtained by using
Method 8260 rather than 8240. Performance criteria will be based on Method 8260.
Method 5030 has been combined with both Method 8240 and 8260, with which it was
used exclusively. A GC with a selective detector is also useful for the
determination of volatile organic compounds in a monitoring scenario, described
in Sec. 2,2.5.
Methods 8250 and 8270 are both GC/MS methods for semi volatile analytes.
Method 8250 uses a packed column whereas Method 8270 employs a capillary column.
Better chromatographic separation of the semi volatile compounds may be obtained
by using Method 8270 rather than 8250. Performance criteria will be based on
Method 8270.
2.4 CHARACTERISTICS
Figure 2-2 outlines a sequence for determining if a waste exhibits one or
more of the characteristics of a hazardous waste.
2-4.1 EP and TCLP extracts
The leachate obtained from using either the EP (Figure 2-3A) or the TCLP
(Figure 2-3B) is an aqueous sample, and therefore, requires further solvent
extraction prior to the analysis of semi volatile compounds.
The TCLP leachate is solvent extracted with methylene chloride at a pH > 11
and at a pH <2 by either Method 3510 or 3520. Method 3510 should be used unless
the formation of emulsions between the sample and the solvent prevent proper
extraction. If this problem is encountered, Method 3520 should be employed.
The solvent extract obtained by performing either Method 3510 or 3520 at
a basic or neutral pH will contain the base/neutral compounds of interest. Refer
to the specific determinative method for guidance on the pH requirements for
extraction prior to analysis.
Due to the high concentration of acetate in the TCLP extract, it is
recommended that purge-and-trap be used to Introduce the volatile sample into the
gas chromatograph.
2.5 GROUND WATER
Appropriate analysis schemes for the determination of analytes in ground
water are presented in Figures 2-4A, 2-4B, and 2-4C. Quantitation limits for the
metallic analytes should correspond to the drinking water limits which are
available.
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2.5,1 Special Techniques for Hetal Analvtes
All atomic absorption analyses should employ appropriate background
correction systems whenever spectral interferences could be present. Several
background correction techniques are employed in modern atomic absorption
spectrometers. Matrix modification can complement background correction in some
cases. Since no approach to interference correction is completely effective in
all cases, the analyst should attempt to verify the adequacy of correction. If
the interferant is known (e.g. high concentrations of iron in the determination
of selenium), accurate analyses of synthetic solutions of the interferant (with
and without analyte) could establish the efficacy of the background correction.
If the nature of the interferant is not established, good agreement of analytical
results using two substantially different wavelengths could substantiate the
adequacy of the background correction.
To reduce matrix interferences, all. graphite furnace atomic absorption
(GFAA) analyses should be performed using techniques which maximize an isothermal
environment within the furnace cell. Data indicate that two such techniques,
L'vov platform and the Delayed Atomization Cuvette (DAC), are equivalent in this
respect, and produce high quality results.
All furnace atomic absorption analysis should be carried out using the best
matrix modifier for the analysis. Some examples of modifiers are listed below.
(See also the appropriate methods.)
ElementIs) Hodifier|s)
As and Se Nickel nitrate, palladium
Pb Phosphoric acid, ammonium phosphate, palladium
Cd Ammonium phosphate, palladium
Sb Ammonium nitrate, palladium
Tl Platinum, palladium
The ICP calibration standards must match the acid composition and strength
of the acids contained in the samples. Acid strengths in the ICP calibration
standards should be stated in the raw data.
2.5.2 Special Techniques for Indicated Analvtes and Anions
If an Auto-Analyzer is used to read the cyanide distillates, the
spectrophotometer must be used with a 50 mm path length cell. If a sample is
found to contain cyanioa, the sample must be redistilled a second time and
analyzed to confirm the presence of the cyanide. The second distillation must
fall within the 14-day holding time.
2.6 REFERENCES
1. Barcelona, M.J. "TOC Determinations in Ground Water"; Ground Mater 1984,
22(1). 18-24,
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2. Riggin, R.; et al. Development and Evaluation of Methods for Total Organic
Halide and Purqeable Organic Halidein Wastewater; U.S. Environmental
Protection Agency, Office of Research and Development. Environmental
Monitoring and Support Laboratory. ORD Publication Offices of Center for
Environmental Research Information: Cincinnati, OH, 1984; EPA-600/4-84-008.
3. McKee, 6.; et al. Determination of Inorganic Anions in Water by Ion
Chromatography; (Technical addition to Methods for Chemical Analysis of
Water and Wastewater, EPA 600/4-79-020), U.S. Environmental Protection
Agency. Environmental Monitoring and Support Laboratory. ORD Publication
Offices of Center for Environmental Research Information: Cincinnati, OH,
1984; EPA-600/4-84-017.
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TABLE 2-1
DETERMINATIVE ANALYTICAL METHODS FOR ORGANIC COMPOUNDS
Compound
Applicable Method(s)
Acenaphthene
Acenaphthylene
Acetaldehyde
Acetone
Acetonitrile
Acetophenone
2-Acetylami nof 1uorene
1-Acetyl-2-thiourea
Acifluorfen
Acrolein (Propenal)
Acrylamide
Acrylonitrile
Alachlor
Aldicarb (Temik)
Aldicarb Sulfone
Aldrin
Ally! alcohol
Ally! chloride
2-Aminoanthraquinone
Aminoazobenzene
4-Aminobiphenyl
2-Amino-4,6-dinitrotoluene (2-Ara-DNT)
4-Amino-2,6-dinitrotoluene (4-Ara-DNT)
3-Amino-9-ethylcarbazole
Anilazine
Aniline
o-Anisidine
Anthracene
Araraite
Aroclor-1016 (PCB-1016)
Aroclor-1221 (PCB-1221)
Aroclor-1232 (PCB-1232)
Aroclor-1242 (PCB-1242)
Aroclor-1248 (PCB-1248)
Aroclor-1254 (PCB-1254)
Aroclor-1260 (PCB-1260)
Aspon
Asulam
Atrazine
Azinphos-ethyl
Azinphos-methyl
Barban
Bentazon
8100, 8250/8270, 8310, 8410
8100, 8250/8270, 8310, 8410
8315
8240/8260, 8315
8240/8260
8250/8270
8270
8270
8151
8030/8031, 8240/8260, 8315,
8316
8032, 8316
8030/8031, 8240/8260, 8316
8081
8318
8318
8080/8081, 8250/8270, 8275
8240/8260
8010, 8240/8260
8270
8270
8250/8270
8330
8330
8270
8270
8250/8270
8270
8100, 8250/8270, 8310, 8410
8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8253/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8141
8321
8141
8141
8140/8141, 8270
8270
8151
TWO - 10
Revision 2
September 1994
\
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Benzal chloride
Benzaldehyde
Benz(a)anthracene
Benzene
Benzidine
Benzo(b)fluoranthene
Benzo(j)f1uoranthene
Benzo(k)fluoranthene
Benzoic acid
Benzo(g,h,i)perylene
Benzo(a)pyrene
p-Benzoquinone
Benzotrichloride
Benzyl alcohol
Benzyl benzoate
Benzyl chloride
BHC (Hexachlorocyclohexane)
a-BHC (alpha-Hexachlorocyclohexane)
p-BHC (beta-Hexachlorocyclohexane)
5-BHC (delta-Hexachlorocyclohexane}
7-BHC (Lindane, gamma-Hexachlorocyclohexane)
Bi s(2-Chloroethoxy)methane
Bis(2-Chloroethyl)ether
Bi s(2-Chloroethyl)sul fide
Bis (2-Chloroisopropyl) ether
Bis(2-Ethylhexyl) phthalate
Bo!star (Sulprofos)
Broriiqacetone
Broraobenzene
Bromochloromethane
Bromod i ch1orometh ane
4-Bromof1uorobenzene
Bromoform
Bromomethane
4-Bromophenyl phenyl ether
Bromoxynil
Butanal
n-Butanol
2-Butanone (Methyl ethyl ketone, MEK)
n-Butyl benzene
sec-Butyl benzene
tert-Butylbenzene
Butyl benzyl phthalate
8121
8315
8100, 8250/8270, 8310, 8410
8020, 8021, 8240/8260
8250/8270
8100, 8250/8270, 8310
8100
8100, 8250/8270, 8275, 8310
8250/8270, 8410
8100, 8250/8270, 8310
8100, 8250/8270, 8275, 8310,
8410
8270
8121
8250/8270
8061
8010, 8121, 8240/8260
8120
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8080/8081, 8121, 8250/8270
8010, 8110, 8250/8270, 8410
8110, 8250/8270, 8410
8240/8260
8010, 8110, 8250/8270, 8410
8060/8061, 8250/8270, 8410
8140/8141
8010, 8240/8260
8010, 8021, 8260
8021, 8240/8260
8010, 8021, 8240/8260
8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8110, 8250/8270, 8410
8270
8315
8260
8015, 8240/8260
8021, 8260
8021, 8260
8021, 8260
8060/8061, 8250/8270, 8410
TWO - 11
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
2-sec-Butyl-4,6-dinitrophenol (ONBP, Dinoseb)
Captafol
Captan
Carbaryl (Sevin)
Carbazole
Carbofuran (Furaden)
Carbon disulfide
Carbon tetrachlon'de
Carbophenothion (Carbofenthion)
Chloral hydrate
Chloramben
Chlordane (technical)
a-Chlordane
7-Chlordane
Chlorfenvinphos
Chloroacetonitrile
4-Chloroaniline
Chlorobenzene
Chlorobenzilate
2-Chloro-l,3-butadiene
1-Chlorobutane
Chiorodibromomethane (Dibromochloromethane)
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chloromethane
5-Chloro-2-raethylaniline
Chloromethyl methyl ether
4-Chloro-3-methylphenol
Chloroneb
3-(Chloromethyl)pyridine hydrochloride
1-Chioronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
4-Chloro-l,2-phenylenediamine
4-Chloro-l,3-phenylenediamine
4-Chlorophenyl phenyl ether
Chloroprene
3-Chloropropene
3-Chloropropionitrile
ChloropropyTate
8040, 8150/8151, 8270, 8321
8081, 8270
8081, 8270
8270, 8318
8275
8270, 8318
8240/8260
8010, 8021, 8240/8250
8141, 8270
8240/8260
8151
8080, 8250/8270
8081
8081
8141, 8270
8260
8250/8270, 8410
8010, 8020, 8021, 8240/8260
8081, 8270
8260
8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8240/8260
8010, 8240/8260
8010, 8021, 8240/8260
8010, 8260
8010, 8021, 8240/8260
8270
8010
8040, 8250/8270, 8275, 8410
8081
8270
8250/8270, 8275
8120/8121, 8250/8270, 8410
8040, 8250/8270, 8271, 8410
8410
8270
8270
8110, 8250/8270, 8410
8010, 8240/8260
8260
8240/8260
8081
TWO - 12
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Chlorothalonil
2-Chlorotoluene
4-Chlorotoluene
Chlorpyrifos
Chlorpyrifos methyl
Chrysene
Coumaphos
Coumarin Dyes
p-Cres1dine
o-Cresol (2-Methylphenol)
m-Cresol (3-Methylphenol)
p-Cresol (4-Methylphenol)
Cresols (Methylphenols, Cresylic acids)
Crotonaldehyde
Crotoxyphos
Cyclohexanone
2-Cyclohexyl-4,6-di nitrophenol
2,4-D
Dalapon
2,4-DB
DBCP
2,4-D, butoxyethanol ester
DCPA
DCPA diacid
4,4'-DDD
4,4'-DDE
4,4'-DDT
Decanal
Deraeton-0, and -S
2,4-D,ethylhexyl ester
Dial late
2,4-Diaminotoluene
Diazinon
Dibenz{a,h)acridine
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
7H-Dibenzo(c,g)carbazole
Di benzofuran
Di benzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo{a,i)pyrene
Dibenzothiophene
Dibromochloromethane (Chlorodibromomethane)
1,2-Dibrorao-3-chloropropane
8081
8021, 8260
8010, 8021, 8260
8140/8141
8141
8100, 8250/8270, 8310, 8410
8140/8141, 8270
8321
8270
8250/8270, 8410
8270
8250/8270, 8275, 8410
8040
8260, 8315
8141, 8270
8315
8040, 8270
8150/8151, 8321
8150/8151, 8321
8150/8151, 8321
8081
8321
8081
8151
8080/8081, 8250/8270
8080/8081, 8270
8080/8081, 8250/8270
8315
8140/8141, 8270
8321
8081, 8270
8270
8140/8141
8100
8100, 8250/8270
8100, 8250/8270, 8310
8100
8250/8270, 8410
8100, 8270
8100
8100
8275
8010, 8021, 8240/8260
8010, 8011, 8240/8260, 8270
TWO - 13
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Cofpound
Applicable Method(s)
1,2-Dibroraoethane (Ethylene dibromide)
Di bromof1uoromethane
D "omomethane
C 5-butyl phthalate
Dicamba
Dichlone
1,2-Dichlorobenzene
1,3-Dichlorobenzene
4-Di chlorobenzene
J'-Dichlorobenzidine
-,5-Dichlorobenzoic acid
l,4-Dich1oro-2-butene
ci s-1,4-Dichloro-2-butene
•' ins-l,4-Dichloro-2-butene
.hiorodi fl uororaethane
j., 1 -Di chl oroethane
1,2-Dichloroethane
1,1-Dichloroethene (Vinylidene chloride)
cis-l»2-Dichloroethene
trans-1,2-Dichloroethene
Dichlorofenthion
Dichloromethane (Methylene chloride)
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorprop
1,2-Dichloropropane
1,3-Dichloropropane
2,2-Dichloropropane
l,3-Dichloro-2-propanol
1,1-Dichloropropene
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
Dichlorvos (Dichlorovos)
Dichrotophos
Dicofol
Dieldrin
1,2,3,4-Diepoxybutane
Diethyl ether
Diethyl phthalate
Diethylstilbestrol
Diethyl sulfate
8010, 8011, 8021, 8240/8260
8260
8010, 8021, 8240/8260
8060/8061, 8250/8270, 8410
8150/8151, 8321
8081, 8270
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8010, 8020, 8021, 8120/8121,
8250/8270, 8260, 8410
8250/8270
8151
8010, 8240
8260
8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8021, 8260
8010, 8021, 8240/8260
8141
8010, 8021, 8240/8260
8040, 8250/8270, 8275, 8410
8040, 8250/8270
8150/8151, 8321
8010, 8021, 8240/8260
8021, 8260
8021, 8260
8010, 8240/8260
8021, 8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8140/8141, 8270, 8321
8141, 8270
8081
8080/8081, 8250/8270
8240/8260
8015, 8260
8060/8061, 8250/8270, 8410
8270
8270
TWO - 14
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
1,4-Di f1uorobenzene
Dihydrosaffrole
Dimethoate
3,3'-Dimethoxybenzidine
Dimethyl aminoazobenzene
2,5-Dimethylbenzaldehyde
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine
a,a-Dimethylphenethylamine
2,4-Dimethylphenol
Dimethyl phthalate
Dinitrobenzene
1,2-Di n i trobenzene
1,3-Dinitrobenzene (1,3-DNB)
1,4-Di n'1 trobenzene
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene (2,4-DNT)
2,6-Dinitrotoluene (2,6-DNT)
Dinocap
Dinoseb {2-sec-Butyl-4,6-dinitrophenol, DNBP)
Di-n-octyl phthalate
Di-n-propyl phthalate
Dioxacarb
1,4-Dioxane
Dioxathion
Diphenylamine
5,5-Di phenylhydantoi n
1,2-Di phenylhydrazi ne
Disperse Blue 3
Disperse Blue 14
Disperse Brown 1
Disperse Orange 3
Disperse Orange 30
Disperse Red 1
Disperse Red 5
Disperse Red 13
Disperse Red 60
Disperse Yellow 5
Disulfoton
Endosulfan I
Endosulfan II
Endosulfan sulfate
8240/8260
8270
8141, 8270, 8321
8270
8250/8270
8315
8250/8270
8270
8250/8270
8040, 8250/8270
8060/8061, 8250/8270, 8410
8090
8270
8270, 8330
8270
8250/8270, 8410
8040, 8250/8270, 8410
8090, 8250/8270, 8275, 8330,
8410
8090, 8250/8270, 8330, 8410
8270
8040, 8150/8151, 8270, 8321
8060/8061, 8250/8270, 8410
8410
8318
8240/8260
8141, 8270
8250/8270, 8275
8270
8250/8270
8321
8321
8321
8321
8321
8321
8321
8321
8321
8321
8140/8141, 8270, 8321
8080/8081, 8250/8270
8080/8081, 8210/8270
8080/8081, 8210/8270
TWO - 15
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Endrin
Endrin aldehyde
Endrin ketone
Epichlorohydrin
EPN
Ethanol (Ethyl alcohol)
Ethion
Ethoprop
Ethyl acetate
Ethyl benzene
Ethyl carbamate
Ethylene dibromide
Ethylene oxide
Ethyl methacrylate
Ethyl methanesulfonate
Ethyl parathion
Etridiazole
Famphur
Fenitrothion
Fensulfothion
Fenthion
Fluchloralin
Fluoranthene
Fluorene
Fluorescent Brightener 61
Fluorescent Brightener 236
Fluorobenzene
2-Fluorobiphenyl
2-Fluorophenol
Fonophos
Formaldehyde
Halowax-1000
Halowax-1001
Halowax-1013
Halowax-1014
Halowax-1051
Halowax-1099
Heptachlor
Heptachlor epoxide
Heptanal
Hexach1orobenzene
8080/8081, 8250/8270
8080/8081, 8250/8270
8081, 8210/8270
8010, 8240/8260
8141, 8270
8015, 8240/8260
8141, 8270
8140/8141
8260
8020, 8021, 8240/8260
8270
8010, 8011, 8021, 8240/8260
8240/8260
8240/8260
8250/8270
8270
8081
8141, 8270, 8321
8141
8140/8141, 8270, 8321
8140/8141, 8270
8270
8100, 8250/8270, 8310, 8410
8100, 8250/8270, 8275, 8310,
8410
8321
8321
8260
8250/8270
8250/8270
8141
8315
8081
8081
8081
8081
8081
8081
8080/8081, 8250/8270
8080/8081, 8250/8270
8315
8081, 8120/8121, 8250/8270,
8275, 8410
TWO - 16
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Hexachlorobutadiene (1,3-Hexachlorobutadiene)
Hexachlorocyclohexane
a-Hexachlorocyclohexane (a-BHC)
/3-Hexachl orocyclohexane {/3-BHC)
5-Hexachlorocyclohexane (5-BHC)
•y-Hexachl orocycl ohexane (-y-BHC)
Hexachlorocyclopentadiene
Hexachl oroethane
Hexachlorophene
Hexachloropropene
Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX)
Hexamethylphosphoramide (HMPA)
Hexanal
2-Hexanone
HMX
2,3,4,6,7,8-HpCDD
2,3,4,6,7,8-HpCDF
2,3,4,7,8,9-HpCDF
2,3,4,7,8-HxCDD
2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,7,8-HxCDF
1,2,3,6,7,8-HxCDF
1,2,3,7,8,9-HxCDF
2,3,4,6,7,8-HxCDF
Hydroquinone
3-Hydroxycarbofuran
5-Hydroxydicamba
2-Hydroxypropionitrile
Indeno(l»2,3-cd)pyrene
lodoraethane
Isobutyl alcohol (2-Methyl-l-propanol}
Isodrin
Isophorone
Isopropylbenzene
p-Isopropyltoluene
Isosafrole
8021, 8120/8121, 8250/8270,
8260, 8410
8120
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8080/8081, 8120/8121, 8250,
8270
8081, 8120/8121, 8250/8270,
8410
8120/8121, 8250/8270, 8260,
8410
8270
8270
8330
8141, 8270
8315
8240/8260
8330
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8280/8290
8270
8318
8151
8240/8260
8100, 8250/8270, 8310
8240/8260
8240/8260
8081, 8270
8090, 8250/8270, 8410
8021, 8260
8021, 8260
8270
TWO - 17
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Isovaleraldehyde
Kepone
Leptophos
Malathion
Maleic anhydride
Halononitrile
MCPA
MCPP
Merphos
Mestranol
Methacrylonitrile
Methanol
Methapyrilene
Methiocarb (Hesurol)
Methomy! (Lannate)
Methoxychlor (4,4'-Methoxychlor)
Methyl acrylate
Methyl-t-butyl ether
3-Methylcholanthrene
2-Methyl-4,6-dinitrophenol
4,4'-Methylenebi s(2-chloroani1i ne)
4,4'-Methylenebis(N,N-dimethy1aniline)
Methyl ethyl ketone (MEK, 2-Butanone)
Methylene chloride (Dichloromethane)
Methyl iodide
Methyl isobutyl ketone (4-Methyl-2-pentanone)
Methyl methacrylate
Methyl tnethanesulfonate
2-Methylnaphtha!ene
2-Methyl-5-nitroani1ine
Methyl parathion
4-Methyl-2-pentanone (Methyl isobutyl ketone)
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)
4-Methylphenol (p-Cresol)
2-Methylpyridine
Methyl-2,4,6-trinitrophenylnitramine (Tetryl)
Mevinpho'
Mexacarbcte
Mi rex
Monochrotophos
Naled
Naphthalene
8315
8081, 8270
8141, 8270
8141, 8270
8270
8240/8260
8150/8151, 8321
8150/8151, 8321
8140/8141, 8321
8270
8240/8260
8260
8270
8318
8318, 8321
8080/8081, 8250/8270
8260
8260
8100, 8250/8270
8040
8270
8270
8015, 8240/8260
8010, 8021, 8240/8260
8010, 8240/8260
8015, 8240/8260
8240/8260
8250/8270
8250/8270, 8410
8270
8270, 8321
8015, 8240/8260
8250/8270, 8410
8270
8250/8270, 8275, 8410
8270
8330
8140/8141, 8270
8270
8081, 8270
8141, 8270, 8321
8140/8141, 8270, 8321
8021, 8100, 8250/8270, 8260,
8275, 8310, 8410
TWO - 18
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Naphthoquinone
1,4-Naphthoquinone
1-Naphthylaraine
2-Naphthylamine
Nicotine
5-Nitroacenaphthene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
S-Nitro-o-anisidine
Nitrobenzene (NB)
4-Nitrobiphenyl
Nitrofen
2-Nitrophenol
4-Nitrophenol
2-Nitropropane
Nitroquinoline-1-oxide
N-Ni trosodi butyl ami ne
N-Nitrosodiethyl amine
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylami ne
N-Ni trosomethylethyl ami ne
N-Nitrosomorpholine
N-Nitrosopi peridi ne
N-Nitrosopyrrolidine
o-Nitrotoluene (2-NT)
m-Nitrotoluene (3-NT)
p-Nitrotoluene (4-NT)
5-Nitro-o-toluidine
trans-Nonachlor
Nonanal
OCDD
OCDF
Octahydro-l,3,5,7-tetranitro-l,3,5,7-tetrazocine
(HMX)
Octamethyl pyrophosphoramide
Octanal
4,4'-Oxydianiline
Parathion
Parathion, ethyl
Parathion, methyl
PCB-1016 (Aroclor-1016)
8090
8270
8250/8270
8250/8270
8270
8270
8250/8270, 8410
8250/8270, 8410
8250/8270, 8410
8270
8090, 8250/8270, 8260, 8330,
8410
8270
8081, 8270
8040, 8250/8270, 8410
8040, 8151, 8250/8270, 8410
8260
8270
8250/8270
8270
8070, 8250/8270, 8410
8070, 8250/8270, 8410
8070, 8250/8270, 8410
8270
8270
8250/8270
8270
8330
8330
8330
8270
8081
8315
8280/8290
8280/8290
8330
8270
8315
8270
8270
8141
8140/8141
8080/8081, 8250/8270
TWO - 19
Revision 2
September 1994
-------
TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
PCB-1221 (Aroclor-1221)
PCB-1232 (Aroclor-1232)
PCB-1242 (Aroclor-1242)
PCB-1248 (Aroclor-1248)
PCB-1254 (Aroclor-1254)
RCB-1260 (Aroclor-1260)
PCNB
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,7,8-PeCDF
2,3,4,7,8-PeCDF
"antaehlorobenzene
entachloroethane
;entachlorohexane
Pentachloroni trobenzene
Pentachlorophenol
Pentaf1uorobenzene
Pentanal
trans-Permethrin
Perthane
Phenacetin
Phenanthrene
Phenobarbltal
Phenol
1,4-Phenylened1 ami ne
Phorate
Phosalone
Phosmet
Phosphamidion
Phthalic anhydride
Pi cloram
2-Picoline
Piperonyl sulfoxide
Promecarb
Pronaroide
Propachlor
Propanal
Propargyl alcohol
8-Propiolactone
Propionitrile
Propoxur (Baygon)
n-Propylamine
n-Propylbenzene
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8080/8081, 8250/8270
8081
8280/8290
8280/8290
8280/8290
8280/8290
8121, 8250/8270
8240/8260
8120
8250/8270
8040, 8151, 8250/8270, 8410
8260, 4010
8315
8081
8081
8250/8270
8100, 8250/8270, 8275, 8310,
8410
8270
8040, 8250/8270, 8410
8270
8140/8141, 8270, 8321
8270
8141, 8270
8141, 8270
8270
8151
8240/8260, 8250/8270
8270
8318
8250/8270
8081
8315
8240/8260
8240/8260
8240/8260
8318
8240/8260
8021, 8260
TWO - 20
Revision 2
September 1994
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TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Propylthiouracil
Pyrene
Pyridine
RDX
Resorcinol
Ronnel
Safrole
Simazine
Solvent Red 3
Solvent Red 23
Stirophos (Tetrachlorvinphos)
Strobane
Strychnine
Styrene
Sulfall ate
Sulfotepp
2,4,5-T
2,4,5-T, butoxyethanol ester
2,4,5-T» butyl ester
1,2,3,4-TCDD
1,2,7,8-TCDD
1,2,8,9-TCDD
1,3,6,8-TCDD
1,3,7,8-TCDD
1,3,7,9-TCDD
2,3,7,8-TCDD
1,2,7,8-TCDF
2,3,7,8-TCDF
TEPP
Terbuphos (Terbufos)
Terphenyl
1,2,3,4-Tetrachl orobenzene
1,2,3,5-Tetrachlorobenzene
1,2,4,5-Tetrachlorobenzene
Tetrachlorobenzenes
1,1,1,2-Tetrachl oroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
2,3,4,6-Tetrachl orophenol
Tetrachlorophenol s
Tetrachlorvinphos {Stirophos}
Tetraethyl dithiopyrophosphate
Tetraethyl pyrophosphate
8270
8100, 8250/8270, 8275, 8310,
8410
8240/8260, 8270
8330
8270
8140/8141
8270
8141
8321
8321
8140/8141, 8270
8081
8270, 8321
8021, 8240/8260
8270
8141
8150/8151, 8321
8321
8321
8280
8280
8280
8280
8280
8280
8280/8290
8280
8280/8290
8141
8141, 8270
8250/8270
8121
8121
8121, 8250/8270
8120
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8250/8270
8040
8140/8141, 8270
8270
8270
TWO - 21
Revision 2
September 1994
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TABLE 2-1.
(Continued)
Compound
Applicable Method(s)
Tetrazene
Thiofanox
Thlonazine
Thlophenol (Benzenethiol)
TOCP (Tri-o-cresylphosphate)
Tokuthion (Prothiofos)
m-Tolualdehyde
o-Tolualdehyde
p-Tolualdehyde
Toluene
Toluene diisocyanate
o-Toluidine
Toxaphene
2,4,5-TP (SHvex)
2,4,6-Tribromophenol
1,2,3-Tr1chlorobenzene
1,2,4-Trichlorobenzene
1,3,5-Trichlorobenzene
1,1,1-Trichloroethane
1»1,2-Tri chloroethane
Trichloroethene
Trlchlorof1uoromethane
Trichlorfon
Trichloronate
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Trichlorophenols
1,2,3-Trichloropropane
0,0,0-Triethyl phosphorothioate
Tn'fluralin
2,4,5-Trimethylaniline
1,2,4-Trimethylbenzene
1,3,5-Trimethylbenzene
Trimethyl phosphate
1,3,5-Trinitrobenzene (1,3,5-TNB)
2,4,6-Trlnltrotoluene (2,4,6-TNT)
Tri-o-cresyl phosphate (TOCP)
Tri-p-tolyl phosphate
Tris(2,3-Dibroraopropyl) phosphate (Tris-BP)
Vinyl acetate
Vinyl chloride
8331
8321
8141, 8270
8270
8141
8140/8141
8315
8315
8315
8020, 8021, 8240/8260
8270
8270
8080/8081, 8250/8270
8150/8151, 8321
8250/8270
8021, 8121, 8260
8021, 8120/8121, 8250/8270,
8260, 8410
8121
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8010, 8021, 8240/8260
8141, 8321
8140/8141
8250/8270, 8410
8040, 8250/8270, 8410
8040
8010, 8021, 8240/8260
8270
8081, 8270
8270
8021, 8260
8021, 8260
8270
8270, 8330
8330
8141
8270
8270, 8321
8240/8260
8010, 8021, 8240/8260
TWO - 22
Revision 2
September 1994
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TABLE 2-1.
(Continued)
Compound Applicable Method(s)
o-Xylene 8021, 8260
m-Xylene 8021, 8260
p-Xylene 8021, 8260
Xylene (Total) 8020, 8240
TABLE 2-2A.
HETHOD 3650 - BASE/NEUTRAL FRACTION
Benz(a)anthracene Hexachlorobenzene
Benzo(a)pyrene Hexachlorobutadi ene
Benzo(b)fluoranthene Hexachloroethane
Chiordane Hexac hiorocyclopentad i ene
Chlorinated dibenzodioxins Naphthalene
Chrysene Nitrobenzene
Creosote Phorate
Dichlorobenzene(s) 2-Picoline
Dinitrobenzene Pyridine
2,4-Di ni trotoluene Tetrachlorobenzene(s)
Heptachlor Toxaphene
TABLE 2-2B.
METHOD 3650 - ACID FRACTION
2-Chlorophenol 4-Nitrophenol
Cresol(s) Pentachlorophenol
Creosote Phenol
Dichlorophenoxyacetic acid Tetrachlorophenol(s)
2,4-Dimethylphenol Trichlorophenol(s)
4,6-Dinitro-o-cresol 2,4,5-TP (Silvex)
TWO - 23 Revision 2
September 1994
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TABLE 2-3.
METHOD 5041 - SORBENT CARTRIDGES FROM
VOLATILE ORGANIC SAMPLING TRAIN (VOST)
Acetone 1,2-Dichloropropane
Acrylonitrile cis-l»3-Dichloropropene
Benzene trans-l,3-Dichloropropene
Bromodichloromethane Ethyl benzene3
Bromoform8 lodomethane
Bromomethane Methylene chloride
Carbon disulfide Styrene3
Carbon tetrachloride 1,1,2,2-Tetrachloroethane*
Chi orobenzene Tetrachloroethene
Chi orodlbrompmethane To!uene
Chioroethane 1,1,1-Trlchloroethane
Chloroform 1,1,2-Trichloroethane
Chloromethane Trichloroethene
Dibromomethane Trichlorofluoromethane
1,1-DIchloroethane 1,2,3-Trichlorppropane8
1,2-Dichloroethane Vinyl chloride
1,1-Dichloroethene Xylenes3
trans-1,2-Dichloroethene
3 Boiling point of this compound is above 132DC, Method 0030 is not
appropriate for quantitative sampling of this analyte.
b Boiling point of this compound is below 30°C. Special precautions must be
taken when sampling for this analyte by Method 0030. Refer to Sec. 1.3 of
Method 5041 for discussion.
TWO - 24 Revision 2
September 1994
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TABLE 2-4.
METHOD 8010 - HALOGENATED VOLATILES
Ally! chloridi
Benzyl chloride
Bis(2-chloroethoxy)methane
Bis(2-chloroisopropyl) ether
Bromoacetone
Bromobenzene
Bromodichloromethane
Bromoform
Bromomethane
Carbon tetrachloride
Chlorobenzene
Chloroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane
Chioromethane
Chioromethyl methyl ether
Chioroprene
4-Chlorotoluene
Dibromochloromethane
l,2-D1bromo-3-chloropropane
Dibromomethane
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Di chlorobenzene
l,4-Dichloro-2-butene
Dichlorodifluoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene (Vinylidene chloride)
trans-1,2-Dichloroethene
Dichloromethane (Methylene Chloride)
1,2-Dichloropropane
1,3-Di chloro-2-propanol
cis-l,3-Dichloropropene
trans-1,3-Dichloropropene
Epichlorhydrin
Ethylene dibromide
Methyl iodide
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethene
1,1,1-Trichloroethane
1,1,2-Trichloroethane
Trichloroethene
Tri chlorof1uoromethane
1,2,3-Trichloropropane
Vinyl chloride
For Method 8011, see Table 2-7
TABLE 2-5.
METHOD 8015 - NONHALOGENATED VOLATILES
TABLE 2-6.
METHOD 8020 - AROMATIC VOLATILES
Diethyl ether
Ethanol
Methyl ethyl ketone (MEK)
Methyl isobutyl ketone (MIBK)
Benzene
Chlorobenzene
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Di chlorobenzene
Ethyl benzene
Toluene
Xylenes
TWO - 25
Revision 2
September 1994
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TABLE 2-7.
METHOD 8021 (METHOD 8011*) - HALOGENATED AND AROMATIC VOLATILES
Benzene 1,3-Dichloropropane
Bromobenzene 2,2-Dichloropropane
Bromochloromethane 1,1-Di chloropropene
Bromodichloromethane cis-l,3-Dichloropropene
Bromoform trans-l,3-Dichloropropene
Bromomethane Ethyl benzene
n-Butyl benzene Hexachlorobutadiene
sec-Butyl benzene Isopropyl benzene
tert-Butylbenzene p-Isopropyltoluene
Carbon tetrachloride Methylene chloride (DCM)
Chlorobenzene Naphthalene
Chlorodibromomethane n-Propylbenzene
Chloroethane Styrene
Chloroform 1,1,1,2-Tetrachloroethane
Chloromethane 1,1,2,2-Tetrachloroethane
2-Chlorotoluene Tetrachloroethene
4-Chlorotoluene Toluene
l,2-Dibromo-3-chloropropane* 1,2,3-Trichlorobenzene
1,2-Di bromoethane* 1,2,4-Tri chlorobenzen e
Di bromomethane 1,1,1-Tri chloroethane
1,2-Dichlorobenzene 1,1,2-Trichloroethane
1,3-Dichi obenzene Trichloroethene
1,4-Dichlorobenzene Trichlorofluoromethane
Dichlorodifluoromethane 1,2,3-Trichloropropane
1,1-Di chloroethane 1,2,4-Trlmethylbenzene
1,2-Dlchloroethane 1,3,5-Trimethyl benzene
1,1-Dichloroethene (Vinylidene chloride) Vinyl chloride
cis-l,2-Dichloroethene o-Xylene
trans-l,2-Dichloroethene ra-Xylene
1,2-Dichloropropane p-Xylene
* Indicates the only two target analytes of Method 8011. These constituents are
also target analytes of Method 8021.
TABLE 2-8. TABLE 2-9
METHODS 8030/8031 - METHOD 8032 -
ACROLEIN, ACRYLONITRILE ACRYLAMIDE
Acrolein (Propenal)* Acrylamide
Acrylonitrile
Target analyte of Method 8030 only.
TWO - 26 Revision 2
September 1994
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TABLE Z-10.
METHOD 8040 - PHENOLS
2-sec-Butyl-4,6-dinitrophenol (DNBP, Dinoseb)
4-Chloro-3-methylphenol
2-Chlorophenol
Cresols (Methylphenols)
2-Cyclohexyl-4,6-dinitrophenol
2,4-Dichlorophenol
2,6-Dichlorophenol
2,4-Dimethylphenol
2,4-Dinitrophenol
2-Hethyl -4,6-dinitrophenol
2-Nitrophenol
4-Nitrophenol
Pentachlorophenol
Phenol
Tetrachlorophenols
2,4,6-Trichlorophenol
TrichlorophenolIs
TABLE 2-11.
METHODS 8060/8061 - PHTHALATE ESTERS
Benzyl benzoate*
Butyl benzyl phthalate
Bis(2-ethylhexyl) phthalate
Di-n-butyl phthalate
Diethyl phthalate
Dimethyl phthalate
Di-n-oetyl phthalate
* Target analyte of Method 8061 only.
TABLE 2-12.
METHOD 8070 - NITROSAMINES
N-Nitrosodinethylaiine
N-Nitrosodiphenylamine
N-Ni trosodi-n-propylami ne
TWO - 27
Revision 2
September 1994
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TABLE 2-13.
METHODS 8080/8081 - ORGANOCHLORINE PESTICIDES AND PCBs
Aroelor-1016 (PCB-1016)
Aroclor-1221 (PCB-1221)
Aroclor-1232 (PCB-1232)
Aroclor-1242 (PCB-1242)
Aroclor-1248 (PCB-1248)
Aroclor-1254 (PCB-1254)
Aroclor-1260 (PCB-1260)
Alachlor*
Odrin
a-BHC
0-BHC
5-BHC
-BHC (Lindane)
rtafol*
.iptan*
Cnlorobenzilate*
Chlordane (technical)**
a-Chlordane*
y-Chlordane*
Chloroneb*
Chloropropylate*
Chlorothalonil*
DBCP*
DCPA*
4,4'-DDD
4,4'-DDE
4,4'-DDT
Dial!ate*
Dichlone*
Dicofol*
Dieldrin
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone*
Etridiazole*
Halowax-1000*
Halowax-1001*
Halowax-1013*
* Target analyte of Method 8081 only.
** Target analyte of Method 8080 only.
Halowax-1014*
Halowax-lOSl*
Halowax-1099*
Heptachlor
Heptachlor epoxide
Hexachlorobenzene*
Hexachlorocyclo-
pentadiene*
Isodrin*
Kepone*
Hethoxychlor
Hi rex*
Nitrofen*
trans-Nonachlor*
PCNB*
trans-Permethrin*
Perthane*
Propachlor*
Strobane*
Toxaphene
Trifluralin*
TABLE 2-14.
METHOD 8090 - NITROAROMATICS AND
CYCLIC KETONES
Dinitrobenzene
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Isophorone
Naphthoquinone
Nitrobenzene
TWO - 28
Revision 2
September 1994
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TABLE 2-15,
METHODS 8100 - POLYNUCLEAR AROMATIC HYDROCARBONS
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)fluoranthene
Benzo(j)f1uoranthene
Benzo(k)fluoranthene
Benzo (g»h»i)perylene
Benzo(a)pyrene
Chrysene
Dibenz(a»h)acridine
D1benz(a,j)acr1dine
Dibenzo(a,h)anthracene
7H-Dibenzo(c»i)carbazole
Dibenzo(a,e)pyrene
Dibenzo(a,h)pyrene
Dibenzo(a,i)pyrene
Fluoranthene
Fl uorene
Indeno(l,2,3-cd)pyrene
3-Methylcholanthrene
Naphthalene
Phenanthrene
Pyrene
TABLE 2-16
METHOD 8110 - HALOETHERS
Bis{2-Chloroethoxy)methane
Bis(Z-Chloroethyl) ether
Bis(Z-Chloroisopropyl) ether
4-Bromophenyl phenyl ether
4-Chlorophenyl phenyl ether
TABLE 2-17.
METHODS 8120/8121 - CHLORINATED HYDROCARBONS
Benzal chloride*
Benzotrichloride*
Benzyl chloride*
2-Chloronaphthalene
1,2-Di chlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
Hexachlorobenzene
Hexachlorobutadi ene
Hexachlorocyclohexane**
o-Hexachlorocyclohexane (a-BHC)*
p-Hexachlorocyclohexane (
5-Hexachlorocyclohexane (5-BHC)*
y-Hexachlorocyclohexane (y-BHC}*
Hexachlorocyclopentad i ene
Hexachloroethane
Pentachlorobenzene*
Pentachlorohexane**
Tetrac h1orobenzene s**
1,2,3,4-Tetrachl orobenzene*
1,2,3,5-Tetrachl orobenzene*
1,2(4,5-Tetrachl orobenzene*
1,2,3-Trichlorobenzene*
1,2,4-Trichlorobenzene
l»3»S-Trichlorobenzene*
* Target analyte of Method 8121 only.
** Target analyte of Method 8120 only.
TWO - 29
Revision 2
September 1994
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TABLE 2-18.
METHODS 8140/8141 - ORGANOPHOSPHORUS COMPOUNDS
(PACKED AND CAPILLARY COLUMNS)
Aspon* Fenthion
Atrazine* Fonophos*
Azinphos ethyl* Hexamethylphosphoramide* (HMPA)
Azinphos methyl Leptophos*
Bolstar (Sulprofos) Malathion*
Carbophenothion* Merphos
Chlorofenvinphos* Mevinphos
Chlorpyrifos Monochrotophos*
Chlorpyrifos methyl* Naled
Coumaphos Parathlon, ethyl*
Crotoxypos* Parathlon, methyl
Demeton-0, and -S Phorate
Dlazinon Phosmet*
Dichlorofenthion* Phosphamidon*
Dichlorvos (DDVP) Ronnel
Dichrotophos* Simazine*
Dimethoate* Stirophos (Tetrachlorvinphos)
Dioxathion* Sulfotep*
Disulfoton TEPP*
EPN* Terbufos*
Ethion* Thionazin*
Ethoprop Tokuthion (Prothiofos)
Famphur* Trichlorfon*
Fen1 trothion* Trichloronate
Fensulfothlon Trl-o-cresylphosphate (TOCP)*
* Target analyte of Method 8141 only.
TABLE 2-19.
METHODS 8150/8151 - CHLORINATED HERBICIDES
Acifluorfen* Dicamba MCPA
Bentdzon* 3,5-Dichlorobenzoic acid* MCPP
Chloramben* 'Dichlorprop 4-Nitrophenol*
2,4-D Dinoseb (DNBP) Pentachlorophenol*
Dalapon 5-Hydroxydicamba* Piclorara*
2,4-DB 2,4,5-TP (Silvex)
DCPA diacid* 2,4,5-T
* Target analyte of Method 8151 only.
TWO - 30 Revision 2
September 1994
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TABLE 2-20,
METHODS 8240/8260 - VOLATILES
Acetone
Acetonitrlle
Acrole i n (Propenal)
Acrylonltrile
Allyl alcohol
Allyl chloride
Benzene
Benzyl chloride
Bis(2-chloroethyl) sulflde
Bromoacetone
Bromobenzene*
Bromochloromethane
Bromodichloromethane
4-Bromof1uorobenzene
Bromoform
Bromomethane
n-Butanol*
2-Butanone (Methyl ethyl
ketone)
n-Butylbenzene*
sec-Butyl benzene*
tert-Butylbenzene*
Carbon disulfide
Carbon tetrachlorlde
Chloral hydrate
Chioroacetoni trl1e*
Chlorobenzene
2-Chloro-l,3-butadiene*
1-Chlorobutane*
Chiorod1bromomethane
Chioroethane
2-Chloroethanol
2-Chloroethyl vinyl ether
Chloroform
1-Chlorohexane*
Chloromethane
Chloroprene
3-Chloropropene*
3-Chl oropropi oni tri1e
2-Chlorotoluene*
4-Chlorotoluene*
Crotonaldehyde*
l,2-Dibromo-3-
chloropropane
1,2-Dibromoethane
Dibromomethane
Di bromofluoromethane*
1,2-Di chlorobenzene*
1,3-Dichlorobenzene*
1,4-Dichlorobenzene*
l,4-Dichloro-2-butene**
cis-l,4-Diehloro-
2-butene*
trans-l»4-Dichloro-2-
butene*
l,4-Dichloro-2-butene**
Di chlorodi f1uoromethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
ci s-1,2-Di chloroethene*
trans -1,2-Dichloroethene
1,2-Dichloropropane
1,3-Di chloropropane*
2,2-Di chloropropane*
l,3-Dichloro-2-propanol
1,1-Di chloropropene*
cis-l,3-Dichloropropene
trans-l,3-Dichloropropene
1,2,3,4-Diepoxybutane
Diethyl ether*
1,4-Difluorobenzene
1,4-Qioxane
Epichlorohydrln
Ethanol
Ethyl acetate*
Ethyl benzene
Ethylene oxide
Ethyl ntethacrylate
Fluorobenzene*
Hexachlorobutadi ene*
Hexachloroethane*
2-Hexanone
2-Hydroxypropionitrile
lodomethane
Isobutyl alcohol
Isopropylbenzene*
p-Isopropyltoluene*
Malononitrile
Methacrylonitrile
Methanol*
Methyl acrylate*
Methyl-t-butyl ether*
Methylene chloride (DCM)
Methyl iodide
Methyl methacrylate
4-Methyl-2-pentanone
(MIBK)
Naphthalene*
Nitrobenzene*
2-Nitropropane*
Pentachloroethane
Pentafluorobenzene*
2-Picoline
Propargyl alcohol
6-Propiolactone
Propionitrile
n-Propylamine
n-Propylbenzene*
Pyridine
Styrene
1,1,1,2-Tetrachloroethane
1,1,2,2-Tetrachloroethane
Tetrachloroethene
Toluene
1,2,3-Trichlorobenzene*
1,2,4-Trichlorobenzene*
1,1,1-Tri chloroethane
1,1,2-Tri chloroethane
Trichloroethene
Trichlorofluoromethane
1,2,3-Trichloropropane
1,2,4-Trimethylbenzene*
1,3,5-Trimethylbenzene*
Vinyl acetate
Vinyl chloride
Xylene (Total)**
o-Xylene*
m-Xylene*
p-Xylene*
* Target analyte of Method 8260 only.
** Target analyte of Method 8240 only.
TWO - 31
Revision 2
September 1994
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TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES
Acenaphthene
Acenaphthyl ene
Acetophenone
2 -Acetyl ami nof 1 uorene*
1 -Acetyl -2-th iourea*
Aldrin
2 - Ami noanthraqu i none*
Ami noazobenzene*
4-Aminobiphenyl
3-Amino-9-ethylcarbazole*
Anilazine*
Aniline
o-Anisidine*
Anthracene
Aramite*
Aroclor-1016 (PCB-10I6)
Aroclor-1221 (PCB-1221)
Aroclor-1232 (PCB-1232)
Ar-"? or- 1242 (PCB-I242)
Ar or-1248 (PCB-1248)
Ar ;or-1254 (PCB-1254)
Arcclor-1260 (PCB-1268)
Azinphos-methyl*
Barban*
Benz{a)anthracene
Benzidine
Benz f b) f 1 uoranthene
Benzo{ k) f 1 uoranthene
Benzole acid
Benzofgjhjijperylene
Benzo|a)pyrene
p-Benzoquinone*
Benzyl alcohol
a-BHC
5-BHC
7-BHC (Lindane)
Bis(2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl) ether
Bis(2-ethylhexyl) phthalate
4-Bromophenyl phenyl ether
Bromoxynil*
Butyl benzyl phthalate
2-sec-Butyl-4,6-dinitrophenol (Dinoseb)
Captafol*
Captan*
Carbaryl*
Carbofuran*
Carbophenothion*
Chlordane (technical)
Chlorfenvinphos*
4-Chloroaniline
Chi orobenz Hate*
5-Chloro-2-methylani1ine*
4-Chloro-3-methylphenol
3-(Ch1oromethy1)pyridine hydrochloride*
1-Chioronaphthalene
2-Chloronaphthalene
2-Chlorophenol
4-Chloro-1,2-phenylenedi ami ne*
4-Chloro-l,3-phenylenediamine*
4-Chlorophenyl phenyl ether
Chrysene
Coumaphos*
p-Cresidine*
Crotoxyphos*
2-Cyclohexyl-4,6-dinitrophenol*
4,4'-ODD
4,4'-DDE*
4,4'-DDT
Demeton-0*
Demeton-S*
Diallate (cis or trans)*
2,4-Diaminotoluene*
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
Dibenzofuran
Dibenzo(a,e)pyrene*
l,2-Dibromo-3-chloropropane*
Di-n-butyl phthalate
Dichlone*
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3'-Dichlorobenzidine
2,4-Dichlorophenol
2,6-Dichlorophenol
Dichlorovos*
Dicrotophos*
Dieldrin
Diethyl phthalate
D1ethylstilbestrol*
Diethyl sulfate*
Dihydrosaffrole*
Dimethoate*
3,3'-Dimethoxybenzidine*
Dimethyl aminoazobenzene
TWO - 32
Revision 2
September 1994
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TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
7,12-Dimethylbenz(a)anthracene
3,3'-Dimethylbenzidine*
a»Q!-Dimethylphenethylainine
2,4-Dimethylphenol
Dimethyl phthalatt
1,2-Dinitrobenzene*
1,3-Dinitrobenzene*
1,4-Dinitrobenzene*
4,6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Dinocap*
Dioxathion*
Diphenylaraine
5,5-Diphenylhydantoi n*
1,2-Diphenylhydrazine
Di-n-octyl phthalate
Disulfoton*
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrin aldehyde
Endrin ketone
EPN*
Ethion*
Ethyl carbamate*
Ethyl methanesulfonate
Ethyl parathion*
Famphur*
Fensulfothion*
Fenthion*
Fluchloralin*
Fluoranthene
Fluorene
2-Fluorobiphenyl
2-Fluorophenol
Heptachlor
Heptachlor epoxide
Hexachlorobenzene
Hexachlorobutad i ene
Hexachlorocyclopentadiene
Hexachloroethane
Hexachlorophene*
Hexachloropropene*
Hexamethylphosphoramide*
Hydroquinone*
Indeno(l,2,3-cd)pyrene
Isodrin*
Isophorone
Isosafrole*
Kepone*
Leptophos*
Malathion*
Maleic anhydride*
Mestranol*
Methapyrilene*
Methoxychlor
3-Methylcholanthrene
4,4'-Methylenebis(2-chloroaniline)*
4,4'-Methylenebis(N,N-dimethyl aniline)*
Methyl methanesulfonate
2-Hethylnaphthalene
2-Methyl-5-nitroaniline*
Methyl parathion*
2-Methylphenol (o-Cresol)
3-Methylphenol (m-Cresol)*
4-Methylphenol (p-Cresol)
2-Methylpyridine*
Mevinphos*
Mexacarbate*
Mi rex*
Monocrotophos*
Nal ed*
Naphthalene
1,4-Naphthoquinone*
1-Naphthylamine
2-Naphthylamine
Nicotine*
5-Nitroaeenaphthene*
2-Nitroaniline
3-Nitroaniline
4-Nitroanil ine
5-Nitro-o-anisidine*
Nitrobenzene
4-Nitrobiphenyl*
Nitrofen*
2-Nitrophenol
4-Nitrophenol
Nitroquino!ine-1-oxide*
N-Nitrosodibutyl amine
N-Nitrosodiethylamine*
N-Nitrosodimethylamine
N-N i trosodi phenylami ne
N-Nitrosodi-n-propylamine
TWO - 33
Revision 2
September 1994
-------
TABLE 2-21.
METHODS 8250/8270 - SEMIVOLATILES (CONTINUED)
N-Nitrosomethyl ethyl ami m*
N-Nitrosomorphol ine*
N-Nitrosopfperidine
N-Nitrosopyrrolidine*
5-Nitro-o-toluid1ne*
Octamethyl pyrophosphoramide*
4,4'-Qxydianiline*
Parathion*
Pentachlorobenzene
Pentachloronitrobenzene
Pentachlorophenol
Phenacetin
Phenanthrene
Phenobarbital*
Phenol
1,4-Phenylenediamine*
Phorate*
Phosalone*
Phos«ji=t*
Phospnamidion*
Phthas vc anhydride*
2-Picoline
Piperonyl sulfoxide*
Pronamide
Propylthiouracil*
'yrene
Jyr1d1ne*
Resorcinol*
Safrole*
Strychnine*
Sulfall ate*
* Target analyte of Method 8270 only.
Terbuphos*
Terphenyl
1,2,4,5-Tetrachlorobenzene
2,3,4,6-Tetrachlorophenol
Tetrachlorvinphos (Stlrophos)*
Tetraethyl dlthiopyrophosphate*
Tetraethyl pyrophosphate*
Thionazine*
Thiophenol (Benzenethiol)*
Toluene dilsocyanate*
o-Toluidine*
Toxaphene
2,4,6-Tri broroophenol
1,2,4-Tri chlorobenzene
2,4»5-Trichlorophenol
2,4,6-Trichlorophenol
0,0,0-Triethyl phosphorothioate*
Trifluralin*
2,4,5-Trimethylaniline*
Trimethyl phosphate*
1,3,5-Tr1nitrobenzene*
Tris(2,3-dibromopropyl} phosphate*
Trl-p-tolyl phosphate*
TABLE 2-22.
METHOD 8275 - SEMIVOLATILES (SCREENING)
Aldrin
Benzo(k)fl uoranthene
Benzo(a)pyrene
Carbazole
4-Chloro-3-methylphenol
1-Chloronaphthalene
2-Chlorophenol
Dibenzothlophene
2,4-Dichlorophenol
2,4-Dinltrotoluene
Diphenylamine
Fluorene
Hexachlorobenzene
4-Methylphenol
Naphthalene
Phenanthrene
Pyrene
TWO - 34
Revision 2
September 1994
\.
\
-------
2,3,7,8-TCDD
1,2,3,4-TCDD*
1,3,6,8-TCDD*
1,3,7,9-TCDD*
1,3,7,8-TCDD*
1,2,7,8-TCDD*
1,2,8,9-TCDD*
TABLE 2-23.
METHODS 8280/8290 - DIOXINS AND DIBENZOFURANS
1,2,3,4,7-PeCDD
1,2,3,7,8-PeCDD
1,2,3,4,7,8-HxCDD
1,2,3,6,7,8-HxCDD
1,2,3,7,8,9-HxCDD
1,2,3,4,6,7,8-HpCDD
OCDD
Target analyte of 8280 only
1,2,7,8-
2,3,7,8-
1,2,3,7,
2,3,4,7,
1,2,3,4,
1,2,3,6,
1,2,3,7,
2,3,4,6,
1,2,3,4,
1,2,3,4,
OCDF
TCDF
TCDF
8-PeCDF
8-PeCDF
7,8-HxCOF
7,8-HxCOF
8,9-HxCDF
7,8-HxCDF
6,7,8-HpCDF
7,8,9-HpCDF
TABLE 2-24.
METHOD 8310 - POLYNUCLEAR AROMATIC HYDROCARBONS
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)f1uoranthene
Benzo(g,h,1)perylene
Benzo(k)f1uoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
TWO - 35
Revision 2
September 1994
\
\
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TABLE 2-25.
METHOD 8315 - CARBONYL COMPOUNDS
Acetaldehyde Heptanal
Acetone Hexanal (Hexaldehyde)
Acrolein (Propanol) Isovaleraldehyde
Benzaldehyde Nonanal
Butanal (Butyraldehyde) Octanal
Crotonaldehyde Pentanal (Valeraldehyde)
Cyclohexanone Propanal (Propionaldehyde)
Decanal m-Tolualdehyde
2,5-Dimethylbenzaldehyde o-Tolualdehyde
Formaldehyde p-Tolualdehyde
TABLE 2-26. TABLE 2-27.
METHOD 8316 - ACRYLAMIDE, METHOD 8318 - N-HETHYLCARBAHATES
ACRYLONITRILE AND ACROLEIN
Aldicarb (Temlk)
Acrolein {Propanol) Aldicarb Sulfone
Acrylamide Carbaryl (Sevin)
Acrylonitrile Carbofuran (Furadan)
Dioxacarb
3-Hydroxycarbofuran
Methiocarb (Mesurol)
Methomyl (Lannate)
Promecarb
Propoxur (Baygon)
TWO - 36 Revision 2
September 1994
-------
TABLE 2-28.
METHOD 8321 - NONVOLATILES
Azo Dv.es..
Disperse Red 1
Disperse Red 5
Disperse Red 13
Disperse Yellow 5
Disperse Orange 3
Disperse Orange 30
Disperse Brown 1
Solvent Red 3
Solvent Red 23
Anthraquinone Dves
Disperse Blue 3
Disperse Blue 14
Disperse Red 60
Coumarin Dyes
(Fluorescent Brighteners)
Fluorescent Brightener 61
Fluorescent Brightener 236
Chlorinated Phenoxvacid Compounds
2,4-D
2,4-D, butoxyethanol ester
2,4-D, ethylhexyl ester
2,4-OB
Dalapon
Dicamba
Dichlorprop
Dinoseb
MCPA
MCPP
Silvex (2,4,S-TP)
2,4,5-T
2,4,5-T, butyl ester
2,4,5-T, butoxyethanol ester
Alkaloids
Strychnine
Qrganophpsphorus Compounds
Asulam
Dichlorvos
Dimethoate
Disulfoton
Famphur
Fensulfothion
Merphos
Methomyl
Methyl parathion
Monocrotophos
Naled
Phorate
Trichlorfon
Thiofanox
Tris-(2,3-dibromopropyl) phosphate,
(Tris-BP)
TWO - 37
Revision 2
September 1994
-------
TABLE 2-29.
METHOD 8330 - NITROAROHATICS AND NITRAMINES
4-Amino-2»6-dinitrotoluene (4-Am-DNT)
2-Amino-4,6-dinitrotoluene (2-Am-DNT)
1,3-Dinitrobenzene (1,3-DNBJ
2,4-Dinitrotoluene (2,4-DNT)
2,6-Dinitrotoluene (2,6-DNT)
Hexahydro-l,3,5-trinitro-l,3,5-triazine (RDX)
Methyl-2,4,6-trin1trophenylnitramine (Tetryl)
Nitrobenzene (NB)
2-Nitrotoluene (2-NT)
3-Nitrotoluene (3-NT)
4-Nitrotoluene (4-NT)
Octahydro-MjSJ-tetnnitro-M^S^-tetrazocine (HMX)
1,3,5-THnitrobenzene (1,3,5-TNB)
2,4,6-THnitrotoluene (2,4,6-TNT)
TABLE 2-30.
METHOD 8331 - TETRAZENE
Tetrazene
TWO - 38 Revision 2
September 1994
-------
TABLE 2-31
METHOD 8410 - SEHIVOLATILES
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(b)pyrene
Benzole acid
Bi s(2-chloroethoxyjmethane
Bis(2-chloroethyl)ether
Bis(2-chloroisopropyljether
Bis(2-ethylhexyl)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
4-Chloroaniline
4-Chl oro-3-methyl phenol
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
Chrysene
Dibenzofuran
Di-n-butyl phthalate
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
2,4-Dichlorophenol
Diethyl phthalate
Dimethyl phthalate
4»6-Dinitro-2-methylphenol
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Di ni trotoluene
Di-n-octyl phthalate
Di-n-propyl phthalate
Fluoranthene
Fluorene
Hexachlorobenzene
1,3-Hexachlorobutadi ene
Hexachlorocyclopentadiene
Hexachloroethane
Isophorone
2-Methylnaphthalene
2-Methylphenol
4-Hethylphenol
Naphthalene
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-N1trophenol
4-N1trophenol
N-Ni trosodi methyl ami ne
N-Nitrosodiphenylamine
N-Nitroso-di-n-propylamine
Pentachlorophenol
Phenanthrene
Phenol
Pyrene
1,2,4-Tri chlorobenzene
2,4,5-Trichlorophenol
2,4,6-Tri chlorophenol
TWO - 39
Revision 2
September 1994
-------
TABLE 2-32.
ANALYSIS METHODS FOR INORGANIC COMPOUNDS
Compound
Aluminum
Antimony
Arsenic
Barium
Beryl 1 i urn
Bromide
Cadmium
Calcium
Chloride
Chromium
Chromium, hexavalent
Cobalt
Copper
Cyanide
Fluoride
Iron
Lead
Lithium
Magnesium
Manganese
Mercury
Molybdenum
Nickel
Nitrate
Nitrite
Osmi urn
Phosphate
Phosphorus
Potassium
Selenium
Silver
Sodium
Strontium
Sulfate
Sulfide
Thallium
Tin
Vanadium
Zinc
Applicable Hethod(s)
6010,
6010,
6010,
6010,
6010,
9056
6010,
6010,
9056,
6010,
7195,
6010,
6010,
9010,
9056
6010,
6010,
6010,
6010,
6010,
7470,
6010,
6010,
9056,
9056
7550
9056
6010
6010,
6010,
6010,
6010,
6010,
9035,
9030,
6010,
7870
6010,
6010,
6020,
6020,
6020,
6020,
6020,
6020,
7140
9250,
6020,
7196,
6020,
6020,
9012,
7380,
6020,
7430
7450
6020,
7471
7480,
6020,
9200
7610
7740,
6020,
7770
7780
9036,
9031
6020,
7310,
6020,
7020
7040,
7060,
7080,
7090,
7130,
9251,
7190,
7197,
7200,
7210,
9013
7381
7420,
7460,
7481
7520
7741,
7760,
9038,
7840,
7911
7950,
7041,
7061,
7081
7091
7131
9252,
7191
7198
7201
7211
7421
7461
7742
7761
9056
7841
7951
7062
7062
9253
TWO - 40
Revision 2
September 1994
-------
TABLE 2-33,
CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TINES FOR AQUEOUS MATRICES*
Name
Bacterial Tests:
Col i form, total
Inorganic Tests:
Chloride
Cyanide, total and amenable
to ch lor (nation
Container
P, C
P, C
P, G
Preservation
Cool, 4*C. 0.008% Ma,S,0,
None required
Cool, 4t; if oxidizing
agents present add 5 ml
Maximum holding
6 hours
28 days
14 days
time
0.1N NaAsO., per L or 0.06 g
of ascorbic ecid per L;
adjust pH>12 with SOX NaOH.
See Method 9010 for other
interferences.
Hydrogen ion
0.
008% Na2S,0,
dark
0.
008% Ka,S,0, ,
dark
,e»«C
4°C
4°C
4°C
4°C
4"C
4'C
in
4°C
4"C
4"C
£
7 days until extraction,
after extraction
7 days until extraction,
after extraction
7 days until extraction,
after extraction
7 days until extraction.
after extraction
7 days until extraction.
after extraction
7 days until extraction,
after extraction
28 days
28 days
7 days until extraction,
after extraction
7 days until extraction,
i
0.
008% Na,S,033
after extraction
7 days until extraction,
after extraction
7 days until extraction.
,
0.
008% Na.S.0,3
dark
i
2
0.
0.
008% Ma,SA '
008% NatSA3
to pH<2
after extraction
7 days until extraction,
after extraction
14 days
14 days
28 days
6 months
40
40
40
40
40
40
40
40
40
40
40
days
days
days
days
days
days
days
days
days
days
days
1
Table excerpted, in part, from Table II, 49 FR 209, October 26, 1984, p 28.
Polyethylene (P) or Glass
-------
TABLE 2-34. PREPARATION METHODS FOR ORGANIC ANALYTES
Acids
Acrolein
Acrylonitrile
Acetonitrile
Aromatic Volatile*
Base/Neutral
Chlorinated
Herbicides
Chlorinated
Hydrocarbons
Halogenated
Volatiles
Nitroaromatic and
Cyclic Ketones
Non-halogenated
VolatHes
Organochlorine
Pesticides and PCBs
Organophosphorus
Pesticides
Phenol s
Phthalate Esters
Polynuclear
Aromatic
Hydrocarbons
Volatile Organics
Aqueous (pH)3
3510
3520
(PH <2)
5030
S030
3510
3S20
(pH >11)
8150
8151
(PH <2)
3510
3520
(pH 7)
5030
3510
3520
(pH 5-9)
5030
3510
3520
3665
(pH 5-9)
3510
3520
{pH 6-8)
3510
3520
(pH <2)
3510
3520
(pH 7)
3510
3520
(PH 7)
5030
Solids
3540, 3541
3550
35802
5030
5030
3540
3541
3550
35802
8150
8151
35802
3540
3541
3550
35802
5030
3540
3541
3550
35802
5030
3540
3541
35802
3665
3540
3541
35802
3540
3541
3550
35802
3540
3541
3550
35802
3540, 3541
3550
35802
5030
Sludges
Emulsions1 (pH)3
3520
(PH <2)
5030
5030
3520
(pH >11)
8150
8151
(pH <2)
3520
(pH 7)
5030
3520
(pH 5-9)
5030
3520
(pH 5-9)
3520
(pH 6-8)
3520
(pH <2)
3520
(pH 7)
3520
(PH 7)
5030
Oils
3650,
35802
5030
5030
3650
35802
35802
35802
5030
35802
5030
35802
35802
3650
35802
35802
3560
35802
5030
1 If attempts to break up emulsions are unsuccessful,
2 Method 3580 is only appropriate if the sample is sol
3 pH at which extraction should be performed.
these methods may be used.
uble in the specified solvent,
TWO - 42
Revision 2
September 1994
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TABLE 2-3i,
CLEANUP OF ORGANIC ANALYTE EXTRACTS
Analyte Type
Acids
Base/Neutral
Chlorinated
Herbicides
Chlorinated
Hydrocarbons
Nitroaromatics &
Cyclic Ketones
Organophosphorus
Pesticides
Organochlorine
Pesticides &
PCBs
Phenol s
Phthalate
Esters
Polynuclear
Aromatic
Hydrocarbons
Method(s)
3610
3650
8150
8151
3620
3640
3620
3640
3620
3620
3630
3640
3660
3665
3630
3640
3650
3610
3611
3620
3640
3610
3611
3630
3640
TWO - 43
Revision 2
September 1994
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TABLE 2-36.
DETERMINATION OF ORGANIC ANALYTES
SC/MS Determination
Methods
Specific SC Detection
Methods
1
HPIC
SOttVOlATILES
Acids
Base/Neutral
Carbamates
Chlorinated Herbicides
Chlorinated Hydrocarbons
Oves
Explosives
Haloethers
Nitroaromatics and Cyclic
Ketones
Nitrcsoamines
Qrganochlorine Pesticides and
PCBs
Organophosphorous Pesticides
Phenols
Phthalate Esters
Polynuelear Aromatic
Hydrocarbons
8270
8250
8270
8250
8270*
8270
8250
8270
8250
8270
8250
827D
8250
8270*
8270*
8270
8250
8270
8250
8270
8250
8150
8151
8120
8121
8110
8090
8070
8080
8081
8140
8141
8040
8060
8061
8100
8318
83Z1
8330
8331
8321
8310
WEATIIES
Acrolein, Acrylonitrile,
Ac*1" wilt rile
Acr> : amide
Aromatic Volatile:
Formaldehyde
Halogenated Volatiles
Non-haloejenated Volatiles
Volatile Organies
8240
8260
8240
8260
8240
8260
8240
8240
8260
8030
8031
8032
8020
8021
8010
8011
8021
8015
8010
8011
8020
8021
8030
8031
8316
8315
8316
8315
8315
8316
*This method is an alternative confirmation method. It is not the method of choice.
TWO - 44
Revision 2
September 1994
-------
FIGURE 2-1.
ORGANIC ANALYSIS OPTIONS
Sample
lo be Analyzed
lor Exlractables
Volaliles
GC/MS Analysis
Procedure:
Packed Column: 6240
Capillary Column: 8260
GC Analysis Procedure
Halogenated Volatile Organics: 8010
EDBandDBCP: 8011
Nonhalogenated Volatile Organics 8015
Aromatic Volatile Organics: 8020
Halogenated Volatile Compounds: 6021
Acrolein, Acrylonittile: 6030
Acrylamlde 6032
Cleanup Procedure:
Alumina Column:
Alumina Column lor Petroleum Wastes:
Ftorisil Column:
Silica Gel Column:
Gel Permeation:
Acid Base Partitioning:
Sullur:
3610
3611
3620
3630
3640
36SO
3660
HPLC Analysis Procedures:
8310.6318,8321.6330.6331
HPLC Analysis Procedures:
Acrolein, Acrylonitrile, Acrylamide: 8316
Formaldehyde: 8315
:/MS
GC/MS Procedures:
Packed Column: 8250
Capillary Column: B270
GC Analysis Procedures:
Phenols: 8040
Phthalate Esters: B060
NKrosamines: 8070
Organochlorine Pesticides and PCBs: 80BO
Nitroaromatics and Cyclic Ketones: 8090
Polynuclear Aromatic Hydrocarbons: 8100
Haloelhers: 8110
Chlorinated Hydrocarbons: 8120, 8121
Organophosphorus Pesticides: 6140, 6141
Chlorinated Herbicides: 6150.8151
TWO - 45
Revision 2
September 1994
-------
FIGURE 2-2,
SCHEMATIC OF SEQUENCE TO DETERMINE
IF A WASTE IS HAZARDOUS BY CHARACTERISTIC
DOT(49CFR173.3QO)
Is waste
ignttable?
is
waste
reactive to
strand/or
water1?
Nonhazardous by
reason of
ignrtabiltty
characteristic
Is waste
explosive?
Generator Knowledge
DOT (49 CFH 173.151)
What is
physical state
of waste?
Is waste
tanitabte?
Perform Paint
FtterTest
(Method 9095)
Methods iroand9040
Yes
f Nonhazardous X
( for corrosivlty )
Methods 1010 or 1020
Yas
TWO - 46
Revision 2
September 1994
-------
FIGURE 2-2.
(Continued)
Nonhazardous
for ignitabilily
characteristic
Reactive CN
and Sulfide Tests
Nonhazardous
tor toxic gas generation
(reactivity) characteristic
istotai
concert, of TC
constituents-^ 20 <
TC regutaBJiy
limit?
Nonhazardous
(ortoxicity
characteristic
is waste
teachaWe and
toxic?
(Method 1311)
Nonhazardous
for toxicity
charactarisSc
TWO - 47
Revision 2
September 1994
\
-------
FIGURE 2-3A.
EP
3010
(7760 Aq)
6010
I Sample I
i 1310
7470
Hg
3510
Neutral
Ba-
Cr --
Ag -
-- As
-- Cd
-- Pb
- Se
8080
8081
Pesticides
8150
8151
Herbicides
TWO - 48
Revision 2
September 1994
-------
FIGURE 2-3B.
RECOMMENDED SH-846 METHODS OF ANALYSIS FOR TCLP•LEACHATES
3010
6010
Ba -
Cr -
Ag -
- As
- Cd
- Pb
- Se
7470
Hg
Sampl e
.
TCLP
3S10
Neutral
8240 3510
8260 (Acidic
Volatile and
Orqanics Basic)
8080
8081
Pestic-
ides
8270
Semivol -
atile
Organ ics
81SO
8151
Herbic-
ides
TWO - 49
Revision 2
September 1994
-------
FIGURE 2-4A.
GROUND WATER ANALYSIS
1
r
VOA
1
8240 or
8260
r
Sam ivola tiles
1
i
3510 or
3520
!
8270 or
8250
Organic
Sample
1
' if \ i
Pesticides
Herbicides Dioxins
1 1 1
3510 or
3520
Neutral
1
1 3620, 3640
and/or 3660
I
8080
S1SO 8280
1 -Optional: Cleanup required only u a anees prevent analysis
TWO - 50
Revision 2
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FIGURE 2-4B.
INDICATOR ANALYTE
1
POC
1 - Barcelona, 19B4, (See Reference 1)
2 • Riggin. 1984. (See Reference 2}
TWO - 51
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FIGURE 2-4C.
GROUND WATER
SAMPLE PREPARATION
3005 OR 3015
1
SAMPLE PREPARATION
3015 OR 3020
i
i
I
Ag, A). As, Ba. Be,
Cd, Co, Ct, Cu, Fe,
Mg, Mn, Mo, Ni, Pb,
Sb. Se, Tl, V, Zn
Ag, Al, As, Ba, Be,
Cd, Co, Cr, Cu, Mn,
Ni. Pb. Sb, Tl. Zn
AS- 7760
Ba-7080
Cd - 7130
Cr-7190
Fe-7380
Mn - 7460
Ni-7520
Sb-7040
Tl-7840
Zn-7950
AI-7020
Be-7090
Co- 7200
Cu - 7210
Mg - 7450
Mo- 7480
Pb-7420
5n- 7870
V-7910
Ag-7761"
Ba-7081*
Be -7091
Cd-7131
Co -7201
Cf-7191
Cu- 7211*
F»-7381*
Mn-7461'
Mo - 7481
Pb - 7421 '
Tl-7841
Sb-7041"
Toer
V-7911
Zn-7951'
* Fallow the digestion procedures as detailed in the individual
determinative methods.
1 Whan analyzing tor total dissolved metals, digestion is not'
necessary if Vie samples are filtered at the time of
collection, and then acidified to the same concentration as the standards
TWO - 52
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CHAPTER THREE
METALLIC ANALYTES
3,1 SAMPLING CONSIDERATIONS
3.1.1 Introduction
This manual contains procedures for the analysis of metals in a variety of
matrices. These methods are written as specific steps in the overall analysis
scheme -- sample handling and preservation, sample digestion or preparation, and
sample analysis for specific metal components. From these methods, the analyst
must assemble a total analytical protocol which is appropriate for the sample to
be analyzed and for the information required. This introduction discusses the
options available in general terms, provides background information on the
analytical techniques, and highlights some of the considerations to be made when
selecting a total analysis protocol.
3.1.2 Definition of Terms
Optimum concentration range: A range, defined by limits expressed in
concentration, below which scale expansion must be used and above which curve
correction should be considered. This range will vary with the sensitivity of
the instrument and the operating conditions employed.
Sensitivity: a) Atomic Absorption: The concentration in milligrams of
metal per liter that produces an absorption of 1%; b) Inductively Coupled Plasma
(ICP): The slope of the analytical curve, i.e., the functional relationship
between emission intensity and concentration.
Method detection limit (HDL): The minimum concentration of a substance
that can be measured and reported with 99% confidence that the analyte
concentration is greater than zero. The MDL is determined from analysis of a
sample in a given matrix containing analyte which has been processed through the
preparative procedure.
Total recoverable metals: The concentration of metals in an unfiltered
sample following treatment with hot dilute mineral acid (Method 3005).
Dissolved metals: The concentration of metals determined in a sample after
the sample is filtered through a 0.45-um filter (Method 3005).
Suspended metals: The concentration of metals determined in the
portion of a sample that is retained by a 0.45-um filter (Method 3005).
Total metals: The concentration of metals determined in a sample following
digestion by Methods 3010, 3015, 3020, 3050 or 3051.
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Instrument detection limit (IDL): The concentration equivalent to a signal
due to the analyte which is equal to three times the standard deviation of a
series of 7 replicate measurements of a reagent blank's signal at the same
wavelength.
Interference check sample (ICS): A solution containing both interfering
and analyte elements of known concentration that can be used to verify background
and interelement correction factors.
Initial calibration verification standard (ICV): A certified or
independently prepared solution used to verify the accuracy of the initial
calibration. For ICP analysis, it must be run at each wavelength used in the
analysis.
Continuing calibration verification (CCV): Used to assure calibration
accuracy during each analysis run. It must be run for each analyte as described
in the particular analytical method. At a minimum, it should be analyzed at the
beginning of the run and after the last analytical sample. Its concentration
should be at or near the mid-range levels of the calibration curve.
Calibration standards: A series of known standard solutions used by the
analyst for calibration of the instrument (i.e., preparation of the analytical
curve).
Lineardynamic range: The concentration range over which the analytical
curve remains linear.
Method blank: A volume of reagent water processed through each sample
preparation procedure.
CalIbration bl ank: A volume of reagent water acidified with the same
amounts of acids as were the standards and samples.
Laboptpry control standard: A volume of reagent water spiked with known
concentrations of analytes and carried through the preparation and analysis
procedure as a sample. It is used to monitor loss/recovery values.
Method of standard addition (MSA): The standard-addition technique
involves the "se of the unknown and the unknown plus several known amounts of
standard. St Method 7000, Section 8.7 for detailed instructions.
Sample holding time: The storage time allowed between sample collection
and sample analysis when the designated preservation and storage techniques are
employed.
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3.1.3 Sample Handling and Preservation
Sample holding times, digestion procedures and suggested collection volumes
are listed in Table 1. The sample volumes required depend upon the number of
different digestion procedures necessary for analysis. This may be determined
by the application of graphite-furnace atomic absorption spectrometry (GFAA),
flame atomic absorption spectrometry (FLAA), inductively coupled argon plasma
emission spectrometry (ICP), hydride-generation atomic absorption spectrometry
(HGAA), inductively coupled plasma mass spectrometry (ICP-MS) or cold-vapor
atomic absorption spectrometry (CVAA) techniques, each of which may require
different digestion procedures. The indicated volumes in Table 3-1 refer to that
required for the individual digestion procedures and recommended sample
collection volumes.
In the determination of trace metals, containers can introduce either
positive or negative errors in the measurement of trace metals by (a)
contributing contaminants through leaching or surface desorption, and (b)
depleting concentrations through adsorption. Thus the collection and treatment
of the sample prior to analysis require particular attention. The following
cleaning treatment sequence has been determined to be adequate to minimize
contamination in the sample bottle, whether borosilicate glass, linear
polyethylene, polypropylene, or Teflon; detergent, tap water, 1:1 nitric acid,
tap water, 1:1 hydrochloric acid, tap water, and reagent water.
NOTE: Chromic acid should not be used to clean glassware, especially
if chromium is to be included in the analytical scheme. Commercial,
non-chromate products (e.g., Nochromix) may be used in place of
chromic acid if adequate cleaning is documented by an analytical
quality control program. (Chromic acid should also not be used with
plastic bottles.)
3.1.4
The toxicity or carcinogenicity of each reagent used in these methods 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 these
methods. 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. They are:
1. "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.
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TABLE 3-1.
SAMPLE HOLDING TIMES, REQUIRED DIGESTION VOLUMES AND RECOMMENDED COLLECTION
VOLUMES FOR METAL DETERMINATIONS IN AQUEOUS AND SOLID SAMPLES
Measurement
Digestion
Vol. Reci."
(mL)
Collection
Volume (mL)a
Treatment/
Preservative
Holding Timec
tetals (except hexavalent chromium and mercury):
Aqueous
Total
Dissolved
Suspended
Solid
Total
Chromium VI:b
Aqueous
Solid
Mercury:
Aqueous
Total
Dissolved
100
100
100
2g
100
Solid
Total
100
100
0.2g
600
600
600
200g
400
200g
400
400
ZOOg
HN03 to pH <2
6 months
Filter on site;
HN03 to pH <2
6 months
Filter on site
6 months
6 months
24 hr
HN03 to pH <2
28 days
Filter;
HN03 to pH <2
28 days
28 days
"Unless stated otherwise.
bThe holding time for the analysis of hexavalent chromium in solid samples has
not yet been determined, A holding time of "as soon as possible" is recommended.
CA11 non-aqueous samples and all aqueous samples that are to be analyzed for
mercury and hexavalent chromium must be stored at 4"" ± 2°C until analyzed,
either glass or plastic containers may be used.
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2, "OSHA Safety and Health Standards, General Industry" (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, revised
January 1976.
3, "Proposed OSHA Safety and Health Standards, Laboratories," Occupational
Safety and Health Administration, Federal Register, July 24, 1986, p. 26660.
4. "Safety in Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd edition, 1979.
3.2 SAMPLE PREPARATION METHODS
The methods in SW-846 for sample digestion or preparation are as
follows1:
Method 3005 prepares ground water and surface water samples for total
recoverable and dissolved metals determination by FLAA, ICP-AES, or ICP-HS. The
unfiltered or filtered sample is heated with dilute HC1 and HN03 prior to metal
determination.
Method3010 prepares waste samples for total metal determination by
FLAA, ICP-AES, or ICP-MS. The samples are vigorously digested with nitric acid
followed by dilution with hydrochloric acid. The method is applicable to aqueous
samples, EP and mobility-procedure extracts.
Method 3015 prepares aqueous samples, mobility-procedure extracts, and
wastes that contain suspended solids for total metal determination by FLAA, GFAA,
ICP-AES, or ICP-MS. Nitric acid is added to the sample in a Teflori digestion
vessel and heated in a microwave unit prior to metals determination.
Method 3020 prepares waste samples for total metals determination by
furnace GFAA or ICP-MS. The samples are vigorously digested with nitric acid
followed by dilution with nitric add. The method is applicable to aqueous
samples, EP and mobility-procedure extracts.
Hethod 3040 prepares oily waste samples for determination of soluble
metals by FLAA, GFAA, and ICP-AES methods. The samples are dissolved and diluted
in organic solvent prior to analysis. The method is applicable to the organic
extract in the oily waste EP procedure and other samples high in oil, grease, or
wax content.
Hethod 3050 prepares waste samples for total metals determination by
FLAA and ICP-AES, or ICP-HS. The samples are vigorously digested in nitric acid
and hydrogen peroxide followed by dilution with either nitric or hydrochloric
acid. The method is applicable to soils, sludges, and solid waste samples.
Method 3051 prepares sludges, sediments, soils and oils for total
metals determination by FLAA, GFAA, ICP-AES or ICP-MS. Nitric acid is added to
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the representative sample in a Teflon digestion vessel and heated in a microwave
unit prior to metals determination,
1 Please note that chlorine is an interferent in ICP-MS analyses and its use
should be discouraged except when absolutely necessary.
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3.3 METHODS FOR DETERMINATION OF METALS
This section of the manual contains seven analytical techniques for
trace metal determinations: inductively coupled argon plasma atomic emission
spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS),
direct-aspiration or flame atomic absorption spectrometry (FLAA), graphite-
furnace atomic absorption spectrometry (GFAA), hydride-generation atomic
absorption spectrometry (HGAA), cold-vapor atomic absorption spectrometry (CVAA),
and several procedures for hexavalent chromium analysis. Each of these is
briefly discussed below in terms of advantages, disadvantages, and cautions for
analysis of wastes.
ICP's primary advantage is that it allows simultaneous or rapid
sequential determination of many elements in a short time. The primary
disadvantage of ICP is background radiation from other elements and the plasma
gases. Although all ICP instruments utilize high-resolution optics and back-
ground correction to minimize these interferences, analysis for traces of metals
in the presence of a large excess of a single metal is difficult. Examples would
be traces of metals in an alloy or traces of metals in a limed (high calcium)
waste. ICP and Flame AA have comparable detection limits (within a factor of 4)
except that ICP exhibits greater sensitivity for refractories (Al, Ba, etc.).
Furnace AA, in general, will exhibit lower detection limits than either ICP or
FLAA. Detection limits are drastically improved when ICP-MS is used. In general
ICP-MS exhibits greater sensitivity than either GFAA of FLAA for most elements.
The greatest disadvantage of ICP-MS is isobaric elemental interferences. These
are caused by different elements forming atomic ions with the same nominal mass-
to-charge ratio. Mathematical correction for interfering ions can minimize these
interferences.
Flame AAS (FLAA) direct aspiration determinations, as opposed to ICP,
are normally completed as single element analyses and are relatively free of
interelement spectral interferences. Either a nitrous-oxide/acetylene or
air/acetylene flame is used as an energy source for dissociating the aispirated
sample into the free atomic state making analyte atoms available for absorption
of light. In the analysis of some elements the temperature or type of flame used
is critical. If the proper flame and analytical conditions are not used,
chemical and ionization interferences can occur.
Graphite Furnace AAS (GFAA) replaces the flame with an electrically
heated graphite furnace. The furnace allows for gradual heating of the sample
aliquot in several stages. Thus, the processes of desolvation, drying,
decomposition of organic and inorganic molecules and salts, and formation of
atoms which must occur in a flame or ICP in a few milliseconds may be allowed to
occur over a much longer time period and at controlled temperatures in the
furnace. This allows an experienced analyst to remove unwanted matrix components
by using temperature programming and/or matrix modifiers. The major advantage
of this technique is that it affords extremely low detection limits. It is the
easiest to perform on relatively clean samples. Because this technique is so
sensitive, interferences can be a real problem; finding the optimum combination
of digestion, heating times and temperatures, and matrix modifiers can be a
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challenge for complex matrices.
Hydride AA utilizes a chemical reduction to reduce and separate arsenic
or selenium selectively from a sample digestate. The technique therefore has the
advantage of being able to isolate these two elements from complex samples which
may cause interferences for other analytical procedures. Significant
interferences have been reported when any of the following is present: 1) easily
reduced metals (Cu, Ag, Hg); 2) high concentrations of transition metals (>200
mg/L); 3) oxidizing agents (oxides of nitrogen) remaining following sample
digestion.
Cold-Vapor AA uses a chemical reduction to reduce mercury selectively.
The procedure is extremely sensitive but is subject to interferences from some
volatile organics, chlorine, and sulfur compounds.
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CHAPTER FOUR
ORGANIC ANALYTES
4.1 SAMPLING CONSIDERATIONS
4.1.1 Introduction
Following the initial and critical step of designing a sampling plan
(Chapter Nine) is the implementation of that plan such that a representative
sample of the solid waste is collected. Once the sample has been collected it
must be stored and preserved to maintain the chemical and physical properties
that it possessed at the time of collection. The sample type, type of containers
and their preparation, possible forms of contamination, and preservation methods
are all items which must be thoroughly examined in order to maintain the
integrity of the samples. This section highlights considerations which must be
addressed in order to maintain a sample's integrity and representativeness. This
section is, however, applicable only to trace analyses.
Quality Control (QC) requirements need not be met for all compounds
presented in the Table of Analytes for the method in use, rather, they must be
met for all compounds reported. A report of non-detect is considered a
quantitative report, and must meet all applicable QC requirements for that
compound and the method used.
4.1.2 Sample Handlino. and Preservation
This section deals separately with volatile and semivolatile organics.
Refer to Chapter Two and Table 4-1 of this section for sample containers, sample
preservation, and sample holding time information.
Volatile Organics
Standard 40 ml glass screw-cap VOA vials with Teflon lined silicone septa
may be used for both liquid and solid matrices. The vials and septa should be
washed with soap and water and rinsed with distilled deionized water. After
thoroughly cleaning the vials and septa, they should be placed in an oven and
dried at 100°C for approximately one hour.
NOTE: Do not heat the septa for extended periods of time (i.e., more than one
hour, because the silicone begins to slowly degrade at 105'C).
When collecting the samples, liquids and solids should be introduced into
the vials gently to reduce agitation which might drive off volatile compounds.
In general, liquid samples should be poured into the vial without introducing any
air bubbles within the vial as it is being filled. Should bubbling occur as a
result of violent pouring, the sample must be poured out and the vial refilled.
The vials should be completely filled at the time of sampling, so that when the
septum cap is fitted and sealed, and the vial inverted, no headspace is visible.
The sample should be hermetically sealed in the vial at the time of sampling, and
must not be opened prior to analysis to preserve their integrity.
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due to differing solubility and diffusion properties of gases in
LIQUID matrices at different temperatures, it is possible for the
sample to generate some headspace during storage. This headspace
will appear in the form of micro bubbles, and should not invalidate
a sample for volatiles analysis.
The presence of a macro bubble in a sample vial generally indicates
either improper sampling technique or a source of gas evolution
within the sample. The latter case is usually accompanied by a
buildup of pressure within the vial, (e.g. carbonate-containing
samples preserved with acid). Studies conducted by the USEPA
(EMSL-Ci, unpublished data) indicate that "pea-sized" bubbles (i.e.,
bubbles not exceeding 1/4 inch or 6 mm in diameter) did not
adversely affect volatiles data. These bubbles were generally
encountered in wastewater samples, which are more susceptible to
variations in gas solubility than are groundwater samples.
At the time of analysis, the aliquot to be analyzed should be taken from the
vial with a gas-tight syringe inserted directly through the septum of the vial.
Only one analytical sample can be taken from each vial. If these guidelines are
not followed, the validity of the data generated from the samples is suspect.
VOA vials for samples with solid or semi-solid matrices (e.g., sludges)
should be completely filled as best as possible. The vials should be tapped
slightly as they are filled to try and eliminate as much free air space as
possible. Two vials should also be filled per sample location.
At least two VOA vials should be filled and labeled immediately at the
point at which the sample is collected. They should NOT be filled near a running
motor or any type of exhaust system because discharged fumes and vapors may
contaminate the samples. The two vials from each sampling location should then
be sealed 'in separate plastic bags to prevent cross-contamination between
samples, particularly if the sampled waste is suspected of containing high levels
of volatile organics. {Activated carbon may also be included in the bags to
prevent cross-contamination from highly contaminated samples). VOA samples may
also be contaminated by diffusion of volatile organics through the septum during
shipment and storage. To monitor possible contamination, a trip blank prepared
from organic-free reagent water (as defined in Chapter One) should be carried
throughout the sampling, storage, and shipping process.
Semi volatile Organics (including Pesticides, PCBs and Herbicides.)
Containers used to collect samples for the determination of semivolatile
organic compounds should be soap and water washed followed by methanol (or
isopropanol) rinsing (see Sec. 4.1.4 for specific instructions on glassware
cleaning). The sample containers should be of glass or Teflon, and have screw-
caps with Teflon lined septa. In situations where Teflon is not available,
solvent-rinsed aluminum foil may be used as a liner. However, acidic or basic
samples may react with the aluminum foil, causing eventual contamination of the
sample. Plastic containers or lids may NOT be used for the storage of samples
due to the possibility of sample contamination from the phthalate esters and
other hydrocarbons within the plastic. Sample containers should be filled with
care so as to prevent any portion of the collected sample coming in contact with
FOUR - 2 Revision 2
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the sampler's gloves, thus causing contamination. Samples should not be
collected or stored in the presence of exhaust fumes. If the sample comes in
contact with the sampler {e.g. if an automatic sampler is used), run organic-free
reagent water through the sampler and use as a field blank.
4.1.3 Safety
Safety should always be the primary consideration in the collection of
samples. A thorough understanding of the waste production process, as well as
all of the potential hazards making up the waste, should be investigated whenever
possible. The site should be visually evaluated just prior to sampling to
determine additional safety measures. Minimum protection of gloves and safety
glasses should be worn to prevent sample contact with the skin and eyes. A
respirator should be worn even when working outdoors if organic vapors are
present. More hazardous sampling missions may require the use of supplied air
and special clothing.
4-1.4 Cleaning of Glassware
In the analysis of samples containing components in the parts per billion
range, the preparation of scrupulously clean glassware is necessary. Failure to
do so can lead to a myriad of problems in the interpretation of the final
chromatograms due to the presence of extraneous peaks resulting from
contamination. Particular care must be taken with glassware such as Soxhlet
extractors, Kuderna-Danish evaporative concentrators, sampling-train components,
or any other glassware coming in contact with an extract that will be evaporated
to a smaller volume. The process of concentrating the compounds of interest in
this operation may similarly concentrate the contaminating substance(s), which
may seriously distort the results.
The basic cleaning steps are:
1. Removal of surface residuals immediately after use;
2. Hot soak to loosen and float most particulate material;
3. Hot water rinse to flush away floated particulates;
4. Soak with an oxidizing agent to destroy traces of organic compounds;
5. Hot water rinse to flush away materials loosened by the deep penetrant
soak;
6. Distilled water rinse to remove metallic deposits from the tap water;
7. Alcohol, e.g., isopropanol or methanol, rinse to flush off any final
traces of organic materials and remove the water; and
8. Flushing the item immediately before use with some of the same solvent
that will be used in the analysis.
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Each of these eight fundamental steps are discussed here in the order in
which they appeared on the preceeding page.
1. As soon possible after glassware (i.e., beakers, pi pets, flasks, or
bottles) has come in contact with sample or standards, the glassware
should be flushed with alcohol before it is placed in the hot
detergent soak. If this is not done, the soak bath may serve to
contaminate all other glassware placed therein.
2. The hot soak consists of a bath of a suitable detergent in water of
50°C or higher. The detergent, powder or liquid, should be entirely
synthetic and not a fatty acid base. There are very few areas of the
country where the water hardness is sufficiently low to avoid the
formation of some hard-water scum resulting from the reaction between
calcium and magnesium salts with a fatty acid soap. This hard-water
scum or curd would have an affinity particularly for many chlorinated
compounds and, being almost wholly water-insoluble, would deposit on
all glassware in the bath in a thin film.
There are many suitable detergents on the wholesale and retail market.
Most of the common liquid dishwashing detergents sold at retail are
satisfactory but are more expensive than other comparable products
sold industrially. Alconox, in powder or tablet form, is manufactured
by Alconox, Inc., New York, and is marketed by a number of laboratory
supply firms. Sparkleen, another powdered product, is distributed by
Fisher Scientific Company.
3. No comments required.
4. The most common and highly effective oxidizing agent for removal of
traces of organic compounds is the traditional chromic acid solution
made up of concentrated sulfuric acid and potassium or sodium
dichromate. For maximum efficiency, the soak solution should be hot
(40-506C), Safety precautions must be rigidly observed in the
handling of this solution. Prescribed safety gear should include
safety goggles, rubber gloves, and apron. The bench area where this
operation is conducted should be covered with fluorocarbon sheeting
because spattering will disintegrate any unprotected surfaces.
The potential hazards of using chromic-sulfuric acid mixture are great
and have been well publicized. There are now commercially available
substitutes that possess the advantage of safety in handling. These
are biodegradable concentrates with a claimed cleaning strength equal
to the chromic acid solution. They are alkaline, equivalent to ca.
0.1 N NaOH upon dilution, and are claimed to remove dried blood,
silicone greases, distillation residues, insoluble organic residues,
etc. They are further claimed to remove radioactive traces and will
not attack glass or exert a corrosive effect on skin or clothing. One
such product is "Chem Solv 2157," manufactured by Mallinckrodt and
available through laboratory supply firms. Another comparable product
is "Detex," a product of Borer-Chemie, Solothurn, Switzerland.
FOUR - 4 Revision 2
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5, 6, and 7. No comments required,
8. There is always a possibility that between the time of washing and the
next use, the glassware could pick up some contamination from either
the air or direct contact. To ensure against this, it is good
practice to flush the item immediately before use with some of the
same solvent that will be used in the analysis.
The drying and storage of the cleaned glassware is of critical importance
to prevent the beneficial effects of the scrupulous cleaning from being
nullified. Pegboard drying is not recommended. It is recommended that
laboratory glassware and equipment be dried at 100°C. Under no circumstances
should such small items be left in the open without protective covering. The
dust cloud raised by the daily sweeping of the laboratory floor can most
effectively recontaminate the clean glassware.
As an alternate to solvent rinsing, the glassware can be heated to a
minimum of 300°C to vaporize any organics. Do not use this high temperature
treatment on volumetric glassware, glassware with ground glass joints, or
sintered glassware.
4.1.5 High Concentration Samples
Cross contamination of trace concentration samples may occur when
prepared in the same laboratory with high concentration samples. Ideally,
if both type samples are being handled, a laboratory and glassware
dedicated solely to the preparation of high concentration samples would be
available for this purpose. If this is not feasible, as a minimum when
preparing high concentration samples, disposable glassware should be used
or, at least, glassware dedicated entirely to the high concentration
samples. Avoid cleaning glassware used for both trace and high
concentration samples in the same area.
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TABLE 4-1.
SAMPLE CONTAINERS, PRESERVATION, TECHNIQUES, AND HOLDING TIMES
Analyte Class
Container
Preservative
Holding Time
Volatile Orqanics
Concentrated Waste Samples
Liquid Samples
No Residual Chlorine
Present
Residual Chlorine Present
Acrolein and
Acrylonitrile
Soil/Sediments and Sludges
125 mL widemouth glass
container with Teflon
lined lid
2 X 40 mL vials with
Teflon lined septum caps
2 X 40 mL vials with
Teflon lined septum caps
2 X 40 mL vials with
Teflon lined septum caps
125 mL widemouth glass
container sealed with a
septum
Cool, 4'C
Cool, 4'C1
Collect sample in a 125 mL
container which has been pre-
preserved with 4 drops of 10%
sodium thiosulfate solution.
Gently swirl to mix sample and
transfer to a 40 mL VGA vial.1
Cool, 4'C
Adjust to pH 4-5; cool, 4'C
Cool, 4'C
14 days
14 days
14 days
14 days
14 days
Adjust pH <2 with H2S04, HC1 or solid NaHS04.
FOUR - 6
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TABLE 4-1, Continued
Analyte Class
Container
Preservative
Holding Time
Semivolatile Organics/Orqanochlorine Pesticides/PCBs and Herbicides
Concentrated Waste Samples 125 ml widemouth glass None
with Teflon lined lid
Water Samples
No Residual Chlorine
Present
1-gal. or 2 x 0.5-gal.,or
4 x 1-L, amber glass
container with Teflon
lined lid
Cool, 4°C
Residual Chlorine Present 1-gal. or 2 x 0.5-gal., or Add 3 ml 10% sodium thiosulfate
4 x 1-U amber glass solution per gallon.2 Cool, 4°C
container with Teflon
lined lid
Soil/Sediments and Sludges 250 ml widemouth glass Cool, 4°C
container with Teflon
lined lid
Samples must be
extracted within 14
days and extracts
analyzed within 40
days following
extraction.
Samples must be
extracted within 7
days and extracts
analyzed within 40
days following
extraction.
Samples must be
extracted within 7
days and extracts
analyzed within 40
days following
extraction.
Samples must be
extracted within 14
days and extracts
analyzed within 40
days following
extraction.
2 Pre-preservation may be performed in the laboratory prior to field use.
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4.2 SAMPLE PREPARATION METHODS
4.2.1 EXTRACTIONS AND PREPARATIONS
The following methods are included in this section:
Method 3500A: Organic Extraction and Sample Preparation
Method 3510B: Separatory Funnel Liquid-Liquid Extraction
Method 3520B: Continuous Liquid-Liquid Extraction
Method 3540B: Soxhlet Extraction
Method 3541: Automated Soxhlet Extraction
Method 3550A: Ultrasonic Extraction
Method 3580A: Waste Dilution
Method 5030A; Purge-and-Trap
Method 5040A: Analysis of Sorbent Cartridges from Volatile
Organic Sampling Train (VOST): Gas
Chromatography/Mass Spectrometry Technique
Method 5041: Protocol for Analysis of Sorbent Cartridges from
Volatile Organic Sampling Train (VOST): Wide-
bore Capillary Column Technique
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4.2 SAMPLE PREPARATION METHODS
4.2.2 CLEANUP
The following methods are included in this section;
Method 3600B:
Method 3610A:
Method 3611A:
Method 3620A:
Method 3630B:
Method 3640A:
Method 3650A:
Method 3660A:
Method 3665:
Cleanup
Alumina Column Cleanup
Alumina Column Cleanup and Separation of
Petroleum Wastes
Florisil Column Cleanup
Silica Gel Cleanup
Gel-Permeation Cleanup
Acid-Base Partition Cleanup
Sulfur Cleanup
Sulfuric Ac id/Permanganate Cleanup
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4.3 DETERMINATION OF ORGANIC ANALYTES
4.3.1 GAS CHROMATOGRAPHIC METHODS
The following methods are included in this section:
Method 8000A:
Method 801OB:
Method 8011:
Method 80ISA:
Method 8020A:
Method 8021A:
Method B030A:
Method 8031:
Method 8032:
Method 8040A;
Method 8060:
Method 8061:
Method 8070:
Method B080A:
Method 8081:
Method 8090:
Method 8100:
Method 8110:
Method 8120A:
Method 8121:
Method 8140:
Method B141A:
Method 81SOB:
Method 8151:
Gas Chromatography
Halogenated Volatile Organics by Gas
Chromatography
1,2-Dibromoethane and l,2-Dibromo-3-chloropropane
by Microextraction and Gas Chromatography
Nonhalogenated Volatile Organics by Gas
Chromatography
Aromatic Volatile Organics by Gas Chromatography
Halogenated Volatiles by Gas Chromatography Using
Photoionization and Electrolytic Conductivity
Detectors in Series: Capillary Column Technique
Acrolein and Acrylonitrile by Gas Chromatography
Acrylonitrile by Gas Chromatography
Acrylamide by Gas Chromatography
Phenols by Gas Chromatography
Phthalate Esters
Phthalate Esters by Capillary Gas Chromatography
with Electron Capture Detection (6C/ECD)
Nitrosamines by Gas Chromatography
Organochlorine Pesticides and Polychlorinated
Biphenyls by Gas Chromatography
Organochlorine Pesticides and PCBs as Aroclors by
Gas Chromatography: Capillary Column Technique
Nitroaromatics and Cyclic Ketones
Polynuclear Aromatic Hydrocarbons
Haloethers by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography
Chlorinated Hydrocarbons by Gas Chromatography:
Capillary Column Technique
Organophosphorus Pesticides
Organophosphorus Compounds by Gas Chromatography:
Capillary Column Technique
Chlorinated Herbicides by Gas Chromatography
Chlorinated Herbicides by GC Using Methylation or
Pentafluorobenzylation Derivatization: Capillary
Column Technique
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4.3 DETERMINATION OF ORGANIC ANALYTES
4.3,3 HIGH PERFORMANCE LIQUID CHRQMATQGRAPHIC METHODS
The following methods are included in this section:
Method 8310:
Method 8315:
Appendix A:
Method 8316:
Method 8318;
Method 8321:
Method 8330;
Method 8331;
Polynuclear Aromatic Hydrocarbons
Determination of Carbonyl Compounds by High
Performance Liquid Chromatography (HPLC)
Recrystallization of 2,4-
Dinitrophenylhydrazine (DNPH)
Acrylamide, Acrylonitrile and Acrolein by High
Performance Liquid Chromatography (HPLC)
N-Methylcarbamates by High Performance Liquid
Chromatography (HPLC)
Solvent Extractable Non-Volatile Compounds by
High Performance Liquid
Chromatography/Thermospray/Mass Spectrometry
(HPLC/TSP/MS) or Ultraviolet (UV) Detection
Nitroaromatics and Nitramines by High Performance
Liquid Chromatography (HPLC)
Tetrazene by Reverse Phase High Performance
Liquid Chromatography (HPLC)
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4.3 DETERMINATION OF ORGANIC ANALYTES
4,3,4 FOURIER TRANSFORM INFRARED METHODS
The following method is included in this section:
Hethod 8410: Gas Chromatography/Fourier Transform Infrared
(GC/FT-IR) Spectrometry for Semivolatile
Organics: Capillary Column
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4.4 MISCELLANEOUS SCREENING METHODS
The following methods are included in this section:
Method 3810:
Method 3820:
Method 4010:
Method 8275:
Headspace
Hexadecane Extraction and Screening of Purgeable
Organics
Screening for Pentachlorophenol by Immunoassay
Thermal Chromatography/Mass Spectrometry (TC/MS)
for Screening Semi volatile Organic Compounds
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CHAPTER FIVE
MISCELLANEOUS TEST METHODS
The following methods are found in Chapter Five:
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
5050:
9010A:
9012:
9013:
9020B:
9021:
9022:
9030A:
9031:
903i:
9036:
9038:
9056:
9060:
9065:
9066:
9067:
9070:
9071A:
9075:
Method 9076:
Method 9077:
Method 9131:
Method 9132:
Method 9200:
Method 9250:
Method 9251:
Method 9252A:
Method 9253:
Method 9320:
Bomb Preparation Method for Solid Waste
Total and Amenable Cyanide (Colorimetric, Manual)
Total and Amenable Cyanide (Colorimetric,
Automated UV)
Cyanide Extraction Procedure for Solids and Oils
Total Organic Hal ides (TOX)
Purgeable Organic Hal ides (POX)
Total Organic Hal ides (TOX) by Neutron Activation
Analysis
Acid-Soluble and Acid-Insoluble Sulfides
Extractable Sulfides
Sulfate (Colorimetric, Automated, Chloranilate)
Sulfate (Colorimetric, Automated, Methylthymol
Blue, AA II)
Sulfate (Turbidimetric)
Determination of Inorganic
Chromatography Method
Total Organic Carbon
Phenolics (Spectrophotometric,
Distillation)
Phenolics (Colorimetric, Automated
Distillation)
Phenolics (Spectrophotometric,
Distillation)
Total Recoverable Oil & Grease
Separatory Funnel Extraction)
Oil and Grease Extraction Method for Sludge and
Sediment Samples
Chlorine in New and Used
by X-Ray Fluorescence
Anions by Ion
Manual 4-AAP with
4-AAP with
MBTH with
(Gravimetric,
Chlorine in New and Used
Oxidative Combustion and
Test Method for Total
Petroleum Products
Spectrometry {XRFJ
Test Method for Total
Petroleum Products by
Microcoulometry
Test Methods for Total Chlorine in New and Used
Petroleum Products (Field Test Kit Methods)
Total Coliform: Multiple Tube Fermentation
Technique
Total Coliform: Membrane Filter Technique
Nitrate
Automated Fern"cyanide AAI)
Automated FerricyanideAAII)
Mercuric Nitrate)
Silver Nitrate}
Chloride (Colorimetric,
Chloride (Colorimetric,
Chloride (Titrimetric,
Chloride (Titrimetric,
Radium-228
FIVE - 1
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CHAPTER SIX
PROPERTIES
The following methods are found in Chapter Six:
Method
Method
Method
Method
Method
Method
Method
Method
1312:
1320:
1330A:
9040A:
9041A:
9045B:
9050:
9080:
Method 9081:
Method 9090A:
Method 9095:
Method 9096:
Method 9100:
Method 9310:
Method 9315:
Synthetic Precipitation Leaching Procedure
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Electrometric Measurement
pH Paper Method
Soil and Waste pH
Specific Conductance
Cation-Exchange Capacity of Soils (Ammonium
Acetate)
Cat ion-Exchange Capacity of Soils (Sodium Acetate)
Compatibility Test for Wastes and Membrane Liners
Paint Filter Liquids Test
Liquid Release Test (LRT) Procedure
Saturated Hydraulic Conductivity, Saturated
Leachate Conductivity, and Intrinsic Permeability
Gross Alpha and Gross Beta-
Alpha-Emitting Radium Isotopes
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CHAPTER SEVEN
INTRODUCTION AND REGULATORY DEFINITIONS
7.1 IGNITABILITY
7.1.1 Introduction
This section discusses the hazardous characteristic of ignitability. The
regulatory background of this characteristic is summarized, and the regulatory
definition of ignitability is presented. The two testing methods associated with
this characteristic, Methods 1010 and 1020, can be found in Chapter Eight.
The objective of the ignitability characteristic is to identify wastes that
either present fire hazards under routine storage, disposal, and transportation
or are capable of severely exacerbating a fire once started.
7.1.2 Regulatory Definition
The following definitions have been taken nearly verbatim from the RCRA
regulations (40 CFR 261,21) and the DOT regulations (49 CFR §§ 173.300 and
173.151).
Characteristics Of Ignitabilitv Regulation
A solid waste exhibits the characteristic of ignitability if a
representative sample of the waste has any of the following properties:
1. It is a liquid, other than an aqueous solution, containing < 24%
alcohol by volume, and it has a flash point < 60°C (140°F), as
determined by a Pensky-Martens Closed Cup Tester, using the test
method specified in ASTM Standard D-93-79 or D-93-80, or a Setaflash
Closed Cup Tester, using the test method specified in ASTM standard
D-3278-78, or as determined by an equivalent test method approved by
the Administrator under the procedures set forth in Sections 260.20
and 260.21. {ASTM standards are available from ASTM, 1916 Race
Street, Philadelphia, PA 19103.)
2. It is not a liquid and is capable, under standard temperature and
pressure, of causing fire through friction, absorption of moisture,
or spontaneous chemical changes and, when ignited, burns so
vigorously and persistently that it creates a hazard.
3. It is an ignitable compressed gas, as defined in 49 CFR 173.300 and
as determined by the test methods described in that regulation or by
equivalent test methods approved by the Administrator under Sections
260.20 and 260.21.
4. It is an oxidizer, as defined in 49 CFR 173.151,
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gnitable Compressed
For the purpose of this regulation the following terminology is defined:
1. Compressed gas. The term "compressed gas" shall designate any
material or mixture having in the container an absolute pressure
exceeding 40 psi at 21 °C (70°F) or, regardless of the pressure at
21 °C (70°F), having an absolute pressure exceeding 104 psi at 54 °C
(130°F), or any liquid flammable material having a vapor pressure
exceeding 40 psi absolute at 38°C (100'F), as determined by ASTM
Test D-323.
2. ...I.gn.1table compressed gas. Any compressed gas, as defined in
Paragraph 1, above, shall be classed as an "ignitable compressed
gas" if any one of the following occurs:
a. Either a mixture of 13% or less (by volume) with air forms a
flammable mixture, or the flammable range with air is wider than
12%, regardless of the lower, limit. These limits shall be
determined at atmospheric temperature and pressure. The method
of sampling and test procedure shall be acceptable to the Bureau
of Explosives.
b. Using the Bureau of Explosives' Flame Projection Apparatus (see
Note, below), the flame projects more than 18 in. beyond the
ignition source with valve opened fully, or the flame flashes
back and burns at the valve with any degree of valve opening.
c. Using the Bureau of Explosives' Open Drum Apparatus (see Note,
below), there is any significant propagation of flame away from
the ignition source.
d. Using the Bureau of Explosives' Closed Drum Apparatus (see Note,
below), there is any explosion of the vapor-air mixture in the
drum.
NOTE: Descriptions of the Bureau of Explosives' Flame Projection
Apparatus, Open Drum Apparatus, Closed Drum Apparatus, and method of
tests may be procured from the Association of American Railroads,
Operations and Maintenance Dept., Bureau of Explosives, American
Railroad Building, Washington, DC. 20036; 202-293-4048.
Qxidizer (as defined in 49 CFR 173.151)
For the purpose of this regulation, an oxidizer is any material that yields
oxygen readily to stimulate the combustion of organic matter (e.g., chlorate,
permanganate, inorganic peroxide, or a nitrate).
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7.2 CORROSIVITY
7.2.1 Introduction
The corrosivlty characteristic, as defined in 40 CFR 261.22, is designed
to identify wastes that might pose a hazard to human health or the environment
due to their ability to:
1. Mobilize toxic metals if discharged into a landfill environment;
2. Corrode handling, storage, transportation, and management equipment;
or
3. Destroy human or animal tissue in the event of inadvertent contact.
In order to identify such potentially hazardous materials, EPA has selected
two properties upon which to base the definition of a corrosive waste. These
properties are pH and corrosivity toward Type SAE 1020 steel.
The following sections present the regulatory background and the regulation
pertaining to the definition of corrosivity. The procedures for measuring pH of
aqueous wastes are detailed in Method 9040, Chapter Six. Method 1110, Chapter
Eight, describes how to determine whether a waste is corrosive to steel. Use
Method 9095, Paint Filter Liquids Test, Chapter Six, to determine free liquid.
7-2.2 Regulatory Definition
The following material has been taken nearly verbatim from the RCRA
regulations.
1. A solid waste exhibits the characteristic of corrosivity if a
representative sample of the waste has either of the following
properties:
a. It is aqueous and has a pH < 2 or > 12.5, as determined by a pH
meter using either the test method specified in this manual
(Method 9040) or an equivalent test method approved by the
Administrator under the procedures set forth in Sections 260.20
and 260.El.
b. It is a liquid and corrodes steel (SAE 1020) at rate > 6.35 mm
(0,250 in.) per year at a test temperature of 55°C (130°F), as
determined by the test method specified in NACE (National
Association of Corrosion Engineers) Standard TM-01-69, as
standardized in this manual (Method 1110) or an equivalent test
method approved by the Administrator under the procedures set
forth in Sections 260.20 and 260.21.
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7,3 REACTIVITY
7.3.1 Introduction
The regulation in 40 CFR 261.23 defines reactive wastes to include wastes
that have any of the following properties: (1) readily undergo violent chemical
change; (2) react violently or form potentially explosive mixtures with water;
(3) generate toxic fumes when mixed with water or, in the case of cyanide- or
sulfide-bearing wastes, when exposed to mild acidic or basic conditions; (4)
explode when subjected to a strong initiating force; (5) explode at normal
temperatures and pressures; or (6) fit within the Department of transportation's
forbidden explosives, Class A explosives, or Class 8 explosives classifications.
This definition is intended to identify wastes that, because of their
extreme instability and tendency to react violently or explode, pose a problem
at all stages of the waste management process. The definition is to a large
extent a paraphrase of the narrative definition employed by the National Fire
Protection Association. The Agency chose to rely almost entirely on a
descriptive, prose definition of reactivity because most of the available tests
for measuring the variegated class of effects embraced by the reactivity
definition suffer from a number of deficiencies.
7.3.2 Regulatory Definition
7.3.2.1 Characteristic Of Reactivity Regulation
A solid waste exhibits the characteristic of reactivity if a
representative sample of the waste has any of the following
properties:
1. It is normally unstable and readily undergoes violent change
without detonating.
2. It reacts violently with water.
3. It forms potentially explosive mixtures with water.
4. When mixed with water, it generates toxic gases, vapors, or
fumes in a quantity sufficient to present a danger to human
health or the environment.
5. It is a cyanide- or sulfide-bearing waste which, when exposed to
pH conditions between 2 and 12.5, can generate toxic gases,
vapors, or fumes in a quantity sufficient to present a danger to
human health or the environment. (Interim Guidance for Reactive
Cyanide and Reactive Sulfide, Steps 7.3.3 and 7.3.4 below, can
be used to detect the presence of reactive cyanide and reactive
sulfide in wastes.)
6. It is capable of detonation or explosive reaction if it is
subjected to a strong initiating source or if heated under
confinement.
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7, It is readily capable of detonation or explosive decomposition
or reaction at standard temperature and pressure.
8. It is a forbidden explosive, as defined in 49 CFR 173.51, or a
Class A explosive, as defined in 49 CFR 173.53, or a Class B
explosive, as defined in 49 CFR 173.88.
7.3.3 Interim Guidance For Reactive Cyanide
7.3.3.1 The current EPA guidance level is:
Total releasable cyanide: 250 mg HCN/kg waste.
7.3.3.2 Test Method to Determine Hydrogen Cyanide Released from
Wastes
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to all wastes, with the condition that
wastes that are combined with acids do not form explosive mixtures.
1.2 This method provides a way to determine the specific rate of
release of hydrocyanic acid upon contact with an aqueous acid.
1.3 This test measures only the hydrocyanic acid evolved at the test
conditions. It is not intended to measure forms of cyanide other than those
that are evolvable under the test conditions.
2.0 SUMMARY OF METHOD
2.1 An aliquot of acid is added to a fixed weight of waste in a closed
system. The generated gas is swept into a scrubber. The analyte is
quantified. The procedure for quantifying the cyanide is Method 9010, Chapter
Five, starting with Step 7.2.7 of that method.
3.0 INTERFERENCES
3.1 Interferences are undetermined.
4.0 APPARATUS AND MATERIALS (See Figure 1}
4.1 Round-bottom flask - 500-mL, three-neck, with 24/40 ground-glass
joints.
4.2 Gas scrubber - 50 mL calibrated scrubber
4.3 Stirring apparatus - To achieve approximately 30 rpm. This may be
either a rotating magnet and stirring bar combination or an overhead motor-
driven propeller stirrer.
4.4 Addition funnel - With pressure-equalizing tube and 24/40 ground-
glass joint and Teflon sleeve,
SEVEN - 5 Revision 2
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4,5 Flexible tubing - For connection from nitrogen supply to
apparatus.
4.i Water-pumped or oil-pumped nitrogen gas - With two-stage
regulator.
4.7 Rotometer - For monitoring nitrogen gas flow rate.
4.8 Analytical balance - capable of weighing to 0.001 g.
5.0 REAGENTS
5.1 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.
5.2 Reagent water. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Sulfuric acid (0.01N), H?S04. Add 2.8 ml concentrated H2SO to
reagent water and dilute to 1 L. Withdraw 100 ml of this solution and dilute
to 1 L to make the 0.01N H2S04.
5.4 Cyanide reference solution, (1000 mg/L). Dissolve approximately
2.5 g of KOH and 2.51 g of KCN in 1 liter of reagent water. Standardize with
0.0192N AgNOg. Cyanide concentration in this solution should be 1 mg/mL.
5.5 Sodium hydroxide solution (1.25N), NaOH. Dissolve 50 g of NaOH in
reagent water and dilute to 1 liter with reagent water.
5.6 Sodium hydroxide solution (0.25N), NaOH. Dilute 200 ml of 1.25N
sodium hydroxide solution (Step 5.5) to 1 liter with reagent water.
5.7 Silver nitrate solution (0.0192N). Prepare by crushing
approximately 5 g of AgN03 crystals and drying to constant weight at 40°C.
Weigh 3.265 g of dried AgNO,, dissolve in reagent water, and dilute to 1
liter.
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 Samples containing, or suspected of containing, sulfide or a
combination of sulfide and cyanide wastes should be collected with a minimum
of aeration. The sample bottle should be filled completely, excluding all
head space, and stoppered. Analysis should commence as soon as possible, and
samples should be kept in a cool, dark place until analysis begins.
6.2 It is suggested that samples of cyanide wastes be tested as
quickly as possible. Although they can be preserved by adjusting the sample
pH to 12 with strong base, this will cause dilution of the sample, increase
the ionic strength, and, possibly, change other physical or chemical
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characteristics of the waste which may affect the rate of release of the
hydrocyanic acid. Storage of samples should be under refrigeration and in the
dark.
6.3 Testing should be performed in a ventilated hood.
7.0 PROCEDURE
7.1 Add 50 ml of 0.25N NaOH solution (Step 5.6) to a calibrated
scrubber and dilute with reagent water to obtain an adequate depth of liquid.
7.2 Close the system and adjust the flow rate of nitrogen, using the
rotometer. Flow should be 60 raL/min.
7.3 Add 10 g of the waste to be tested to the system.
7.4 With the nitrogen flowing, add enough sulfuric acid to fill the
flask half full. Start the 30 minute test period.
7.5 Begin stirring while the acid is entering the round-bottom flask.
The stirring speed must remain constant throughout the test.
NOTE: The stirring should not be fast enough to create a vortex.
7.6 After 30 minutes, close off the nitrogen and disconnect the
scrubber. Determine the amount of cyanide in the scrubber by Method 9010,
Chapter Five, starting with Step 7.2.7 of the method.
NOTE: Delete the "C" and "D" terms from the spectrophotometric procedure
calculation and the "E" and "F" terms from the titration procedure
calculation in Method 9010. These terms are not necessary for the
reactivity determination because the terms determine the amount of
cyanide in the entire sample, rather than only in the aliquot taken for
analysis.
8.0 CALCULATIONS
8.1 Determine the specific rate of release of HCN, using the following
parameters:
X = Concentration of HCN in diluted scrubber solution (mg/L)
(This is obtained from Method 9010.)
L = Volume of solution in scrubber (L)
W = Weight of waste used (kg)
S = Time of measurement (sec.) = Time N2 stopped - Time N2 started
X • L
R - specific rate of release (mg/kg/sec.) » —
W • S
Total releasable HCN (rag/kg) = R x S
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9.0 METHOD PERFORMANCE
9.1 The operation of the system can be checked and verified using the
cyanide reference solution (Step 5,4). Perform the procedure using the
reference solution as a sample and determine the percent recovery. Evaluate
the standard recovery based on historical laboratory data, as stated in
Chapter One.
10.0 REFERENCES
10.1 No references are available at this time.
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FIGURE 1.
APPARATUS TO DETERMINE HYDROSEN CYANIDE RELEASED FROM WASTES
Stirrer
Flowmeter
N2ln
Reaction Flask
Gas Scrubber
Waste Sample
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7.3.4 Interim GuidanceFor Reactive Sulfide
7.3.4.1 The current EPA guidance level is:
Total releasable sulfide: 500 mg H2S/kg waste.
7.3.4.2 Test Method to Determine Hydrogen Sulfide Released from
Wastes
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to all wastes, with the condition that
waste that are combined with acids do not form explosive mixtures.
1.2 This method provides a way to determine the specific rate of
release of hydrogen sulfide ypon contact with an aqueous acid.
1.3 This procedure releases only the hydrogen sulfide evolved at the
test conditions. It is not intended to measure forms of sulfide other than
those that are evolvable under the test conditions.
2.0 SUMMARY OF METHOD
2.1 An aliquot of acid is added to a fixed weight of waste in a closed
system. The generated gas is swept into a scrubber. The analyte is
quantified. The procedure for quantifying the sulfide is given in Method
9030, Chapter Five, starting with Step 7.3 of that method.
3.0 INTERFERENCES
3.1 Interferences are undetermined.
4.0 APPARATUS AND MATERIALS (See Figure 2)
4.1 Round-bottom flask - 500-mL, three-neck, with 24/40 ground-glass
joints.
4.2 Sas scrubber - 50 ml calibrated scrubber.
4.3 Stirring apparatus - To achieve approximately 30 rpm. This may be
either a rotating magnet and stirring bar combination or an overhead motor-
driven propeller stirrer.
4.4 Addition funnel - With pressure-equalizing tube and 24/40 ground-
glass joint and Teflon sleeve.
4.5 Flexible tubing - For connection from nitrogen supply to
apparatus.
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4.6 Water-pumped or oil-pumped nitrogen gas - With two-stage
regulator.
4.7 Rotometer - For monitoring nitrogen gas flow rate.
4.8 Analytical balance - capable of weighing to 0.001 g.
5.0 REAGENTS
5.1 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.
5.2 Reagent water. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Sulfuric acid (0.01N), H,S04. Add 2.8 ml concentrated H.S04
to reagent water and dilute to 1 L Withdraw 100 ml of this solution and
dilute to 1 L to make the 0.01N HES04.
5.4 Sulfide reference solution - Dissolve 4.02 g of NagS * 9HJ) in
1.0 L of reagent water. This solution contains 570 mg/L hydrogen sultide.
Dilute this stock solution to cover the analytical range required (100-570
rag/L).
5.5 Sodium hydroxide solution (1.25N), NaOH. Dissolve 50 g of NaOH in
reagent water and dilute to 1 L with reagent water.
5.6 Sodium hydroxide solution (0.25N), NaOH. Dilute 200 ml of 1.25N
sodium hydroxide solution (Step 5.5} to 1 L with reagent water.
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 Samples containing, or suspected of containing, sulfide wastes
should be collected with a minimum of aeration. "The sample bottle should be
filled completely, excluding all head space, and stoppered. Analysis should
commence as soon as possible, and samples should be kept in a cool, dark place
until analysis begins.
6.2 It is suggested that samples of sulfide wastes be tested as
quickly as possible. Although they can be preserved by adjusting the sample
pH to 12 with strong base and adding zinc acetate to the sample, these will
cause dilution of the sample, increase the ionic strength, and, possibly,
change other physical or chemical characteristics of the waste which may
affect the rate of release of the hydrogen sulfide. Storage of samples should
be under refrigeration and in the dark.
6.3 Testing should be performed in a ventilated hood.
SEVEN - 11 Revision 2
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7.0 PROCEDURE
7,1 Add 50 ml of 0.25N NaOH solution to a calibrated scrubber and
dilute with reagent water to obtain an adequate depth of liquid.
7,2 Assemble the system and adjust the flow rate of nitrogen, using
the rotometer. Flow should be 60 mL/min,
7,3 Add 10 g of the waste to be tested to the system.
7,4 With the nitrogen flowing, add enough sulfuric acid to fill the
flask half full, while starting the 30 minute test period.
7,5 Begin stirring while the acid is entering the round-bottom flask.
The stirring speed must remain constant throughout the test.
NOTE: The stirring should not be fast enough to create a vortex.
7.6 After 30 minutes, close off the nitrogen and disconnect the
scrubber. Determine the amount of sulfide in the scrubber by Method 9030,
Chapter Five, starting with Step 7.3 of that method.
7.7 Substitute the following for Step 7.3.2 in Method 9030: The
trapping solution must be brought to a pH of 2 before proceeding. Titrate a
small aliquot of the trapping solution to a pH 2 end point with 6N HC1 and
calculate the amount of HC1 needed to acidify the entire scrubber solution.
Combine the small acidified aliquot with the remainder of the acidified
scrubber solution.
8.0 CALCULATIONS
8.1 Determine the specific rate of release of H2S, using the following
parameters:
X = Concentration of H.S in scrubber (mg/L)
(This is obtained from Method 9030.)
L - Volume of solution In scrubber (1)
W = Weight of waste used (kg)
S = Time of experiment (sec.) = Time N2 stopped - Time N2 started
R = specific rate of release (mg/kg/sec.) =
X • L
Total releasable H2S (mg/kg) = R x S
W • S
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9,0 METHOD PERFORMANCE
9.1 The operation of the system can be checked and verified using the
sulfide reference solution (Step 5.4). Perform the procedure using the
reference solution as a sample and determine the percent recovery. Evaluate
the standard recovery based on historical laboratory data, as stated in
Chapter One.
10.0 REFERENCES
10.1 No references are available at this time.
SEVEN - 13 Revision 2
Septenter 1994
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FIGURE 2.
APPARATUS TO DETERMINE HYDROGEN SULFIDE RELEASED FROM WASTES
Flowmeter
N2 In m+*~J
1N H2SO4
Reaction Flask
Gas Scrubber
waste Sample
SEVEN - 14
Revision 2
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7.4 TOXICITY CHARACTERISTIC LEACHING PROCEDURE
7.4.1 Introduction
The Toxicity Characteristic Leaching Procedure (TCLP) is designed to
simulate the leaching a waste will undergo if disposed of in a sanitary
landfill. This test is designed to simulate leaching that takes place in a
sanitary landfill only. The extraction fluid employed is a function of the
alkalinity of the solid phase of the waste. A subsample of a waste is
extracted with the appropriate buffered acetic acid solution for 18 ± 2 hours.
The extract obtained from the TCLP (the "TCLP extract") is then analyzed to
determine if any of the thresholds established for the 40 Toxicity
Characteristic (TC) constituents (listed in Table 7-1) have been exceeded or
if the treatment standards established for the constituents listed in 40 CFR
§268,41 have been met for the Land Disposal Restrictions (LDR) program. If
the TCLP extract contains any one of the TC constituents in an amount equal to
or exceeding the concentrations specified in 40 CFR §261.24, the waste
possesses the characteristic of toxicity and is a hazardous waste. If the
TCLP extract contains LDR constituents in an amount exceeding the
concentrations specified in 40 CFR §268.41, the treatment standard for that
waste has not been met, and further treatment is necessary prior to land
disposal.
7.4.2 SummaryofProcedure
The TCLP consists of five steps (refer to Figure 3):
1. Separation Procedure
For liquid wastes (i.e...., those containing less than 0.5% dry solid
material), the waste, after filtration through a 0.6 to 0.8 pm glass fiber
filter, is defined as the TCLP extract.
For wastes containing greater than or equal to 0.5% solids, the liquid,
if any, is separated from the solid phase and stored for later analysis.
Z, Particle Size Reduction
Prior to extraction, the solid material must pass through a 9.5-mm
(0.375-in.) standard sieve, have s. surface area per crarr o^ material equal tc
or greater than 3.1 cm2, or, be smaller than 1 cm in its narrowest dimension.
If the surface area is smaller or the particle size larger than described
above, the solid portion of the waste is prepared for extraction by crushing,
cutting, or grinding the waste to the surface area or particle size described
above. (Special precautions must be taken if the solids are prepared for
organic volatiles extraction.)
3. Extraction of Solid Material
The solid material from Step 2 is extracted for 18 + 2 hours with an
amount of extraction fluid equal to 20 times the weight of the solid phase.
The extraction fluid employed is a function of the alkalinity of the solid
SEVEN - 15 Revision 2
September 1994
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phase of the waste. A special extractor vessel is used when testing for
volatile analytes.
4. Final Separation of the Extraction from the Remaining Solid
Following extraction, the liquid extract is separated from the solid
phase by filtration through a 0.6 to 0.8 urn glass fiber filter. If
compatible, the initial liquid phase of the waste is added to the liquid
extract, and these are analyzed together. If incompatible, the liquids are
analyzed separately and the results are mathematically combined to yield a
volume-weighted average concentration.
5. Testing (Analysis) of TCLP Extract
Inorganic and organic species are identified and quantified using
appropriate methods in the 6000, 7000, and 8000 series of methods in this
manual or by equivalent methods.
7.4.3 Regulatory Definition
Under the Toxicity Characteristic, a solid waste exhibits the
characteristic of toxicity if the TCLP extract from a subsample of the waste
contains any of the contaminants listed in Table 7-1 at a concentration
greater than or equal to the respective value given in that table. If a waste
contains <0.5% filterable solids, the waste itself, after filtering, is
considered to be the extract for the purposes of analysis.
Under the Land Disposal Restrictions program, a restricted waste
identified in 40 CFR §268.41 may be land disposed only if a TCLP extract of
the waste or a TCLP extract of the treatment residue of the waste does not
exceed the values shown in Table CCWE of 40 CFR §268.41 for any hazardous
constituent listed in Table CCWE for that waste. If a waste contains <0.5%
filterable solids, the waste itself, after filtering, is considered to be the
extract for the purposes of analysis.
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TABLE 7-1.
MAXIMUM CONCENTRATION OF CONTAMINANTS FOR TOXICITY CHARACTERISTIC
Contaminant
Regulatory Level
(mg/L)
Arsenic
Barium
Benzene
Cadmi urn
Carbon tetrachloride
Chlordane
Chlorobenzene
Chloroform
Chromium
o-Cresol
m-Cresol
p-Cresol
Cresol
2,4-D
1 ,4-Dichl oro benzene
1,2-Dichloroethane
1 , 1 -Di chl oroethyl ene
2,4-Dinitrotoluene
Endrin
Heptachlor (and its hydroxide)
Hexachl orobenzene
Hexachl oro-l,3-butadi ene
Hexachl oroethane
Lead
Lindane
Mercury
Methoxychlor
Methyl ethyl ketone
Nitrobenzene
Pentachl orophenol
Pyridine
Selenium
Silver
Tetrachl oroethyl ene
Toxaphene
SEVEN - 17
5.0
100.0
0.5
1.0
0.5
0.03
100.0
6.0
5.0
200. O1
200. O1
200. O1
200. O1
10.0
7.5
0.5
0.7
0.132
0.02
0.008
0.132
0,5
3.0
5.0
0.4
0.2
10.0
200.0
2.0
100.0
5.02
1.0
5.0
0.7
0.5
^continued)
Revision 2
Septa*erl994
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Table 7-1
(continued)
Regulatory Level
Contaminant
Trichloroethylene 0.5
2,4,5-Trichlorophenol 400.0
2,4,6-Trichlorophenol 2.0
2,4,5-TP (Silvex) 1.0
Vinyl chloride 0.2
1lf o-, m-, and p-cresol concentrations cannot be differentiated, the total
cresol (D026) concentration is used. The regulatory level of total cresol is
200 mg/L.
2Quantitation limit is greater than the calculated regulatory level. The
quantitation limit therefore becomes the regulatory level.
SEVEN - 18 Revision 2
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FIGURE 3.
TOXICITY CHARACTERISTIC LEACHATE PROCEDURE FLOWCHART
Iiqutd» from
telid* «ilk 06
- C ,8 am gl*sj
fib.r filt.r
appro pna t* f iuid
1 ) Bottl* MtriclBr
foe non* voia t il»*
2) EKE d*vic« for
Reduc*
particia 31.21
io <9 S mm
SEVEN - 19
Revision 2
Septent3er 1994
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FIGURE 3
(continued)
r* msicun t 0!
liquid xnd mnmiyxm
(m*lh«n*LiC«liy
covibin* rvaiui t «/
r»»ui t of «)i t r»ct
Canbin*
••tract «/
liquid
ph,***
of w«ct*
Analyse*
liquid
STOP
SEVEN « 20
Revision 2
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CHAPTER EIGHT
METHODS FOR DETERMINING CHARACTERISTICS
Methods for determining the characterisitics of Ignitability for liquids,
Corrosivity for liquids, and Toxicity are included. Guidance for determining
Toxic Gas Generation is found in Chapter Seven, Sections 7.3,3 and 7.3.4.
EIGHT - 1 Revision 1
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8.1 Ignitability
The following methods are found in Section 8.1:
Hethod 1010: Pensky-Martens Closed-Cup Method for Determining
Ignitability
Hethod 1020A: Setaflash Closed-Cup Hethod for Determining
Ignitability
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8.2 Corrosivity
The following method is found in Section 8.2:
Method 1110; Corrosivity Toward Steel
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8.3 Reactivity
Refer to guidance given in Chapter Seven, especially Section 7.3.3 and
7.3.4.
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8,4 Toxicity
The following methods are found in Section 8.4:
Method I310A: Extraction Procedure (EP) Toxicity Test Method
and Structural Integrity Test
Method 1311: Toxicity Characteristic Leaching Procedure
EIGHT - 5 Revision- 1
Septenfcer 1994
•U.S. G.P.O.-,1995-386-824: 33251
-------
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METHOD 1312
SYNTHETIC PRECIPITATION LEACHING PROCEDURE
1.0 SCOPE AND APPLICATION
1.1 Method 1312 is designed to determine the mobility of both organic
and inorganic analytes present in liquids, soils, and wastes.
2.0 SUMMARY OF METHOD
2.1 For liquid samples (jue_.,, those containing less than 0.5 % dry
solid material), the sample, after filtration through a 0.6 to 0.8 /xm glass
fiber filter, is defined as the 1312 extract.
2.2 For samples containing greater than 0.5 % solids, the liquid phase,
if any, is separated from the solid phase and stored for later analysis; the
particle size of the solid phase is reduced, if necessary. The solid phase is
extracted with an amount of extraction fluid equal to 20 times the weight of the
solid phase. The extraction fluid employed is a function of the region of the
country where the sample site is located if the sample is a soil. If the sample
is a waste or wastewater, the extraction fluid employed is a pH 4.2 solution.
A special extractor vessel is used when testing for volatile analytes (see Table
1 for a list of volatile compounds). Following extraction, the liquid extract
is separated from the solid phase by filtration through a 0.6 to 0.8 pm glass
fiber filter.
2.3 If compatible (i.e., multiple phases will not form on combination),
the initial liquid phase of the waste is added to the liquid extract, and these
are analyzed together. If incompatible, the liquids are analyzed separately and
the results are mathematically combined to yield a volume-weighted average
concentration.
3.0 INTERFERENCES
3.1 Potential interferences that may be encountered during analysis are
discussed in the individual analytical methods,
4.0 APPARATUS AND MATERIALS
4.1 Agitation apparatus: The agitation apparatus must be capable of
rotating the extraction vessel in an end-over-end fashion (see Figure 1) at 30
± 2 rpm. Suitable devices known to EPA are identified in Table 2.
4.2 Extraction Vessels
4.2.1 Zero Headspace Extraction Vessel (ZHE). This device is for
use only when the sample is being tested for the mobility of volatile
analytes (i.e., those listed in Table 1). The ZHE (depicted in Figure 2)
allows for liquid/solid separation within the device and effectively
precludes headspace. This type of vessel allows for initial liquid/solid
separation, extraction, and final extract filtration without opening the
1312 - 1 Revision 0
September 1994
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vessel (see Step 4.3.1). These vessels shall have an internal volume of
500-600 ml and be equipped to accommodate a 90-110 mm filter. The devices
contain VITOhf1 0-rings which should be replaced frequently. Suitable ZHE
devices known to EPA are identified in Table 3.
For the ZHE to be acceptable for use, the piston within the ZHE
should be able to be moved with approximately 15 psig or less. If it
takes more pressure to move the piston, the 0-rings in the device should
be replaced. If this does not solve the problem, the ZHE is unacceptable
for 1312 analyses and the manufacturer should be contacted.
The ZHE should be checked for leaks after every extraction. If the
device contains a built-in pressure gauge, pressurize the device to 50
psig, allow it to stand unattended for 1 hour, and recheck the pressure.
If the device does not have a built-in pressure gauge, pressurize the
device to 50 psig, submerge it in water, and check for the presence of air
bubbles escaping from any of the fittings. If pressure is lost, check all
fittings and inspect and replace 0-rings, if necessary. Retest the
device. If leakage problems cannot be solved, the manufacturer should be
contacted.
Some ZHEs use gas pressure to actuate the ZHE piston, while others
use mechanical pressure (see Table 3). Whereas the volatiles procedure
(see Step 7.3} refers to pounds-per-square-inch (psig), for the
mechanically actuated piston, the pressure applied is measured in torque-
inch-pounds. Refer to the manufacturer's instructions as to the proper
conversion.
4.2.2 Bottle Extraction Vessel. When the sample is being
evaluated using the nonvolatile extraction, a jar with sufficient capacity
to hold the sample and the extraction fluid is needed. Headspace is
allowed in this vessel.
The extraction bottles may be constructed from various materials,
depending on the analytes to be analyzed and the nature of the waste (see
Step 4.3.3). It is recommended that borosilicate glass bottles be used
instead of other types of glass, especially when inorganics are of
concern. Plastic bottles, other than polytetrafluoroethylene, shall not
be used if organics are to be investigated. Bottles are available from a
number of laboratory suppliers. When this type of extraction vessel is
used, the filtration device discussed in Step 4.3.2 is used for initial
liquid/solid separation and final extract filtration.
4,3 Filtration Devices: It is recommended that all filtrations be
performed in a hood.
4.3.1 Zero-Headspace Extraction Vessel (ZHE): When the sample
is evaluated for volatiles, the zero-headspace extraction vessel described
in Step 4.2.1 is used for filtration. The device shall be capable of
is a trademark of Du Pont.
1312 - 2 Revision 0
September 1994
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supporting and keeping in place the glass fiber filter and be able to
withstand the pressure needed to accomplish separation (50 psig).
NOTE: When it is suspected that the glass fiber filter has been
ruptured, an in-line glass fiber filter may be used to filter the
material within the ZHE.
4.3.2 Filter Holder: When the sample is evaluated for other than
volatile analytes, a filter holder capable of supporting a glass fiber
filter and able to withstand the pressure needed to accomplish separation
may be used. Suitable filter holders range from simple vacuum units to
relatively complex systems capable of exerting pressures of up to 50 psig
or more. The type of filter holder used depends on the properties of the
material to be filtered (see Step 4.3.3). These devices shall have a
minimum internal volume of 300 ml and be equipped to accommodate a minimum
filter size of 47 mm (filter holders having an internal capacity of 1.5 L
or greater, and equipped to accommodate a 142 mm diameter filter, are
recommended). Vacuum filtration can only be used for wastes with low
solids content (<10 %) and for highly granular, liquid-containing wastes.
All other types of wastes should be filtered using positive pressure
filtration. Suitable filter holders known to EPA are listed in Table 4.
4.3.3 Materials of Construction: Extraction vessels and
filtration devices shall be made of inert materials which will not leach
or absorb sample components of interest. Glass, polytetrafluoroethylene
(PTFE), or type 316 stainless steel equipment may be used when evaluating
the mobility of both organic and inorganic components. Devices made of
high-density polyethylene (HOPE), polypropylene (PP), or polyvinyl
chloride (PVC) may be used only when evaluating the mobility of metals.
Borosilicate glass bottles are recommended for use over other types of
glass bottles, especially when inorganics are analytes of concern.
4.4 Filters: Filters shall be made of borosilicate glass fiber, shall
contain no binder materials, and shall have an effective pore size of 0.6 to
0.8-jum . Filters known to EPA which meet these specifications are identified
in Table. 5. Pre-filters must not be used. When evaluating the mobility of
metals, filters shall be acid-washed prior to use by rinsing with IN nitric acid
followed by three consecutive rinses with reagent water (a minimum of 1-L per
rinse is recommended). Glass fiber filters are fragile and should be handled
with care.
4.5 pH Meters: The meter should be accurate to + 0.05 units at 25"C.
4.6 ZHE Extract Collection Devices: TEDLAR*2 bags or glass, stainless
steel or PTFE gas-tight syringes are used to collect the initial liquid phase and
the final extract when using the ZHE device. These devices listed are
recommended for use under the following conditions:
4.6.1 If a waste contains an aqueous liquid phase or if a waste
does not contain a significant amount of nonaqueous liquid (i.e., <1 % of
2TEDLARffi is a registered trademark of Du Pont.
1312 - 3 Revision 0
September 1994
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total waste), the TEDLAR* bag or a 600 ml syringe should be used to collect
and combine the initial liquid and solid extract.
4.6.2 If a waste contains a significant amount of nonaqueous
liquid in the initiaj liquid phase (i.e., >1 % of total waste), the
syringe or the TEDLAR* bag may be used for both the initial solid/liquid
separation and the final extract filtration. However, analysts should use
one or the other, not both.
4.6.3 If the waste contains no initial liquid phase (is 100 %
solid) or has no significant solid phase (is <0.5% solid) , either the
TEDLAR* bag or the syringe lay be used. If the syringe is used, discard
the first 5 mL of liquid expressed from the device. The remaining
aliquots are used for analysis.
4.7 ZHE Extraction Fluid Transfer Devices: Any device capable of
transferring the extraction fluid into the ZHE without changing the nature of the
extraction fluid is acceptable (e.g., a positive displacement or peristaltic
pump, a gas-tight syringe, pressure filtration unit (see Step 4.3.2), or other
ZHE device).
4.8 Laboratory Balance: Any laboratory balance accurate to within ±
0.01 grams may be used (all weight measurements are to be within +0.1 grams).
4.9 Beaker or Erlenmeyer flask, glass, 500 mL.
4.10 Watchglass, appropriate diameter to cover beaker or Erlenmeyer
flask.
4.11 Magnetic stirrer.
5.0 REAGENTS
5.1 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.
5.2 Reagent Water. Reagent water is defined as water in which an
interferant is not observed at or above the method's detection limit of the
analyte(s) of interest. For nonvolatile extractions, ASTM Type II water or
equivalent meets the definition of reagent water. For volatile extractions, it
is recommended that reagent water be generated by any of the following methods.
Reagent water should be monitored periodically for impurities.
5.2.1 Reagent water for volatile extractions may be generated
by passing tap water through a carbon filter bed containing about 500
grams of activated carbon (Calgon Corp., Filtrasorb-300 or equivalent).
1312 - 4 Revision 0
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5.2.2 A water purification system (Millipore Super-Q or
equivalent) may also be used to generate reagent water for volatile
extractions.
5.2.3 Reagent water for volatile extractions may also be prepared
by boiling water for 15 minutes. Subsequently, while maintaining the
water temperature at 90 ± 5 degrees C, bubble a contaminant-free inert gas
(e.g. nitrogen) through the water for 1 hour. While still hot, transfer
the water to a narrow mouth screw-cap bottle under zero-headspace and seal
with a Teflon-lined septum and cap.
5.3 Sulfuric acid/nitric acid {60/40 weight percent mixture) H2S04/HN03.
Cautiously mix 60 g of concentrated sulfuric acid with 40 g of concentrated
nitric acid. If preferred, a more dilute H2S04/HN03 acid mixture may be
prepared and used in steps 5.4.1 and 5.4.2 making it easier to adjust the pH of
the extraction fluids.
5.4 Extraction fluids.
5.4.1 Extraction fluid #1: This fluid is made by adding the
60/40 weight percent mixture of sulfuric and nitric acids (or a suitable
dilution) to reagent water (Step 5.2) until the pH is 4.20 + 0.05. The
fluid is used to determine the Teachability of soil from a site that is
east of the Mississippi River, and the Teachability of wastes and
wastewaters.
NOTE: Solutions are unbuffered and exact pH may not be attained.
5.4.2 Extraction fluid 12: This fluid is made by adding the
60/40 weight percent mixture of sulfuric and nitric acids (or a suitable
dilution) to reagent water (Step 5.2) until the pH is 5,00 + 0.05. The
fluid is used to determine the Teachability of soil from a site that is
west of the Mississippi River.
5.4.3 Extraction fluid #3: This fluid is reagent water (Step
5.2) and is used to determine cyanide and volatiles Teachability.
NOTE: These extraction fluids should be monitored frequently for
impurities. The pH should be checked prior to use to ensure that
these fluids are made up accurately. If impurities are found or
the pH is not within the above specifications, the fTuid shall be
discarded and fresh extraction fluid prepared.
5.5 Analytical standards shall be prepared according to the appropriate
analytical method.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples shall be collected using an appropriate sampling plan.
6.2 There may be requirements on the minimal size of the field sample
depending upon the physical state or states of the waste and the analytes of
concern. An aliquot is needed for the preliminary evaluations of the percent
1312 - 5 Revision 0
September 1994
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solids and the particle size. An aliquot may be needed to conduct the
nonvolatile analyte extraction procedure. If volatile organics are of concern,
another aliquot may be needed. Quality control measures may require additional
aliquots. Further, it is always wise to collect more sample just in case
something goes wrong with the initial attempt to conduct the test.
6.3 Preservatives shall not be added to samples before extraction.
6.4 Samples may be refrigerated unless refrigeration results in
irreversible physical change to the waste. If precipitation occurs, the entire
sample (including precipitate) should be extracted.
6.5 When the sample is to be evaluated for volatile analytes, care
shall be taken to minimize the loss of volatiles. Samples shall be collected and
stored in a manner intended to prevent the loss of volatile analytes (e...g.,
samples should be collected in Teflon-lined septum capped vials and stored at
4°C. Samples should be opened only immediately prior to extraction).
6.6 1312 extracts should be prepared for analysis and analyzed as soon
as possible following extraction. Extracts or portions of extracts for metallic
analyte determinations must be acidified with nitric acid to a pH < 2» unless
precipitation occurs {see Step 7.2.14 if precipitation occurs). Extracts should
be preserved for other analytes according to the guidance given in the individual
analysis methods. Extracts or portions of extracts for organic analyte
determinations shall not be allowed to come into contact with the atmosphere
(i.e., no headspace) to prevent losses. See Step 8.0 (Quality Control) for
acceptable sample and extract holding times.
7.0 PROCEDURE
7.1 Preliminary Evaluations
Perform preliminary 1312 evaluations on a minimum 100 gram aliquot of
sample. This aliquot may not actually undergo 1312 extraction. These
preliminary evaluations include: (1) determination of the percent solids (Step
7.1.1); (2) determination of whether the waste contains insignificant solids and
is, therefore, its own extract after filtration (Step 7.1.2); and (3)
determination of whether the solid portion of the waste requires particle size
reduction (Step 7.1.3).
7.1.1 Preliminary determination of percent solids: Percent
solids is defined as that fraction of a waste sample (as a percentage of
the total sample) from which no liquid may be forced out by an applied
pressure, as described below.
7.1.1.1 If the sample will obviously yield no free
liquid when subjected to pressure filtration (i.e., is 100% solid),
weigh out a representative subsample (100 g minimum) and proceed
to Step 7.1.3.
7.1.1.2 If the sample is liquid or multiphasic,
liquid/solid separation to make a preliminary determination of
percent solids is required. This involves the filtration device
1312 - 6 Revision 0
September 1994
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discussed in Step 4.3.2, and is outlined in Steps 7.1.1.3 through
7.1.1.9.
7.1.1.3 Pre-weigh the filter and the container that will
receive the filtrate.
7,1.1.4 Assemble filter holder and filter following the
manufacturer's instructions. Place the filter on the support
screen and secure.
7.1.1.5 Weigh out a subsample of the waste (100 gram
minimum) and record the weight.
7.1.1.6 Allow slurries to stand to permit the solid phase
to settle. Samples that settle slowly may be centrifuged prior to
filtration. Centrifugation is to be used only as an aid to
filtration. If used, the liquid should be decanted and filtered
followed by filtration of the solid portion of the waste through
the same filtration system.
7.1.1.7 Quantitatively transfer the sample to the filter
holder (liquid and solid phases). Spread the sample evenly over
the surface of the filter. If filtration of the waste at 4°C
reduces the amount of expressed liquid over what would be expressed
at room temperature, then allow the sample to warm up to room
temperature in the device before filtering.
Gradually apply vacuum or gentle pressure of 1-10 psig,
until air or pressurizing gas moves through the filter. If this
point is not reached under 10 psig, and if no additional liquid has
passed through the filter in any 2-minute interval, slowly increase
the pressure in 10 psig increments to a maximum of 50 psig. After
each incremental increase of 10 psig, if the pressurizing gas has
not moved through the filter, and if no additional liquid has
passed through the filter in any 2-minute interval, proceed to the
next 10-psig increment. When the pressurizing gas begins to move
through the filter, or when liquid flow has ceased at 50 psig
(i.e., filtration does not result in any additional filtrate within
any 2-minute period), stop the filtration.
NOTE: If sample material (>1 % of original sample weight) has
obviously adhered to the container used to transfer the sample to
the filtration apparatus, determine the weight of this residue and
subtract it from the sample weight determined in Step 7.1.1.5 to
determine the weight of the sample that will be filtered.
NOTE: Instantaneous application of high pressure can degrade the
glass fiber filter and may cause premature plugging.
7.1.1.8 The material in the filter holder is defined as
the solid phase of the sample, and the filtrate is defined as the
liquid phase.
1312 - 7 Revision 0
September 1994
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NOTE: Some samples, such as oily wastes and some paint wastes,
will obviously contain some material that appears to be a liquid,
but even after applying vacuum or pressure filtration, as outlined
in Step 7.1.1.7, this material may not filter. If this is the
case, the material within the filtration device is defined as a
solid. Do not replace the original filter with a fresh filter
under any circumstances. Use only one filter.
7.1.1.9 Determine the weight of the liquid phase by
subtracting the weight of the filtrate container (see Step 7.1.1.3)
from the total weight of the filtrate-filled container. Determine
the weight of the solid phase of the sample by subtracting the
weight of the liquid phase from the weight of the total sample, as
determined in Step 7.1.1.5 or 7.1.1.7.
Record the weight of the liquid and solid phases.
Calculate the percent solids as follows:
Weight of solid (Step 7.1.1.9)
Percent solids = x 100
Total weight of waste (Step 7.1.1.5 or 7.1.1.7}
7.1.2 If the percent solids determined in Step 7.1.1.9 is equal
to or greater than 0.5%, then proceed either to Step 7.1.3 to determine
whether the solid material requires particle size reduction or to Step
7.1.2.1 if it is noticed that a small amount of the filtrate is entrained
in wetting of the filter. If the percent solids determined in Step
7.1.1.9 is less than 0.5%, then proceed to Step 7.2.9 if the nonvolatile
1312 analysis is to be performed, and to Step 7.3 with a fresh portion of
the waste if the volatile 1312 analysis is to be performed.
7.1.2.1 Remove the solid phase and filter from the
filtration apparatus.
7.1.2.2 Dry the filter and solid phase at 100 + 20°C
until two successive weighings yield the same value within + 1 %.
Record the final weight.
Caution: The drying oven should ie vented tc a hood or other
appropriate device to eliminate the possibility of fumes from the
sample escaping into the laboratory. Care should be taken to
ensure that the sample will not flash or violently react upon
heating.
7.1.2.3 Calculate the percent dry solids as follows:
Percent (Weight of dry sample + filter) - tared weight of filter
dry solids = ; x 100
Initial weight of sample (Step 7.1.1.5 or 7.1.1.7)
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7.1.2.4 If the percent dry solids is less than 0.5%,
then proceed to Step 7.2.9 if the nonvolatile 1312 analysis is to
be performed, and to Step 7.3 if the volatile 1312 analysis is to
be performed. If the percent dry solids is greater than or equal
to 0.5%, and if the nonvolatile 1312 analysis is to be performed,
return to the beginning of this Step (7.1) and, with a fresh
portion of sample, determine whether particle size reduction is
necessary (Step 7.1,3).
7.1.3 Determination of whether the sample requires particle-size
reduction (particle-size is reduced during this step): Using the solid
portion of the sample, evaluate the solid for particle size. Particle-
size reduction is required, unless the solid has a surface area per gram
of material equal to or greater than 3.1 cm2, or is smaller than 1 cm in
its narrowest dimension (i. e., is capable of passing through a 9.5 mm
(0,375 inch) standard sieve). If the surface area is smaller or the
particle size larger than described above, prepare the solid portion of
the sample for extraction by crushing, cutting, or grinding the waste to
a surface area or particle size as described above. If the solids are
prepared for organic volatiles extraction, special precautions must be
taken (see Step 7.3.6).
NOTE: Surface area criteria are meant for filamentous (e.g.,
paper, cloth, and similar) waste materials. Actual measurement of
surface area is not required, nor is it recommended. For materials
that do not obviously meet the criteria, sample-specific methods
would need to be developed and employed to measure the surface
area. Such methodology is currently not available.
7,1.4 Determination of appropriate extraction fluid:
7.1.4.1 For soils, if the sample is from a site that is
east of the Mississippi River, extraction fluid #1 should be used.
If the sample is from a site that is west of the Mississippi River,
extraction fluid 12 should be used.
7.1,4.2 For wastes and wastewater, extraction fluid #1
should be used.
7.1.4.3 for cyanide-containing wastes anc'/or sc:Ts,
extraction fluid #3 (reagent water) must be used because leaching
of cyanide-containing samples under acidic conditions may result
in the formation of hydrogen cyanide gas.
7.1.5 If the aliquot of the sample used for the preliminary
evaluation (Steps 7.1.1 - 7.1.4) was determined to be 100% solid at Step
7.1.1.1, then it can be used for the Step 7.2 extraction (assuming at
least 100 grams remain), and the Step 7.3 extraction (assuming at least 25
grams remain). If the aliquot was subjected to the procedure in Step
7.1.1.7, then another aliquot shall be used for the volatile extraction
procedure in Step 7.3. The aliquot of the waste subjected to the
procedure in Step 7.1.1.7 might be appropriate for use for the Step 7.2
extraction if an adequate amount of solid (as determined by Step 7.1.1.9)
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was obtained. The amount of solid necessary is dependent upon whether a
sufficient amount of extract will be produced to support the analyses. If
an adequate amount of solid remains, proceed to Step 7.2.10 of the
nonvolatile 1312 extraction.
7.2 Procedure When Volatiles Are Not Involved
A minimum sample size of 100 grams (solid and liquid phases) is
recommended. In some cases, a larger sample size may be appropriate, depending
on the solids content of the waste sample (percent solids, See Step 7.1.1),
whether the initial liquid phase of the waste will be miscible with the aqueous
extract of the solid, and whether inorganics, semivolatile organics, pesticides,
and herbicides are all analytes of concern. Enough solids should be generated
for extraction such that the volume of 1312 extract will be sufficient to support
all of the analyses required. If the amount of extract generated by a single
1312 extraction will not be sufficient to perform all of the analyses, more than
one extraction may be performed and the extracts from each combined and aliquoted
for analysis.
7.2.1 If the sample will obviously yield no liquid when subjected
to pressure filtration (i.e., is 100 % solid, see Step 7.1.1), weigh out
a subsample of the sample (100 gram minimum) and proceed to Step 7.2.9.
7.2.2 If the sample is liquid or multiphasiCj liquid/solid
separation is required. This involves the filtration device described in
Step 4.3.2 and is outlined in Steps 7.2.3 to 7.2.8.
7.2.3 Pre-weigh the container that will receive the filtrate.
7.2.4 Assemble the filter holder and filter following the
manufacturer's instructions. Place the filter on the support screen and
secure. Acid wash the filter if evaluating the mobility of metals (see
Step 4.4).
NOTE: Acid washed filters may be used for all nonvolatile
extractions even when metals are not of concern.
7.2.5 Weigh out a subsample of the sample (100 gram minimum) and
record the weight. If the waste contains <0.5 % dry solids (Step 7.1.2),
the liquid portion of the waste, after f:"!trat:cr, 'is defined ss the 1312
extract. Therefore, enough of the sample should be filtered so that the
amount of filtered liquid will support all of the analyses required of the
1312 extract. For wastes containing >0.5 % dry solids (Steps 7.1.1 or
7.1.2), use the percent solids information obtained in Step 7.1.1 to
determine the optimum sample size (100 gram minimum) for filtration.
Enough solids should be generated by filtration to support the analyses to
be performed on the 1312 extract.
7.2.6 Allow slurries to stand to permit the solid phase to settle.
Samples that settle slowly may be centrifuged prior to filtration. Use
centrifugation only as an aid to filtration. If the sample is
centrifuged, the liquid should be decanted and filtered followed by
filtration of the solid portion of the waste through the same filtration
system.
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7.2.7 Quantitatively transfer the sample (liquid and solid phases)
to the filter holder (see Step 4.3.2). Spread the waste sample evenly
over the surface of the filter. If filtration of the waste at 4°C reduces
the amount of expressed liquid over what would be expressed at room
temperature, then allow the sample to warm up to room temperature in the
device before filtering.
Gradually apply vacuum or gentle pressure of 1-10 psig, until air
or pressurizing gas moves through the filter. If this point if not
reached under 10 psig, and if no additional liquid has passed through the
filter in any 2-minute interval, slowly increase the pressure in 10-psig
increments to maximum of 50 psig. After each incremental increase of 10
psig, if the pressurizing gas has not moved through the filter, and if no
additional liquid has passed through the filter in any 2-minute interval,
proceed to the next 10-psig increment. When the pressurizing gas begins
to move through the filter, or when the liquid flow has ceased at 50 psig
(i.e.. filtration does not result in any additional filtrate within a
2-minute period), stop the filtration.
NOTE: If waste material (>1 % of the original sample weight) has
obviously adhered to the container used to transfer the sample to
the filtration apparatus, determine the weight of this residue and
subtract it from the sample weight determined in Step 7.2.5, to
determine the weight of the waste sample that will be filtered.
NOTE:Instantaneous application of high pressure can degrade the
glass fiber filter and may cause premature plugging.
7.2.8 The material in the filter holder is defined as the solid
phase of the sample, and the filtrate is defined as the liquid phase.
Weigh the filtrate. The liquid phase may now be either analyzed (see Step
7.2.12) or stored at 4°C until time of analysis.
NOTE: Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material which appears to be a liquid. Even
after applying vacuum or pressure filtration, as outlined in Step
7.2.7, this material may not filter. If this is the case, the
material within the filtration device is defined as a solid, and
is carried through the extraction as a solid. Do not replace the
original filter w:th c fresh filter ^nder any circumstances. Use
only one filter.
7.2.9 If the sample contains 0.5 % dry solids (see
Step 7.1.1 or 7.1.2), and if particle-size reduction of the solid was
needed in Step 7.1.3, proceed to Step 7.2.10. If the sample as received
passes a 9.5 mm sieve, quantitatively transfer the solid material into the
extractor bottle along with the filter used to separate the initial liquid
from the solid phase, and proceed to Step 7.2.11.
7.2.10 Prepare the solid portion of the sample for extraction by
crushing, cutting, or grinding the waste to a surface area or particle-
size as described in Step 7.1.3. When the surface area or particle-size
has been appropriately altered, quantitatively transfer the solid material
1312 - 11 Revision 0
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Into an extractor bottle. Include the filter used to separate the initial
liquid from the solid phase.
NOTE: Sieving of the waste is not normally required. Surface area
requirements are meant for filamentous (e.g., paper, cloth) and
similar waste materials. Actual measurement of surface area is not
recommended. If sieving is necessary, a Teflon-coated sieve should
be used to avoid contamination of the sample.
7.2.11 Determine the amount of extraction fluid to add to the
extractor vessel as follows:
20 x % solids (Step 7.1.1) x weight of waste
filtered (Step 7.2.5 or 7.2.7)
Weight of =
extraction fluid
100
Slowly add this amount of appropriate extraction fluid (see Step
7.1.4) to the extractor vessel. Close the extractor bottle tightly (it is
recommended that Teflon tape be used to ensure a tight seal), secure in
rotary extractor device, and rotate at 30 + 2 rpm for 18 + 2 hours.
Ambient temperature (j e;....., temperature of room in which extraction takes
place) shall be maintained at 23 + 2°C during the extraction period.
NOTE: As agitation continues, pressure may build up within the
extractor bottle for some types of sample (e.g.. limed or calcium
carbonate-containing sample may evolve gases such as carbon
dioxide). To relieve excess pressure, the extractor bottle may be
periodically opened (e.g., after 15 minutes, 30 minutes, and 1
hour) and vented into a hood.
7.2.12 Following the 18 + 2 hour extraction, separate the material
in the extractor vessel into its component liquid and solid phases by
filtering through a new glass fiber filter, as outlined in Step 7.2,7.
For final filtration of the 1312 extract, the glass fiber filter may be
changed, if necessary, to facilitate filtration. Filter(s) shall be
acid-washed (see Step 4,4) if evaluating the mobility of metals.
7.2.13 Prepare the 1312 extract as fcl'cws:
7.2.13.1 If the sample contained no initial liquid phase,
the filtered liquid material obtained from Step 7.2.12 is defined
as the 1312 extract. Proceed to Step 7.2.14.
7.2.13.2 If compatible (e.g.. multiple phases will not
result on combination), combine the filtered liquid resulting from
Step 7.2.12 with the initial liquid phase of the sample obtained
in Step 7.2.7. This combined liquid is defined as the 1312
extract. Proceed to Step 7.2.14.
7.2.13.3 If the initial liquid phase of the waste, as
obtained from Step 7.2.7, is not or may not be compatible with the
filtered liquid resulting from Step 7.2.12, do not combine these
1312 - 12 Revision 0
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liquids. Analyze these liquids, collectively defined as the 1312
extract, and combine the results mathematically, as described in
Step 7,2.14.
7,2.14 Following collection of the 1312 extract, the pH of the
extract should be recorded. Immediately aliquot and preserve the extract
for analysis. Metals aliquots must be acidified with nitric acid to pH <
2. If precipitation is observed upon addition of nitric acid to a small
aliquot of the extract, then the remaining portion of the extract for
metals analyses shall not be acidified and the extract shall be analyzed
as soon as possible. All other aliquots must be stored under
refrigeration (4"C) until analyzed. The 1312 extract shall be prepared
and analyzed according to appropriate analytical methods, 1312 extracts
to be analyzed for metals shall be acid digested except in those instances
where digestion causes loss of metallic analytes. If an analysis of the
undigested extract shows that the concentration of any regulated metallic
analyte exceeds the regulatory level, then the waste is hazardous and
digestion of the extract is not necessary. However, data on undigested
extracts alone cannot be used to demonstrate that the waste is not
hazardous. If the individual phases are to be analyzed separately,
determine the volume of the individual phases (to + 0.5 %), conduct the
appropriate analyses, and combine the results mathematically by using a
simple volume-weighted average:
(VJ (C,) + (V2) (C2)
Final Analyte Concentration =
V, + V2
where:
V1 = The volume of the first phase (L).
C, = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L).
C2 = The concentration of the analyte of concern in the second phase
(mg/L).
7.2.15 Compare the analyte concentrations in the 1312 extract with
the levels identified in the appropriate regulations. Refer to Section
8.0 for quality assurance requirements.
7.3 Procedure When Volatiles Are Involved
Use the ZHE device to obtain 1312 extract for analysis of volatile
compounds only. Extract resulting from the use of the ZHE shall not be used to
evaluate the mobility of non-volatile analytes {e.g., metals, pesticides, etc.).
The ZHE device has approximately a 500 ml internal capacity. The ZHE can
thus accommodate a maximum of 25 grams of solid (defined as that fraction of a
sample from which no additional liquid may be forced out by an applied pressure
of 50 psig), due to the need to add an amount of extraction fluid equal to 20
times the weight of the solid phase.
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Charge the ZHE with sample only once and do not open the device until the
final extract (of the solid) has been collected. Repeated filling of the ZHE to
obtain 25 grams of solid is not permitted.
Do not allow the sample, the initial liquid phase, or the extract to be
exposed to the atmosphere for any more time than is absolutely necessary. Any
manipulation of these materials should be done when cold (4°C) to minimize loss
of volatiles.
7.3.1 Pre-weigh the (evacuated) filtrate collection container
(see Step 4.6) and set aside. If using a TEDLAR* bag, express all liquid
from the ZHE device into the bag, whether for the initial or final
liquid/solid separation, and take an aliquot from the liquid in the bag
for analysis. The containers listed in Step 4,6 are recommended for use
under the conditions stated in Steps 4,6.1-4.6.3.
7.3.2 Place the ZHE piston within the body of the ZHE (it may be
helpful first to moisten the piston 0-rings slightly with extraction
fluid). Adjust the piston within the ZHE body to a height that will
minimize the distance the piston will have to move once the ZHE is charged
with sample (based upon sample size requirements determined from Step 7.3,
Step 7.1.1 and/or 7.1.2). Secure the gas inlet/outlet flange (bottom
flange) onto the ZHE body in accordance with the manufacturer's
instructions. Secure the glass fiber filter between the support screens
and set aside. Set liquid inlet/outlet flange (top flange) aside.
7.3.3 If the sample is 100% solid (see Step 7.1.1), weigh out
a subsample (25 gram maximum) of the waste, record weight, and proceed to
Step 7.3.5.
7.3.4 If the sample contains <0.5% dry solids (Step 7.1.2), the
liquid portion of waste, after filtration, is defined as the 1312 extract.
Filter enough of the sample so that the amount of filtered liquid will
support all of the volatile analyses required. For samples containing
>0.5% dry solids (Steps 7.1.1 and/or 7.1.2), use the percent solids
information obtained in Step 7.1.1 to determine the optimum sample size to
charge into the ZHE. The recommended sample size is as follows:
7.3,4.1 For samples containing <5% solids (see Step
weight.
, weign Ouz a 03 grain subsampTs of waste and record the
7.3.4.2 For wastes containing >5% solids (see Step
7.1.1), determine the amount of waste to charge into the ZHE as
follows:
25
Weight of waste to charge ZHE = x 100
percent solids (Step 7,1.1)
Weigh out a subsample of the waste of the appropriate size and
record the weight.
1312 - 14 " Revision 0
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7.3,5 If particle-size reduction of the solid portion of the
sample was required in Step 7,1.3, proceed to Step 7.3.6. If particle-
size reduction was not required in Step 7.1,3, proceed to Step 7.3.7.
7.3,6 Prepare the sample for extraction by crushing, cutting, or
grinding the solid portion of the waste to a surface area or particle size
as described in Step 7.1.3.1. Wastes and appropriate reduction equipment
should be refrigerated, if possible, to 4°C prior to particle-size
reduction. The means used to effect particle-size reduction must not
generate heat in and of itself. If reduction of the solid phase of the
waste is necessary, exposure of the waste to the atmosphere should be
avoided to the extent possible.
NOTE: Sieving of the waste is not recommended due to the
possibility that volatiles may be lost. The use of an
appropriately graduated ruler is recommended as an acceptable
alternative. Surface area requirements are meant for filamentous
(e.g., paper, cloth) and similar waste materials. Actual
measurement of surface area is not recommended.
When the surface area or particle-size has been appropriately
altered, proceed to Step 7.3.7.
7.3.7 Waste slurries need not be allowed to stand to permit the
solid phase to settle. Do not centrifuge samples prior to filtration.
7.3.8 Quantitatively transfer the entire sample (1 iquid and sol id
phases) quickly to the ZHE. Secure the filter and support screens into
the top flange of the device and secure the top flange to the ZHE body in
accordance with the manufacturer's instructions. Tighten all ZHE fittings
and place the device in the vertical position (gas inlet/outlet flange on
the bottom). Do not attach the extraction collection device to the top
plate.
Note: If sample material (>1% of original sample weight) has
obviously adhered to the container used to transfer the sample to
the ZHE, determine the weight of this residue and subtract it from
the sample weight determined in Step 7.3.4 to determine the weight
of the waste sample that will be filtered.
Attach a gas line to the gas inlet/outlet valve (bottom flange)
and, with the liquid inlet/outlet valve (top flange) open, begin applying
gentle pressure of 1-10 psig (or more if necessary) to force all headspace
slowly out of the ZHE device into a hood. At the first appearance of
liquid from the liquid inlet/outlet valve, quickly close the valve and
discontinue pressure. If filtration of the waste at 4°C reduces the
amount of expressed liquid over what would be expressed at room
temperature, then allow the sample to warm up to room temperature in the
device before filtering. If the waste is 100 % solid (see Step 7.1.1),
slowly increase the pressure to a maximum of 50 psig to force most of the
headspace out of the device and proceed to Step 7.3.12.
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7.3.9 Attach the evacuated pre-weighed filtrate collection
container to the liquid inlet/outlet valve and open the valve. Begin
applying gentle pressure of 1-10 psig to force the liquid phase of the
sample into the filtrate collection container. If no additional liquid
has passed through the filter in any 2-minute interval, slowly increase
the pressure in 10-psig increments to a maximum of 50 psig. After each
incremental increase of 10 psig, if no additional liquid has passed
through the filter in any Z-minute interval, proceed to the next 10-psig
increment. When liquid flow has ceased such that continued pressure
filtration at 50 psig does not result in any additional filtrate within a
2-minute period, stop the filtration. Close the liquid inlet/outlet
valve, discontinue pressure to the piston, and disconnect and weigh the
filtrate collection container.
NOTE: Instantaneous application of high pressure can degrade the
glass fiber filter and may cause premature plugging.
7.3.10 The material in the ZHE is defined as the solid phase of
the sample and the filtrate is defined as the liquid phase.
NOTE: Some samples, such as oily wastes and some paint wastes,
will obviously contain some material which appears to be a liquid.
Even after applying pressure filtration, this material will not
filter. If this is the case, the material within the filtration
device is defined as a solid, and is carried through the 1312
extraction as a solid.
If the original waste contained <0.5 % dry solids (see Step 7.1.2),
this filtrate is defined as the 1312 extract and is analyzed directly.
Proceed to Step 7.3.15.
7.3.11 The liquid phase may now be either analyzed immediately
(see Steps 7.3.13 through 7.3.15) or stored at 4°C under minimal headspace
conditions until time of analysis. Determine the weight of extraction
fluid #3 to add to the ZHE as follows:
20 x % solids (Step 7.1.1) x weight
of waste filtered (Step 7.3.4 or 7.3.8)
Weight of extraction fluid =
100
7.3.12 The following steps detail how to add the appropriate
amount of extraction fluid to the solid material within the ZHE and
agitation of the ZHE vessel. Extraction fluid #3 is used in all cases
(see Step 5.4.3).
7.3.12.1 With the ZHE in the vertical position, attach a
line from the extraction fluid reservoir to the liquid inlet/outlet
valve. The line used shall contain fresh extraction fluid and
should be preflushed with fluid to eliminate any air pockets in the
line. Release gas pressure on the ZHE piston (from the gas
inlet/outlet valve), open the liquid inlet/outlet valve, and begin
transferring extraction fluid (by pumping or similar means) into
1312 - 16 Revision 0
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the ZHE. Continue pumping extraction fluid into the ZHE until the
appropriate amount of fluid has been introduced into the device.
7.3.12,2 After the extraction fluid has been added,
immediately close the liquid inlet/outlet valve and disconnect the
extraction fluid line. Check the ZHE to ensure that all valves are
in their closed positions. Manually rotate the device in an
end-over-end fashion 2 or 3 times. Reposition the ZHE in the
vertical position with the liquid inlet/outlet valve on top.
Pressurize the ZHE to 5-10 psig (if necessary) and slowly open the
liquid inlet/outlet valve to bleed out any headspace (into a hood)
that may have been introduced due to the addition of extraction
fluid. This bleeding shall be done quickly and shall be stopped
at the first appearance of liquid from the valve. Re-pressurize
the ZHE with 5-10 psig and check all ZHE fittings to ensure that
they are closed.
7.3.12.3 Place the ZHE in the rotary extractor apparatus
(if it is not already there) and rotate at 30 + 2 rpm for 18+2
hours. Ambient temperature (i.e., temperature of room in which
extraction occurs) shall be maintained at 23 + 2°C during
agitation.
7,3.13 Following the 18 ± 2 hour agitation period, check the
pressure behind the ZHE piston by quickly opening and closing the gas
inlet/outlet valve and noting the escape of gas. If the pressure has not
been maintained (i.e., no gas release observed), the ZHE is leaking.
Check the ZHE for leaking as specified in Step 4.2.1, and perform the
extraction again with a new sample of waste. If the pressure within the
device has been maintained, the material in the extractor vessel is once
again separated into its component liquid and solid phases. If the waste
contained an initial liquid phase, the liquid may be filtered directly
into the same filtrate collection container (i .e., TEDLAR" bag) holding the
initial liquid phase of the waste. A separate filtrate collection
container must be used if combining would create multiple phases, or there
is not enough volume left within the filtrate collection container.
Filter through the glass fiber filter, using the ZHE device as discussed
in Step 7.3.9. All extracts shall be filtered and collected if the TEDLAff
bag is used, if the extract is multiphasic, or if the waste contained an
fnitiaT liquid phase (see Steps 4,5 and 7.3.1).
NOTE: An in-line glass fiber filter may be used to filter the
material within the ZHE if it is suspected that the glass fiber
filter has been ruptured
7.3.14 If the original sample contained no initial liquid phase,
the filtered liquid material obtained from Step 7.3.13 is defined as the
1312 extract. If the sample contained an initial liquid phase, the
filtered liquid material obtained from Step 7.3.13 and the initial liquid
phase (Step 7.3.9) are collectively defined as the 1312 extract.
7.3.15 Following collection of the 1312 extract, immediately
prepare the extract for analysis and store with minimal headspace at 4°C
1312 - 17 Revision 0
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until analyzed. Analyze the 1312 extract according to the appropriate
analytical methods. If the individual phases are to be analyzed
separately (Le;, are not miscible), determine the volume of the
individual phases (to 0,5%), conduct the appropriate analyses, and combine
the results mathematically by using a simple volume- weighted average:
(Vt) (C,) + (V2) (C2)
Final Analyte
Concentration V, + V2
where:
V1 = The volume of the first phases (L).
G! = The concentration of the analyte of concern in the first phase (mg/L).
V2 = The volume of the second phase (L).
C2 = The concentration of the analyte of concern in the second phase
(mg/L).
7.3.16 Compare the analyte concentrations in the 1312 extract with
the levels identified in the appropriate regulations. Refer to Step 8.0
for quality assurance requirements.
8.0 QUALITY CONTROL
8.1 A minimum of one blank (using the same extraction fluid as used for
the samples) for every 20 extractions that have been conducted in an extraction
vessel. Refer to Chapter One for additional quality control protocols.
8.2 A matrix spike shall be performed for each waste type (e.g..
wastewater treatment sludge, contaminated soil, etc.) unless the result exceeds
the regulatory level and the data is being used solely to demonstrate that the
waste property exceeds the regulatory level. A minimum of one matrix spike must
be analyzed for each analytical batch. As a minimum, follow the matrix spike
addition guidance provided in each analytical method,
8.2.1 Matrix spikes are to be added after filtration of the 1312
extract and before preservation. Matrix spikes should not be added prior
to 1312 extraction of the sample.
8.2.2 In most cases, matrix spike levels should be added at a
concentration equivalent to the corresponding regulatory level. If the
analyte concentration is less than one half the regulatory level, the
spike concentration may be as low as one half of the analyte
concentration, but may not be less than five times the method detection
limit. In order to avoid differences in matrix effects, the matrix spikes
must be added to the same nominal volume of 1312 extract as that which was
analyzed for the unspiked sample.
8.2.3 The purpose of the matrix spike is to monitor the
performance of the analytical methods used, and to determine whether
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matrix interferences exist. Use of other internal calibration methods,
modification of the analytical methods, or use of alternate analytical
methods may be needed to accurately measure the analyte concentration in
the 1312 extract when the recovery of the matrix spike is below the
expected analytical method performance.
8.2.4 Matrix spike recoveries are calculated by the following
formula:
%R (% Recovery) = 100 (X. - XJ / K
where:
Xs = measured value for the spiked sample
Xu = measured value for the unspiked sample, and
K = known value of the spike in the sample.
8.3 All quality control measures described in the appropriate analytical
methods shall be followed.
8.4 The use of internal calibration quantitation methods shall be
employed for a metallic contaminant if: (1) Recovery of the contaminant from the
1312 extract is not at least 50% and the concentration does not exceed the
appropriate regulatory level, and (2) The concentration of the contaminant
measured in the extract is within 20% of the appropriate regulatory level.
8,4.1. The method of standard additions shall be employed as the
internal calibration quantitation method for each metallic contaminant.
8.4.2 The method of standard additions requires preparing
calibration standards in the sample matrix rather than reagent water or
blank solution. It requires taking four identical aliquots of the
solution and adding known amounts of standard to three of these aliquots.
The forth aliquot is the unknown. Preferably, the first addition should
be prepared so that the resulting concentration is approximately 50% of
the expected concentration of the sample. The second and third additions
should be prepared so that the concentrations are approximately 100% and
150% of the expected concentration of the sample. All four aliquots are
maintained at the same final volume by adding reagent water or a blank
solution, and may need dilution adjustment to maintain the signals in the
linear range of the instrument technique. All four aliquots are analyzed.
8.4.3 Prepare a plot, or subject data to linear regression, of
instrument signals or external-calibration-derived concentrations as the
dependant variable (y-axis) versus concentrations of the additions of
standards as the independent variable (x-axis). Solve for the intercept
of the abscissa (the independent variable, x-axis) which is the concentra-
tion in the unknown.
8.4.4 Alternately, subtract the instrumental signal orexternal-
calibration-derived concentration of the unknown (unspiked) sample from
the instrumental signals or external-calibration-derived concentrations of
the standard additions. Plot or subject to linear regression of the
corrected instrument signals or external-calibration-derived concentra-
1312 - 19 Revision 0
September 1994
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tions as the dependant variable versus the independent variable. Derive
concentrations for the unknowns using the internal calibration curve as if
it were an external calibration curve.
8.5
periods:
Samples must undergo 1312 extraction within the following time
SAMPLE MAXIMUM HOLDING TIMES (days)
Volatiles
Semi-
volatiles
Mercury
Metals,
except
mercury
From: Field
Collec-
tion
To: 1312
extrac-
tion
14
14
28
180
From: 1312
extrac-
tion
To: Prepara-
tive
extrac-
tion
NA
7
NA
NA
From: Prepara-
tive
extrac-
tion
To: Determi-
native
analysis
14
40
28
180
Total
Elapsed
Time
28
61
56
360
NA = Not Applicable
If sample holding times are exceeded, the values obtained will be considered
minimal concentrations. Exceeding the holding time is not acceptable in
establishing that a waste does not exceed the regulatory level. Exceeding the
holding tine will not invalidate characterization if the waste exceeds the
regulatory level.
9.0 METHOD PERFORMANCE
9.1 Precision results for semi-volatiles and metals: An eastern soil
with high organic content and a western soil with low organic content were used
for the semi-volatile and metal leaching experiments. Both types of soil were
analyzed prior to contaminant spiking. The results are shown in Table 6. The
concentration of contaminants leached from the soils were reproducible, as shown
by the moderate relative standard deviations (RSDs) of the recoveries (averaging
29% for the compounds and elements analyzed).
9,2 Precision results for volatiles: Four different soils were spiked
and tested for the extraction of volatiles. Soils One and Two were from western
and eastern Superfund sites. Soils Three and Four were mixtures of a western
soil with low organic content and two different municipal sludges. The results
are shown in Table 7. Extract concentrations of volatile organics from the
eastern soil were lower than from the western soil. Replicate Teachings of Soils
1312 - 20
Revision 0
September 1994
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Three and Four showed lower precision than the leachates from the Superfund
soils.
10.0 REFERENCES
1. Environmental Monitoring Systems Laboratory, "Performance Testing of
Method 1312; QA Support for RCRA Testing: Project Report". EPA/600/4-
89/022. EPA Contract 68-03-3249 to Lockheed Engineering and Sciences
Company, June 1989.
Z, Research Triangle Institute, "Inter!aboratory Comparison of Methods 1310,
1311, and 1312 for Lead in Soil". U.S. EPA Contract 68-01-7075, November
1988.
1312 - 21 Revision 0
Septerrber 1994
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Table 1. Volatile Analytes1
Compound CAS No.
Acetone 67-64-1
Benzene 71-43-2
n-Butyl alcohol 71-36-3
Carbon distil fide 75-15-0
Carbon tetrachloride 56-23-5
Chlorobenzene 108-iO-7
Chloroform 67-66-3
1,2-Dichloroethane 107-06-2
1,1-Dichloroethylene 75-35-4
Ethyl acetate 141-78-6
Ethyl benzene 100-41-4
Ethyl ether 60-29-7
Isobutanol 78-83-1
Methanol 67-56-1
Methylene chloride 75-09-2
Methyl ethyl ketone 78-93-3
Methyl isobutyl ketone 108-10-1
Tetrachloroethylene 127-18-4
Toluene 108-88-3
1,1,1,-Trichloroethane 71-55-6
Trichloroethylene 79-01-6
Trichlorofluoromethane 75-69-4
UM-Trichloro-l^Z-trifluoroethane 76-13-1
Vinyl chloride 75-01-4
Xylene 1330-20-7
1 When testing for any or all of these analytes, the zero-headspace extractor
vessel shall be used instead of the bottle extractor.
1312 - 22 Revision 0
Septenfcer 1994
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Table 2. Suitable Rotary Agitation Apparatus1
Company
Location
Model No.
Analytical Testing and
Consulting Services,
Inc.
Associated Design and
Manufacturing Company
Environmental Machine and
Design, Inc.
IRA Machine Shop and
Laboratory
Lars Lande Manufacturing
Millipore Corp.
Warrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Lynchburg, VA
(804) 845-6424
Santurce, PR
(809) 752-4004
4-vessel extractor (DC20S);
8-vessel extractor (DC20);
12-vessel extractor (DC20B)
2-vessel
4-vessel
6-vessel
8-vessel
12-vessel
24-vessel
(3740-2);
(3740-4);
(3740-6);
(3740-8);
(3740-12);
(3740-24)
8-vessel (08-00-00)
4-vessel (04-00-00)
8-vessel (011001)
Whitmore Lake, MI 10-vessel (10VRE)
(313) 449-4116 5-vessel (5VRE)
Bedford, MA
(800) 225-3384
4-ZHE or
4 1-liter
bottle extractor
(YT300RAHW)
1 Any device that rotates the extraction vessel in an end-over-end fashion at 30
+2 rpm is acceptable.
1312 - 23
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September 1994
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Table 3. Suitable Zero-Headspace Extractor Vessels1
Company
Location
Model No.
Analytical Testing &
Consulting Services, Inc.
Associated Design and
Manufacturing Company
Lars Lande Manufacturing2
Millipore Corporation
Environmental Machine
and Design, Inc.
Warrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
C102, Mechanical
Pressure Device
3745-ZHE, Gas
Pressure Device
Whitmore Lake, MI ZHE-11, Gas
(313) 449-4116 Pressure Device
Bedford, MA
(800) 225-3384
Lynchburg, VA
(804) 845-6424
YT30090HW, Gas
Pressure Device
VOLA-TOX1, Gas
Pressure Device
1 Any device that meets the specifications listed in Step 4.2.1 of the method is
suitable.
2 This device uses a 11-0 mm filter.
1312 - 24
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September 1994
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Table 4. Suitable Filter Holders1
Company
Nucleopore Corporation
Micro Filtration
Systems
Mi Hi pore Corporation
Location
Pleasanton, CA
(800) 882-7711
Dublin, CA
(800) 334-7132
(415) 828-6010
Bedford, MA
(800) 225-3384
Model/
Catalogue #
425910
410400
302400
311400
YT30142HW
XX1004700
Size
142 mm
47 mm
142 mm
47 mm
142 mm
47 mm
1 Any device capable of separating the liquid from the solid phase of the waste
is suitable, providing that it is chemically compatible with the waste and the
constituents to be analyzed. Plastic devices (not listed above) may be used when
only inorganic analytes are of concern. The 142 ram size filter holder is
recommended.
Table 5. Suitable Filter Media1
Company
Mi Hi pore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Location Model
Bedford, MA AP40
(800) 225-338^
Pleasanton, CA 211625
(415) 463-2530
Clifton, NJ 6FF
(201) 773-5800
Dublin, CA GF75
(800) 334-7132
(415) 828-6010
Pore
Size
(Mm)
0.7
0.7
0.7
0.7
1 Any filter that meets the specifications in Step 4.4 of the Method is suitable.
1312 - 25
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September 1994
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TABLE 6 - METHOD 1312 PRECISION RESULTS FOR SEMI-VOLATILES AND METALS
Eastern Soil (oH 4.2)
FORTIFIED ANALYTES
bis(2-chloroethyl)-
ether
2 - Chlorophenol
1 , 4-Diehlorobenzene
1 , 2 -Dichlorobenzene
2-Methylphenol
Nitrobenzene
2 , 4-Dimethylphenol
Hexachlorobutadiene
Acenaphthene
2 , 4-Dinitrophenol
2 ,4-Dinitrotoluene
Hexachlorobenzene
famma BHC (Lindane)
eta BHC
METALS
Lead
Cadmium
Amount
Spiked
(MS)
1040
1620
2000
8920
3940
1010
1460
6300
3640
1300
1900
1840
7440
640
5000
1000
Amount
Recovered*
(MB)
834
1010
344
1010
1860
812
200
95
210
896**
1150
3.7
230
35
70
387
f ESP
12.5
6.8
12.3
8.0
7.7
10.0
18.4
12.9
8.1
6.1
5.4
12.0
16.3
13.3
4.3
2.3
Western Soil ft>H 5.0)
Amount
Recovered*
(Mg)
616
525
272
1520
1130
457
18
280
310**
23**
585
10
1240
65.3
10
91
% RSD
14.2
54.9
34.6
28.4
32.6
21.3
87,6
22.8
7.7
15.7
54.4
173.2
55.2
51.7
51.7
71.3
* - Triplicate analyses.
** - Duplicate analyses; one value was rejected as an outlier at the 90%
confidence level using the Dixon Q test.
1312 - 26
Revision 0
Septenber 1994
-------
TABLE 7 - METHOD 1312 PRECISION RESULTS FOR VQIATILES
Soil
No. 1
(Western)
Compound Name
Acetone
Acrylonitrile
Benzene
n- Butyl Alcohol
(1-Butanol)
Carbon disulflde
Carbon tetrachloride
Chlorobenzene
Chloroform
1, 2-Dichloroethane
1 , 1-Mchloroethane
Ethyl acetate
Ethylbenzene
Ethyl ether
Isooutanol (4-Methyl
-1-propanol)
Methylene chloride
Methyl ethyl ketone
(2-Butanone)
Methyl isobutyl
ketone
1,1,1, 2 - Tetrachloro -
ethane
1,1,2, 2 - Tetrachloro -
ethane
fetrachloroethene
Toluene
1,1,1-Trichloro-
ethane
1,1,2-Trichloro-
e thane
Trichloroethene
Trichloro-
f luorome thane
1,1,2-Trichloro-
trifluoroe thane
Vinyl chloride
Avg.
%Rec.*
44.0
52,5
47.8
55.5
21.4
40.6
64.4
61.3
73.4
31.4
76.4
56.2
48.0
0.0
47.5
56.7
81.1
69,0
85.3
45.1
59.2
47.2
76.2
54.5
20.7
18.1
10.2
iRSD
12.4
68.4
8.29
2.91
16.4
18.6
6.76
8.04
4.59
14.5
9.65
9.22
16,4
ND
30.3
5.94
10.3
6.73
7.04
12.7
8.06
16.0
5.72
11.1
24.5
26.7
20.3
Soil
No. 2
(Eastern)
Avg.
%Rec,*
43.8
50.5
34.8
49.2
12.9
22.3
41.5
54.8
68.7
22.9
75.4
23.2
55.1
0.0
42.2
61.9
88.9
41.1
58.9
15.2
49.3
33.8
67.3
39.4
12.6
6.95
7.17
IRSD
2.25
70.0
16.3
14.6
49.5
29.1
13.1
16.4
11.3
39.3
4.02
11.5
9.72
ND
42.9
3.94
2.99
11.3
4.15
17.4
10.5
22,8
8.43
19.5
60.1
58.0
72.8
Soil No
(Western
Sludge)
Avg.
%Rec . **
116.0
49.3
49.8
65.5
36.5
36.2
44.2
61.8
58.3
32,0
23,0
37.5
37.3
61.8
52.0
73.7
58.3
50.8
64.0
26.2
45.7
40.7
61.7
38.8
28.5
21.5
25.0
, 3
and
$RSD
11.5
44.9
36.7
37.2
51.5
41.4
32.0
29,1
33.3
54.4
119.8
36.1
31.2
37.7
37.4
31.3
32,6
31.5
25.7
44.0
35.2
40.6
28.0
40.9
34.0
67.8
61.0
Soil, No. 4
(Western and
Sludge)
Avg.
%Rec.*** %RSD
21.3 71.4
51.8 4.6
33.4 41.1
73.0 13.9
21.3 31.5
24.0 34.0
33.0 24.9
45.8 38.6
41.2 37.8
16.8 26.4
11.0 115.5
27.2 28,6
42.0 17.6
76.0 12.2
37.3 16.6
40.6 39.0
39.8 40.3
36.8 23.8
53.6 15.8
18.6 24.2
31.4 37.2
26.2 38.8
46,4 25.4
25.6 34.1
19.8 33. S
15.3 24,8
11.8 25.4
* Triplicate analyses
** Six replicate analyses
*** Five replicate analyses
1312 - 27
Revision 0
September 1994
-------
Motor
(30±2rpm)
Extraction vmael Holder
n
Figure 1. Rotary Agitation Apparatus
UqukJ Irtst/Outt* VHv»
TopFlangt.
Support Screw*
Fi
Support Scratn'
Bottom Rang*—*£
Prt«suriz«d Gas •
SampJ*
PWon
Gas
Prtssurt
Gaugt
Figure 2. Zero-Headspace Extractor (ZHE)
1312 - 28
Revision 0
September 1994
-------
METHOD 1312
SYNTHETIC PRECIPITATION LEACHING PROCEDURE
Liquid
Prepare filtrate
according to
appropriate
methods.
Analyze filtrate.
Stop
Start
Select
representative
sample.
Separate liquid*
from solids,
filtrate
become* SPLP
extract.
Separate liquids
from solids.
is
particle
reduction
required?
Extract w/
appropriate fluid via:
1. Bottle extraction
for non-volatiies,
2. ZHE for volatiles.
Reduce particle
size to <9.5 mm.
1312 - 29
Revision 0
Septsiter 1994
-------
METHOD 1312
SYNTHETIC PRECIPITATION LEACHING PROCEDURE (continued)
o
Discard
Solids
Solids
^
r
Separate liquids
from solids.
Extract
Is
extract
compatible
with initial
liquid
phase?
Prepare and analyze
each liquid
separately,
mathematically
combine results.
Combine extract
with liquid phase
of waste.
^
r
Stop
1 Prepare extract
according to
appropriate
methods.
^
r
Analyze extract.
^
r
Stop
1312 - 30
Revision 0
Septenter 1994
-------
METHOD 3015
MICROWAVE ASSISTED ACID DIGESTION OF AQUEOUS
SAMPLES AND EXTRACTS
1.0 SCOPE AND APPLICATION
1.1 This digestion procedure is used for the preparation of aqueous
samples, nobility-procedure extracts, and wastes that contain suspended solids
for analysis, by flame atomic absorption spectroscopy (FLAA), graphite furnace
absorption spectroscopy (GFAA), inductively coupled argon plasma spectroscopy
(ICP), or inductively coupled irgon plasma mass spectrometry (ICP-MS). The
procedure is a hot acid leach for determining available metals. Due to the rapid
advances in microwave technology, consult your manufacturer's recommended
instructions for guidance on their microwave digestion system and refer to the
SW-846 "DISCLAIMER" when conducting analyses using Method 3015.
1.2 Samples prepared by Method 3015 using nitric acid digestion may be
analyzed by FLAA, GFAA, 1CP-AES, or ICP-MS for the following:
Aluminum Lead
Antimony • Magnesium
Arsenic* Manganese
Barium Molybdenum
Beryllium Nickel
Cadmium Potassium
Calcium Selenium*
Chromium Silver
Cobalt Sodium
Copper Thallium
Iron Vanadium
Zinc
*Cannot be analyzed by FLAA
2.0 SUMMARY OF METHOD
2.1 A representative 45 ml aqueous sample is digested in 5 ml of
concentrated nitric acid in a fluorocarbon (PFA or TFM) digestion vessel for 20
minutes using microwave heating. After the digestion process, the sample is
cooled, and then filtered, centrifuged, or allowed to settle in a clean sample
bottle prior to analysis.
3.0 INTERFERENCES
3,1 Many samples that contain organics, such as TCLP extracts, will
result in higher vessel pressures which have the potential to cause venting of
the vessels. Venting can result in either loss of analytes and/or sample, which
must be avoided. A smaller sample size can be used but the final water volume
3015 - 1 Revision 0
September 1994
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prior to nitric acid addition must remain at 45 mL. This is required to retain
the heat characteristics of the calibration procedure. Limits of quantitation
will change with sample quantity (dilution) as with instrumentation."
4.0 APPARATUS AND MATERIALS
4.1 Microwave apparatus requirements
4.1.1 The microwave unit provides programmable power with a
minimum of 574 W, which can be programmed to within ± 10 W of the
required power. Typical units provide a nominal 600 W to 1200 W of
power. Temperature monitoring and control of the microwave unit are
desirable.
4.1.2 The microwave unit cavity is corrosion resistant and
well ventilated.
4.1.3 All electronics are protected against corrosion for safe
operation.
4.1.4 The system requires fluorocarbon (PFA or TFM) digestion
vessels (120 mL capacity) capable of withstanding pressures up to 7.5
± 0.7 atm (110 ± 10 psig) and capable of controlled pressure relief at
pressures exceeding 7.5 ± 0.7 atm (110 ± 10 psig).
4.1.5 A rotating turntable is employed to insure homogeneous
distribution of microwave radiation within the unit. The speed of the
turntable should be a minimum of 3 rpm.
CAUTION: Those laboratories now using or contemplating the use of
kitchen type microwave ovens for this method should be aware of
several significant safety issues. First, when an acid such as
nitric is used to assist sample digestion in microwave units in
open vessels, or sealed vessels equipped with venting features,
there is the potential for the acid gases released to corrode the
safety devices that prevent the microwave magnetron from shutting
off when the door is opened. This can result in operator exposure
to microwave energy. Use of a unit with corrosion resistant safety
devices prevents this from occurring.
CAUTION; The second safety concern relates to the use of sealed
containers without pressure relief valves in the unit. Tempera-
ture is the important variable controlling the reaction. Pressure
is needed to attain elevated temperatures but must be safely con-
tained. However, many digestion vessels constructed from certain
fluorocarbons may crack, burst, or explode in the oven under
certain pressures. Only unlined fluorocarbon (PFA or TFM)
containers with pressure relief mechanisms or containers with
fluorocarbon (PFA or TFM) liners and pressure relief mechanisms
are considered acceptable at present.
3015 - 2 Revision 0
September 1994
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Users are therefore advised not to use kitchen type microwave
ovens or to use sealed containers without pressure relief valves
for microwave acid digestions by this method. Use of laboratory
grade microwave equipment is required to prevent safety hazards.
For further information consult reference 1.
CAUTIQN: In addition, there are many safety and operational
recommendations specific to the model and manufacturer of the
microwave equipment used in individual laboratories. These
specific suggestions are beyond the scope of this method and
require the analyst to consult the specific equipment manual,
manufacturer and literature for proper and safe operation of the
microwave equipment and vessels.
4.2 Volumetric graduated cylinder, 50 or 100 ml capacity or equivalent.
4.3 Filter paper, qualitative or equivalent.
4.4 Analytical balance, 300 g capacity, minimum accuracy ± 0.01 g.
4.5 Filter funnel, glass or disposable polypropylene.
5.0 REAGENTS
5.1 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. If the
purity of a reagent is questionable, analyze the reagent to determine the level
of impurities. The reagent blank must be less than the MDL in order to be used.
5.2 Reagent Water. Reagent water shall be interference free. All
references to water in the method refer to reagent water unless otherwise specif-
ied (Ref. 2).
5.3 Concentrated nitric acid, HNO». Acid should be analyzed to
determine levels of impurities. If the method blank is less than the MDL, the
acid can be used.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
water. Plastic containers are preferable. See Chapter Three, Step 3.1.3 of this
manual, for further information.
6.3 Aqueous waste waters must be acidified to a pH of < 2 with
3015 - 3 Revision 0
September 1994
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7.0 PROCEDURE
7.1 Calibration of Microwave Equipment
NOTE: If the microwave unit uses temperature feedback control
capable of replicating the performance specifications of the
method, then the calibration procedure may be omitted.
7.1.1 Measurement of the available power for heating is
evaluated so that absolute power in watts may be transferred from one
microwave unit to another. For cavity type microwave equipment, this
is accomplished by measuring the temperature rise in 1 kg of water
exposed to microwave radiation for a fixed period of time. The analyst
can relate power in watts to the partial power setting of the unit. The
calibration format required for laboratory microwave units depends on
the type of electronic system used by the manufacturer to provide
partial microwave power. Few units have an accurate and precise linear
relationship between percent power settings and absorbed power. Where
linear circuits have been utilized, the calibration curve can be deter-
mined by a three-point calibration method (7.1.3), otherwise, the
analyst must use the multiple point calibration method (7.1.2).
7.1.2 The multiple point calibration involves the measurement
of absorbed power over a large range of power settings. Typically, for
a 600 W unit, the following power settings are measured; 100,11,98,97,
95,90,80,70,60,50, and 40% using the procedure described in section
7.1.4. This data is clustered about the customary working power ranges.
Nonlinearity has been commonly encountered at the upper end of the
calibration. If the unit's electronics are known to have nonlinear
deviations in any region of proportional power control, it will be
necessary to make a set of measurements that bracket the power to be
used. The final calibration point should be at the partial power
setting that will be used in the test. This setting should be checked
periodically to evaluate the integrity of the calibration. If a
significant change is detected {±10 W), then the entire calibration
should be reevaluated.
7.1.3 The three-point calibration involves the measurement of
absorbed power at three different power settings. Measure the power at
100% and 50% using the procedure described in section 7.1.4, and
calculate the power setting corresponding to the required power in watts
specified in the procedure from the (2-point) line. Measure the
absorbed power at that partial power setting. If the measured absorbed
power does not correspond to the specified power within ±10 W, use the
multiple point calibration in 7.1.2. This point should also be used to
periodically verify the integrity of the calibration.
7.1.4 Equilibrate a large volume of water to room temperature
(23 ± 2 *C), One kg of reagent water is weighed (1,000.0 g ± 0.1 g)
into a fluorocarbon (PFA or TFM) beaker or a beaker made of some other
material that does not significantly absorb microwave energy (glass
3015 - 4 Revision 0
September 1994
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absorbs microwave energy and is not recommended). The initial
temperature of the water should be 23 ± 2 *C measured to ± 0.05 *C. The
covered beaker is circulated continuously (in the normal sample path)
through the microwave field for 2 minutes at the desired partial power
setting with the unit's exhaust fan on maximum (as it will be during
normal operation). The beaker is removed and the water vigorously
stirred. Use a magnetic stirring bar inserted immediately after
microwave irradiation and record the maximum temperature within the
first 30 seconds to ± 0.05 °C. Use a new sample for each additional
measurement. If the water is reused both the water and the beaker must
have returned to 23 ± 2 *C. Three measurements at each power setting
should be made.
The absorbed power is determined by the following relationship
P • (K) (Cp) (m) (AT)
Eq. 1
Where :
P - the apparent power absorbed by the sample in watts (W).
(W=joule-sec )
K = the conversion factor for thermochemical calories- sec"1 to watts
(-4.184)
C - the heat capacity, thermal capacity, or specific heat
-g^-C'1), of water
m - the mass of the water sample 1n grams (g)
AT « the final temperature minus the initial temperature ("C)
t • the time in seconds (s)
Using the experimental conditions of 2 minutes and 1 kg of distilled
water (heat capacity at 25 "C is 0.9997 cal -g~1- T1) the calibration
equation simplifies to:
P = (AT) (34.86)
NOTE: Stable line voltage is necessary for accurate and reproduc-
ible calibration and operation. The line voltage should be within
manufacturer's specification, and during measurement and operation
not vary by more than ±2 V. A constant power supply may be
necessary for microwave use if the source of the line voltage is
unstable.
3015 - 5 Revision 0
September 1994
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Electronic components in most microwave units are matched to the units'
function and output. When any part of the high voltage circuit, power
source, or control components In the unit have been serviced or
replaced, it will be necessary to recheck the units' calibration power.
If the power output has changed significantly (±10 W), then the entire
calibration should be reevaluated.
7.2 All digestion vessels and volumetric ware must be carefully acid
washed and rinsed with reagent water. When switching between high solids
(concentrated) samples and low solids (low concentration) samples all digestion
vessels should be cleaned by leaching with hot (1:1) hydrochloric acid (greater
than 80°C, but less than boiling) for a minimum of two hours followed with hot
(1:1) nitric acid (greater than 8Q°C, but less than boiling) for a minimum of two
hours, rinsed with reagent water, and dried in a clean environment. This
cleaning procedure should also be used whenever the prior use of the digestion
vessels is unknown or cross contamination from vessels is suspected. Polymeric
or glass volumetric ware and storage containers should be cleaned by leaching
with more dilute acids (approximately 10% V/V) appropriate for the specific
plastics used and then rinsed with reagent water and dried in a clean environ-
ment. In addition, to avoid precipitation of silver, ensure that all HC1 has
been rinsed from the vessels.
7.3 Sample Digestion
7.3.1 Weigh the fluorocarbon (PFAorTFM) digestion vessel, valve
and cap assembly to 0.01 g prior to use.
7.3.2 A 45 ml aliquot of a well shaken sample is measured in a
graduated cylinder. This aliquot is poured into the digestion vessel
with the number of the vessel recorded on the preparation sheet.
7.3.3 A blank sample of reagent water is treated in the same
manner along with spikes and duplicates.
7.3.4 Add 5 mL of concentrated nitric acid tc sach vessel that
will be used. Check to make sure the pressure relief disks are in the
caps with the smooth side toward the sample and start the caps a few
turns on the vessels.- Finish tightening the caps in the capping station
which will tighten them to a uniform torque pressure of 12 ft-lbs.
(16 N-nt) or to the manufacturers recommended specifications. Weigh each
capped vessel to the nearest 0.01 g.
CAUTION: Toxic nitrogen oxide fumes nay be evolved, therefore all
work must be performed in a properly operating ventilation system.
The analyst should also be aware of the potential for a vigorous
reaction. If a vigorous reaction occurs, allow to cool before
capping the vessel.
7.3.5 Evenly distributed the vessels in the carousel according
to the manufacturer's recommended specifications. Blanks are treated
as samples for the purpose of balancing the power input. When fewer
3015 - 6 Revision 0
September 1994
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than the recommended number of samples are digested, the remaining
vessels should be filled with 45 ml of reagent water and 5 ml of nitric
acid to achieve the full compliment of vessels. This provides an energy
balance since the microwave power absorbed is proportional to the total
mass in the cavity (Ref, 1).
7,3.6 Program the microwave unit according to the manufacturer's
recommended specifications and, if used, connect the pressure vessels
to the central overflow vessel with PFA-fluorocarbon tubes. The chosen
sequence will bring the samples to 160"C 4 4"C in 10 minutes and will
permit a slow rise to 165-170 "C during the second 10 minutes (Ref. 3),
Start the turntable motor and be sure the vent fan is running on high
and the turntable is turning. Start the microwave generator.
7.3.6.1 Newer microwave units are capable of higher
power that permit digestion of a larger number of samples per
batch. If the analyst wishes to digest more samples at a tine,
the analyst may use different power settings as long as they
result in the same time and temperature conditions defined in
7.3.6. That is, any sequence of power that brings the samples to
160*C ± 4*C in 10 minutes and permits a slow rise to 1S5-170*C
during the second 10 minutes (Ref. 2).
Issues of safety, structural integrity (both temperature and
pressure limitations), heat loss, chemical compatibility,
microwave absorption of vessel material, and energy transport will
be considerations made in choosing alternative vessels. If all
of the considerations are met and the appropriate power settings
are provided to reproduce the reaction conditions defined in
7.3.6, then these alternative vessels may be used (Ref. 1,3)
7.3.7 At the end of the microwave program, allow the vessels
to cool for at least 5 minutes in the unit before removal to avoid
possible injury if a vessel vents immediately after microwave heating.
The samples may be cooled outside the unit by removing the carousel and
allowing the samples to cool on the bench or in a water bath. When the
vessels have cooled to room temperature, weigh and record the weight of
each vessel assembly. If the weight of the sample plus acid has
decreased by more than 10% discard the sample.
7.3.8 Complete the preparation of the sample by carefully
uncapping and venting each vessel in a fume hood. Transfer the sample
to an acid-cleaned bottle. If the digested sample contains par-
ticulates whtch may clog nebulizers or interfere with injection of the
sample into the instrument, the sample may be centrifuged, allowed to
settle or filtered.
7.3.8.1 Centrifugation: Centrifugalion at 2,000-3,000 rpm
for 10 minutes is usually sufficient to clear the supernatant.
3015 - 7 Revision 0
September 1994
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7.3.8.2 Settling: Allow the sample to stand until the
supernatant is clear. Allowing a sample to stand overnight will
usually accomplish this. If it does not, centrifuge or filter the
sample.
7.3.8.3 Filtering: The filtering apparatus must be
thoroughly cleaned and prerinsed with dilute (approximately 10%
V/V) nitric acid. Filter the sample through qualitative filter
paper into a second acid-cleaned container.
7.3.9 The concentration values obtained from analysis must be
corrected for the dilution factor from the acid addition. If the sample
will be analyzed by ICP-HS additional dilution will generally be
necessary. For example, the sample may be diluted by a factor of 20
with reagent water and the acid strength adjusted back to 10% prior to
analysis. The dilutions used should be recorded and the measured con-
centrations adjusted accordingly (e.g., for a 45 ml sample and 5 ml of
add the correction factor is 1.11).
8.0 QUALITY CONTROL
8.1 All quality control measures described in Chapter One, of this
Manual, should be followed.
8.2 For each analytical batch of samples processed, analytical reagent
blanks (also field blanks if they were taken) should be carried throughout the
entire sample preparation and analytical process. These blanks will be useful
in determining if samples are being contaminated.
8.3 Duplicate samples should be processed on a routine basis. A
duplicate sample is a real sample brought through the whole sample preparation
and analytical process. A duplicate sample should be processed with each
analytical batch or every 20 samples, whichever is the greater number.
8.4 Spiked samples or standard reference materials should be employed
to determine accuracy. A spiked sample should be included with each group of
samples processed and whenever a new sample matrix is being analyzed.
9.0 METHOD PERFORMANCE
9.1 Refer to Table 1 for a summary of performance data.
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10,0 REFERENCES
1- Introduction to Microwave Sample Preparation: Theory andPractice.
Kingston, H, M.; Jassie, L. B., Eds.; ACS Professional Reference Book
Series: American Chemical Society, Washington, DC, 1988; Ch 6 & 11,
2. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification
for Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
3. Kingston, H. M., Final Report EPA IAG fDWI3932541-01-I, September 30,
1988, Appendix A,
4. Shannon, M., Alternate Test Procedure Application, USEPA Region V,
Central Regional Laboratory, 536 S. Clark Street, Chicago, IL 60606,
1989.
5, Kingston, H, M., Walter, P. J., "Comparison of Microwave Versus
Conventional Dissolution for Environmental Applications", Spectroscopy,
vol. 7 No. 9,20-27,1992.
6. Sosinski, P., and Sze C., "Absolute Accuracy Study, Microwave Digestion
Method 3015 (Nitric acid only)"; EPA Region III Central Regional
Laboratory, 1991.
3015 - 9 Revision 0
Septenter 1994
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TABLE 1
MICROWAVE DieESTION METHOD 3015 (Nitric Acid Only)
Elea
Al
At
At
At
Ba
Ba
Ba
Cd
Cd
Cd
Cd
Zn
Zn
In
Zn
As
As
Co
Co
K
K
Hi
Ni
Hi
fb
Pb
Pb
Po
Sb
£'*>
?~ '-
Se
Tt
Tl
V
V
8*
Be
Ca
Ca
Material
Tm-11
In- 12
T-107
T-109
Tm-11
Tm-12
T-107
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
T-109
T-107
T-109
Tm-11
Tin- 12
T-9S
T-109
Tw-11
Tn-12
T-109
Tdl-11
TIB- 12
T-107
'109
VP9BO-1
UP980-2
T-95
T-1C?
W980-1
UP980-2
Tra- 11
Tm-12
T-107
T-109
T-107
T-109
Certified
Nean
510.0
2687.0
220,0
113.0
450.0
2529.0
192.0
40.8
237.0
14.3
12.1
55.4
314.0
75.8
74.0
10.8
8.15
227.0
1067.0
4700,0
2330.0
264.0
1234.0
57.0
275.0
1526.0
26.0
34.9
16.9
101.5
60.1
11.0
50.0
6.3
491.0
2319.0
11.0
22.1
11700.0
35400.0
Observed
Nean
485.5
2770.6
213.5
117.7
441.4
2431 .4
196.6
44.6
242.3
12.4
10.3
55.9
316.5
81.6
69.9
12.8
90.6
242.6
1153.3
5080.3
2601.5
284.3
1293.0
60 .8
275.9
1359.0
30.0
39.3
18.3
108.9
65.9
13.0
55,1
7.0
532.6
2412.8
11.3
25.6
12364.0
38885.0
Std. Dev.
26.3
88.2
19.3
30.6
23.4
70.3
15.9
2.1
8
0.9
1.7
2.6
8.9
3.3
4.1
0.84
11.0
14.1
35.9
784
383.4
16.5
39.4
3.09
32.2
35.0
0.2
1.2
0.47
34.4
2.6
0.9
2
0.52
26.1
60.6
0.53
0.91
783.6
999
Relative
Standard
Deviation
5.4
3.2
9.0
2.6
5.3
2.9
8.1
4.7
3.3
7.2
16.5
4.6
2.8
4.0
5.8
6.5
12.2
5.8
3.1
15.4
14.7
5.8
3.0
5.0
11.7
2.6
0.66
3.0
2.6
31.6
3.94
6.9
3.6
7.4
4.9
2.5
4.7
3.6
6.3
2.6
Relative
•fas
-4.80%
3.11X
-2.95X
4.16%
•1.90X
-3.86%
2.44%
9.46%
2.25%
-12.94X
-14.55%
1.06X
0.82X
7.68%
-5. 46%
19.26%
11.26X
6.90%
8.09X
8.092
11.65X
7.71%
4.79%
6.72%
0.36X
2.49%
15.65%
12.69%
8.27%
7.33%
9.77%
19.00X
10.26%
11.66%
8.48%
4.05%
3.00%
15.97%
5.68%
9.84%
3015 - 10
Revision 0
Septaiter 1994
-------
TABLE 1 (continued)
Elan
Ca
Ca
Hg
Mg
Mg
Ma
Ma
Ma
Or
Cr
Cr
Cr
Cu
Cu
Cu
Cu
Fe
Fe
Fe
Fe
Hn
Hn
Mr.
Hn
*g
Katerial
T-107
T-109
T-95
T-107
T-109
T-95
T-107
T-109
Tm-11
Tm-12
T-107
T-109
Tm-11
Tm-12
T-107
T-109
Tm-11
Tin-IE
T-107
T-109
Tm-11
Tm-12
T-107
T-109
WS378-1
Certified
Mean
11700,0
35400.0
32800.0
2100.0
9310,0
190000.0
20700.0
12000.0
52.1
299.0
13,0
18.7
46.3
288.0
30.0
21.4
249.0
1089.0
52,0
106.0
46.0
263.0
45.0
34.0
48.0
Observed
Mean
12364,0
38885,0
35002.0
2246.7
10221.7
218130.0
22528.0
1379i,5
64.3
346.0
22.3
32.6
76.5
324.0
42.3
54.0
289.3
1182.5
63.8
134.0
SO. 9
304.4
52.6
46.8
19.4
Std. Dev.
783.6
999
1900
110.5
218.6
10700
1060
516.2
4,1
9.8
1.5
6.4
4.4
8.9
4.0
3.6
16.4
43.5
8.7
6.6
3.2
9.1
3.1
3.0
5,6
Relative
Standard
Deviation
6.3
2.6
5.4
4.9
2.1
4.9
4.7
3.7
6.4
2.8
6.7
19.6
5.7
2.7
9.4
6.7
5.7
3.7
13.6
4.9
5.2
3.0
5.8
6.4
2.9
Relative
Bias
5.68%
9,84%
6.71X
6.99%
9.79%
14.81%
8.83%
15,00%
23.51%
li.74%
71.77%
74.71%
65.36%
12.52%
41.17%
152.38%
16.18%
8.59%
22.69%
26.50%
32.48%
15.77%
17.Q9X
37,18%
-57.83%
3015 - 11
Revision 0
Septartoer 1994
-------
METHOD 3015
MICROWAVE ASSISTED ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS
7,1 Ctfilmft*
I
7.2 AeM *M
mnt
•II i
vw
ftemnra.
7.3.3
4«
lnt»th*
7.3.$ U** M»*
*l
7.1.* Ai
MNOgt*
7.1,1
M»»».l
oarvu
M«nk»tt
7.3,7 Alto*
in
3015 - 12
Revision 0
Septenter 1994
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METHOD 3051
MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS.
SLUDGES, SOILS, AND OILS
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to the microwave assisted acid digestion of
sludges, sediments, soils, and oils for the following elements:
Aluminum Cadmium Iron Molybdenum Sodium
Antimony Calcium Lead Nickel Strontium
Arsenic Chromium Magnesium Potassium Thallium
Boron Cobalt Manganese Selenium Vanadium
Barium Copper Mercury Silver " Zinc
Beryl1i urn
1.2 This method is provided as an alternative to Method 3050. It is
intended to provide a rapid multielement acid leach digestion prior to analysis
so that decisions can be made about site cleanup levels, the need for TCLP
testing of a waste and whether a BOAT process is providing acceptable
performance. If a decomposition including hydrochloric acid is required for
certain elements, it is recommended that Method 3050A be used. Digests produced
by the method are suitable for analysis by flame atomic absorption (FLAA),
graphite furnace atomic absorption (GFAA), inductively coupled plasma emission
spectroscopy (ICP-ES) and inductively coupled plasma mass spectrometry (ICP-MS).
Due to the rapid advances in microwave technology, consult your manufacturer's
recommended instructions for guidance on their microwave digestion system and
refer to the SW-846 "DISCLAIMER" when conducting analyses using Method 3051.
2.0 SUMMARY OF METHOD
2.1 A representative sample of up to 0.5 g is digested in 10 ml of
concentrated nitric acid for 10 min using microwave heating with a suitable
laboratory microwave unit. The sample and acid are placed in a fluorocarbon (PFA
or TFM) microwave vessel. The vessel is capped and heated in the microwave unit.
After cooling, the vessel contents are filtered, centrifuged, or allowed to
settle and then diluted to volume and analyzed by the appropriate SW-846 method
(Ref. 1).
3.0 INTERFERENCES
3.1 Very reactive or volatile materials that may create high pressures
when heated may cause venting of the vessels with potential loss of sample and
analytes. The complete decomposition of either carbonates, or carbon based
samples, may cause enough pressure to vent the vessel if the sample size is
greater than 0.25 g when used in the 120 mL vessels with a pressure relief device
that has an upper limit of 7.5± 0.7 atm (110 ± 10 psi).
3051 - 1 Revision 0
September 1194
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4.0 APPARATUS AND MATERIALS
4.1 Microwave apparatus requirements.
4.1.1 The microwave unit provides programmable power with a
minimum of 574 W, which can be programmed to within ± 10 W of the required
power. Typical units provide a nominal 600 W to 1200 W of power.
Pressure, or especially temperature, monitoring and control of the
microwave unit are desirable.
4.1.2 The microwave unit cavity is corrosion resistant and well
ventilated.
4.1.3 All electronics are protected against corrosion for safe
operation.
4.1.4 The system requires fluorocarbon (PFA or TFH) digestion
vessels {120 ml capacity) capable of withstanding pressures up to 7.5 ±
0.7 atm (110 ± 10 psi) and capable of controlled pressure relief at
pressures exceeding 7.5 ± 0.7 atm (110 ± 10 psi).
4.1.5 A rotating turntable is employed to insure homogeneous
distribution of microwave radiation within the unit. The speed of the
turntable should be a minimum of 3 rpm.
CAUTION: Those laboratories now using or contemplating the
use of kitchen type microwave ovens for this method should be
aware of several signifant safety issues. First, when an acid
such as nitric is used to assist sample digestion in microwave
units in open vessels, or sealed vesselsequippedres, there is
the potential for the acid gases released to corrode the
safety devices that prevent the microwave magnetron from
shutting off when the door is opened. This can result in
operator exposure to microwave energy. Use of a unit with
corrosion resistant safety devices prevents this from
occurring.
CAUTION: The second safety concern relates to the use of
sealed containers without pressure relief valves in the unit.
Temperature is the important variable controlling the
reaction. Pressure is needed to attain elevated temperatures
but must be safely contained. However, many digestion vessels
constructed from certain f1uorocarbons may crack, burst, or
explode in the unit under certain pressures. Only unlined
fluorocarbon (PFA or TFH) containers with pressure relief
mecahnisms or containers with PFA-fluorocarbon liners and
pressure relief mechanisms are considered acceptable at
present.
Users are therefore advised not to use kitchen type microwave
ovens or to use sealed containers without pressure relief
3051 - 2 Revision 0
Septenter 1994
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valves for microwave acid digestions by this method. Use of
laboratory-grade microwave equipment is required to prevent
safety hazards. For further details consult reference 2.
CAUTION; There are many safety and operational
recommendations specific to the model and manufacturer of the
microwave equipment used in individual laboratories. These
specific suggestions are beyond the scope of this method and
require the analyst to consult the specific equipment manual,
manufacturer and literature for proper and safe operation of
the microwave equipment and vessels.
4.2 Volumetric graduated cylinder, 50 or 100 ml capacity or equivalent.
4.3 Filter paper, qualitative or equivalent.
4.4 Filter funnel, glass or disposable polypropylene.
4.5 Analytical balance, 300 g capacity, and minimum ± 0.01 g.
5.0 REAGENTS
5.1 All acids should be sub-boiling distilled where possible to minimize
the blank levels due to metallic contamination. Other grades may be used,
provided it is first ascertained that the reagent is of sufficient purity to
permit its use without lessening the accuracy of the determination. If the
purity of a reagent is questionable, analyze the reagent to determine the level
of impurities. The reagent blank must be less than the MDL in order to be used.
5.1.1 Concentrated nitric acid, HN03. Acid should be analyzed to
determine levels of impurity. If the method blank is less than the MDL,
the acid can be used.
5.2 Reagent Water. Reagent water shall be interference free. All
references to water in the method refer to reagent water unless otherwise
specified (Ref. 3).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids and
water. Plastic and glass containers are both suitable. See Chapter Three, sec.
3.1.3 of this manual, for further information.
6.3 Samples must be refrigerated upon receipt and analyzed as soon as
possible.
3051 - 3 Revision 0
September 1994
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7.0 PROCEDURE
7.1 Calib -ation of Microwave Equipment
NOTE: If the microwave unit uses temperature feedback control
capable of replicating the performance specifications of the method,
then the calibration procedure may be omitted.
7.1.1 Measurement of the available power for heating is evaluated
so that absolute power in watts may be transferred from one microwave unit
to another. For cavity type microwave equipment, this is accomplished by
measuring the temperature rise in 1 kg of water exposed to microwave
radiation for a fixed period of time. The analyst can relate power in
watts to the partial power setting of the unit. The calibration format
required for laboratory microwave units depends on the type of electronic
system used by the manufacturer to provide partial microwave power. Few
units have an accurate and precise linear relationship between percent
power settings and absorbed power. Where linear circuits have been
utilized, the calibration curve can be determined by a three-point
calibration method (7.1.3), otherwise, the analyst must use the multiple
point calibration method (7.1.2).
7.1.2 The multiple point calibration involves the measurement of
absorbed power over a large range of power settings. Typically, for a
600 W unit, the following power settings are measured; 100, 99, 98, 97,
95, 90, 80, 70, 60, 50, and 40% using the procedure described in section
7.1.4. This data is clustered about the customary working power ranges.
Nonlinearity has been commonly encountered at the upper end of the
calibration. If the unit's electronics are known to have nonlinear
deviations in any region of proportional power control, it will be
necessary to make a set of measurements that bracket the power to be used.
The final calibration point should be at the partial power setting that
will be used in the test. This setting should be checked periodically to
evaluate the integrity of the calibration. If a significant change is
detected (±10 W), then the entire calibration should be reevaluated.
7.1.3 The three-point calibration involves the measurement of
absorbed power at three different power settings. Measure the power at
100% id 50% using athe procedure described in sact ion 7.1.4. From the
2-point line calculate the power setting corresponding to the required
power in watts specified in the procedure. Measure the absorbed power at
that partial power setting. If the measured absorbed power does not
correspond to the specified power within tlO W, use the multiple point
calibration in 7.1.2. This point should also be used to periodically
verify the integrity of the calibration.
7.1.4 Equilibrate a large volume of water to room temperature
(23 ± 2°C). One kg of reagent water is weighed (1,000.0 g + 0.1 g) into
a fluorocarbon beaker or a beaker made of some other material that does
not significantly absorb microwave energy (glass absorbs microwave energy
and is not recommended). The initial temperature of the water should be
3051 - 4 Revision 0
September 1994
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23 ± 2"C measured to ± 0,05'C, The covered beaker is circulated
continuously (in the normal sample path) through the microwave field for
2 minutes at the desired partial power setting with the unit's exhaust fan
on maximum (as it will be during normal operation). The beaker is removed
and the water vigorously stirred. Use a magnetic stirring bar inserted
immediately after microwave irradiation and record the maximum temperature
within the first 30 seconds to ± 0.05°C. Use a new sample for each
additional measurement. If the water is reused both the water and the
beaker must have returned to 23 t 2°C. Three measurements at each power
setting should be made.
The absorbed power is determined by the following relationship:
P - (K) (CJ (m) (AT)
Eq. 1
Where:
P = the apparent power absorbed by the sample in watts (W)
(W=joule-sec*1)
K = the conversion factor for thermochemical calories-sec"1 to watts
(=4.184)
Cp = the heat capacity, thermal capacity, or specific heat
(cal-g-1 T1) of water
m = the mass of the water sample in grams (g)
AT * the final temperature minus the initial temperature (°C)
t = the time in seconds (s)
Using the experimental conditions of 2 minutes and 1 kg of distilled water
(heat capacity at 25 °C is 0.9997 cal-g^-'C1) the calibration equation
simplifies to:
Eq. 2 P = (AT) (34.86)
NOTE: Stable line voltage is necessary for accurate and
reproducible calibration and operation. The line voltage should be
within manufacturer's specification, and during measurement and
operation should not vary by more than ±2 V. A constant power
supply may be necessary for microwave use if the source of the
line voltage is unstable.
Electronic components in most microwave units are matched to the
units' function and output. When any part of the high voltage
3051 - 5 Revision 0
September 1994
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circuit, power source, or control components in the unit have been
serviced or replaced, it will be necessary to recheck the units'
calibration. If the power output has changed significantly (±10 W),
then the entire calibration should be reevaluated.
7.2 All digestion vessels and volumetric ware must be carefully acid
washed and rinsed with reagent water. When switching between high concentration
samples and low concentration samples, all digestion vessels should be cleaned
by leaching with hot (1:1) hydrochloric acid (greater than 80°C, but less than
boiling) for a minimum of two hours followed with hot (1:1) nitric acid (greater
than 80°C, but less than boiling) for a minimum of two hours and rinsed with
reagent water and dried in a clean environment. This cleaning procedure should
also be used whenever the prior use of the digestion vessels is unknown or cross
contamination from vessels is suspected. Polymeric or glass volumetric ware and
storage containers should be cleaned by leaching with more dilute acids
(approximately 10% V/V) appropriate for the specific plastics used and then
rinsed with reagent water and dried in a clean environment. To avoid
precipitation of silver, ensure that all HC1 has been rinsed from the vessels.
7.3 Sample Digestion
7.3.1 Weigh the fluorocarbon (PFA or TFM) digestion vessel, valve
and capassembly to 0.001 g prior to use,
7.3.2 Weigh a well-mixed sample to the nearest 0.001 g into the
fluorocarbon sample vessel equipped with a single-ported cap and a
pressure relief valve. For soils, sediments, and sludges use no more than
0.500 g. For oils use no more than 0.250 g.
7.3.3 Add 10 ± 0.1 mL concentrated nitric acid in a fume hood.
If a vigorous reaction occurs, allow the reaction to stop before capping
the vessel. Cap the vessel and torque the cap to 12 ft-lbs (16 N-m) or
according to the unit manufacturer's directions. Weigh the vessels to the
nearest 0.001 g. Place the vessels in the microwave carousel.
CAUTION: Toxic nitrogen oxide fumes may be evolved, therefore all
work must be performed in a properly operating ventilation system.
The analyst should also be aware of the potential for a vigorous
reaction. If a vigorous reaction occurs, allow to cool before
capping the vessel.
CAUTION: When digesting samples containing volatile or easily
oxidized organic compounds, Initially weigh no more than 0.10 g and
observe the reaction before capping the vessel. If a vigorous
reaction occurs, allow the reaction to cease before capping the
vessel. If no appreciable reaction occurs, a sample weight up to
0.25 g can be used.
3051 - 6 Revision 0
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CAUTION: All samples known or suspected of containing more than 5-
10% organic material should be predigested in a hood for at least 15
minutes.
7.3.4 Properly place the carousel in the microwave unit according
to the manufacturer's recommended specifications and, if used, connect the
pressure vessels to the central overflow vessel with PFA-fluorocarbon
tubes. Any vessels containing 10 ml of nitric acid for analytical blank
purposes are counted as sample vessels. When fewer than the recommended
number of samples are to be digested, the remaining vessels should be
filled with 10 ml of nitric acid to achieve the full complement of
vessels. This provides an energy balance since the microwave power
absorbed is proportional to the total mass in the cavity (Ref. 4).
Irradiate each group of sample vessels for 10 minutes. The temperature of
each sample should rise to 175 °C in less than 5,5 minutes and remain
between 170-180 °C for the balance of the 10 minute irradiation period.
The pressure should peak at less than 6 atm for most soil, sludge, and
sediment samples (Ref. 5). The pressure will exceed these limits in the
case of high concentrations of carbonate or organic compounds. In these
cases the pressure will be limited by the relief pressure of the vessel to
7.5 ± 0.7 atm (110 ± 10 psi). All vessels should be sealed according to
the manufacturers recommended specifications.
7.3.4.1 Newer microwave units are capable of higher power (W)
that permits digestion of a larger number of samples per batch. If
the analyst wishes to digest more samples at a time, the analyst may
use different values of power as long as they result in the same
time and temperature conditions defined in 7.3.4. That is, any
sequence of power that brings the samples to 175°C in 5.5 minutes
and permits a slow rise to 175 - 180°C during the remaining 4.5
minutes (Ref. 5).
Issues of safety, structural integrity (both temperature and
pressure limitations), heat loss, chemical compatibility, microwave
absorption of vessel material, and energy transport will be
considerations made in choosing alternative vessels. If all of the
considerations are met and the appropriate power settings provided
to reproduce the reaction conditions defined in 7.3.4, then these
alternative vessels may be used (Ref. 1,2).
7.3.5 At the end of the microwave program, allow the vessels to
cool for a minimum of 5 minutes before removing them from the microwave
unit. When the vessels have cooled to room temperature, weigh and record
the weight of each vessel assembly. If the weight of acid plus sample
has decreased by more than 10 percent from the original weight,
discard the sample. Determine the reason for the weight loss. These are
typically attributed to loss of vessel seal integrity, use of a digestion
time longer than 10 minutes, too large a sample, or improper heating
conditions. Once the source of the loss has been corrected, prepare
a new sample or set of samples for digestion beginning at 7.3.1.
3051 - 7 Revision 0
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7.3.6 Complete the preparation of the sample by carefully uncapping
and venting each vessel in a fume hood. Transfer the sample to an acid-
cleaned bottle. If the digested sample contains participates which may
clog nebulizers or interfere with injection of the sample into the
instrument, the sample may be centrifuged, allowed to settle, or filtered.
7.3.6.1 Centrifugation: Centrifugation at 2,000-3,000 rpm
for 10 minutes is usually sufficient to clear the supernatant.
7.3.6.2 Settling: Allow the sample to stand until the
supernatant is clear. Allowing a sample to stand overnight will
usually accomplish this. If it does not, centrifuge or filter the
sample.
7.3.6.3 Filtering: The filtering apparatus must be
thoroughly cleaned and prerinsed with dilute (approximately 10% V/V)
nitric acid. Filter the sample through qualitative filter paper
into a second acid-cleaned container.
7.3.7 Dilute the digest to a known volume ensuring that the samples
and standards are matrix matched. The digest is now ready for analysis
for elements of interest using the appropriate SW-846 method.
7.4 Calculations: The concentrations determined are to be reported on the
b ;s of the actual weight of the original sample.
8.0 QUALITY CONTROL
8.1 All quality control data must be maintained and available for
reference or inspection for a period of three years. This method is restricted
to use by, or under supervision of, experienced analysts. Refer to the
appropriate section of Chapter One for additional quality control guidance,
8.2 Duplicate samples should be processed on a routine basis. A duplicate
sample is a sample brought through the whole sample preparation and analytical
process. A duplicate sample should be processed with each analytical batch or
every 20 samples, whichever is the greater number. A duplicate sample should be
prepared for each matrix type (i.e., soil, sludge, etc.).
8.3 Spiked samples or standard reference materials should be included with
each group of samples processed or every 20 samples, whichever is the greater
number. A spiked sample should also be included whenever a new sample matrix is
being analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision: Precision data for Method 3051, as determined by the
statistical examination of inter!aboratory test results, is located in Tables 1
and 2.
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9.2 Repeatability: If successive results are obtained by the same analyst
with the same apparatus under constant operating conditions on identical test
material, then the difference between these successive results will not, with 95%
probability, exceed the repeatability value. For example, in the case of lead,
an average of only 1 case in 20 would exceed
0.206 x
in the long ryn, where x is one result in fjg/g (Ref. 6).
9,3 Reproducibility: If two successive measurements are made independently
by each of two different analysts working in different laboratories on identical
test material, then the difference between the average result for each analyst
will not, with 95% probability, exceed the reproducibility value. For example,
in the case of lead, an average of only 1 case in 20 would exceed
0.303 x
in the long run, where x is the average of two successive measurements in /Aj/g
(Ref. 2).
As can be seen in Table 1, repeatability and reproducibility differ between
elements, and usually depend on that element's concentration. Table 2 provides
an example of how users of the method can determine expected values for
repeatability and reproducibility; nominal values of lead have been used for this
model (Ref. 6).
9.4 Bias: In the case of SRM 1085 - Wear Metals in Oil, the bias of this
test method is different for each element. An estimate of bias, as shown in
Table 3, is:
Bias = Amount found - Amount expected.
However, the bias estimate inherits both the uncertainty in the
measurements made using Method 3051 and the uncertainty on the certificate, so
whether the bias is real or only due to measurement error must also be con-
sidered. The concentrations found for Al, Cr, and Cu using Method 3051 fall
within their certified ranges on SRM 1085, and 95% confidence intervals for Fe
and Ni overlap with their respective certified ranges; therefore, the observed
biases for these elements are probably due to chance and should be considered
insignificant. Biases should not be estimated at all for Ag and Pb because these
elements were not certified. Therefore, the only two elements considered in this
table for which the bias estimates are significant are Mg and Mo.
10.0 REFERENCES
1. TestMethods for Evaluating Solid Waste, Physical/Chemical Methods, 3rd
ed; U.S. Environmental Protection Agency, Office of Solid Waste and
Emergency Response. U.S. Government Printing Office: Washington, DC,
1986; SW-846.
3051 - 9 Revision 0
September 1994
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2. Kingston, H. M. and L. B. Jassie, "Safety Guidelines for Microwave Systems
in the Analytical Laboratory", In Introduction to Microwave Acid
Decomposition: Theory and Practice; Kingston, H. M. and Jassie, L. B.,
eds.; ACS Professional Reference Book Series; American Chemical Society:
Washington, DC, 1988,
3. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification
for Reagent Water ; ASTM, Philadelphia, PA, 1985, D1193-77.
4. Introduction to Microwave Sample Preparation: Theory and Practice,
Kingston, H. H. and Jassie, L. B., Eds.; ACS Professional Reference Book
Series; American Chemical Society: Washington, DC, 1988.
5. Kingston, H. M. EPA IAG IDWI-393254-01-0 January 1-March 31, 1988,
quarterly Report.
6. Binstock, D. A., Yeager, W. M., Grohse, P. M. and Cask/ill, A. Validation
of a Method for Determining Elements in Solid Waste_by_H1croMave Diges-
tion, Research Triangle Institute Technical Report Draft, RTI Project
Number 321U-3579-24, November, 1989, prepared for the Office of Solid
Waste, U.S. Environmental Protection Agency, Washington, DC 20450.
7. Kingston, H. M,, Walter, P. J., "Comparison of Microwave Versus
Conventional Dissolution for Environmental Applications", Spectroscopy,
vol. 7 No. 9,20-27,1992.
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September 1994
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TABLE 1.
EQUATIONS RELATING REPEATABILITY AND REPRODUCIBILITY TO MEAN
CONCENTRATION OF DUPLICATE DETERMINATION WITH 95 PERCENT CONFIDENCE
Element Repeatability Reproducibility
Ag
AT
B
Ba
Be
Ca
Cd
Co
Cr
Cu
Fe
Mg
Hn
Mo
Ni
Pb
Sr
V
Zn
0.195X8
0.232X
12. 9b
0.238X
0.082b
0.356X
0.385X
0.291X
0.187X
0.212X
0.257X
0.238X
1.96X1/2C
0.701X
0.212X
0.206X
0.283X
1.03X1/2
3.82X1/2
0.314X
0.444X
22. 6b
0.421X
0.082b
1.27X
0.571X
0.529X
0.195X
0.322X
0.348X
0.399X
4.02X1/2
0.857X
0.390X
0.303X
0.368X
2.23X1/2
7.69X1/2
"Log transformed variable based on one-way analysis of variance.
^Repeatability and reproducibility were independent of concentration.
c$quare root transformed variable based on one-way analysis of variance.
3051 - 11 Revision 0
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TABLE 2.
REPEATABILITY AND REPRODUCIBILITY FOR LEAD
BY METHOD 3051
Average Value Repeatability Reproducibility
50 10.3 15.2
100 20.6 30,3
200 41,2 60.6
300 61.8 90.9
400 82.4 121
500 103 152
All results are in ing/Kg
3051 - 12 Revision 0
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TABLE 3.
RECOVERY AN0, BIAS DATA FOR SRH 1085 - HEAR HETALS IN OIL
Element
Amount
Expected
(Certified
Range)
Amount
Found*
(95% Conf
Interval)
Absolute
Bias
(w/g)
Relative
Bias
(Percent)
Significant
(due to more
than chance)
Ag
Al
Cr
Cu
Fe
Mg
Mo
Ni
Pb
(291)**
296±4
298+5
295±10
300+4
297+3
292+11
303±7
(305)**
All values in mg/Kg
234116
295+12
293110
28919
311+14
270111
238111
293+9
279+8
-1
-5
-6
+ 11
-27
-54
-10
0
-2
_2
+4
-9
-18
-3
No
No
No
No
Yes
Yes
No
*Results taken from table 4-7, Ref. 2.
**Value not certified, so should not be used in bias detection and estimation,
3051 - 13
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METHOD 3051
(MICROWAVE ASSISTED ACID DIGESTION OF SEDIMENTS, SLUDGES, SOILS, AND OILS)
3051 - 14
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METHOD 3510B
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds
from aqueous samples. The method also describes concentration techniques
suitable for preparing the extract for the appropriate determinative methods
described in Sec. 4,3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly water-soluble organics in preparation for a variety
of chromatographic procedures.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample, usually 1 liter, at a specified pH (see
Table 1), is serially extracted with methylene chloride using a separator^
funnel. The extract is dried, concentrated (if necessary), and, as necessary,
exchanged into a solvent compatible with the cleanup or determinative method to
be used (see Table 1 for appropriate exchange solvents).
3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 Under basic extraction conditions required to separate analytes for
the packed columns of Method 8250, the decomposition of some analytes has been
demonstrated. Organochlorine pesticides may dechlorinate, phthalate esters may
exchange, and phenols may react to form tannates. These reactions increase with
increasing pH, and are decreased by the shorter reaction times available in
Method 3510. Methods 3520/8270, 3510/8270, and 3510/8250, respectively, are
preferred over Method 3520/8250 for the analysis of these classes of compounds.
4.0 APPARATUS AND MATERIALS
4.1 Separatory funnel - 2 liter, with Teflon stopcock.
4.2 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 ml of
acetone followed by 50 mL of elution solvent prior to packing the
column with adsorbent.
3510B - 1 Revision 2
September 1994
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4.3 Kuderna-Danish (K-D) apparatus.
4.3.1 Concentrator tube - 10 mL, graduated (Kontes K-570050-1025 or
equivalent). A ground-glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporatior flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.4 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath - Heated, with concentric ring cover, capable of
temperature control (±5°C). The bath should be used in a hood.
4.6 Vials - 2 ml, glass with Teflon lined screw-caps or crimp tops.
4.7 pH indicator paper - pH range including the desired extraction pH.
4.8 Erlenmeyer flask - 250 ml.
4.9 Syringe - 5 mL.
4.10 Graduated cylinder - 1 liter.
5.0 REAGENTS
5.1 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. Reagents should be stored
in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in
organic-free reagent water and dilute to 100 ml,
5,4 Sodium sulfate (granular, anhydrous), Na2S04, Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
3510B - 2 Revision 2
September 1994
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methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.5 Sulfuric acid solution (1:1 v/v), H2S04. Slowly add 50 ml of H2S04
(sp. gr. 1.84} to 50 ml of organic-free reagent water.
5.6 Extraction/exchange solvents
5.6.1 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.6.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, CH3CH(OH)CH3 - Pesticide quality or equivalent.
5.6.4 Cyclohexane, CQH12 - Pesticide quality or equivalent.
5.6.5 Acetonitrile, CH3CN - Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Using a 1 liter graduated cylinder, measure 1 liter (nominal) of
sample and transfer it quantitatively to the separatory funnel. If high
concentrations are anticipated, a smaller volume may be used and then diluted
with organic-free reagent water to 1 liter. Add 1.0 mL of the .surrogate
standards to all samples, spikes, and blanks (see Hethod 3500 and the
determinative method to be used, for details on the surrogate standard solution
and the matrix spike solution). For the sample in each analytical batch selected
for spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking compounds should
result in a final concentration of 100 ng/jui of each base/neutral analyte and
200 ng/jiL of each acid analyte in the extract to be analyzed (assuming a 1 yl
injection). If Method 3640, Gel-Permeation Cleanup, is to be used, add twice the
volume of surrogates and matrix spiking compounds since half the extract is lost
due to loading of the GPC column.
7.2 Check the pH of the sample with wide-range pH paper and, if
necessary, adjust the pH to that indicated in Table 1 for the specific
determinative method that will be used to analyze the extract.
7.3 Add 60 ml of methylene chloride to the separatory funnel.
7.4 Seal and shake the separatory funnel vigorously for 1-2 minutes with
periodic venting to release excess pressure.
3510B - 3 Revision 2
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NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once. Venting of the
separatory funnel should be into a hood to avoid needless exposure
of the analyst to solvent vapors.
7.5 Allow the organic layer to separate from the water phase for a
minimum of 10 minutes. If the emulsion interface between layers is more than
one-third the size of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. The optimum technique depends upon
the sample and may include stirring, filtration of the emulsion through glass
wool, centrifugation, or other physical methods. Collect the solvent extract in
an Erlenmeyer flask. If the emulsion cannot be broken (recovery of < 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 Method 3520, Continuous Liquid-
Liquid Extraction.
7.6 Repeat the extraction two more times using fresh portions of solvent
(Sees. 7.3 through 7.5). Combine the three solvent extracts.
7.7 If further pH adjustment and extraction is required, adjust the pH
of the aqueous phase to the desired pH indicated in Table 1. Serially extract
three times with 60 ml of methylene chloride, as outlined in Sees. 7.3
through 7.5. Collect and combine the extracts and label the combined extract
appropriately.
7.8 If performing SC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration. However, in some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
acid/neutral or base compounds at low concentrations must be determined, separate
extract analyses may be warranted}.
7.9 Perform the concentration {if necessary) using the Kuderna-Danish
(K-D) Technique (Sees. 7.10.1 through 7.10.4).
7.10 K-D Technique
7.10.1 Assemble a Kuderna-Danish (K-D) concentrator by
attaching a 10 mL concentrator tube to a 500 ml evaporation flask. Dry
the extract by passing it through a drying column containing about 10 cm
of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Rinse the Erlenmeyer flask, which contained the solvent
extract, with 20-30 mL of methylene chloride and add it to the column to
complete the quantitative transfer.
"".10.2 Add one or two clean boiling chips to the flask and
attacr, a three ball Snyder column. Prewet the Snyder column by adding
about 1 mL of methylene chloride to the top of the column. Place the K-D
apparatus on a hot water bath (15-20°C above the boiling point of the
solvent) 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
3510B - 4 Revision 2
September 1994
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vapor. Adjust the vertical position of the apparatus and the water
temperature as required to complete the concentration in 10-20 minutes.
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 1 ml, remove the K-D apparatus from the water bath and
allow it to drain and cool for at least 10 minutes.
7.10.3 If a solvent exchange is required (as indicated in Table
I), momentarily remove the Snyder column, add 50 ml of the exchange
solvent, a new boiling chip, and reattach the Snyder column. Concentrate
the extract, as described in Sec. 7.11, raising the temperature of the
water bath, if necessary, to maintain proper distillation.
7.10.4 Remove the Snyder column and rinse the flask and its
lower joints into the concentrator tube with 1-2 roL of methylene chloride
or exchange solvent. If sulfur crystals are a problem, proceed to
Method 3660 for cleanup. The extract may be further concentrated by using
the technique outlined in Sec. 7.11 or adjusted to 10,0 ml with the
solvent last used.
y
7.11 If further concentration is indicated in Table 1, either the micro-
Snyder column technique (7.11.1) or nitrogen blowdown technique (7.11.2) is used
to adjust the extract to the final volume required.
7.11.1 Micro-Snyder Column Technique
7.11.1.1 If further concentration is indicated in Table 1,
add another clean boiling chip to the concentrator tube and attach
a two ball micro-Snyder column. Prewet the column by adding 0.5 ml
of methylene chloride or exchange solvent to the top of the column.
Place the K-D apparatus in a hot 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 5-10 minutes. 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 from the water bath and allow it to
drain and cool for at least 10 minutes. Remove the Snyder column
and rinse the flask and its lower joints into the concentrator tube
with 0.2 ml of extraction solvent. Adjust the final volume to 1.0-
2.0 ml, as indicated in Table 1, with solvent.
7.11.2 Nitrogen Blowdown Technique
7.11.2.1 Place the concentrator tube in a warm bath (35°C)
and evaporate the solvent volume to 0.5 ml using a gentle stream of
clean, dry nitrogen {filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the
carbon trap and the sample, since it may
introduce interferences.
3510B - 5 Revision 2
September 1994
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7.11.2.2 The internal wall of the tube must be rinsed down
several times with methylene chloride or appropriate solvent during
the operation. During evaporation, the tube solvent level must be
positioned to avoid water condensation. Under normal procedures,
the extract must not be allowed to become dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semi volatile analytes may be lost.
7.12 The extract may now be analyzed for the target analytes using the
appropriate determinative technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored longer
than 2 days it should be transferred to a vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 HETHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
3510B - 6 Revision 2
September 1994
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TABU 1.
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250bc
8270bd
8310
8321
8410
Initial
extraction
PH
<2
as received
as received
as received
5-9
5-9
5-9
as received
as received
as received
as received
6-8
as received
>11
<2
as received
as received
as received
Secondary
extraction
PH
none
none
none
none
none
none
none
none
none
none
none
none
none
<2
>11
none
none
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
-
-
-
-
methylene chloride
Volume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
-
-
10.0
Final
extract
volume
for
analysis (ml)
1.0,
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0
10. 08
(dry)
a Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also contains an optional
derivatization procedure for phenols which results in a 10 ml hexane extract to be analyzed by GC/ECD.
b The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance on the cleanup
procedures available if required.
c Loss of phthalate esters, organochlorine pesticides and phenols can occur under these extraction conditions (see Sec. 3.2).
d Extraction pH sequence may be reversed to better separate acid and neutral waste components. Excessive pH adjustments may
result in the loss of some analytes (see Sec. 3.2).
3510B - 7
Revision 2
September 1994
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METHOD 35106
SEPARATORY FUNNEL LIQUID-LIQUID EXTRACTION
7.1 Add surrogate
standards to all
camples, spikes,
and blanks.
7.7 Collect
and combine
extracts and label
7.8
GC/MS
analysis (Metho
8270} being
performed?
7.2 Chack
and adjust pH
7.8 Combine
base/neutral
extracts prior
to concentration
7.3 - 7.6
Extract 3
times.
7,9 - 7.11
Concentrate
extract.
7.7
Further
extractions
required?
7.12
Ready for
analysis.
3510B - 8
Revision 2
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METHOD 3520B
CONTINUOUS LIQUID-LIQUID EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a procedure for isolating organic compounds
from aqueous samples. The method also describes concentration techniques
suitable for preparing the extract for the appropriate determinative steps
described in Sec. 4.3 of Chapter Four.
1.2 This method is applicable to the isolation and concentration of
water-insoluble and slightly soluble organics in preparation for a variety of
chromatographic procedures.
1.3 Method 3520 is designed for extraction solvents with greater density
than the sample. Continuous extraction devices are available for extraction
solvents that are less dense than the sample. The analyst must demonstrate the
effectiveness of any such automatic extraction device before employing it in
sample extraction.
2.0 SUMMARY OF METHOD
2.1 A measured volume of sample, usually 1 liter, is placed into a
continuous liquid-liquid extractor, adjusted, if necessary, to a specific pH {see
Table 1), and extracted with organic solvent for 18-24 hours. The extract is
dried, concentrated {if necessary), and, as necessary, exchanged into a solvent
compatible with the cleanup or determinative method being employed (see Table 1
for appropriate exchange solvents).
3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 Under basic extraction conditions required to separate analytes for
the packed columns of Method 8250, the decomposition of some analytes has been
demonstrated. Organochlorine pesticides may dechlorinate, phthalate esters may
exchange, and phenols may react to form tannates. These reactions increase with
increasing pH, and are decreased by the shorter reaction times available in
Method 3510. Methods 3520/8270, 3510/8270, and 3510/8250, respectively, are
preferred over Method 3520/8250 for the analysis of these classes of compounds,
4.0 APPARATUS AND MATERIALS
4.1 Continuous liquid-liquid extractor - Equipped with Teflon or glass
connecting joints and stopcocks requiring no lubrication (Kontes 584200-0000,
584SOO-0000, 583250-0000, or equivalent).
4.2 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom and a Teflon stopcock.
3520B - 1 Revision 2
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NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex glass wool to
retain the adsorbent, Prewash the glass wool pad with 50 ml of
acetone followed by 50 mL of elution solvent prior to packing the
column with adsorbent,
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.3.4 Snyder column - Two ball micro (Kontes K-569Q01-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4,4 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath - Heated, with concentric ring cover, capable of
temperature control (+ 5°C). The bath should be used in a hood.
4.6 Vials - 2 mL, glass with Teflon lined screw-caps or crimp tops.
4.7 pH indicator paper - pH range including the desired extraction pH.
4.8 Heating mantle - Rheostat controlled.
4.9 Syringe - 5 ml.
5.0 REAGENTS
5.1 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. Reagents should be stored
in glass to prevent the leaching of contaminants from plastic containers.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
3520B - 2 Revision 2
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5.3 Sodium hydroxide solution (ION), NaOH. Dissolve 40 g NaOH in
organic-free reagent water and dilute to 100 ml.
5.4 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400*0 for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. If the sodium sulfate is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate,
5.5 Sulfuric acid solution (1:1 v/v), H2S04. Slowly add 50 ml of H2S04
(sp. gr, 1.84) to 50 ml of organic-free reagent water.
5.6 Extraction/exchange solvents
5.6.1 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.6.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, (CH3)2CHOH - Pesticide quality or equivalent.
5.6,4 Cyclohexane, C6H12 - Pesticide quality or equivalent.
5.6.5 Acetonitrile, CH3CN - Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
7.0 PROCEDURE
7.1 Using a 1 liter graduated cylinder, measure out 1 liter (nominal) of
sample and transfer it quantitatively to the continuous extractor. If high
concentrations are anticipated, a smaller volume may be used and then diluted
with organic-free reagent water to 1 liter. Check the pH of the sample with wide-
range pH paper and adjust the pH, if necessary, to the pH indicated in Table 1
using 1:1 (V/V) sulfuric acid or 10 N sodium hydroxide. Pipet 1.0 mL of the
surrogate standard spiking solution into each sample into the extractor and mix
well. (See Method 3500 and the determinative method to be used, for details on
the surrogate standard solution and the matrix spike solution.) For the sample
in each analytical batch selected for spiking, add 1.0 mL of the matrix spiking
standard. For base/neutral-acid analysis, the amount of the surrogates and
matrix spiking compounds added to the sample should result in a final
concentration of 100 ng/^L of each base/neutral analyte and 200 ng/^L of each
acid analyte in the extract to be analyzed (assuming a 1 jtL injection). If
Method 3640, Gel-Permeation Cleanup, is to be used, add twice the volume of
surrogates and matrix spiking compounds since half the extract is lost due to
loading of the GPC column.
7.2 Add 300-500 mL of methylene chloride to the distilling, flask. Add
several boiling chips to the flask.
35208 - 3 Revision 2
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7.3 Add sufficient water to the extractor to ensure proper operation and
extract for 18-24 hours.
7.4 Allow to cool; then detach the boiling flask. If extraction at a
secondary pH is not required (see Table 1), the extract is dried and concentrated
using one of the techniques referred to in Sec, 7.7.
7.5 Carefully, while stirring, adjust the pH of the aqueous phase to the
second pH indicated in Table 1. Attach a clean distilling flask containing
500 ml of methylene chloride to the continuous extractor. Extract for 18-24
hours, allow to cool, and detach the distilling flask.
7.6 If performing GC/MS analysis (Method 8270), the acid/neutral and base
extracts may be combined prior to concentration. However, in some situations,
separate concentration and analysis of the acid/neutral and base extracts may be
preferable (e.g. if for regulatory purposes the presence or absence of specific
acid/neutral and base compounds at low concentrations must be determined,
separate extract analyses may be warranted).
7.7 Perform concentration (if necessary) using the Kuderna-Danish (K-D)
Technique (Sees. 7.8.1 through 7.8.4).
7.8 K-D Technique
7.8.1 Assemble a Kuderna-Danish (K-D) concentrator by attaching a 10
mL concentrator tube to a 500 mL evaporation flask. Dry the extract by
passing it through a drying column containing about 10 cm of anhydrous
sodium sulfate. Collect the dried extract in a K-D concentrator. Rinse
the flask which contained the solvent extract with 20-30 mL of methylene
chloride and add it to the column to complete the quantitative transfer.
7.8.2 Add one or two clean boiling chips to the flask and attach a
three ball Snyder column. Prewet the Snyder column by adding about 1 mL
of methylene chloride to the top of the column. Place the K-D apparatus
on a hot water bath (15-20°C above the boiling point of the solvent) 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 10-20 minutes. 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 1 ml, remove the K-D apparatus from the water bath and allow it to
drain and cool for at least 10 minutes. Remove the Snyder column and
rinse the flask and its lower joints into the concentrator tube with 1-2
mL of extraction solvent.
7.8.3 If a solvent exchange is required (as indicated in Table 1),
momentarily remove^ the Snyder column, add 50 mL of the exchange solvent,
a new boiling chip, and reattach the Snyder column. Concentrate the
extract, as described in Sec. 7.9, raising the temperature of the water
bath, if necessary, to maintain proper distillation.
3520B - 4 Revision 2
September 1994
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7.8.4 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1-2 ml of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method
3660 for cleanup. The extract may be further concentrated by using the
techniques outlined in Sec. 7.9 or adjusted to 10.0 ml with the solvent
last used.
7.9 If further concentration is indicated in Table 1, either the micro-
Snyder column technique (7.9.1) or nitrogen blowdown technique (7.9.2) is used
to adjust the extract to the final volume required.
7.9.1 Micro-Snyder Column Technique
7.9.1.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two ball miero-Snyder column. _Prewet
the column by adding 0.5 mL of methylene chloride or exchange
solvent to the top of the column. Place the K-D apparatus in a hot
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
5-10 minutes. 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 from the water bath and allow it to drain and cool for at
least 10 minutes. Remove the Snyder column, rinse the flask and its
lower joints into the concentrator tube with 0.2 ml of methylene
chloride or exchange solvent, and adjust the final volume to 1.0 to
2.0 ml, as indicated in Table 1, with solvent.
7.9.2 Nitrogen Blowdown Technique
7.9.2.1 Place the concentrator tube in a warm bath (35°C)
and evaporate the solvent volume to 0.5 ml using a gentle stream of
clean, dry nitrogen (filtered through a column of activated carbon).
CAUTION: New plastic tubing must not be used between the
carbon trap and the sample, since it may
introduce interferences.
7.9.2.2 The internal wall of the tube must be rinsed down
several times with methylene chloride or appropriate solvent during
the operation. During evaporation, the tube solvent level must be
positioned to avoid water condensation. Under normal procedures,
the extract must not be allowed to become dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.10 The extract may now be analyzed for the target analytes using the
appropriate determinative technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store refrigerated. If the extract will be stored longer
3520B - 5 Revision 2
September 1994
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than 2 days it should be transferred to a vial with a Teflon lined screw-cap or
crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
3.1 Any reagent blanks, matrix spike, or replicate samples should be
subjected to exactly the same analytical procedures as those used on actual
samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample-preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
3S20B - 6 Revision 2
September 1994
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TABLt 1.
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250b'c
8270M
8310
8321
8410
Initial
extraction
pH
<2
as received
as received
as received
5-9
5-9
5-9
as received
as received
as received
as received
6-8
as received
>11
<2
as received
as received
as received
Secondary
extraction
pH
none
none
none
none
none
none
none
none
none
none
none
none
none
<2
>11
none
none
none
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methylene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
-
-
-
-
methylene chloride
Volume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
-
-
-
-
10.0
Final
extract
volume
for
analysis
1.0,10
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
(ml)
.oa
0.0 (dry)
a Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also contains an optional
derivatization procedure for phenols which results in a 10 ml hexane extract to be analyzed by GC/ECD.
b The specificity of GC/MS may make cleanup of the extracts unnecessary. Refer to Method 3600 for guidance on the cleanup
procedures available if required.
c Loss of phthalate esters, organochlorine pesticides and phenols can occur under these extraction conditions (see Sec. 3.2).
d If further separation of major acid and neutral components is required, Method 3650, Acid-Base Partition Cleanup, is
recommended. Reversal of the Method 8270 pH sequence is not recommended as analyte losses are more severe under the base first
continuous extraction (see Sec. 3.2).
3520B - 7
Revision 2
September 1994
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METHOD 3520B
CONTINUOUS LIQUID-LIQUID EXTRACTION
start
^
7
r
1 Add appropriate
surrogate and
matrix spiking
solutions.
7.7 - 7.8
Concentrate extract
7.2 Add methylene
chloride to ,
distilling flask.
7.8.3 Is
iolvent
exchange
required7
7,8.3 Add
exchange solvent;
eoncsntntion extract
7.3 Add reagent
water to extractor
extract for 18-24
hours.
7.9 Further
concentrate extract
if necessary;
adjust final volume.
7.5 Adjust pH of
aqueous phase;
extract for 18-24
hours with clean
flask.
7.10 Analyze using
organic techniques.
7,6
GC/'MS
analysis
{Method 8270)
performed?
8000
Series
Methods
7.6 Combine acid
and base/neutral
extracts prior to
concentration.
3520B - 8
Revision 2
September 1994
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METHOD 3540B
SOXHLET EXTRACTION
1.0 SCOPE AND APPLICATION
1,1 Method 3540 is a procedure for extracting nonvolatile and semi-
volatile organic compounds from solids such as soils, sludges, and wastes. The
Soxhlet extraction process ensures intimate contact of the sample matrix with the
extraction solvent.
1,2 This method is applicable to the isolation and concentration of water
insoluble and slightly water soluble organics in preparation for a variety of
chromatographic procedures.
2.0 SUMMARY OF METHOD
2.1 The solid sample is mixed with anhydrous sodium sulfate, placed in
an extraction thimble or between two plugs of glass wool, and extracted using an
appropriate solvent in a Soxhlet extractor. The extract is then dried,
concentrated (if necessary), and, as necessary, exchanged into a solvent
compatible with the cleanup or determinative step being employed.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Soxhlet extractor - 40 m ID, with 500 mL round bottom flask.
4.2 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits nay be purchased. Use a small pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 mL of
acetone followed by 50 ml of elution solvent prior to packing the
column with adsorbent.
4.3 Kuderna-Danish (K-D) apparatus
4.3.1 Concentrator tube - 10 mL, graduated (Kontes K-57005Q-1Q25 or
equivalent}. A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
3540B - 1 Revision 2
September 1994
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4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent),
4.3,4 Snyder column - Two ball micro (Kontes K-5690Q1-0219 or
equivalent).
4.3.5 Springs - 1/2 inch {Kontes K-662750 or equivalent).
4.4 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.5 Water bath - Heated, with concentric ring cover, capable of
temperature control (± 5°C). The bath should be used in a hood.
4.6 Vials - Glass, 2 ml capacity, with Teflon lined screw or crimp top.
4.7 Glass or paper thimble or glass wool - Contaminant free.
4.8 Heating mantle - Rheostat controlled.
4.9 Disposable glass pasteur pipet and bulb.
4.10 Apparatus for determining percent dry weight.
4.10.1 Oven - Drying.
4.10.2 Desiccator.
4.10.3 Crucibles - Porcelain or disposable aluminum.
4.11 Apparatus for grinding
4.12 Analytical balance - 0.0001 g.
5.0 REAGENTS
5.1 Reagent grade inorganic 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.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. 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 is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
3540B - 2 Revision 2
September 1994
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5.4 Extraction solvents
5,4.1 Soil/sediment and aqueous sludge samples shall be extracted
using either of the following solvent systems;
5.4.1.1 Acetone/Hexane (1:1) (v/v), CH3COCH3/C6HU.
Pesticide quality or equivalent.
NOTE: This solvent system has lower disposal cost and lower
toxicity.
5.4.1.2 Methylene chloride/Acetone (1:1 v/v),
CH2C12/CH3COCH3. Pesticide quality or equivalent.
5.4.2 Other samples shall be extracted using the following:
5.4.2.1 Methylene chloride, CH2C12- Pesticide quality or
equivalent.
5,4.2.2 Toluene/Methanol (10:1) (v/v), C6H5CH3/CH3OH.
Pesticide quality or equivalent.
5.5 Exchange solvents
5.5.1 Hexane, CSH14. Pesticide quality or equivalent.
5.5,2 2-Propanol, (CH3)2CHOH. Pesticide quality or equivalent.
5.5.3 Cyclohexane, CeH12. Pesticide quality or equivalent.
5.5.4 Acetonitrile, CH3CN. Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analysis, Sec.
4.1.
7.0 PROCEDURE
7.1 Sample Handling
7.1.1 Sediment/soil samples - 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.
7.1.2 Waste samples - Samples consisting of multiphases must be
prepared by the phase separation method in Chapter Two before extraction.
This procedure is for solids only.
7.1.3 Dry waste samples amenable to grinding - Grind or otherwise
subdivide the waste so that it either passes through a 1 mm sieve or can
3540B - 3 Revision 2
September 1994
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be extruded through a 1 mm hole. Introduce sufficient sample into the
grinding apparatus to yield at least 10 g after grinding.
7.1.4 Gummy, fibrous, or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to allow mixing, and
maximum exposure of the sample surfaces for extraction. The professional
judgment of the analyst is required for handling these difficult matrices,
7.2 Determination of sample % dry weight - In certain cases, sample
results are desired based on dry weight basis. When such data are desired, a
portion of sample for this determination should be weighed out at the same time
as the portion used for analytical determination.
HARMING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from a heavily
contaminated hazardous waste sample.
However, samples known or suspected to contain significant concentrations
of toxic, flammable, or explosive constituents should not be oven dried because
of concerns for personal safety. Laboratory discretion is advised. It may be
prudent to delay oven drying of the weighed-out portion until other analytical
results are available.
7,2.1 Immediately after weighing the sample for extraction, weigh 5-
10 g of the sample into, a tared crucible. Determine the % dry weight of
the sample by drying overnight at 105°C. Allow to cool in a desiccator
before weighing:
% dry weight = q of dry sample x 100
g of sample
7.3 Blend 10 g of the solid sample with 10 g of anhydrous sodium sulfate
and place in an extraction thimble. The extraction thimble must drain freely for
the duration of the extraction period. A glass wool plug above and below the
sample in the Soxhlet extractor is an acceptable alternative for the thimble.
Add 1.0 ml of the surrogate standard spiking solution onto the sample {see Method
3500 for details on the surrogate standard and matrix spiking solutions). For
the sample in each analytical batch selected for spiking, add 1.0 ml of the
matrix spiking standard. For base/neutral-acid analysis, the amount added of the
surrogates and matrix spiking compounds should result in a final concentration
of 100 ng/^iL of each base/neutral analyte and 200 ng/jiL of each acid analyte in
the extract to be analyzed (assuming a 1 #L injection). If Method 3640, Gel
Permeation Chromatography Cleanup, is to be used, add twice the volume of
surrogates and matrix spiking compounds since half the extract is lost due to
loading of the GPC column.
7.4 Place approximately 300 mL of the extraction solvent (Sec. 5.4) into
a 500 ml round bottom flask containing one or two clean boiling chips. Attach
the flask to the extractor and extract the sample for 16-24 hours at 4-6
cycles/hr.
7.5 Allow the extract to cool after the extraction is complete.
3540B - 4 Revision 2
September 1994
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7.6 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching a 10 mi concentrator tube to a 500 ml evaporation flask.
7,7 Dry the extract by passing it through a drying column containing
about 10 cm of anhydrous sodium sulfate. Collect the dried extract in a K-D
concentrator. Wash the extractor flask and sodium sulfate column with 100 to 125
ml of extraction solvent to complete the quantitative transfer.
7.8 Add one or two clean boiling chips to the flask and attach a three
ball Snyder column. Prewet the Snyder column by adding about 1 ml of methylene
chloride to the top of the column. Place the K-D apparatus on a hot water bath
(15-20°C above the boiling point of the solvent) 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 10-20 minutes. 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 1-2 ml, remove the K-D apparatus from the water bath and allow
it to drain and cool for at least 10 minutes.
7.9 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add approximately 50 ml of the exchange
solvent and a new boiling chip, and reattach the Snyder column. Concentrate the
extract as described in Sec. 7.8, raising the temperature of the water bath, if
necessary, to maintain proper distillation. When the apparent volume again
reaches 1-2 ml, remove the K-D apparatus from the water batch and allow it to
drain and cool for at least 10 minutes.
7.10 Remove the Snyder column and rinse the flask and its lower joints
into the concentrator tube with 1-2 ml of methylene chloride or exchange solvent.
If sulfur crystals are a problem, proceed to Method 3660 for cleanup. The
extract may be further concentrated by using the techniques described in Sec.
7.11 or adjusted to 10.0 ml with the solvent last used.
7.11 If further concentration is indicated in Table 1, either micro Snyder
column technique (Sec. 7.11.1) or nitrogen blowdown technique (Sec. 7.11.2) is
used to adjust the extract to the final volume required.
7.11.1 Micro Snyder Column Technique
7.11,1.1 Add another one or two clean boiling chips to the
concentrator tube and attach a two ball micro Snyder column. Prewet
the column by adding about 0.5 ml of methylene chloride or exchange
solvent to the top of the column. Place the K-D apparatus in a hot
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
5-10 minutes. 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 from the water bath and allow it to drain and cool for at
least 10 minutes. Remove the Snyder column and rinse the flask and
its lower joints with about 0.2 ml of solvent and add to the
3540B - 5 Revision 2
September 1994
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concentrator tube. Adjust the final volume to 1.0-2.0 mL, as
indicated in Table 1, with solvent.
7.11.2 Nitrogen Slowdown Technique
7.11.2.1 Place the concentrator tube in a warm water bath
{approximately 35°C) and evaporate the solvent volume to the
required level using a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the carbon
trap and the sample.
7.11.2.2 The internal wall of the tube must be rinsed down
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be positioned
to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
operating conditions, the extract should not be allowed to become
dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semi volatile analytes may be lost.
7.12 The extracts obtained may now be analyzed for the target analytes
using the appropriate organic technique(s) (see Sec. 4.3 of this Chapter). If
analysis of the extract will not be performed immediately, stopper the
concentrator tube and store in a refrigerator. If the extract will be stored
longer than 2 days, it should be transferred to a vial with a Teflon lined screw
cap or crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
3540B - 6 Revision 2
September 1994
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TABU 1.
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040"
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8140
8141
8250"'c
8270a'c
8310
8321
8410
Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
hexane
hexane
none
none
acetonitrile
methanol
methyl ene chloride
Exchange Volume
solvent of extract
required required
for for
cleanup cleanup (ml)
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
hexane
hexane
--
--
--
--
methylene chloride
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
10.0
10.0
--
--
--
--
10.0
Final
extract
volume
for
analysis (ml)
1.0, 10. Ob
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
10.0
10.0
1.0
1.0
1.0
1.0
0.0 (dry)
8 To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
of the extract to 10.0 ml.
b Phenols may be analyzed by Method 8040 using a 1.0 ml 2-propanol extract and analysis by GC/FID. Method 8040
also contains an optical derivatization procedure for phenols which results in a 10 ml hexane extract to be
analyzed by GC/ECD.
The specificity of GC/MS may make cleanup of the extracts unnecessary.
on the cleanup procedures available if required.
Refer to Method 3600 for guidance
3540B - 7
Revision 2
September 1994
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METHOD 3540B
SOXHLET EXTRACTION
7.1
Use appropriate
sample handling
technique
7.2
Determine sample %
dry weight
7.3
Add appropriate
surrogate and matrix
spiking standards
7.4
Add extraction
solvent to flask:
extract for 16-24
hours
7.5
Cool extract
7.6
Assemble K-D
concentrator
7.7
Dry and collect
extract in K-D
concentrator
7,8
Concentrate using
Sryder column
and K-D apparatus
7.9
Is servant
exchange required?
T.12
Analyze using
organic techniques
Proceed
toMetfwd
3660 far
deanup
8000
Series
Methods
7.9
Add exchange
solvent,
reogncentrate extract
35408 - 8
Revision 2
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METHOD 3541
AUTOMATED SOXHLET EXTRACTION
1.0 SCOPE AND APPLICATION
1.1 Method 3541 describes the extraction of organic analytes from soil,
sediment, sludges, and waste solids. The method uses a commercially available,
unique, three stage extraction system to achieve analyte recovery comparable to
Method 3540, but in a much shorter time. There are two differences between this
extraction method and Method 3540. In the initial extraction stage of Method
3541, the sample-loaded extraction thimble is immersed into the boiling solvent.
This ensures very rapid intimate contact between the specimen and solvent and
rapid extraction of the organic analytes. In the second stage the thimble is
elevated above the solvent, and is rinse-extracted as in Method 3540. In the
third stage, the solvent is evaporated, as would occur in the Kuderna-Danish
(K-D) concentration step in Method 3540. The concentrated extract is then ready
for cleanup (Method 3600) followed by measurement of the organic analytes.
1.2 The method is applicable to the extraction and concentration of water
insoluble or slightly water soluble polychlorinated biphenyls (PCBs) in
preparation for gas chromatographic determination using either Method 8080 or
8081. This method is applicable to soils, clays, solid wastes and sediments
containing from 1 to 50 ^g of PCBs (measured as Arochlors) per gram of sample.
It has been statistically evaluated at 5 and 50 Mi/9 of Arochlors 1254 and 1260,
and found to be equivalent to Method 3540 (Soxhlet Extraction). Higher
concentrations of PCBs are measured following volumetric dilution with hexane.
1.3 The method is also applicable the extraction and concentration of
semivolatile organics in preparation for GC/MS analysis by Method 8270 or by
analysis using specific GC or HPLC methods.
2.0 SUMMARY OF METHOD
2.1 PCBs: Moist solid samples (e.g., soil/sediment samples) may be air-
dried and ground prior to extraction or chemically dried with anhydrous sodium
sulfate. The prepared sample is extracted using 1:1 (v/v) acetone:hexane in the
automated Soxhlet following the same procedure as outlined for semivolatile
organics in Sec. 2.1. The extract is then concentrated and exchanged into pure
hexane prior to final gas chromatographic PCB measurement.
2.2 Other semivolatile organics: A 10-g solid sample (the sample is pre-
mixed with anhydrous sodium sulfate for certain matrices) is placed in an
extraction thimble and usually extracted with 50 ml of 1:1 (v/v) acetone/hexane
for 60 minutes in the boiling extraction solvent. The thimble with sample is
then raised into the rinse position and extracted for an additional 60 minutes.
Following the extraction steps, the extraction solvent is concentrated to 1 to
2 ml.
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3.0 INTERFERENCES
3.1 Refer to Method 3500.
3.2 The extraction thimble and the o-rings used to seal the extraction
cup are both a source of interference. Both should be checked by including a
method blank and following the extraction procedure as written. Solvent rinsing
or extraction, prior to use, may be necessary to eliminate or reduce
interferences. Viton seals contributed least to the interference problem,
however, even they contributed some interference peaks when the extraction
solvent was analyzed by the electron capture detector. Use of butyl or EPDM
rings are not recommended since they were found to contribute significant
background when the extraction solvent was 1:1 v/v hexane/acetone or 1:1 v/v
methylene chloride/acetone.
4.0 APPARATUS AND MATERIALS
4.1 Automated Soxhlet Extraction System - with temperature-controlled oil
bath (Soxtec, or equivalent). Tecator bath oil (catalog number 1000-1886) should
be used with the Soxtec. Silicone oil must not be used because it destroys the
rubber parts. See Figure 1. The apparatus is used in a hood.
4.2 Accessories and consumables for the automated Soxhlet system. {The
catalog numbers are Fisher Scientific based on the use of the Soxtec HT-6,
however, other sources that are equivalent are acceptable.)
4.2.1 Cellulose extraction thimbles - 26 mm ID x 60 mm
contamination free, catalog number 1522-0034, or equivalent.
4.2.2 Glass extraction cups (80 ml) - (set of six required for the
HT-6), catalog number 1000-1820.
4.2.3 Thimble adapters - (set of six required for the HT-6),
catalog number 1000-1466.
4.2.4 Viton seals - catalog number 1000-2516.
4.3 Syringes - 100 and 1000 ^i and 5 ml.
4.4 Apparatus for Determining Percent Dry Weight
4.4.1 Drying Oven.
4.4.2 Desiccator.
4.4.3 Crucibles, porcelain.
4.4.4 Balance, analytical.
4.5 Apparatus for grinding - Fisher Cyclotec, Fisher Scientific catalog
number 1093, or equivalent.
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4.6 Spatula
4.7 Graduated cylinder - 100 ml,
4.8 Aluminum weighing dish - VWR Scientific catalog number 25433-008 or
equivalent,
4,9 Graduated, conical-bottom glass tubes - 15 mL, Kimble catalog number
45166 or equivalent, or 10 ml KD concentrator tube.
5.0 REAGENTS
5.1 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.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
4QQ°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. A method blank must be analyzed, demonstrating that there
is no interference from the sodium sulfate.
5.4 Extraction solvents:
5.4.1 Organochlorine pesticides/PCB extraction:
5.4.1.1 Acetone/hexane (1:1 v/v), CH3COCH3/C6H14.
Pesticide quality or equivalent.
5.4.2 Semi volatile organics extraction:
5.4.2.1 Acetone/hexane (1:1 v/v), CH3COCH3/C6H14.
Pesticide quality or equivalent.
5.4.2,2 Acetone/methyline chloride (1:1 v/v),
CH3COCH3/CH2C12. Pesticide quality or equivalent.
5.5 Hexane, C6H14. Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Sec. 4.1.
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7.0 PROCEDURE
7.1 Sample handling
7.1.1 Sediment/soil samples - Decant and discard any water layer
on a sediment sample. Mix sample thoroughly, especially composited
samples. Discard any foreign objects such as s:icks, leaves, and rocks.
7.1.1.1 PCBs or high-boiling organochlorine pesticides -
Air-dry the sample at room temperature for 48 hours in a glass tray
or on hexane-cleaned aluminum foil, or dry the sample by mixing with
anhydrous sodiui sulfate until a free-flowing powder is obtained
(see Sec. 7.2).
NOTE: Dry, finely ground soil/sediment allows the best
extraction efficiency for non-volatile, non-polar
organics, e.g., PCBs, 4,4'-DDT, etc. Air-drying
is not appropriate for the analysis of the more
volatile organochlorine pesticides (e.g. the
BHCs) or the more volatile of the semivolatile
organics because of losses during the drying
process.
7.1.2 Dried sediment/soil and dry waste samples amenable to
grinding - Grind or otherwise subdivide the waste so that it either passes
through a 1 mm sieve or can be extruded through a 1 mm hole. Introduce
sufficient sample into the grinding apparatus to yield at least 20 g after
grinding. Disassemble grinder between samples, according to
manufacturer's instructions, and clean with soap and water, followed by
acetone and hexane rinses.
NOTE: The same warning on loss of volatile analytes applies to the
grinding process. Grinding should only be performed when
analyzing for non-volatile organics.
7.1.3 Gummy, fibrous, or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to allow mixing, and
maximum exposure of the sample surfaces for extraction. If grinding of
these materials is preferred, the addition and mixing of anhydrous sodium
sulfate with the sample (1:1) may improve grinding efficiency. The
professional judgment of the analyst is required for handling such
difficult matrices.
7.1.4 Multiple phase waste samples - Samples consisting of multiple
phases must be prepared by the phase separation method in Chapter Two
before extraction. This procedure is for solids only.
7.2 For sediment/soil (especially gummy clay) that is moist and cannot
be air-dried because of loss of volatile analytes - Mix 5 g of sample with 5 g
of anhydrous sodium sulfate in a small beaker using a spatula. Use this approach
for any solid sample that requires dispersion of the sample particles to ensure
greater solvent contact throughout the sample mass.
3541 - 4 Revision 0
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7.3 Determination of sample percent dry weight - In certain cases, sample
results are desired based on dry weight basis. When such data are desired, a
portion of sample for this determination should be weighed out at the same time
as the portion used for analytical determination,
WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from the
drying of a heavily contaminated hazardous waste sample.
7.3.1 Immediately after weighing the sample for extraction, weigh
5-10 g of the sample into a tared crucible. Determine the % dry weight of
the sample by drying overnight at 105°C. Allow to cool in a desiccator
before weighing:
% dry weight •= q of dry sample x 100
g of sample
7.4 Check the heating oil level in the automated Soxhlet unit and add oil
if needed. See service manual for details. Set the temperature on the service
unit at 140°C when using hexane-acetone (1:1, v/v) as the extraction solvent.
7.5 Press the "MAINS" button; observe that the switch lamp is now "ON".
7.6 Open the cold water tap for the reflux condensers. Adjust the flow
to 2 L/niin to prevent solvent loss through the condensers.
7.7 Weigh 10 g of sample into extraction thimbles. For samples mixed
with anhydrous sodium sulfate, transfer the entire contents of the beaker (Sec.
7.2) to the thimble. Add surrogate spikes to each sample and the matrix
spike/matrix spike duplicate to the selected sample.
NOTE: When surrogate spikes and/or matrix spikes contain relatively
volatile compounds (e.g., trichlorobenzenes, BHCs, etc.), steps 7.8,
7.9, and 7.10 must be performed quickly to avoid evaporation losses
of these compounds. As the spike is added to the sample in each
thimble, the thimble should immediately be transferred to the
condenser and lowered into the extraction solvent.
7.8 Immediately transfer the thimbles containing the weighed samples into
the condensers. Raise the knob to the "BOILING" position. The magnet will now
fasten to the thimble. Lower the knob to the "RINSING" position. The thimble
will now hang just below the condenser valve.
7.9 Insert the extraction cups containing boiling chips, and load each
with 50 ml of extraction solvent (normally 1:1 (v/v) hexane .-acetone, see Sec.
5.4). Using the cup holder, lower the locking handle, ensuring that the safety
catch engages. The cups are now clamped Into position. (The seals must be pre-
rinsed or pre-extracted with extraction solvent prior to initial use.)
7.10 Move the extraction knobs to the "BOILING" position. The thimbles
are now immersed in solvent. Set the timer for 60 minutes. The condenser valves
must be in the "OPEN" position. Extract for the preset time.
3541 - 5 Revision 0
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7.11 Move the extraction knobs to the "RINSING" position. The thimbles
will now hang above the solvent surface. Set timer for 60 minutes. Condenser
valves are still open. Extract for the preset time.
7.12 After rinse time has elapsed, close the condenser valves by turning
each a quarter-turn, clockwise.
7.13 When all but 2 to 5 ml of solvent have been collected, open the
system and remove the cups.
7.14 Transfer the contents of the cups to 15 ml graduated, conical-bottom
glass tubes. Rinse the cups using hexane {methylene chloride if 1:1 methylene
chloride-acetone was used for extraction and analysis is by GC/MS) and add the
rinsates to the glass tubes. Concentrate the extracts to 1 to 10 ml. The final
volume is dependent on the determinative method and the quantitation limit
required. Transfer a portion to a GC vial and store at 4°C until analyses are
performed.
NOTE: The recovery solvent volume can be adjusted by adding
solvent at the top of the condensers. For more details
concerning use of the extractor, see the operating manual
for the automated extraction system.
7.15 Shutdown
7.15.1 Turn "OFF" main switch.
7.15.2 Turn "OFF" cold water tap.
7.15.3 Ensure that all condensers are free of solvent. Empty
the solvent that is recovered in the evaporation step into an appropriate
storage container.
7.16 The extract is now ready for cleanup or analysis, depending on the
extent of interfering co-extractives. See Method 3600 for guidance on cleanup
methods and Method 8000 for guidance on determinative methods,. Certain cleanup
and/or determinative methods may require a solvent exchange prior to cleanup
and/or determination.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for general quality control procedures and to
Method 3500 for specific extraction and sample preparation QC procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of an organic-free solid matrix (e.g., reagent sand) method blank
that all glassware and reagents are interference-free. Each time a set of
samples is extracted, or when there is a change in reagents, a method blank
should be processed as a safeguard against chronic laboratory contamination. The
blank samples should be carried through all stages of the sample preparation and
measurement. This is especially important because of the possibility of
interferences being extracted from the extraction cup seal.
3541 - 6 Revision 0
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8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique. Each analysis batch of 20 or less samples must contain: a method
blank, either a matrix spike/matrix spike duplicate or a matrix spike and
duplicate sample analysis, and a laboratory control sample, unless the
determinative method provides other guidance. Also, routinely check the
integrity of the instrument seals.
8.4 Surrogate standards must be added to all samples when specified in
the appropriate determinative method.
9.0 METHOD PERFORMANCE
9,1 Multi-laboratory accuracy and precision data were obtained for PCBs
in soil. Eight laboratories spiked Arochlors 1254 and 1260 into three portions
of 10 g of Fuller's Earth on three non-consecutive days followed by immediate
extraction using Method 3541. Six of the laboratories spiked each Arochlor at
5 and 50 mg/kg and two laboratories spiked each Arochlor at 50 and 500 mg/kg.
All extracts were analyzed by Oak Ridge National Laboratory, Oak Ridge, TN, using
Method 8081. These data are listed in a table found in Method 8081, and were
taken from Reference 1.
9.2 Single-laboratory accuracy data were obtained for chlorinated
hydrocarbons, nitroaromatics, haloethers, and organochlorine pesticides in a clay
soil. The spiking concentrations ranged from 500 to 5000 M9/kg, depending on
the sensitivity of the analyte to the electron capture detector. The spiking
solution was mixed into the soil during addition and then immediately transferred
to the extraction device and immersed in the extraction solvent. The data
represents a single determination. Analysis was by capillary column gas
chroraatography/electron capture detector following Methods 8081 for the
organochlorine pesticides, 8091 for the nitroaromatics, 8111 for the
hydrocarbons, and 8121 for the chlorinated hydrocarbons. These data are listed
in a table located in their respective methods and were taken from Reference 2,
9,3. Single-laboratory accuracy and precision data were obtained for
semivolatile organics in soil by spiking at a concentration of 6 mg/kg for each
compound. The spiking solution was mixed into the soil during addition and then
allowed to equilibrate for approximately 1 hr prior to extraction. Three
determinations were performed and each extract was analyzed by gas
chromatography/mass spectroroetry following Method 8270. The low recovery of the
more volatile compounds 1s probably due to volatilization losses during
equilibration. These data are listed in a Table located in Method 8270 and were
taken from Reference 2.
10.0 REFERENCES
1. Stewart, J. "Intra-Laboratory Recovery Data for the PCB Extraction
Procedure"; Oak Ridge National Laboratory, Oak Ridge, TN, 37831-6138;
October 1989.
3541 - 7 Revision 0
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2. Lopez-Avila, V. (Beckert, W., Project Officer), "Development of a Soxtec
Extraction Procedure for Extracting Organic Compounds from Soils and
Sediments", EPA 600/X-91/140, US EPA, Environmental Monitoring Systems
Laboratory-Las Vegas, October 1991.
3541 - 8 Revision 0
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Figure 1
Automated Soxhlet Extraction System
Condenser
Thimble
Glass Wool Plug
Sample
Aluminum beaker (cup)
Hot plate
3541 - 9
Revision 0
September 1994
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METHOD 3541
AUTOMATED SOXHLET EXTRACTION
Start
7.1
Use appropriate
sample handling
technique.
7.2
Add anhydrous
necessary
7.3
Determine percent
dry weight.
7.4
Check oil
level in
Soxhlet unit.
©
7.5
Press "Mains"
button.
7.6
Open Cold water
tap. Adjust flow.
7.7
Weigh sample into
extraction thimbles.
Add surrogate
spike.
7.8
Transfer samples
into condensers.
Adjust position of
magnet and thimble.
7.9
Insert extraction
cups and toad
with solvent.
7.10
Move extraction
knobs to
"Boiling" for
60 mins.
©
3S41 - 10
7.11
Move extraction
knobs to
"Rinsing" for
60 mins.
7.12
Close
condenser valves.
I
7.13
Remove cups.
7.14
Transfer contents
to collection
vials, dilute or
concentrate to
volume.
7.15
Shutdown
i
t
Stop
Rtvlsion 0
September 1994
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METHOD 3550A
ULTRASONIC EXTRACTION
See DISCLAIMER-1. See manufacturer's specifications for operational settings.
1.0 SCOPE AND APPLICATION
1.1 Method 3550 is a procedure for extracting nonvolatile and semi-
volatile organic compounds from solids such as soils, sludges, and wastes. The
ultrasonic process ensures intimate contact of the sample matrix with the
extraction solvent.
1.2 The method is divided into two sections, based on the expected
concentration of organics in the sample. The low concentration method
(individual organic components of < 20 mg/kg) uses a larger sample size and a
more rigorous extraction procedure (lower concentrations are more difficult to
extract). The medium/high concentration method (individual organic components
of > 20 mg/kg) is much simpler and therefore faster.
1.3 It is highly recommended that the extracts be cleaned up prior to
analysis. See Chapter Four (Cleanup), Sec. 4.2.2, for applicable methods.
2.0 SUMMARY OF METHOD
2.1 Low concentration method - A 30 g sample is mixed with anhydrous
sodium sulfate to form a free-flowing powder. This is solvent extracted three
times using ultrasonic extraction. The extract is separated from the sample by
vacuum filtration or centrifugation. The extract is ready for cleanup and/or
analysis following concentration.
2.2 Medium/high concentration method - A 2 g sample is mixed with
anhydrous sodium sulfate to form a free-flowing powder. This is solvent
extracted once using ultrasonic extraction. A portion of the extract is removed
for cleanup and/or analysis.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Apparatus for grinding dry waste samples.
4.2 Ultrasonic preparation - A horn type device equipped with a titanium
tip, or a device that will give equivalent performance, shall be used.
3550A - 1 Revision 1
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4.2,1 Ultrasonic Disrupter - The disrupter must have a minimum power
wattage of 300 watts, with pulsing capability. A device designed to
reduce the cavitation sound is recommended. Follow the manufacturers
instructions for preparing the disrupter for extraction of samples with
low and medium/high concentration.
Use a 3/4" horn for the low concentration method and a 1/8" tapered
raicrotip attached to a 1/2" horn for the medium/high concentration method.
4.3 Sonabox - Recommended with above disrupters for decreasing cavitation
sound (Heat Systems - Ultrasonics, Inc., Model 432B or equivalent).
4.4 Apparatus for determining percent dry weight.
4.4.1 Oven - Drying.
4,4.2 Desiccator.
4.4.3 Crucibles - Porcelain or disposable aluminum.
4.5 Pasteur glass pipets - 1 ml, disposable.
4.6 Beakers - 400 ml.
4.7 Vacuum or pressure filtration apparatus.
4.7.1 Buchner funnel.
4.7.2 Filter paper - Whatman No. 41 or equivalent.
4.8 Kuderna-Danish (K-D) apparatus.
4.8.1 Concentrator tube - 10 ml, graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.8.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4,8.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent),
4.8.4 Snyder column - Two ball micro (Kontes K-5690Q1-Q219 or
equivalent),
4.8.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.9 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
3550A - 2 Revision 1
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4.10 Water bath - Heated, with concentric ring cover, capable of
temperature control (+ 5°C). The batch should be used in a hood.
4.11 Balance - Top loading, capable of accurately weighing to the nearest
•0.01 g.
4.12 Vials - 2 ml, for GC autosarapler, with Teflon lined screw caps or
crimp tops.
4.13 Glass scintillation vials - 20 mL, with Teflon lined screw caps.
4.14 Spatula - Stainless steel or Teflon.
4.15 Drying column - 20 mm ID Pyrex chrotnatographic column with Pyrex
glass wool at bottom.
NOTE: Fritted glass discs are difficult to decontaminate after
highly contaminated extracts have been passed through.
Columns without frits may be purchased. Use a small pad of
Pyrex glass wool to retain the adsorbent. Prewash the glass
wool pad with 50 mL of acetone followed by 50 mL of elution
solvent prior to packing the column with adsorbent.
4.16 Syringe - 5 mL.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests. Unless
otherwise specified, it is intended that all inorganic 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.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium sulfate (granular, anhydrous), Na2S04. 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 is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.4 Extraction solvents.
5.4.1 Low concentration soil/sediment and aqueous sludge samples
shall be extracted using a solvent system that gives optimum, reproducible
recovery for the matrix/analyte combination to be measured. Suitable
solvent choices are given in Table 1.
3550A - 3
Revision 1
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\
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4.1.
5.4.2 Methylene chloride:Acetone, CH2C;j:CH3COCH3 (1:1, v:v).
Pesticide quality or equivalent.
5.4.3 Methylene chloride, CH2C12. Pesticide quality or equivalent.
5.4.4 Hexane, C6H14. Pesticide quality or equivalent.
5.5 Exchange solvents.
5.5.1 Hexane, C6H14. Pesticide quality or equivalent.
5.5.2 2-Propanol, (CH3)2CHOH, Pesticide quality or equivalent.
5.5.3 Cyclohexane, C6H12. Pesticide quality or equivalent.
5.5.4 Acetonitrile, CH3CN. Pesticide quality or equivalent.
5.5.5 Methanol , CH3OH. Pesticide quality or equivalent.
SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this Chapter, Organic Analytes, Sec.
7.0 PROCEDURE
7.1 Sample handling
7.1.1 Sediment/soil samples - 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.
7.1.1.2 Determine the dry weight of the sample (Sec. 7.2)
remaining after decanting. Measurement of soil pH may be required.
7.1.2 Waste samples - Samples consisting of multiphases must be
prepared by the phase separation method in Chapter Two before extraction.
This procedure is for solids only.
7.1.3 Dry waste samples amenable to grinding - Grind or otherwise
subdivide the waste so that it either passes through a 1 mm sieve or can
be extruded through a 1 mm hole. Introduce sufficient sample into the
grinder to yield at least 100 g after grinding.
7.1.4 Gummy, fibrous or oily materials not amenable to grinding
should be cut, shredded, or otherwise broken up to allow mixing, and
maximum exposure of the sample surfaces for extraction. The professional
judgment of the analyst is required for handling of these difficult
matrices.
3550A - 4 Revision 1
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7.2 Determination of percent dry weight - In certain cases, sample
results are desired based on a dry weight basis. When such data are desired, or
required, a portion of sample for this determination should be weighed out at the
same time as the portion used for analytical determination,
WARNING: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from drying a
heavily contaminated hazardous waste sample.
However, samples known or suspected to contain significant concentrations
of toxic, flammable, or explosive constituents should not be overdried because
of concerns for personal safety. Laboratory discretion is advised. It may be
prudent to delay overdrying of the weighed-out portion until other analytical
results are available.
7.2.1 Immediately after weighing the sample for extraction, weigh 5-
10 g of the sample into a tared crucible. Determine the % dry weight of
the sample by drying overnight at I05°C. Allow to cool in a desiccator
before weighing:
% dry weight = g of dry sample x 100
g of sample
7.3 Extraction method for samples expected to contain low concentrations
of organics and pesticides (< 20 mg/kg):
7.3.1 The following step should be performed rapidly to avoid loss
of the more volatile extractables. Weigh approximately 30 g of sample
into a 400 ml beaker. Record the weigh to the nearest 0.1 g. Nonporous
or wet samples (gummy or clay type) that do not have a free-flowing sandy
texture must be mixed with 60 g of anhydrous sodium sulfate, using a
spatula. If required, more, sodium sulfate may be added. After addition
of sodium sulfate, the sample should be free flowing. Add 1 ml of
surrogate standards to all samples, spikes, standards, and blanks (see
Method 3500 for details on the surrogate standard solution and the matrix
spike solution). For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking compounds
should result in a final concentration of 100 ng/fiL of each base/neutral
analyte and 200 ng/pL of each acid analyte in the extract to be analyzed
(assuming a 1 ^L injection). If Method 3640, Gel-Permeation Cleanup, is
to be used, add twice the volume of surrogates and matrix spiking
compounds since half of the extract is lost due to loading of the GPC
column. Immediately add 100 ml of 1:1 methylene chloride:acetone.
7.3.2 Place the bottom surface of the tip of the 1207 3/4 in.
disrupter horn about 1/2 in. below the surface of the solvent, but above
the sediment laver.
7.3.2 Place the bottom surface of the tip of the 1207 3/4 in.
jjter horn abou'
the sediment layer.
7.3.3 Extract ultrasonically for 3 minutes, with output control knob
set at 10 (full power) and with mode switch on Pulse (pulsing energy
3550A - 5 Revision 1
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rather than continuous energy) and percent-duty cycle knob set at 50%
(energy on 50% of time and off 50% of time). Do not use microtip probe.
7.3.4 Decant the extract and filter it through Whatman No. 41 filter
paper (or equivalent) in a Buchner funnel that is attached to a clean 500
ml filtration flask. Alternatively, decant the extract into a centrifuge
bottle and centrifuge at low speed to remove particles.
7.3.5 Repeat the extraction two or more times with two additional
100 roL portions of solvent. Decant off the solvent after each ultrasonic
extraction. On the final ultrasonic extraction, pour the entire sample
into the Buchner funnel and rinse with extraction solvent. Apply a vacuum
to the filtration flask, and collect the solvent extract. Continue
filtration until all visible solvent is removed from the funnel, but do
not attempt to completely dry the sample, as the continued application of
a vacuum may result in the loss of some analytes. Alternatively, if
centrifugation is used in Sec. 7.3.4, transfer the entire sample to the
centrifuge bottle. Centrifuge at low speed, and then decant the solvent
from the bottle,
7.3.6 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching a 10 ml concentrator tube to a 500 ml evaporator flask.
Transfer filtered extract to a 500 ml evaporator flask and proceed to the
next section.
7,3.7 Add one to two clean boiling chips to the evaporation flask,
and attach a three ball Snyder column, Prewet the Snyder column by adding
about 1 ml methylene chloride to the top. Place the K-D apparatus on a
hot water bath (80-90 °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 10-15 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.
7.3.8 If a solvent exchange is required (as indicated in Table 1),
momentarily remove the Snyder column, add 50 ml of the exchange solvent
and a new boiling chip, and re-attach the Snyder column. Concentrate the
extract as described in Sec. 7.3.10, raising the temperature of the water
bath, if necessary, to maintain proper distillation. When the apparent
volume again reaches 1-2 ml, remove the K-D apparatus and allow it to
drain and cool for at least 10 minutes.
7.3.9 Remove the Snyder column and rinse the flask and its lower
joints into the concentrator tube with 1-2 ml of methylene chloride or
exchange solvent. If sulfur crystals are a problem, proceed to Method
3660 for cleanup. The extract may be further concentrated by using the
technique outlined in Sec. 7.3.10 or adjusted to 10.0 ml with the solvent
last used.
3550A - 6 Revision 1
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7.3.10 If further concentration is indicated in Table 1, either
micro Snyder column technique {Sec. 7.3.10.1) or nitrogen blow down
technique (Sec. 7.3,10.2) is used to adjust the extract to the final
volume required.
7,3.10.1 Micro Snyder Column Technique
7.3.10.1.1 Add a clean boiling chip and attach a
two ball micro Snyder column to the concentrator tube. Prewet
the column by adding approximately 0.5 mL of methylene
chloride or exchange solvent 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 approximately 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 with approximately 0.2 ml of appropriate solvent
and add to the concentrator tube. Adjust the final volume to
the volume required for cleanup or for the determinative
method (see Table 1).
7,3.10.2 Nitrogen Slowdown Technique
7.3.10,2.1 Place the concentrator tube in a warm
water bath (approximately 35 °C) and evaporate the solvent
volume to the required level using a gentle stream of clean,
dry nitrogen (filtered through a column of activated carbon).
CAUTION: Do not use plasticized tubing between the
carbon trap and the sample.
7.3.10.2.2 The internal wall of the tube must be
rinsed down several times with the appropriate solvent during
the operation. During evaporation, the solvent level in the
tube must be positioned to prevent water from condensing into
the sample (i.e., the solvent level should be below the level
of the water bath). Under normal operating conditions, the
extract should not be allowed to become dry,
CAUTION: When the volume of solvent is reduced below
1 ml, semivolatile analytes may be lost,
7.4. If analysis of the extract will not be performed immediately, stopper
the concentrator tube and store refrigerated. If the extract will be stored
longer than 2 days, it should be transferred to a vial with a Teflon lined cap
and labeled appropriately.
3550A - 7 Revision 1
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7.5 Extraction method for samples expected to contain high concentrations
of organics {> 20 tng/kg):
7.5.1 Transfer approximately 2 g (record weight to the nearest 0.1
g) of sample to a 20 ml vial. Wipe the mouth of the vial with a tissue to
remove any sample material. Record the exact weight of sample taken. Cap
the vial before proceeding with the next sample to avoid any cross
contamination.
7.5.2 Add 2 g of anhydrous sodium sulfate to sample in the 20 ml
vial and mix well.
7.5.3 Surrogate standards are added to all samples, spikes, and
blanks (see Method 3500 for details on the surrogate standard solution and
on the matrix spike solution). Add 1.0 ml of surrogate spiking solution
to sample mixture. For the sample in each analytical batch selected for
spiking, add 1.0 ml of the matrix spiking standard. For base/neutral-acid
analysis, the amount added of the surrogates and matrix spiking compounds
should result in a final concentration of 100 ng/^L of each base/neutral
analyte and 200 ng/^L of each acid analyte in the extract to be analyzed
(assuming a 1 ^L injection). If Method 3640, Gel-Permeation Cleanup, is
to be used, add twice the volume of surrogates and matrix spiking
compounds since half the extract is lost due to loading of the GPC column.
7.5.4 Immediately add whatever volume of solvent is necessary to
bring the final volume to 10.0 ml considering the added volume of
surrogates and matrix spikes. Disrupt the sample with the 1/8 in. tapered
microtip ultrasonic probe for 2 minutes at output control setting 5 and
with mode switch on pulse and percent duty cycle at 50%. Extraction
solvents are:
1. For nonpolar compounds (i.e., organochlorine pesticides and
PCBs), use hexane or appropriate solvent.
2. For extractable priority pollutants, use methylene chloride.
7.5.5 Loosely pack disposable Pasteur pipets with 2 to 3 cm Pyrex
glass wool plugs. Filter the extract through the glass wool and collect
5.0 ml in a concentrator tube if further concentration is required.
Follow Sec. 7.3.10 for details on concentration. Normally, the 5.0 ml
extract is concentrated to approximately 1.0 raL or less.
7.5.6 The extract is ready for cleanup or analysis, depending on the
extent of interfering co-extractives.
8.0 QUALITY CONTROL
8.1 Any reagent blanks or matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
3550A - 8 Revision 1
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\
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8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative method for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Finil Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
2. U.S. EPA, Interlaboratory Comparison Study: Methods for Volatile and
Serai-Volatile Compounds, Environmental Monitoring Systems Laboratory,
Office of Research and Development, Las Vegas, NV, EPA 600/4-84-027, 1984.
3. Christopher S. Hein, Paul J, Marsden, Arthur S. Shurtleff, "Evaluation of
Methods 3540 (Soxhlet) and 3550 (Sonication) for Evaluation of Appendix IX
Analytes form Solid Samples", S-CUBED, Report for EPA Contract 68-03-33-
75, Work Assignment No. 03, Document No. SSS-R-88-9436, October 1988.
3550A - 9 Revision 1
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\
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TABLE 1.
EFFICIENCY OF EXTRACTION SOLVENT SYSTEMS3
Solvent Systemd
Compound CAS No.b ABNC
4-Bromophenyl phenyl ether 101-55-3
4-Chloro-3-methylphenol 59-50-7
bis(2-Chloroethoxy)methane 111-91-1
bis(2-Chloroethyl) ether 111-44-4
2-Chloronaphthalene 91-58-7
4-Chlorophenyl phenyl ether 7005-72-3
1,2-Dichlorobenzene 95-50-1
1,3-Dichlorobenzene 541-73-1
Diethyl phthalate 84-66-2
4,6-Dinitro-o-cresol 534-52-1
2,4-Dinitrotoluene 121-14-2
2,6-Dinitrotoluene 606-20-2
Heptachlor epoxide 1024-57-3
Hexachlorobenzene 118-74-1
Hexachlorobutadiene 87-68-3
Hexachlorocyclopentadiene 77-47-4
Hexachloroethane 67-72-1
5-Nitro-o-toluidine 99-55-8
Nitrobenzene 98-95-3
Phenol 108-95-2
1,2,4-Trichlorobenzene 120-82-1
a Percent recovery of analytes spiked
b Chemical Abstracts Service Registry
c Compound Type: A = Acid, B = Base,
d A = Methylene chloride
B = Methylene chloride/Acetone (1/1)
C = Hexane/Acetone (1/1)
D = Methyl t-butyl ether
N
A
N
N
N
N
N
N
N
A
N
N
N
N
N
N
N
B
N
A
N
at 200
Number
%R
64.2
66.7
71.2
42.0
86.4
68.2
33.3
29.3
24.8
66.1
68.9
70.0
65.5
62.1
55.8
26.8
28.4
52.6
59.8
51.6
66.7
mg/kg
SO
6.5
6.4
4.5
4.8
8.8
8.1
4.5
4.8
1.6
8.0
1.6
7.6
7.8
8.8
8.3
3.3
3.8
26.7
7.0
2.4
5.5
%R
56.4
74.3
58.3
17.2
78.9
63.0
15.8
12.7
23.3
63.8
65.6
68.3
58.7
56.5
41.0
19.3
15.5
64.6
38.7
52.0
49.9
SO
0.5
2.8
5.4
3.1
3.2
2.5
2.0
1.7
0.3
2.5
4.9
0.7
1.0
1.2
2.7
1.8
1.6
4.7
5.5
3.3
4.0
into NIST sediment
%R
86.7
97.4
69.3
41.2
100.8
96.6
27.8
20.5
121.1
74.2
85.6
88.3
86.7
95.8
63.4
35.5
31.1
74.7
46.9
65.6
73.4
SRM 1645
SO
1.9
3.4
2.4
8.4
3.2
2.5
6.5
6.2
3.3
3.5
1.7
4.0
1.0
2.5
4.1
6.5
7.4
4.7
6.3
3.4
3.6
%R
84.5
89.4
74.8
61.3
83.0
80.7
53.2
46.8
99.0
55.2
68.4
65.2
84.8
89.3
76.9
46.6
57.9
27.9
60.6
65.5
84.0
SO
0.4
3.8
4.3
11.7
4.6
1.0
10.1
10.5
4.5
5.6
3.0
2.0
2.5
1.2
8.4
4.7
10.4
4.0
6.3
2.1
7.0
%R
73.4
84.1
37.5
4.8
57.0
67.8
2.0
0.6
94.8
63 4
64. a
59.8
77.0
78.1
12.5
9.2
1.4
34.0
13.6
50.0
20.0
SO
1.0
1.6
5.8
1.0
2.2
1.0
1.2
0.6
2.9
2.0
2.3
0.8
0.7
4.4
4.6
1.7
1.2
4.0
3.2
8.1
3.2
N = neutral
E = Methyl t-butyl ether/Methanol (2/1)
3550A - 10
Revision 1
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TABLE 2.
SPECIFIC EXTRACTION CONDITIONS FOR VARIOUS DETERMINATIVE METHODS
Determinative
method
8040"
8060
8061
8070
8080
8081
8090
8100
8110
8120
8121
8250"'c
8270C
8310
8321
8410
Extraction
PH
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
as received
Exchange
solvent
required
for
analysis
2-propanol
hexane
hexane
methanol
hexane
hexane
hexane
none
hexane
hexane
hexane
none
none
acetonitrile
methanol
methylene chloride
Exchange
solvent
required
for
cleanup
hexane
hexane
hexane
methylene chloride
hexane
hexane
hexane
cyclohexane
hexane
hexane
hexane
--
--
methylene chloride
Volume
of extract
required
for
cleanup (ml)
1.0
2.0
2.0
2.0
10.0
10.0
2.0
2.0
2.0
2.0
2.0
' --
--
--
--
10.0
Final
extract
volume
for
analysis (ml)
1.0, 10. Ob
10.0
10.0
10.0
10.0
10.0
1.0
1.0
10.0
1.0
1.0
1.0
1.0
1.0
1.0
0.0 (dry)
" To obtain separate acid and base/neutral extracts, Method 3650 should be performed following concentration
of the extract to 10.0 ml.
b Phenols may be analyzed, by Method 8040, using a 1.0 ml 2-propanol extract by GC/FID. Method 8040 also
contains an optical derivatization procedure for phenols which results in a 10 ml hexane extract to be
analyzed by GC/ECD.
The specificity of GC/MS may make cleanup of the extracts unnecessary.
on the cleanup procedures available if required.
Refer to Method 3600 for guidance
3550A - 11
Revision 1
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METHOD 3550A
ULTRASONIC EXTRACTION
7.1 Prepare *empiae
uiing appropriate method
for th* WMt* matrix
7,2 Determine th*
percent dry we
of tne eempla
7.5.2 Add anhydrous
sodium »ulfat« to
•ample
7.5.2
It organic
concentration
exp act*d to be
< 2O mg/kg?
7.3.1 Add surrogate
standard* to ill
•ampl»f. tpifcet,
•nd blank*
7.S.3 Add »urrogate
«t«nd«rd« to ill
• ample*, (pikee,
and blank*
7.3.2 - 7.3.S
Sonicate •ample at
lea*t 3 time*
7.5.4 Adjust
volume: disrupt
aampl* with taperad
mtcrotip ultratomc
probe
7.3.7 Dry and
collect extract in
K-D concentrator
7.5.5 Rlter
through gloee wool
7.3.8 Concentrate
extract and collect
in K-D concentrator
3550A - 12
Revision 1
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METHOD 3550A
continued
7.3.9 Add exchange
solvent;
concentrate extract
Yes
7.3,1O Use Method
3660 for cleanup
Yes
7.3.9 is
* •orvent
exchenge
required?
7.3,10 Do
sulfur cry>t*lf
form?
7.3.11 Furthtr
concentrate and/or
adjust volume
(Cleanup or ]
analyze J
3550A - 13
Revision 1
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METHOD 3580A
WASTE DILUTION
1.0 SCOPE AND APPLICATION
1.1 This method describes a solvent dilution of a non-aqueous waste
sample prior to cleanup and/or analysis. It is designed for wastes that may
contain organic chemicals at a concentration greater than 20,000 mg/kg and that
are soluble in the dilution solvent.
1.2 It is recommended that an aliquot of the diluted sample be cleaned
up. See this chapter, Organic Analytes, Section 4.2.2 (Cleanup).
2.0 SUMMARY OF METHOD
2.1 One gram of sample is weighed into a capped tube, and the sample is
diluted to 10.0 ml with an appropriate solvent.
3.0 INTERFERENCES
3.1 Refer to Method 3500.
4.0 APPARATUS AND MATERIALS
4.1 Glass scintillation vials: At least 20 mL, with Teflon or aluminum
foil lined screw-cap, or equivalent.
4.2 Spatula: Stainless steel or Teflon.
4.3 Balance: Capable of weighing 100 g to the nearest 0.01 g.
4.4 Vials and caps: 2 mL for GC autosampler.
4.5 Disposable pipets: Pasteur.
4.6 Test tube rack.
4.7 Pyrex glass wool.
4.8 Volumetric flasks, Class A: 10 mL (optional).
5.0 REAGENTS
5.1 Sodium sulfate (granular, anhydrous), Na2S04. 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 is precleaned with methylene chloride,
3580A - 1 Revision 1
July 1992
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a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.2 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.3 Hexane, C6H14 - Pesticide quality or equivalent.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Samples consisting of multiphases must be prepared by the phase
separation method (Chapter Two) before extraction.
7.2 The sample dilution may be performed in a 10 mL volumetric flask.
If disposable glassware is preferred, the 20 mL scintillation vial may be
calibrated for use. Pipet 10.0 mL of extraction solvent into the scintillation
vial and mark the bottom of the meniscus. Discard this solvent.
7.3 Transfer approximately 1 g of each phase of the sample to separate
20 mL vials or 10 mL volumetric flasks (record weight to the nearest 0.1 g).
Wipe the mouth of the vial with a tissue to remove any sample material. Cap the
vial before proceeding with the next sample to avoid any cross-contamination.
7.4 Add 2.0 mL surrogate spiking solution to all samples and blanks. For
the sample in each analytical batch selected for spiking, add 2.0 mL of the
matrix spiking standard. For base/neutral-acid analysis, the amount added of the
surrogates and matrix spiking compounds should result in a final concentration
of 200 ng//LtL of each base/neutral analyte and 400 ng//iL of each acid analyte in
the extract to be analyzed (assuming a 1 pL injection). If Method 3640, Gel-
permeation cleanup, is to be used, add twice the volume of surrogates and matrix
spiking compounds since half the extract is lost due to loading of the GPC
column. See Method 3500 and the determinative method to be used for details on
the surrogate standard and matrix spiking solutions.
7.5 Immediately dilute to 10 mL with the appropriate solvent. For
compounds to be analyzed by GC/ECD, e.g., organochlorine pesticides and PCBs, the
dilution solvent should be hexane. For base/neutral and acid semivolatile
priority pollutants, use methylene chloride. If the dilution is to be cleaned
up by gel permeation chromatography (Method 3640), use methylene chloride as the
dilution solvent for all compounds.
7,6 Add 2.0 g of anhydrous sodium sulfate to the sample.
7.7 Cap and shake the sample for 2 min.
3580A - 2 Revision 1
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7.8 Loosely pack disposable Pasteur pi pets with 2-3 cm glass wool plugs.
Filter the extract through the glass wool and collect 5 ml of the extract in a
tube or vial.
7.9 The extract is ready for cleanup or analysis, depending on the extent
of interfering co-extractives.
8.0 QUALITY CONTROL
8.1 Any reagent blanks and matrix spike samples should be subjected to
exactly the same analytical procedures as those used on actual samples.
8.2 Refer to Chapter One for specific quality control procedures and
Method 3500 for extraction and sample preparation procedures.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
10.1 None applicable.
3580A - 3 Revision 1
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METHOD 3580A
WASTE DILUTION
STftRT
7. 1 Use phase
separation method
(Chapter 2)
7 . 3 Transfer 1 g of
each phase to
separata vials or
flasks
74 Add surrogate
spiking solution to
all tatnple* and
blank*
7 . 4 Add tna t r i K
spiking standard to
•ample selected for
spiking
7 S DiAute with
apprapnate sol vent
7 6 Add anhydrous
ammonium »yi £»t»
7 ? Cap and shak*
7,8 Filtar through
glass wool
Cleanup or analyse
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METHOD 3600B
CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Method 3600 provides general guidance on selection of cleanup methods
that are appropriate for the target analytes of interest. Cleanup methods are
applied to the extracts prepared by one of the extraction methods, to eliminate
sample interferences. The following table lists the cleanup methods and provides
a brief description of the type of cleanup,
SW-846 CLEANUP METHODS
Method I Method Mame Cleanup Type
3610 Alumina Cleanup Adsorption
3611 Alumina Cleanup & Separation Adsorption
for Petroleum Waste
3620 Fieri si 1 Cleanup Adsorption
3630 Silica Gel Cleanup Adsorption
3640 Gel-Permeation Cleanup Size-Separation
3650 Acid-Base Partition Cleanup Acid-Base Partitioning
3660 Sulfur Cleanup Oxidation/Reduction
3665 Sulfuric Acid/Permanganate Oxidation/Reduction
Cleanup
1.2 The purpose of applying a cleanup method to an extract is to remove
interferences and high boiling material that may result in: (1) errors in
quantisation (data may be biased low because of analyte adsorption in the
injection port or front of the GC column or biased high because of overlap with
an interference peak); (2) false positives because of interference peaks falling
within the analyte retention time window; (3) false negatives caused by shifting
the analyte outside the retention time window; (4) rapid deterioration of
expensive capillary columns; and, {5} instrument downtime caused by cleaning and
rebuilding of detectors and ion sources. Most extracts of soil and waste require
some degree of cleanup, whereas, cleanup for water extracts may be unnecessary.
Highly contaminated extracts (e.g. sample extracts of oily waste or soil
containing oily residue) often require a combination of cleanup methods. For
example, when analyzing for organochlorine pesticides and PCBs, it may be
necessary to use gel permeation chromatography (GPC), to eliminate the high
boiling material and a micro alumina or Florisil column to eliminate
interferences with the analyte peaks on the GC/ECD.
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1,3 The following techniques have been applied to extract purification:
adsorption chromatography; partitioning between immiscible solvents; gel
permeation chromatography; oxidation of interfering substances with acid, alkali,
or oxidizing agents. These techniques may be used individually or in various
combinations, depending on the extent and nature of the co-extractives,
1,3.1 Adsorption column chromatography - Alumina {Methods 3610
and 3611), Florisil (Method 3620), and silica gel (Method 3630) are useful
for separating analytes of a relatively narrow polarity range away from
extraneous, interfering peaks of a different polarity. These are
primarily used for cleanup of a specific chemical group of relatively
non-polar analytes, i.e., organochlorine pesticides, polynuclear aromatic
hydrocarbons (PAHs), nitrosamines, etc.. Solid phase extraction
cartridges have been added as an option.
1.3.2 Acid-base partitioning (Method 3650) - Useful for
separating acidic or basic organics from neutral organics. It has been
applied to analytes such as the chlorophenoxy herbicides and phenols. It
is very useful for separating the neutral PAHs from the acidic phenols
when analyzing a site contaminated with creosote and pentachlorophenol.
1.3.3 Gel permeation chromatography (GPC) (Method 3640) - The
most universal cleanup technique for a broad range of semivolatile
organics and pesticides. It is capable of separating high
molecular-weight, high boiling material from the sample analytes. It has
been used successfully for all the semivolatile base, neutral, and acid
compounds associated with the EPA Priority Pollutant and the Superfund
Target Compound list prior to GC/MS analysis for semivolatiles and
pesticides. GPC may not be applicable to elimination of extraneous peaks
on a chromatogram which interfere with the analytes of interest. It is,
however, useful for the removal of high boiling materials which would
contaminate injection ports and column heads, prolonging column life,
stabilizing the instrument, and reducing column reactivity.
1.3,4 Sulfur cleanup (Method 3660) - Useful in eliminating
sulfur from sample extracts, which may cause chromatographic interference
with analytes of interest.
1.4 Several of the methods are also useful for fractionation of complex
mixtures of analytes. Use the solid phase extraction cartridges in Method 3630
(Silica Gel) for separating the PCBs away from most organochlorine pesticides.
Method 3611 (Alumina) is for the fractionation of aliphatic, aromatic and polar
analytes. Method 3620 (Florisil) provides fractionation of the organochlorine
pesticides.
1.5 Cleanup capacity is another factor that must be considered in
choosing a cleanup technique. The adsorption methods (3610, 3620, and 3630)
provide the option of using standard column chromatography techniques or solid
phase extraction cartridges. The decision process in selecting between the
different options available generally depends on the amount of interferences/high
boiling material in the sample extract and the degree of cleanup required by the
determinative method. The solid phase extraction cartridges require less elution
solvent and less time, however, their cleanup capacity is drastically reduced
when comparing a 0.5 g or 1.0 g Florisil cartridge to a 20 g standard Florisil
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column. The same factor enters into the choice of the 70 g gel permeation column
specified in Method 3640 versus a high efficiency column.
1.6 Table 1 indicates the recommended cleanup techniques for the
indicated groups of compounds. This information can also be used as guidance for
compounds that are not listed. Compounds that are chemically similar to these
groups of compounds should behave similarly when taken through the cleanup
procedure,however, this must be demonstrated by determining recovery of standards
taken through the method.
2.0 SUMMARY OF METHOD
2.1 Refer to the specific cleanup method for a summary of the procedure.
3.0 INTERFERENCES
3.1 Analytical interferences may be caused by contaminants in solvents,
reagents, glassware, and other sample processing hardware. All of these
materials must be routinely demonstrated to be free of interferences, under the
conditions of the analysis, by running laboratory reagent blanks.
3.2 More extensive procedures than those outlined in the methods may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Refer to the specific cleanup method for apparatus and materials
needed.
5.0 REAGENTS
5.1 Refer to the specific cleanup method for the reagents needed.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Prior to using the cleanup procedures, samples normally undergo
solvent extraction. Chapter Two, Section 2.0, may be used as a guide for
choosing the appropriate extraction procedure based on the physical composition
of the waste and on the analytes of interest in the matrix (see also Method 3500
for a general description of the extraction technique). For some organic
liquids, extraction prior to cleanup may not be necessary.
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7.2 Most soil/sediment and waste sample extracts will require some degree
of cleanup. The extract is then analyzed by one of the determinative methods.
If interferences still preclude analysis for the analytes of interest, additional
cleanup may be required.
7.3 Many of the determinative methods specify cleanup methods that should
be used when determining particular analytes (e.g. Method 8061, gas
chromatography of phthalate esters, recommends using either Method 3610 (Alumina
column cleanup) or Method 3620 (Florisil column cleanup) if interferences prevent
analysis. However, the experience of the analyst may prove invaluable in
determining which cleanup methods are needed. As indicated in Section 1.0 of
this method, many matrices may require a combination of cleanup procedures in
order to ensure proper analytical determinations.
7.4 Guidance for cleanup is specified in each of the methods that follow.
The amount of extract cleanup required prior to the final determination depends
on the concentration of interferences in the sample, the selectivity of both the
extraction procedure and the determinative method and the required detection
limit.
7.5 Following cleanup, the sample is concentrated to whatever volume is
required in the determinative method. Analysis follows as specified in the
determinative procedure.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
8.2 The analyst must demonstrate that the compounds of interest are
being quantitatively recovered by the cleanup technique before the cleanup is
applied to actual samples. For sample extracts that are cleaned up, the
associated quality control samples (e.g. spikes, blanks, replicates, and
duplicates) must also be processed through the same cleanup procedure.
8.3 The analysis using each determinative method (GC, GC/MS, HPLC)
specifies instrument calibration procedures using stock standards. It is
recommended that cleanup also be performed on a series of the same type of
standards to validate chromatographic elution patterns for the compounds of
interest and to verify the absence of interferences from reagents.
9.0 METHOD PERFORMANCE
9.1 Refer to the specific cleanup method for performance data.
10.0 REFERENCES
10.1 Refer to the specific cleanup method.
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TABLE 1.
RECOMMENDED CLEANUP TECHNIQUES FOR INDICATED GROUPS OF COMPOUNDS
Analyte Group
Determinative11
Method
Cleanup
Method Options
Phenols
Phthalate esters
Nitrosamines
Organochlorine pesticides & PCBs
PCBs
Nitroaromatics and cyclic ketones
Polynuclear aromatic hydrocarbons
Chlorinated hydrocarbons
Organophosphorus pesticides
Chlorinated herbicides
Semi volatile organics
Petroleum waste
PCODs and PCDFs by LR/MS
PCDDs and PCDFs by HR/MS
N-methyl carbamate pesticides
8040
8060/80$ 1
8070
8080/8081
8080/8081
8090
8100/8310
8120/8121
8140/8141
8150/8151
8250/8270
8250/8270
8280
8290
8318
363Db, 3640, 3650, 8040C
3610, 3620, 3640
3610, 3620, 3640
3620, 3640, 3660
3665
3620, 3640
3611, 3630, 3640
3620, 3640
3620
8150d, 8151d, 3620
3640, 3650, 3660
3611, 3650
8280
8290
8318
The GC/MS Methods, 8250 and 8270, are also appropriate determinative methods
for all analyte groups, unless lower detection limits are required.
Cleanup applicable to derivatized phenols.
Method 8040 includes a derivatization technique followed by GC/ECD analysis,
if interferences are encountered using GC/FID.
Methods 8150 and 8151 incorporate an acid-base cleanup step as an integral
part of the methods.
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METHOD 3600B
CLEANUP
x- x
Start
I
7,1
Do solvent
extraction
I
7.2
Analyze anaJyte
by a determinative
method torn Sec. 4.3
7.2 Are
analytes
undeterminable
due to
7.3
USB dSBnup method
mm ini •i^jfc^ b^
7,5
ConoentratBsampte
to requifsd volume
3600B - 6
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METHOD 3630B
SILICA GEL CLEANUP
1.0 SCOPE AND APPLICATION
I.I Silica gel is a regenerative adsorbent of amorphous silica with
weakly acidic properties. It is produced from sodium silicate and sulfuric acid.
Silica gel can be used in column chromatography for the separation of analytes
from interfering compounds of a different chemical polarity. It may be used
activated, after heating to 150 - 160°C, or deactivated with up to 10% water.
1.2 This method includes guidance for standard column cleanup of sample
extracts containing polynuclear aromatic hydrocarbons, derivatized phenolic
compounds, organochlorine pesticides, and PCBs as Aroclors.
1.3 This method also provides cleanup procedures using solid-phase
extraction cartridges for pentafluorobenzyl bromide-derivatized phenols,
organochlorine pesticides, and PCBs as Aroclors. This technique' also provides
the best separation of PCBs from most single component organochlorine pesticides.
When only PCBs are to be measured, this method can be used in conjunction with
sulfuric acid/permanganate cleanup (Method 3665).
1.4 Other analytes may be cleaned up using this method if the analyte
recovery meets the criteria specified in Sec. 8.0,
2.0 SUMMARY OF METHOD
2.1 This method provides the option of using either standard column
chromatography techniques or solid-phase extraction cartridges. Generally, the
standard column chromatography techniques use larger amounts of adsorbent and,
therefore, have a greater cleanup capacity.
2.2 In the standard column cleanup protocol, the column is packed with
the required amount of adsorbent, topped with a water adsorbent, and then loaded
with the sample to be analyzed. Elution of the analytes is accomplished with a
suitable solvent(s) that leaves the interfering compounds on the column. The
eluate is then concentrated (if necessary).
2.3 The cartridge cleanup protocol uses silica solid-phase extraction
cartridges packed with 1 g or 2 g of adsorbent. Each cartridge is solvent washed
immediately prior to use. Aliquots of sample extracts are loaded onto the
cartridges, which are then eluted with suitable solvent(s). A vacuum manifold
is required to obtain reproducible results. The collected fractions may be
further concentrated prior to gas chromatographic analysis.
2.4 The appropriate gas chromatographic method is listed at the end of
each technique. Analysis may also be performed by gas chromatography/mass
spectrometry (Method 8270).
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3.0 INTERFERENCES
3.1 Solvents, reagents, glassware, and other sample processing hardware
may yield discrete artifacts and/or elevated baselines causing misinterpretation
of gas chromatograms. All these materials must be demonstrated to be free from
interferences under the conditions of the analysis, by analyzing reagent blanks.
See Sec. 8 for guidance on a reagent blank check.
3.2 Phthalate ester contamination may be a problem with certain
cartridges The more inert the column and/or cartridge material (i.e., glass or
Teflon), the less problem with phthalates. Phthalates create interference
problems for all method analytes, not just the phthalate esters themselves.
3.3 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS AND MATERIALS
4.1 Chromatographic column - 250 mm long x 10 mm ID; with Pyrex glass
wool at bottom and a Teflon stopcock.
NOTE: Fritted glass discs are difficult to decontaminate after highly
contaminated extracts have been passed through. Columns without
frits may be purchased. Use a small pad of Pyrex glass wool to
retain the adsorbent. Prewash the glass wool pad with 50 ml of
acetone followed by 50 ml of elution solvent prior to packing the
column with adsorbent.
4.2 Beakers - 500 ml.
4.3 Vials - 2, 10, 25 ml, glass with Teflon lined screw-caps or crimp
tops.
4.4 Muffle furnace.
4.5 Reagent bottle - 500 raL.
4.6 Erlenmeyer flasks - 50 and 250 mL.
4.7 Vacuum manifold: VacElute Manifold SPS-24 (Analytichem
Inte national), Visiprep (Supelco, Inc.) or equivalent, consisting of glass
vacuum basin, collection rack and funnel, collection vials, replaceable stainless
steel delivery tips, built-in vacuum bleed valve and gauge. The system is
connected to a vacuum pump or water aspirator through a vacuum trap made from a
500 ml sidearm flask fitted with a one-hole stopper and glass tubing.
5.0 REAGENTS
5.1 Reagent grade inorganic 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,
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provided it is first ascertained that the reagent is of sufficiently high purity
to permit its use without lessening the accuracy of the determination.
5,2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Silica gel for chromatography columns.
5.3.1 Silica Gel for Phenols and Polynuclear Aromatic Hydrocarbons:
100/200 mesh desiccant (Davison Chemical grade 923 or equivalent). Before
use, activate for at least 16 hr. at 130°C in a shallow glass tray, loosely
covered with foil.
5.3,2 Silica Gel for Organochlorine pesticides/PCBs: 100/200 mesh
desiccant (Davison Chemical grade 923 or equivalent). Before use,
activate for at least 16 hr. at 130°C in a shallow glass tray, loosely
covered with foil. Deactivate it to 3.3% with reagent water in a SOO ml
glass jar. Mix the contents thoroughly and allow to equilibrate for 6
hours. Store the deactivated silica gel in a sealed glass jar inside a
desiccator.
5.4 Silica cartridges: 40 pm particles, 60 A pores. The cartridges with
which this method was developed consist of 6 ml serological-grade polypropylene
tubes, with the 1 g of silica held between two polyethylene or stainless steel
frits with 20 pm pores. 2 g silica cartridges are also used in this method, and
0.5 g cartridges are available. The compound elution patterns must be verified
when cartridges other than the specified size are used.
5.5 Sodium sulfate (granular, anhydrous), Na2S04. Purify by heating at
400°C for 4 hours in a shallow tray, or by precleaning the sodium sulfate with
methylene chloride. A method blank must be analyzed in order to demonstrate that
there is no interference from the sodium sulfate.
5.6 Eluting solvents
5.6.1 Cyclohexane, C6H12 - Pesticide quality or equivalent.
5.6.2 Hexane, CeH14 - Pesticide quality or equivalent.
5.6.3 2-Propanol, (CH3)2CHOH - Pesticide quality or equivalent.
5.6.4 Toluene, C6H5CH3 - Pesticide quality or equivalent.
5.6.5 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.6.6 Pentane, C6H12 - Pesticide quality or equivalent.
5.6.7 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.6.8 Diethyl Ether, C2HSOC2HS. Pesticide quality or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
equivalent). Procedures for removal of peroxides are provided with the
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test strips. After cleanup, 20 ml of ethanol preservative must be added
to each liter of ether.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1.
7.0 PROCEDURE
7.1 General Guidance
7.1.1 The procedure contains two cleanup options for the derivatized
phenols and organochlorine pesticides/Aroclors, but only one technique for
the polynuclear aromatic hydrocarbons (PAHs) (standard column
chromatography). Cleanup techniques by standard column chromatography for
all analytes are found in Sec. 7.2. Cleanup techniques by solid-phase
cartridges for derivatized phenols and PAHs are found in Sec. 7.3. The
standard column chromatography techniques are packed with a greater amount
of silica gel adsorbent and, therefore, have a greater cleanup capacity.
A rule of thumb relating to cleanup capacity is that 1 g of sorbent
material will remove 10 to 30 mg of total interferences. (However,
capacity is also dependent on the sorbent retentiveness of the
interferences.) Therefore, samples that exhibit a greater degree of
sample interference should be cleaned up by the standard column technique.
However, both techniques have limits on the amount of interference that
can be removed. If the interference is caused by high boiling material,
then Method 3640 should be used prior to this method. If the interference
is caused by relatively polar compounds of the same boiling range as the
analytes, then multiple column or cartridge cleanups may be required. If
crystals of sulfur are noted in the extract, then Method 3660 should be
utilized prior to this method. The cartridge cleanup techniques are often
faster and use less solvent, however they have less cleanup capacity.
7.1.2 Allow the extract to reach room temperature if it was in cold
storage. Inspect the extracts visually to ensure that there are no
particulates or phase separations and that the volume is as stated in the
accompanying documents. Verify that the solvent is compatible with the
cleanup procedures. If crystals of sulfur are visible or if the presence
of sulfur is suspected, proceed with Method 3660.
7.1.3 If the extract solvent is methylene chloride, for most cleanup
techniques, it must be exchanged to hexane. (For the PAHs, exchange to
cyclohexane as per Sec. 7.2.1). Follow the standard Kuderna-Danish
concentration technique provided in each extraction method. The volume of
methyl ene chloride should have been reduced to 1 - 2 ml. Add 40 ml of
hexane, a fresh boiling chip and repeat the concentration as written. The
final volume required for the cleanup techniques is normally 2 mL.
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7.2 Standard Column Cleanup Techniques
7.2.1 Polynuclear aromatic hydrocarbons
7.2.1.1 Before the silica gel cleanup technique can be
utilized, the extract solvent must be exchanged to cyclohexane. The
exchange is performed by adding 4 ml of cyclohexane following
reduction of the sample extract to 1-2 ml using the macro Snyder
column. Attach the two ball micro Snyder column and reduce the
volume to 2 ml.
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost. If the
extract goes to dryness, the extraction must be
repeated.
7.2.1.2 Prepare a slurry of 10 g of activated silica gel
(Sec. 5.3.1) 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.
7.2.1.3 Pre-elute the column with 40 ml of pentane. The
rate for all elutions should be about 2 rnL/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.
7.2.1,4 Next, elute the column with 25 ml of methylene
chloride/pentane (2:3)(v/v) into a 500 ml K-D flask equipped with a
10 ml concentrator tube. Concentrate the collected fraction to
whatever volume is required (1-10 ml). Proceed with HPLC (Method
8310) or GC analysis (Method 8100). Validated components that elute
in this fraction are:
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)f1uoranthene
Benzo(g,h,i)perylene
Benzo(k)f1uoranthene
Chrysene
Dibenzo(a,h)anthracene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
Naphthalene
Phenanthrene
Pyrene
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7.Z.2 Derivatized Phenols
7.2.2.1 This silica gel cleanup procedure is performed on
sample extracts that have undergone pentafluorobenzyl bromide
derivatization, as described in Method 8040. The sample extract
must be in 2 ml of hexane at this point.
7.2.2.2 Place 4.0 g of activated silica gel (Sec. 5.3.1)
into a 10 mm ID chromatographic column. Tap the column to settle
the silica gel and add about 2 g of anhydrous sodium sulfate to the
top of the silica gel.
7.2.2.3 Pre-elute the column with 6 ml of hexane. The
rate for all elutions should be about 2 mL/rain. Discard the eluate
and, just prior to exposure of the sodium sulfate layer to the air,
pipet onto the column 2 ml of the hexane solution that contains the
derivatized sample or standard. Elute the column with 10.0 mL of
hexane and discard the eluate.
7,2.2.4 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 1. Fractions may be
combined, as desired, depending upon the specific phenols of
interest or level of interferences. Proceed with GC analysis
(Method 8040).
7.2.3 Organochlorine Pesticides and Aroclors
7.2.3.1 Transfer a 3 g portion of deactivated silica gel
(Sec. 5.3.2) into a 10 mm ID glass chromatographic column and top it
with 2 to 3 cm of anhydrous sodium sulfate.
7.2.3.2 Add 10 ml of hexane to the top of the column to
wet and rinse the sodium sulfate and silica gel. Just prior to
exposure of the sodium sulfate layer to air, stop the hexane eluate
flow by closing the stopcock on the chromatographic column. Discard
the eluate.
7.2.3.3 Transfer the sample extract (2 mL in hexane) onto
the column. Rinse the extract vial twice with 1 to 2 mL of hexane
and add each rinse to the column. Elute the column with 80 mL of
hexane (Fraction I) at a rate of about 5 mL/min. Remove the
collection flask and set it aside for later concentration. Elute
the column with 50 mL of hexane (Fraction II) and collect the
eluate. Perform a third elution with 15 mL of methylene chloride
(Fraction III). The elution patterns for the organochlorine
pesticides, Aroclor-1016, and Aroclor-1260 are shown in Table 2.
7.2.3.4 Prior to gas chromatographic analysis, the
extraction solvent must be exchanged to hexane. Fractions may be
combined, as desired, depending upon the specific
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pesticides/Aroclors of interest or level of interferences. If
mixtures of Aroclors and pesticides are expected, it is best to
analyze Fraction I separately, since it contains the Aroclors
separated from most pesticides. Proceed with GC analysis as per
Method 8081.
7.3 Cartridge Cleanup Techniques
7.3.1 Cartridge Set-up and Conditioning
7.3.1.1 Arrange the 1 g silica cartridges (2 g for phenol
cleanup) on the manifold in the closed-valve position. Other size
cartridges may be used, however the data presented in the Tables are
all based on 1 g cartridges for pesticides/Aroclors and 2 g
cartridges for phenols. Therefore, supporting recovery data must be
developed for other sizes. Larger cartridges will probably require
larger volumes of elution solvents.
7.3.1.2 Turn on the vacuum pump and set pump vacuum to 10
inches (254 mm) of Hg. Do not exceed the manufacturer's
recommendation for manifold vacuum. Flow rates can be controlled by
opening and closing cartridge valves.
7.3.1.3 Condition the cartridges by adding 4 mL of hexane
to each cartridge. Slowly open the cartridge valves to allow hexane
to pass through the sorbent beds to the lower frits. Allow a few
drops per cartridge to pass through the manifold to remove all air
bubbles. Close the valves and allow the solvent to soak the entire
sorbent bed for 5 minutes. Do not turn off the vacuum.
7.3.1.4 Slowly open cartridge valves to allow the hexane
to pass through the cartridges. Close the cartridge valves when
there is still at least 1 ran of solvent above the sorbent bed. Do
not allow cartridges to become dry. If cartridges go dry, repeat
the conditioning step.
7.3.2 Derivatized Phenols
7.3.2.1 Reduce the sample extract volume to E ml prior to
cleanup. The extract solvent must be hexane and the phenols must
have undergone derivatization by pentafluorobenzyl bromide, as per
Method 8040.
7.3.2.2 Transfer the extract to the 2 g cartridge that has
been conditioned as described in Sec. 7.3.1. Open the cartridge
valve to allow the extract to pass through the cartridge bed at
approximately 2 mL/minute.
7.3.2.3 When the entire extract has passed through the
cartridges, but before the cartridge becomes dry, rinse the sample
vials with an additional 0.5 ml of hexane, and add the rinse to the
cartridges to complete the quantitative transfer.
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7.3.2.4 Close the cartridge valve and turn off the vacuum
after the solvent has passed through, ensuring that the cartridge
never gets dry.
7.3.2.5 Place a 5 mL vial or volumetric flask into the
sample rack corresponding to the cartridge position. Attach a
solvent-rinsed stainless steel solvent guide to the manifold cover
and align with the collection vial.
7.3.2.6 Add 5 mL of hexane to the cartridge. Turn on the
vacuum pump and adjust the pump pressure to 10 inches {254 mm) of
Hg. Allow the solvent to soak the sorbent bed for 1 minute or less.
Slowly open the cartridge valve, and collect the eluate (this is
Fraction 1, and should be discarded).
NOTE: If cartridges smaller than 2 g are used, then Fraction
1 cannot be discarded, since it contains some of the
phenols.
7.3.2.7 Close the cartridge valve, replace the collection
vial, and add 5 ml of toluene/hexane (25/75, v/v) to the cartridge.
Slowly open the cartridge valve and collect the eluate into the
collection vial. This is Fraction 2, and should be retained for
analysis.
7.3.2.8 Adjust the final volume of the eluant to a known
volume which will result in analyte concentrations appropriate for
the project requirements (normally 1 - 10 mL). Table 3 shows
compound recoveries for 2 g silica cartridges. The cleaned up
extracts are ready for analysis by Method 8040.
7.3.3 Organochlorine Pesticides/Aroclors
NOTE: The silica cartridge procedure is appropriate when
polychlorinated biphenyls are known to be present.
7.3.3.1 Reduce the sample extract volume to 2 mL prior to
cleanup. The extract solvent must be hexane.
7.3.3.2 Use the 1 g cartridges conditioned as described in
Sec. 7.3.1.
7.3.3.3 Transfer the extract to the cartridge. Open the
cartridge valve to allow the extract to pass through the cartridge
bed at approximately 2 mL/minute,
7.3.3.4 When the entire extract has passed through the
cartridges, but before the cartridge becomes dry, rinse the sample
vials with an additional 0.5 ml of solvent, and add the rinse to the
cartridges to complete the quantitative transfer.
7.3.3.5 Close the cartridge valve and turn off the vacuum
after the solvent has passed through, ensuring that the cartridge
never goes dry.
3630B - 8 Revision 2
September 1994
-------
7.3.3.6 Place a 5 ml vial or volumetric flask into the
sample rack corresponding to the cartridge position. Attach a
solvent-rinsed stainless steel solvent guide to the manifold cover
and align with the collection vial.
7.3.3.7 Add 5 ml of hexane to the cartridge. Turn on the
vacuum pump and adjust the pump pressure to 10 inches (254 mm) of
Hg. Allow the solvent to soak the sorbent bed for 1 minute or less.
Slowly open the cartridge valve and collect the eluate into the
collection vial (Fraction 1).
7.3.3.8 Close the cartridge valve, replace the collection
.vial, and add 5 ml of diethyl ether/hexane (50/50, v/v) to the
cartridge. Slowly open the cartridge valve and collect the eluate
into the collection vial (Fraction 2).
7.3.3.9 Adjust the final volume of each of the two
fractions to a known volume which will result in analyte
concentrations appropriate for the project requirements (normally 1
- 10 ml). The fractions may be combined prior to final adjustment
of volume, if analyte fractionation is not required. Table 4 shows
compound recoveries for 1 g silica cartridges. The cleaned up
extracts are ready for analysis by Method 8081.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 A reagent blank (consisting of the elution solvents) must be passed
through the column or cartridge and checked for the compounds of interest, prior
to the use of this method. This same performance check is required with each new
lot of adsorbent or cartridges. The level of interferences must be below the
method detection limit before this method is performed on actual samples.
8.3 The analyst must demonstrate that the compounds of interest are being
quantitatively recovered before applying this method to actual samples. See the
attached Tables for-acceptable recovery data. For compounds that have not been
tested, recovery must be > 85%.
8.3.1 Before any samples are processed using the solid-phase
extraction cartridges, the efficiency of the cartridge must be verified.
A recovery check must be performed using standards of the target analytes
at known concentration. Only lots of cartridges that meet the recovery
criteria for the spiked compounds can be used to process the samples.
8.3.2 A check should also be performed on each individual lot of
cartridges and for every 300 cartridges of a particular lot.
8.4 For sample extracts that are cleaned up using this method, the
associated quality control samples should also be processed through this cleanup
method.
3630B - 9 Revision 2
September 1994
-------
9.0 METHOD PERFORMANCE
9.1 Table 1 provides performance information on the fractionation of
phenolic derivatives using standard column chromatography.
9.2 Table 2 provides performance information on the fractionation of
organochlorine pesticides/Aroclors using standard column chromatography.
9.3 Table 3 shows recoveries of derivatized phenols obtained using 2 g
silica cartridges.
9,4 Table 4 shows recoveries and fractionation of organochlorine
pesticides obtained using 1 g silica cartridges.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures
for the Analysis of Pollutants Under the Clean Water Act; Final Rule
and Interim Final Rule and Proposed Rule," October 26, 1984.
2. U.S EPA "Evaluation of Sample Extract Cleanup Using Solid-Phase
Extraction Cartridges," Project Report, December 1989,
3630B - 10 Revision 2
September 1994
-------
TABLE 1
SILICA GEL FRACTIONATION OF PFBB DERIVATIVES
Percent Recovery by Fraction3
Parameter 123
2-Chlorophenol
2-Nitrophenol
Phenol
2 , 4-Dimethyl phenol
2,4-Dichlorophenol
2,4, 6-Tri chl orophenol
4-Cnloro-3 -methyl phenol
Pentachl orophenol
4-Nitrophenol
90
90
95
95
50 50
84
75 20
1
9
10
7
1
14
1
90
90
a Eluant composition:
Fraction 1 - 15% toluene in hexane.
Fraction 2 - 40% toluene in hexane.
Fraction 3 - 75% toluene in hexane.
Fraction 4 - 15% 2-propanol in toluene.
Data from Reference 1 (Method 604)
3630B - 11 Revision 2
September 1994
-------
TABLE 2
DISTRIBUTION ANP PERCENT RECOVERIES OF ORGANOCHLORINE
PESTICIDES AND PCBs A' OCLORS IN SILICA GEL COLUMN FRACTIONSa-b'cde
Fraction I
Fraction II
Fraction III
Total Recovery
Compound
alpha-BHCf
beta-BHC
gamma -BHC
delta-BHC
Heptachlor
Aldrin
Heptachlor epoxide
Technical chlordane
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
Endosulfan II
4, 4 '-ODD'
Endrin aldehyde
Endosulfan sulfate
4, 4' -DDT'
4,4'-Methoxychlor
Toxaphene*
Aroclor-1016
Aroclor-1260
COIIL.
1
109(4
97(5
14(5
86(5
86(4
91(4
•1)
.6)
.5)
.4)
.0)
•1)
Cone.
2
118(8
104(1
22(5
94(2
87(6
95(5
•7)
.6)
.3)
.8)
•1)
.0)
Cone. Cone. Cone.
1 2 1
82(1
107(2
91(3
92(3
95(4
19(6.8) 39(3.6) 29(5
95(5
96(6
85(10
97(4
102(4
81(1
93(4
86(13.4) 73(9.1) 15(17
99(9
15(2.4) 17(1.4) 73(9
•7)
•1)
.6)
.5)
•7)
.0)
•1)
.0)
.5)
•4)
.6)
•9)
•9)
•7)
•9)
•4)
Cone.
2
74(8
98(12
85(10
83(10
88(10
37(5
87(10
87(10
71(12
86(10
92(10
76(9
82(9
8.7(15
82(10
84(10
.0)
.5)
•7)
.6)
•2)
•1)
•2)
.6)
.3)
•4)
•2)
.5)
•2)
.0)
•7)
•7)
Cone.
1
82(1.
107(2.
91(3.
92(3.
109(4.
97(5.
95(4.
62(3.
95(5.
86(5.
96(6.
85(10.
97(4.
102(4.
81(1.
93(4.
101(5.
99(9.
88(12.
86(4.
91(4.
7)
1)
6)
5)
1)
6)
7)
3)
1)
4)
0)
5)
4)
6)
9)
9)
3)
9)
0)
0)
1)
Cone.
2
74(8.0)
98(12.5)
85(10.7)
83(10.6)
118(8.7)
104(1.6)
88(10.2)
98(1.9)
87(10.2)
94(2.8)
87(10.6)
71(12.3)
86(10.4)
92(10.2)
76(9.5)
82(9.2)
82(23.7)
82(10.7)
101(10.1)
87(6.1)
95(5.0)
3630B - 12
Revision 2
September 1994
-------
TABLE 2
(Continued)
Effluent composition: Fraction I, 80 ml hexane; Fraction II, 50 ml hexane; Fraction III, 15 ml methylene
chloride.
Concentration 1 is 0.5 /ug per column for BHCs, Heptachlor, Aldrin, Heptachlor epoxide, and Endosulfan I; 1.0
/ng per column for Dieldrin, Endosulfan II, 4,4'-DDD, 4,4'-DDE, 4,4'-DDT, Endrin, Endrin aldehyde, and
Endosulfan sulfate; 5 /ug per column for 4,4'-Methoxychlor and technical Chlordane; 10 /ug per column for
Toxaphene, Aroclor-1016, and Aroclor-1260.
For Concentration 2, the amounts spiked are 10 times as high as those for Concentration 1.
Values given represent the average recovery of three determinations; numbers in parentheses are the standard
deviation; recovery cutoff point is 5 percent.
Data obtained with standards, as indicated in footnotes b and c, dissolved in 2 ml hexane.
It has been found that because of batch-to-batch variation in the silica gel material, these compounds cross
over in two fractions and the amounts recovered in each fraction are difficult to reproduce.
3630B - 13 Revision 2
September 1994
-------
TABLE 3
PERCENT RECOVERIES AND ELUTION PATTERNS FOR 18
PHENOLS FROM 2 g SILICA CARTRIDGES8
Fraction 2
Average Percent
Compound Recovery RSD
Phenol
2-Methyl phenol
3-Methyl phenol
4-Methyl phenol
2, 4-Di methyl phenol
2-Chlorophenol
2,6-Dichlorophenol
4-Chl oro-3-methyl phenol
2,4-Dichlorophenol
2,4,6-Trichloropheriol
2, 3, 6-Tri chl orophenol
2, 4, 5-Tri chl orophenol
2,3, 5-Tri chl orophenol
2,3,5,6-Tetrachlorophenol
2,3,4, 6-Tetrachl orophenol
2, 3, 4-Tri chl orophenol
2,3 , 4, S-Tetrachl orophenol
Pentachl orophenol
74.1
84.8
86.4
82.7
91.8
88.5
90.4
94.4
94.5
97.8
95.6
92.3
92.3
97.5
97.0
72.3
95.1
96.2
5.2
5.2
4.4
5.0
5.6
5.0
4.4
7.1
7.0
6.6
7.1
8.2
8.2
5.3
6.1
8.7
6.8
8.8
a Silica cartridges (Supelco, Inc.) were used; each cartridge was conditioned
with 4 ml of hexane prior to use. Each experiment was performed in duplicate
at three spiking concentrations (0.05 /ig, 0.2 M9i and 0.4 ^g per compound per
cartridge). Fraction 1 was eluted with 5 ml hexane and was discarded.
Fraction 2 was eluted with 5 ml toluene/hexane (25/75, v/v).
Data from Reference 2
3630B - 14 Revision 2
September 1994
\
-------
TABLE 4
PERCENT RECOVERIES AND ELUTION PATTERNS FOR 17 ORGANOCHLORINE
PESTICIDES AND AROCLORS FROM 1 g SILICA CARTRIDGES8
Compound
Fraction 1
Average Percent
Recovery RSD
Fraction 2
Average Percent
Recovery RSD
alpha-BHC
gamma -BHC
beta-BHC
Heptachlor
delta-BHC
Aldrin
Heptachlor epoxide
Endosulfan I
4,4'-DDE
Dieldrin
Endrin
4,4'-DDD
Endosulfan II
4, 4' -DDT
Endrin aldehyde
Endosulfan sulfate
4,4'-Methoxychlor
Aroclor 1016
Aroclor 1221
Aroclor 1232
Aroclor 1242
Aroclor 1248
Aroclor 1254
Aroclor 1264
0
0
0
97.3 1.3
0
95.9 1.0
0
0
99.9 1.7
0
0
10.7 41
0
94.1 2.0
0
0
0
124
93.5
118
116
114
108
112
98.7
94.8
94.3
0
90.8
0
97.9
102
0
92.3
117
92.4
96.0
0
59.7
97.8
98.0
2.3
1.9
3.0
2.5
2.1
2.3
2.0
2.6
3.3
2.2
2.6
2.1
2.4
a Silica cartridges (Supelco, Inc. lot SP0161) were used; each cartridge was
conditioned with 4 mL hexane prior to use. The organochlorine pesticides were
tested separately from PCBs. Each organochlorine pesticides experiment was
performed in duplicate, at three spiking concentrations (0.2 ^g, 1.0 pig, and
2.0 ^g per compound per cartridge). Fraction 1 was eluted with 5 ml of
hexane. Fraction 2 with 5 ml of diethyl ether/hexane (50/50, v/v). PCBs were
spiked at 10 jig per cartridge and were eluted with 3 mL of hexane. The values
given for PCBs are the percent recoveries for a single determination.
Data from Reference 2
3630B - 15
Revision 2
September 1994
-------
METHOD 3630B
SILICA GEL CLEANUP
7.2 Standard
Column Cleanup
7,3.1 Cartridg
S*t-up *
Conditioning.
7.2.2,1 Do PF8B
derivatizatten an
temple extract
(8040),
7.2.2.2 Piece
activated ailica gel
in ehromaiographic
column; add
anhydrous Ne2SO*.
7.2.2.3 Praaluta
column with hexan*;
pioat n»xan«
tolutton onto column;
•lut*.
7.2.2.4 Elut* column
with specified
solvanta.
Analyze
SV GC
(Method
80401.
7.2.3.1 Deactivate
»ilici gal, prepare
column.
I
7.2.3.2 ilute the
<3C colun^
with heiene.
7.2.3.3 Trenefer
extract onto column
and a Jute wltrt
(pacified lolvantt.
7.3.4 Exchange tne
•lution ao
-------
METHOD 3630B
(continued)
0
!PAHs»
7.2 Standard
Column Cleanup.
7.2.1.1 Exchange
extract solvent to
cyclohexana during
K-D procedure.
7,2.1.2 Prepare
slurry activated
silica gel, prepare
column.
7.2.1.3 Prielute
column with
pontano, transfer
extract onto column
and eluto with
pentane.
7.2,1.4 Elute
colymn with
CH2CI2 /pentane;
concentrate
collected fraction;
adjust volume.
Analyze
by GC Method
8100 or
GC/MS
Method
8270.
3630B - 17
Revision 2
September 1994
-------
-------
METHOD 3640A
GEL-PERHEATION CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Gel-permeation chromatography {GPC} is a size exclusion cleanup
procedure using organic solvents and hydrophobic gels in the separation of
synthetic raacromolecules (1). The packing gel is porous and is characterized by
the range or uniformity (exclusion range) of that pore size. In the choice of
gels, the exclusion range must be larger than the molecular size of the molecules
to be separated (2). A cross-linked divinyl benzene-styrene copolymer (SX-3 Bio
Beads or equivalent} is specified for this method.
1.2 General cleanup application - GPC is recommended for the elimination
from the sample of lipids, polymers, copolymers, proteins, natural resins and
polymers, cellular components, viruses, steroids, and dispersed high-molecular-
weight compounds (2). GPC is appropriate for both polar and non-polar analytes,
therefore, it can be effectively used to cleanup extracts containing a broad
range of analytes.
1.3 Specific application - This method includes guidance for cleanup of
sample extracts containing the following analytes from the RCRA Appendix VIII and
Appendix IX lists:
Compound Name CAS No.'
Acenaphthene 83-32-9
Acenaphthylene 208-96-8
Acetophenone 98-86-2
2-Acetylaminofluorene 53-96-3
Aldrin 309-00-2
4-Aminobiphenyl 92-67-1
Aniline 62-53-3
Anthracene 120-12-7
Benomyl 17804-35-2
Benzenethiol 108-98-5
Benzidine 92-87-5
Benz(a)anthracene 56-55-3
Benzo(b)fluoranthene 205-99-2
Benzo(a)pyrene 50-32-8
Benzo(ghi)perylene 191-24-2
Benzo(k)fluoranthene 207-08-9
Benzole acid 61-85-0
Benzotrichloride 98-07-7
Benzyl alcohol 100-51-6
Benzyl chloride 100-44-7
alpha-BHC 319-84-6
beta-BHC 319-85-7
3640A - 1 Revision 1
September 1994
-------
Compound Name
gamma-BHC
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2 -sec-butyl- 4, 6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Ch1oro-3-methyl phenol
4-Chloroaniline
Chi orobenzi late
Bis{2-chloroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl ) ether
2-Chloronaphthalene
2-Chlorophenol
4-Chlorophenol
3-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
3-Cresol
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Diallate
Dibenzo{a,e)pyrene
Dibenzo(a,i)pyrene
Dibenz(a,j)acridine
Dibenz( a, h) anthracene
Dibenzofuran
Di benzoth i ophene
1 ,2-Di brorno-3-chl oropropane
1,2-Dibromoethane
trans- l,4-Dichloro-2-butene
cis-l»4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
3,3' -Dichlorobenzidi ne
2,6-Dlchlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
CAS No."
58-89-9
319-86-8
101-55-3
85-68-7
88-85-7
86-74-8
10605-21-7
5103-71-9
5566-34-7
59-50-7
106-47-8
510-15-6
111-91-1
111-44-4
108-60-1
91-58-7
95-57-8
106-48-9
108-43-0
7005-72-3
542-76-7
218-01-9
95-48-7
108-39-4
106-44-5
50-18-0
72-54-8
72-55-9
50-29-3
84-74-2
2303-16-4
192-65-4
189-55-9
224-42-0
53-70-3
132-64-9
132-65-0
96-12-8
106-93-4
110-57-6
1476-11-5
95-50-1
106-46-7
541-73-1
91-94-1
87-65-0
94-75-7
120-83-2
3640A - 2
Revision 1
September 1994
-------
Compound Name
2,4-Dichlorotoluene
1 ,3-Di chl oro-2-propanol
Dieldrin
Diethyl phthalate
Dlmethoate
Dimethyl phthalate
p-Di methyl ami noazobenzene
7,12-Dimethyl-benz(a)anthracene
2,4-Dimethylphenol
3,3-Dimethylbenzidine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2,4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1 , 2 - Di phenyl hydr az i ne
Disulfoton
Endosulfan sulfate
Endosulfan I
Endosulfan II
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachlorobutadiene
Hexachl orocycl opentadiene
Hexachl oroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans- I sosaf role
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methylcholanthrene
CAS No/
95-73-8
96-23-1
60-57-1
84-66-2
60-51-5
131-11-3
60-11-7
57-97-6
105-67-9
119-93-7
534-52-1
99-65-0
51-28-5
121-14-2
606-20-2
122-39-4
101-84-8
122-66-7
298-04-4
1031-07-8
959-98-8
33213-65-9
72-20-8
7421-93-4
53494-70-5
62-50-0
97-63-2
117-81-7
52-85-7
86-73-7
206-44-0
76-44-8
1024-57-3
118-74-1
87-68-3
77-47-4
67-72-1
1888-71-7
193-39-5
465-73-6
78-59-1
17627-76-8
4043-71-4
143-50-0
109-77-3
150-50-5
72-43-5
56-49-5
3640A - 3
Revision 1
September 1994
-------
Compound Name
2-Methyl naphthalene
Methyl parathion
4,4'-Methylene-bis(2-chloroaniline)
Naphthalene
1,4-Naphthoquinone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroaniline
3-Nitroaniline
4-Nitroaniline
Nitrobenzene
2-N1trophenol
4-Nitrophenol
N-Ni trosodi-n- butyl ami ne
N-Nitrosodiethanolatnine
N-Nitrosodiethylamine
N-Nitrosodimethylamine
N-Nitrosodiphenylamine
N-Ni trosodi -n-propyl amine
N-Ni trosomethyl ethyl ami ne
N-Nitrosomorpholine
N-Ni trosopi peri dine
N-Nitrosopyrol idine
Di-n-octyl phthalate
Parathion
Pentachl orobenzene
Pentachl oroethane
Pentachl oronitrobenzene (PCNB)
Pentachl orophenol
Phenacetin
Phenanthrene
Phenol
1,2-Phenylenediamine
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
1 , 2 , 4, 5-Tetrachl orobenzene
2, 3, 5, 6-Tetrachl oronitrobenzene
2 » 3 , 5 , 6-Tetrachl orophenol
2,3, 4 , 6-Tetrachl orophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluidine
4-Toluidine
CAS No.a
91-57-6
298-00-0
101-14-4
91-20-3
130-15-4
91-59-8
134-32-7
99-55-8
88-74-4
99-09-2
100-01-6
98-95-3
79-46-9
100-02-7
924-16-3
1116-54-7
55-18-5
62-75-9
86-30-6
621-64-7
10595-95-6
59-89-2
100-75-4
930-55-2
117-84-0
56-38-2
608-93-5
76-01-7
82-68-8
87-86-5
62-44-2
85-01-8
108-95-2
95-54-5
298-02-2
109-06-8
23950-58-5
129-00-0
108-46-3
94-59-7
95-94-3
117-18-0
935-95-5
58-90-2
3689-24-5
79-19-6
106-49-0
95-53-4
3640A - 4
Revision 1
September 1994
-------
Compound Name CAS No."
Thiourea, l-(o-chlorophenyl)
Toluene-2,4~diamine
1, 2, 3-Triehloro benzene
1 , 2 » 4-TH chl orobenzene
2 , 4 , 6-Tri chl orophenol
2 j4 , 5-Tri chl orophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4,5-Trichlorophenoxypropionic acid (2,4,5-TP)
Warfarin
5344-82-1
95-80-7
87-61-6
120-82-1
88-06-2
95-91-4
93-76-5
93-72-1
81-81-2
* Chemical Abstract Services Registry Number.
Table 1 presents average percent recovery and percent RSD data for these
analytes, as well as the retention volumes of each analyte on a single GPC
system. Retention volumes vary from column to column. Figure 1 provides
additional information on retention volumes for certain classes of compounds.
The data for the semivolatiles were determined by GC/MS, whereas, the pesticide
data were determined by GC/ECD or GC/FPD. Compounds not amenable to GC were
determined by HPLC. Other analytes may also be appropriate for this cleanup
technique, however, recovery through the GPC should be >70%,
1.4 Normally, this method is most efficient for removing high boiling
materials that condense in the injection port area of a gas ehromatograph (GC)
or the front of the GC column. This residue will ultimately reduce the
chromatographic separation efficiency or column capacity because of adsorption
of the target analytes on the active sites, Pentachlorophenol is especially
susceptible to this problem, GPC, operating on the principal of size exclusion,
will not usually remove interference peaks that appear in the ehromatogram since
the molecular size of these compounds is relative similar to the target analytes.
Separation cleanup techniques, based on other molecular characteristics (i.e.,
polarity), must be used to eliminate this type of interference.
2.0 SUMMARY OF METHOD
2.1 The column is packed with the required amount of preswelled
absorbent, and is flushed with solvent for an extended period. The column is
calibrated and then loaded with the sample extract to be cleaned up. Elution is
effected with a suitable solvent(s) and the product is then concentrated,
3.0 INTERFERENCES
3.1 A reagent blank should be analyzed for the compound of interest prior
to the use of this method. The level of interferences must be below the
estimated quantitation limits (EQLs) of the analytes of interest before this
method is perfoned on actual samples.
3640A - 5 Revision 1
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3.2 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
4.0 APPARATUS
4.1 Gel-permeation chromatography system - 6PC Autoprep Model 1002 A
or B, or equivalent, Analytical Biochemical Laboratories, Inc. Systems that
perform very satisfactorily have also been assembled from the following
components - an HPLC pump, an auto sampler or a valving system with sample loops,
and a fraction collector. All systems, whether automated or manual, must meet
the calibration requirements of Sec. 7.2.2.
4.1.1 Chromatographic column - 700 mm x 25 mm ID glass column. Flow
is upward. (Optional) To simplify switching from the UV detector during
calibration to the GPC collection device during extract cleanup, attach a
double 3-way valve (Rheodyne Type 50 Teflon Rotary Valve #10-262 or
equivalent) so that the column exit flow can be shunted either to the UV
flow-through cell or to the SPC collection device.
4.1.2 Guard column - (Optional) 5 cm, with appropriate fittings to
connect to the inlet side of the analytical column (Supelco 5-8319 or
equivalent).
4.1.3 Bio Beads (S-X3) - 200-400 mesh, 70 g (Bio-Rad Laboratories,
Richmond, CA, Catalog 152-2750 or equivalent). An additional 5 g of Bio
Beads are required if the optional guard column is employed. The quality
of Bio Beads may vary from lot to lot because of excessive fines in some
lots. The UV chromatogram of the Calibration solution should be very
similar to that in Figure 2, and the backpressure should be within 6-
10 psi. Also, the gel swell ratio 1n methylene chloride should be in the
range of 4.4 - 4.8 mL/g. In addition to fines having a detrimental effect
on chromatography, they can also pass through the column screens and
damage the valve.
4.1.4 Ultraviolet detector - Fixed wavelength (254 nm) with a semi-
prep flow-through cell.
4.1.5 Strip chart recorder, recording integrator or laboratory data
system.
4.1.6 Syringe - 10 mL with Luerlok fitting.
4.1.7 Syringe filter assembly, disposable - Bio-Rad "Prep Disc"
sample filter assembly #343-0005, 25 ram, and 5 micron filter discs or
equivalent. Check each batch for contaminants. Rinse each filter
assembly (prior to use) with methylene chloride if necessary.
4.2 Analytical balance - 0.0001 g.
4.3 Volumetric flasks, Class A - 10 mL to 1000 mL
4.4 Graduated cylinders
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5.0 REAGENTS
5.1 Methylene chloride, CH2C12, Pesticide quality or equivalent.
5.1.1 Some brands of methylene chloride may contain unacceptably
high levels of acid (HC1). Check the pH by shaking equal portions of
methylene chloride and water, then check the pH of the water layer.
5.1.1.1 If the pH of the water layer is < 5, filter the
entire supply of solvent through a 2 in. x 15 in. glass column
containing activated basic alumina. This column should be
sufficient for processing approximately 20-30 liters of solvent.
Alternatively, find a different supply of methylene chloride.
5.2 Cyclohexane, C6H12. Pesticide quality or equivalent,
5.3 n-Butyl chloride, CH3CH2CH2CH2C1. Pesticide quality or equivalent.
5.4 GPC Calibration Solution. Prepare a calibration solution in
methylene chloride containing the following analytes (in elution order):
Compound mg/L
corn oil 25,000
bis(2-ethylhexyl) phthalate 1,000
methoxychl or 200
perylene 20
sulfur 80
NOTE: Sulfur is not very soluble in methylene chloride, however, it is
soluble in warm corn oil. Therefore, one approach is to weigh out
the corn oil, warm it and transfer the weighed amount of sulfur into
the warm corn oil. Mix it and then transfer into a volumetric flask
with methylene chloride, along with the other calibration compounds.
Store the calibration solution in an amber glass bottle with a Teflon lined
screw-cap at 4°C, and protect from light. (Refrigeration may cause the corn oil
to precipitate. Before use, allow the calibration solution to stand at room
temperature until the corn oil dissolves.) Replace the calibration standard
solution every 6 months, or more frequently if necessary,
5.5 Corn Oil Spike for Gravimetric Screen. Prepare a solution of corn
oil in methylene chloride (5 g/100 ml).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1.
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7.0 PROCEDURE
7.1 It Is very important to have consistent laboratory temperatures
during an entire 6PC run, which could be 24 hours or more. If temperatures are
not consistent, retention times will shift, and the dump and collect times
determined by the calibration standard will no longer be appropriate. The ideal
laboratory temperature to prevent outgassing of the tnethylene chloride is 72°F.
7.2 SPC Setup and Calibration
7.2.1 Column Preparation
7.2.1.1 Weigh out 70 g of Bio Beads (SX-3), Transfer them
to a quart bottle with a Teflon lined cap or a 500 ml separatory
funnel with a large bore stopcock, and add approximately 300 ml of
methylene chloride. Swirl the container to ensure the wetting of
all beads. Allow the beads to swell for a minimum of 2 hours.
Maintain enough solvent to sufficiently cover the beads at all
times. If a guard column is to be used, repeat the above with 5 g
of Bio Beads in a 125 ml bottle or a beaker, using 25 ml of
methylene chloride.
7.2.1.2 Turn the column upside down from its normal
position, and remove the inlet bed support plunger (the inlet
plunger is longer than the outlet plunger). Position and tighten
the outlet bed support plunger as near the end as possible, but no
closer than 5 cm (measured from the gel packing to the collar).
7.2.1.3 Raise the end of the outlet tube to keep the
solvent in the GPC column, or close the column outlet stopcock if
one is attached. Place a small amount of solvent in the column to
minimize the formation of air bubbles at the base of poured column
packing.
7.2.1.4 Swirl the bead/solvent slurry to get a homogeneous
mixture and, if the wetting was done in a quart bottle, quickly
transfer it to a 500 mL separatory funnel with a large bore
stopcock. Drain the excess methylene chloride directly into the
waste beaker, and then start draining the slurry into the column by
placing the separatory funnel tip against the column wall. This
will help to minimize bubble formation. Swirl occasionally to keep
the slurry homogeneous. Drain enough to fill the column. Place the
tubing from the column outlet into a waste beaker below the column,
open the stopcock (if attached) and allow the excess solvent to
drain. Raise the tube to stop the flow and close the stopcock when
the top of the gel begins to look dry. Add additional methylene
chloride to just rewet the gel.
7.2.1.5 Wipe any remaining beads and solvent from the
inner walls of the top of the column with a laboratory tissue.
Loosen the seal slightly on the other plunger assembly (long
plunger) and insert it into the column. Make the seal just tight
3640A - 8 Revision 1
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enough so that any beads on the glass surface will be pushed
forward, but loose enough so that the plunger can be pushed forward.
CAUTION: Do not tighten the seal if beads are between the
seal and the glass surface because this can
damage the seal and cause leakage.
7.2.1.6 Compress the column as much as possible without
applying excessive force. Loosen the seal and gradually pull out
the plunger. Rinse and wipe off the plunger. Slurry any remaining
beads and transfer them into the column. Repeat Sec. 7.2.1.5 and
reinsert the plunger. If the plunger cannot be inserted and pushed
in without allowing beads to escape around the seal, continue
compression of the beads without tightening the seal, and loosen and
remove the plunger as described. Repeat this procedure until the
plunger is successfully inserted.
7.2.1.7 Push the plunger until it meets the gel, then
compress the column bed about four centimeters.
7.2.1.8 Pack the optional 5 cm column with approximately
5 g of preswelled beads (different guard columns may require
different amounts). Connect the guard column to the inlet of the
analytical column.
7.2.1.9 Connect the column inlet to the solvent reservoir
(reservoir should be placed higher than the top of the column) and
place the column outlet tube in a waste container. Placing a
restrictor in the outlet tube will force air out of the column more
quickly. A restrictor can be made from a piece of capillary
stainless steel tubing of 1/16" OD x 10/1000" ID x 2". Pump
methylene chloride through the column at a rate of 5 mL/min for one
hour,
7.2.1.10 After washing the column for at least one hour,
connect the column outlet tube, without the restrictor, to the inlet
side of the UV detector. Connect the system outlet to the outlet
side of the UV detector. A restrictor (same size as in Sec.
7.2.1.9) in the outlet tube from the UV detector will prevent bubble
formation which causes a noisy UV baseline. The restrictor will not
effect flow rate. After pumping methylene chloride through the
column for an additional 1-2 hours, adjust the inlet bed support
plunger until approximately 6-10 psi backpressure is achieved. Push
the plunger in to increase pressure or slowly pull outward to reduce
pressure.
7.2.1.11 When the GPC column is not to be used for several
days, connect the column outlet line to the column inlet to prevent
column drying and/or channeling. If channeling occurs, the gel must
be removed from the column, reswelled, and repoured as described
above. If drying occurs, methylene chloride should be pumped
through the column until the observed column pressure is constant
and the column appears wet. Always recalibrate after column drying
has occurred to verify retention volumes have not changed.
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7.2.2 Calibration of the GPC Column
7.2.2.1 Using a 10 ml syringe, load sample loop #1 with
calibration solution (Sec. 5,6). With the ABC automated system, the
5 ml sample loop requires a minimum of 8 ml of the calibration
solution. Use a firm, continuous pressure to push the sample onto
the loop. Switch the valve so that GPC flow is through the UV flow-
through cell.
7.2.2.2 Inject the calibration solution and obtain a UV
trace showing a discrete peak for each component. Adjust the
detector and/or recorder sensitivity to produce a UV trace similar
to Figure 2 that meets the following requirements. Differences
between manufacturers' cell volumes and detector sensitivities may
require a dilution of the calibration solution to achieve similar
results. An analytical flow-through detector cell will require a
much less concentrated solution than the semi-prep cell, and
therefore the analytical cell is not acceptable for use.
7.2.2.3 Following are criteria for evaluating the UV
chromatogram for column condition.
7.2.2.3.1 Peaks must be observed, and should be
symmetrical, for all compounds in the calibration solution.
7.2.2.3.2 Corn oil and phthalate peaks must exhibit
>85% resolution.
7.2.2.3.3 Phthalate and methoxychlor peaks must
exhibit >85% resolution.
7.2.2.3.4 Methoxychlor and perylene peaks must exhibit
>85% resolution.
7.2.2.3,5 Perylene and sulfur peaks must not be
saturated and must exhibit >90% baseline resolution.
7.2.2.3.6 Nitroaromatic compounds are particularly
prone to adsorption. For example, 4-nitrophenol recoveries
may be low due to a portion of the analyte being discarded
after the end of the collection time. Columns should be
tested with the semivolatiles matrix spiking solution. GPC
elution should continue until after perylene has eluted, or
long enough to recover at least 85% of the analytes, whichever
time is longer,
7.2.2.4 Calibration for Semivolatiles - Using the
information from the UV trace, establish appropriate collect and
dump time periods to ensure collection of all target analytes.
Initiate column eluate collection just before elution of
bis(2-ethylhexyl) phthalate and after the elution of the corn oil.
Stop eluate collection shortly after the elution of perylene.
Collection should be stopped before sulfur elutes. Use a "wash"
time of 10 minutes after the elution of sulfur. Each laboratory is
3S40A - 10 Revision 1
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required to establish its specific time sequences. See Figure 2 for
general guidance on retention time. Figure 1 illustrates retention
volumes for different classes of compounds.
7.2.2,5 Calibration for Organoehlorine Pesticides/PCBs -
Determine the elution times for the phthalate, methoxychlor,
perylene, and sulfur. Choose a dump time which removes >85% of the
phthalate, but collects >95% of the methoxychlor. Stop collection
after the elution of perylene, but before sulfur elutes.
7.2,2.6 Verify the flow rate by collecting column eluate
for 10 minutes in a graduated cylinder and measure the volume, which
should be 45-55 ml (4.5-5.5 mL/min). If the flow rate is outside of
this range, corrective action must be taken, as described above.
Once the flow rate is within the range of 4,5-5.5 mL/min, record the
column pressure (should be 6-10 psi) and room temperature. Changes
in pressure, solvent flow rate, and temperature conditions can
affect analyte retention times, and must be monitored. If the flow
rate and/or column pressure do not fall within the above ranges, a
new column should be prepared. A UV trace that does not meet the
criteria in Sec. 7.2.2.3 would also indicate that a new column
should be prepared. It may be necessary to obtain a new lot of Bio
Beads if the column fails all the criteria.
7,2.2.7 Reinject the calibration solution after
appropriate collect and dump cycles have been set, and the solvent
flow and column pressure have been established,
7.2.2.7.1 Measure and record the volume of collected
GPC eluate in a graduated cylinder. The volume of GPC eluate
collected for each sample extract processed may be used to
indicate problems with the system during sample processing.
7.2.2.7.2 The retention times for bis(2-ethylhexyl)
phthalate and perylene must not vary more than +5% between
calibrations. If the retention time shift is >5%, take
corrective action. Excessive retention time shifts are caused
by:
7.2.2.7.2.1 Poor laboratory temperature control or
system leaks.
7.2.2.7.2.2 An unstabilized column that requires
pumping methylene chloride through it for several more
hours or overnight.
7.2.2.7.2.3 Excessive laboratory temperatures,
causing outgassing of the methylene chloride.
7.2.2.8 Analyze a GPC blank by loading 5 ml of methylene
chloride into the GPC. Concentrate the methylene chloride that
passes through the system during the collect cycle using a Kuderna-
Danish (KD) evaporator. Analyze the concentrate by whatever
detectors will be used for the analysis of future samples. Exchange
3640A - 11 Revision 1
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the solvent, if necessary. If the blank exceeds the estimated
quantitation limit of the analytes, pump additional methylene
chloride through the system for 1-2 hours. Analyze another 6PC
blank to ensure the system is sufficiently clean. Repeat the
methylene chloride pumping, if necessary.
7.3 Extract Preparation
7.3.1 Adjust the extract volume to 10.0 ml. The solvent extract
must be primarily methylene chloride. All other solvents, e.g.
1:1 methylene chloride/acetone, must be concentrated to 1 ml (or as low as
possible if a precipitate forms) and diluted to 10.0 ml with tnethylene
chloride. Thoroughly mix the extract before proceeding.
7.3.2 Filter the extract through a 5 micron filter disc by attaching
a syringe filter assembly containing the filter disc to a 10 ml syringe.
Draw the sample extract through the filter assembly and into the 10 ml
syringe. Disconnect the filter assembly before transferring the sample
extract into a small glass container, e.g. a 15 ml culture tube with a
Teflon lined screw cap. Alternatively, draw the extract into the syringe
without the filter assembly. Attach the filter assembly and force the
extract through the filter and into the glass container. The latter is
the preferred technique for viscous extracts or extracts with a lot of
solids. Particulate larger than 5 microns may scratch the valve, which
may result in a system leak and cross-contamination of sample extracts in
the sample loops. Repair of the damaged valve is quite expensive.
NOTE: Viscosity of a sample extract should not exceed the viscosity
of 1:1 water/glycerol. Dilute samples that exceed this
viscosity.
7.4 Screening the Extract
7.4.1 Screen the extract to determine the weight of dissolved
residue by evaporating a 100 ^L aliquot to dryness and weighing the
residue. The weight of dissolved residue loaded on the GPC column cannot
exceed 0.500 g. Residues exceeding 0.500 g will very likely result in
incomplete extract cleanup and contamination of the SPC switching valve
(which results in cross-contamination of sample extracts).
7.4.1.1 Transfer 100 ^L of the filtered extract from
Sec. 7.3.2 to a tared aluminum weighing dish.
7.4.1.2 A suggested evaporation technique is to use a heat
lamp. Set up a 250 watt heat lamp in a hood so that it is
8 + 0.5 cm from a surface covered with a clean sheet of aluminum
foil. Surface temperature should be 80-100°C (check temperature by
placing a thermometer on the foil and under the lamp). Place the
weighing dish under the lamp using tongs. Allow it to stay under
the lamp for 1 min. Transfer the weighing dish to an analytical
balance or a micro balance and weigh to the nearest 0.1 mg. If the
residue weight is less than 10 mg/100 jtL, then further weighings are
not necessary. If the residue weight is greater than 10 mg/100 /iL,
3640A - 12 Revision 1
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then determine if constant weight has been achieved by placing the
weighing dish and residue back under the heat lamp for 2 or more
additional 0.5 min. intervals. Reweigh after each interval.
Constant weight is achieved when three weights agree within ±10%.
7.4.1.3 Repeat the above residue analysis on a blank and
a spike. Add 100 pi of the same methylene chloride used for the
sample extraction to a weighing dish and determine residue as above.
Add 100 pi of a corn oil spike (5 g/100 ml) to another weighing dish
and repeat the residue determination.
7.4.2 A residue weight of 10 mg/100 jiL of extract represents 500 mg
in 5 ml of extract. Any sample extracts that exceed the 10 mg/100 pi
residue weight must be diluted so that the 5 ml loaded on the 6PC column
does not exceed 0.500 g. When making the dilution, keep in mind that a
minimum volume of 8 ml is required when loading the ABC 6PC unit.
Following is a calculation that may be used to determine what dilution is
necessary if the residue exceeds 10 mg.
Y ml taken = 10 ml final x 10 mg maximum
for dilution volume X mg of residue
Example:
Y ml taken = 10 ml final x 10 mq maximum
for dilution volume 15 mg of residue
Y mL taken for dilution - 6.7 ml
Therefore, taking 6.7 ml of sample extract from Sec. 7.3.2, and
diluting to 10 mL with methylene chloride, will result in 5 mL of diluted
extract loaded on the GPC column that contains 0.500 g of residue.
NOTE: This dilution factor must be included in the final calculation
of analyte concentrations. In the above example, the dilution
factor is 1.5.
7.5 GPC Cleanup
7.5.1 Calibrate the GPC at least once per week following the
procedure outlined in Sees. 7.2.2 through 7.2.2.6. Ensure that UV trace
requirements, flow rate and column pressure criteria are -acceptable.
Also, the retention time shift must be <5% when compared to retention
times in the last calibration UV trace.
7.5.1.1 If these criteria are not met, try cleaning the
column by loading one or more 5 mL portions of butyl chloride and
running it through the column. Butyl chloride or 9:1 (v/v)
methylene chloride/methanol removes the discoloration and
particulate that may have precipitated out of the methylene chloride
extracts. Backflushing (reverse flow) with methylene chloride to
dislodge particulates may restore lost resolution. If a guard
column is being used, replace it with a new one. This may correct
3640A - 13 Revision 1
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the problem. If column maintenance does not restore acceptable
performance, the column must be repacked with new Bio Beads and
calibrated.
7.5.2 Draw a minimum of 8 ml of extract (diluted, if necessary, and
filtered) into a 10 ml syringe.
7.5.3 Attach the syringe to the turn lock on the injection port.
Use firm, continuous pressure to push the sample onto the 5-mL sample
loop. If the sample is difficult to load, some part of the system may be
blocked. Take appropriate corrective action. If the back pressure is
normal (6-10 psi), the blockage is probably in the valve. Blockage may be
flushed out of the valve by reversing the inlet and outlet tubes and
pumping solvent through the tubes. (This should be done before sample
loading.)
NOTE: Approximately 2 ml of the extract remains in the lines between
the injection port and the sample loop; excess sample also
passes through the sample loop to waste.
7.5.4 After loading a loop, and before removing the syringe from the
injection port, index the 6PC to the next loop. This will prevent loss of
sample caused by unequal pressure in the loops.
7.5.5 After loading each sample loop, wash the loading port with
methylene chloride in a PTFE wash bottle to minimize cross-contamination.
Inject approximately 10 ml of methylene chloride to rinse the common
tubes.
7.5.6 After loading all the sample loops, index the 6PC to the 00
position, switch to the "RUN" mode and start the automated sequence.
Process each sample using the collect and dump cycle times established in
Sec. 7.2.2.
7.5.7 Collect each sample in a 250 ml Erlenmeyer flask, covered with
aluminum foil to reduce solvent evaporation, or directly into a Kuderna-
Danish evaporator. Monitor sample volumes collected. Changes in sample
volumes collected may indicate one or more of the following problems:
7.5.7.1 Change in solvent flow rate, caused by channeling
in the column or changes in column pressure.
7.5.7.2 Increase in column operating pressure due to the
absorption of particles or gel fines onto either the guard column or
the analytical column gel, if a guard column is not used.
7.5.7.3 Leaks in the system or significant variances in
room temperature.
7.6 Concentrate the extract by the standard K-D technique {see any of the
extraction methods, Sec. 4.2.1 of this chapter). See the determinative methods
(Chapter Four, Sec. 4.3) for the final volume.
3640A - 14 Revision 1
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7.7 It should be remembered that only half of the sample extract is
processed by the GPC {5 ml of the 10 ml extract is loaded onto the GPC column),
and thus, a dilution factor of 2 (or 2 multiplied by any dilution factor in Sec.
7.4.2) must be used for quantitation of the sample in the determinative method.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One and Method 3600 for specific quality control
procedures.
8.2 The analyst should demonstrate that the compound(s) of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For sample extracts that are cleaned up using this method, the
associated quality control samples must also be processed through this cleanup
method.
9.0 METHOD PERFORMANCE
9.1 Refer to Table 1 for single laboratory performance data.
10.0 REFERENCES
1. Wise, R.H.; Bishop, D.F.; Williams, R.T.; Austern, B.M. "Gel Permeation
Chromatography in the GC/MS Analysis of Organics in Sludges"; U.S. EPA
Municipal Environmental Research Laboratory: Cincinnati, Ohio 45268.
2, Czuczwa, J.; Alford-Stevens, A. "Optimized Gel Permeation Chromatographic
Cleanup for Soil, Sediment, Waste and Waste Oil Sample Extracts for GC/MS
Determination of Semivolatile Organic Pollutants, JAOAC, submitted April
1989.
3. Marsden, P.J.; Taylor, V.; Kennedy, M.R, "Evaluation of Method 3640 Gel
Permeation Cleanup"; Contract No. 68-03-3375, U.S. Environmental
Protection Agency, Cincinnati, Ohio, pp. 100, 1987.
3640A - 15 Revision 1
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TABLE 1
GPC RECOVERY AND RETENTION VOLUMES FOR RCRA
APPENDIX VIII ANALYTES
Compound
Acenaphthene
Acenaphthylene
Acetophenone
2 - Acety 1 ami nof 1 uorene
Aldrin
4-Aminobi phenyl
An i 1 i ne
Anthracene
Benomyl
Benzenethiol
Benzidine
Benz(a) anthracene
Benzo ( b) f 1 uoranthene
Benzo(a)pyrene
Benzo(ghi)perylene
Benzo(k)fl uoranthene
Benzoic acid
Benzotrichloride
Benzyl alcohol
Benzyl chloride
alpha-BHC
beta-BHC
gamma -BHC
delta-BHC
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
2-sec-butyl-4,6-dinitrophenol (Dinoseb)
Carbazole
Carbendazim
alpha-Chlordane
gamma-Chlordane
4-Chloro-3-methyl phenol
4-Chloroaniline
Chi oroberzi late
Bis(2-ch jroethoxy)methane
Bis(2-chloroethyl) ether
Bis(2-chloroisopropyl } ether
2-CMoronaphthalene
2-Chlorophenol
3-Chlorophenol
4-Chlorophenol
4-Chlorophenyl phenyl ether
3-Chloropropionitrile
Chrysene
2-Cresol
% Rec1
97
72
94
97
99
96
93
89
131
92
95
100
93
93
90
91
66
93
95
99
84
94
93
102
93
104
103
99
131
97
93
87
88
92
89
76
83
89
90
86
87
98
80
102
91
% RSD2
2
10
7
2
9
7
4
2
8
11
5
3
5
3
6
4
7
7
17
4
13
9
4
7
1
3
IB
5
8
2
2
1
3
5
1
2
2
1
1
3
2
2
5
1
1
Ret. Vol.3 (ml
196-235
196-235
176-215
156-195
196-215
176-215
196-235
196-235
146-195
196-235
176-215
196-235
196-235
196-235
196-235
196-235
176-195
176-215
176-215
176-215
196-215
196-215
196-215
216-251
176-215
136-175
176-195
196-255
146-195
196-235
196-215
196-255
196-235
176-235
156-195
156-215
156-195
196-235
196-215
196-215
196-215
176-215
176-215
196-235
196-215
3640A - 16
Revision 1
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TABLE 1 (continued)
\
Compound
3-Cresol
4-Cresol
Cyclophosphamide
ODD
DDE
DDT
Di-n-butyl phthalate
Dial late
Di benzo ( a , e) pyrene
Dibenzo(a»i)pyrene
Dibenz(a,j)acridine
Dibenz(a,h)anthracene
Dibenzofuran
Dibenzothiophene
1 ,2-Dibromo-3-chloropropane
1,2-Dibromoethane
trans-l,4-Dichloro-2-butene
cis~l,4-Dichloro-2-butene
1,2-Dichlorobenzene
1,3-Dichlorobenzene
1 , 4-Di chl orobenzene
3,3'-Dichlorobenzidine
2,6-Dichlorophenol
2,4-Dichlorophenoxyacetic acid (2,4-D)
2,4-Dichlorophenol
2,4-Dichlorotol uene
l,3-Dichloro-2-propanol
Dieldrin
Diethyl phthalate
Dimethoate
3,3'-Dimethoxybenzidinea
Dimethyl phthalate
p-Dimethy 1 ami noazobenzene
7,12-Dimethyl-benz(a)anthracene
2, 4-Dimethyl phenol
3, 3' -Dimethyl benzi dine
4,6-Dinitro-o-cresol
1,3-Dinitrobenzene
2,4-Dinitrophenol
2»4-Dinitrotoluene
2,6-Dinitrotoluene
Diphenylamine
Diphenyl ether
1,2-Diphenylhydrazine
Disulfoton
Endosulfan sulfate
Endosulfan I
% Rec1
70
88
114
94
94
96
104
97
94
99
117
92
94
94
83
121
107
106
81
81
81
98
86
80
87
70
73
100
103
79
15
100
96
77
93
93
100
99
118
93
101
95
67
92
81
94
99
%RSD2
3
2
10
4
2
6
3
6
10
8
9
5
1
3
2
8
5
5
1
1
1
3
3
NA
2
9
13
5
3
15
11
1
1
1
2
2
1
2
7
4
2
6
12
1
15
2
8
Ret. Vol.3 (ml
196-215
196-215
146-185
196-235
196-235
176-215
136-175
156-175
216-235
216-235
176-195
196-235
176-235
196-235
176-215
196-215
176-195
176-215
196-235
196-235 '
196-235
176-215
196-215
76-215
96-215
196-235
176-215
196-215
136-195
146-185
156-195
156-195
176-215
176-215
176-215
156-215
156-195
156-195
176-195
156-195
156-175
176-235
196-215
176-215
146-165
176-195
176-215
3640A - 17
Revision 1
September 1994
-------
TABLE 1 (continued)
Compound
Endosulfan II
Endrin
Endrin aldehyde
Endrin ketone
Ethyl methane sulfonate
Ethyl methacrylate
Bis(2-ethylhexyl) phthalate
Famphur
Fluorene
Fluoranthene
Heptachlor
Heptachlor epoxide
Hexachl orobenzene
Hexachl orobutadi ene
Hexachl orocyclopentadiene
Hexachl oroethane
Hexachl oropropene
Indeno(l,2,3-cd)pyrene
Isodrin
Isophorone
cis-Isosafrole
trans-Isosafrole
Kepone
Malononitrile
Merphos
Methoxychlor
3-Methyl chol anthrene
2-Methy 1 naphthal ene
Methyl parathion
4,4' -Methyl ene-bi s(2-chl oroani 1 ine)
Naphthalene
1,4-Naphthoquinone
2-Naphthylamine
1-Naphthylamine
5-Nitro-o-toluidine
2-Nitroanillne
3-Nitroaniline
4-Nitroanil ine
Nitrobenzene
2-Nitrophenol
4-Nitrophenol
N-Nitroso-di-n-butylamine
N-Nitrosodiethanolamine
N-Ni trosodi ethyl ami ne
N-Nitrosodimethyl atnine
N-Nitrosodiphenylamine
N-Nitrosodi-n-propylamine
% Rec1
92
95
97
94
62
126
101
99
95
94
85
91
108
86
89
85
91
79
98
68
go
88
102
111
93
94
74
67
84
96
95
73
94
96
77
96
96
103
86
95
77
89
104
' 94
86
99
85
%RSD2
6
6
1
4
7
7
1
NA
1
1
2
11
2
2
3
I
Z
13
5
7
4
16
NA
9
12
6
12
6
13
1
7
7
8
6
2
8
2
8
2
3
3
4
3
2
13
2
4
Ret, Vol.3 (ml
196-215
196-215
176-215
176-215
176-235
176-195
120-145
126-165
176-235
196-235
195-215
156-195
196-235
176-215
176-215
196-235
196-235
216-255
196-235
156-195
176-215
156-195
196-235
156-195
126-165
156-195
176-195
196-215
146-185
176-215
196-215
176-215
196-235
196-235
176-195
176-215
176-215
176-215
176-195
176-195
196-215
156-175
146-185
156-175
156-li5
156-195
156-175
3640A - 18 Revision 1
September 1994
-------
TABLE 1 (continued)
Compound
N-Nitrosomethyl ethyl ami ne
N-Nitrosomorphol i ne
N-Nitrosopi peri dine
N-Nitrosopyrol idine
Di-n-octyl phthalate
Parathion
Pentachl orobenzene
Pentachl oroethane
Pentachl oronitrobenzene (PCNB)
Pentachl orophenol
Phenacetin
Phenanthrene
Phenol
1 , 2-Phenyl enedi ami ne
Phorate
2-Picoline
Pronamide
Pyrene
Resorcinol
Safrole
Streptozotocina
1,2,4, 5-Tetrachl orobenzene
2,3,5,6-Tetrachloro-nitrobenzene
2,3,4,6-Tetrachlorophenol
2,3,5,6-Tetrachlorophenol
Tetraethyl dithiopyrophosphate (Sulfotep)
Thiosemicarbazide
2-Toluid1ne
4-Toluidine
Thiourea, I-(o-chlorophenyl)
Toluene-2,4-diamine
1 , 2 ,3-Tri chl orobenzene
1, 2, 4-Trichl orobenzene
2 ,4, 5-Trichl orophenol
2,4,6-Trichlorophenol
2,4,5-Trichlorophenoxyacetic acid (2,4,5-T)
2,4, 5-Tri chl orophenoxypropi oni c aci d
Warf ari n
% Rec1
83
86
84
92
83
109
95
74
91
102
100
94
83
91
74
99
105
98
70
93
6
96
85
95
96
89
74
92
87
75
69
87
89
77
95
71
67
94
%RSD2
7
4
4
1
4
14
2
1
8
1
3
2
2
1
NA
14
15
2
6
1
48
2
9
1
7
14
3
3
8
11
7
1
1
1
1
23
NA
2
Ret. Vol.3 (ml
156-175
156-195
156-195
156-175
120-156
146-170
196-235
196-235
156-195
196-215
156-195
196-235
156-195
196-215
116-135
156-215
156-195
215-235
196-215
176-215
225-245
196-235
176-215
196-215
196-215
116-135
146-185
176-235
176-231
166-185
176-215
196-235
196-235
216-235
216-235
156-235
216-215
166-185
NA = Not applicable, recovery presented as the average of two determinations.
8 Not an appropriate analyte for this method.
1 The percent recovery is based on an average of three recovery values.
2 The % relative standard deviation is determined from three recovery values.
3 These Retention Volumes are for guidance only as they will differ from column to
column and from system to system.
3640A - 19 Revision 1
September 1994
-------
Figure 1
6PC RETENTION VOLUME OF CLASSES OF ANALYTES
W////////////M
W///////////////.
PAH't
CHLORO8ENZENES
PHTHALATB -—
OROANOPHOSPHATE
PESTICIDES
CORN Oil.-*
NJTROSAMINE3, N1TROAROMATJCS
AROMATIC AMINES
MTftOPHiNOi.3
""""" CHLOROPHENOLS
ORQANOCHLORINE
P§STIClOeS/PCB'»
HERBICIDES (8 ISO)
— POP
C-Collect
10
20
30 40
Q TIME (minutes)
50
60
70
3640A - 20
Revision 1
September 1994
\
\
-------
Figure 2
UV CHROMATQGRAN OF THE CALIBRATION SOLUTION
Injection
5 M.S
on column
— 0 minutes
Corn oil
25 rag/oL
B is (2 -ethyIheay 1) phctnia te
1.0 rag/nL
Methoxychlor
0.2 mg/nL
1 : .......:."' 30 minutes
Perylene
0.02 mg/oL
Sulfur
0.08 og/aL
15 iflinuces
45 miauces
700 am X25 nra
70 g Bio-Beads SX
Bed length - 490
CH-Ci, at 5.0 u
254 na
,'1 •;"'
»•»_ . . .:. _ . _. ; _. ... _ ,1
_r_ _.,_„______ , ; ' . 60 minutes
3640A - 21
Revision 1
September 1994
-------
METHOD 3640A
GEL-PERMEATION CLEANUP
7.1 Ensure ambient tamp, consistent
throughout GPC run.
7.2 GPC Setup and Calibration
7.2.1 Column Preparation
7,2.1.1 Place Bio Beads and MeCI
in a container. Swirl and
allow beads to swell.
7,2.1.2 Remove column inlet bed
support plunger. Position and tighten
outlet bed support plunger to column end.
7.2.1.3 Ensure GPC column outlet
contains solvent. Place small amount
solvent in column to minimize
bubble formation.
7.2.1.4 Transfer bead mixture into
sep. tunnel. Drain excess solvent:
drain beads into column. Keep
beads wet throughout
7.2.1.5 Loosen seal on opposite
plunger assembly, insert into column.
7.2.1,6 Compress column. Slurry
remaining beads and repeat Section
7.2.1.5 and column compression
7.2.1.7 Compress column bed
approximately tour cm.
7.2.1,8 Pack option 5 cm. guard
column w/ roughly 5 gm.
preswelleci beads.
7.2.1.9 Connect column inlet to
solvent reservoir. Pump MeCI at
5 ml/min. for 1 hr.
7.2.1,10 Connect column outlet to
UV-Vis detector. Place restrictor
at detector outlet. Run MeCI for
additional 1 -2 hrs, Compress
column bed to provide 6-10 psi
backpressure.
7.2.1.11 Connect outlet tine ID column
inlet when column not in use, Repack
column when channeling is observed.
Assure consistent backpressure when
beads are rewetted after drying.
3640A - 22
Revision 1
September 1994
-------
METHOD 3640A
continued
7.2.2 Calibration at the GPC column
i
7.2.2.1 Load sample loop wrtfi
calibration solution.
I
7.2.2,2 Inject calibration soln.; adjust
recorder or detector sensitivity
to produce similar UV trace 33 Fig, 2.
1
7.2,2.3 Evaluation criteria for
UV chrorratogram.
7.2.2.4 Calibration tor Semivolatiles
Use information torn UV trace to
obtain collect and dump times,
Initiate collection before bis(2-ethylhexyl)
phthalate, stop after perylene. Stop run
before sulfur elutas.
I
7,2.2.5 Calibration for Organochterine
Pesfletdes/PCBs
Choose dump time which removes
> 35% phthaiate, but collects at
times > 95% methoxychlor. Stop
collection between perylene and
sulfur eluttbn.
7.2.2.6 Verify column flow rate and
backpressure. Correct .
inconsistencies when criteria
are not met.
7.2.2.7 fieinject calibration soln. when
collect and dump cycles are set,
and column criteria are met.
7.2.2.7.T Measure and record
volume of GPC eluate
7.2.2.7.2 Correct for retention 8me
shifts of > +/- 5% for
bis<2-ethythexyt) phthalate
and perytene.
7.2.2.8 Inject and analyze OPC blank
for column cleanliness. Pump
through MeCI as column wash.
3640A - 23
Revision 1
September 1994
-------
METHOD 3640A
continued
7.3 Extract Preparation
7,3.1 Adjust extract volume to 10 ml.
Primary solvent should be MeCI.
1
7.3.2 Filter extract through S micron filter
disc/syringe assembly into small
glass container.
7.4 Screening the Extract
7.4.1 Screen extract by determining
residue wt. of 1 00 uL aliquot.
7.4.1 .1 Transfer 1 00 uL of fitered
extract from Section 7.3.2 to tared
aluminum weighing dish.
1
7.4. 1 .2 Evaporate extract solvent under
heating lamp. Weigh residue to nearest
0.1 mg.
1
7.4.1.3 Repeat residue analysis of Section
7.4 . 1 .2 w/blank and spike sample.
7.4 ,2 Use dilution example to determine
necessary dilution when residue
wts, > I0mg
7.5 GPC Cleanup
7.5.1 Calibrate GPC weekly. Assure
column criteria, UV trace, retention
time shift criteria are met.
7.S.1.1 Clean column w/butyl chloride
loadings, or replacement of
guard column.
7.5.S Draw 8 mL extract into syringe.
7.5.3 Load sample into injection loop.
7.5.4 Index GPC to next loop to
prevent sample loss.
I
\
7.5.S Wash sample port w/MeCI
between sample loadings.
7.5.6 At end of loadings, index GPC to
00, switch to 'RUN' mode, start
automated sequence
I
7.5.7 Collect sample into aluminum foil
covered Erlenmeyer flask or into
Kuderna- Danish evaporator.
7.6 Concentrate extract by std.
Kuderna- Danish technique.
7.7 Note dilution (actor of GPC method
into final determinations.
3640A - 24
Revision 1
September 1994
-------
METHOD 3650A
ACID-BASE PARTITION CLEANUP
1.0 SCOPE AND APPLICATION
1.1
manual.
Method 3650 was formerly Method 3530 in the second edition of this
1.2 Method 3650 is a liquid-liquid partitioning cleanup method to
separate acid analytes, e.g. organic acids and phenols, from base/neutral
analytes, e.g. amines, aromatic hydrocarbons, and halogenated organic compounds,
using pH adjustment. It may be used for cleanup of petroleum waste prior to
analysis or further cleanup (e.g., alumina cleanup). The following compounds can
be separated by this method:
Compound Name
CAS No.1
Fraction
Benz(a)anthracene
Benzo(a)pyrene
Benzo (b) f 1 uoranthene
Chlordane
Chlorinated dibenzodioxins
2-Chlorophenol
Chrysene
Creosote
Cresol(s)
Dichlorobenzene(s)
Dichlorophenoxyacetic acid
2, 4-Dimethyl phenol
Dinitrobenzene
4,6-Dinitro-o-cresol
2,4-Dinitrotoluene
Heptachlor
Hexachlorobenzene
Hexachlorobutadiene
Hexachloroethane
Hexachlorocyclopentadiene
Naphthalene
Nitrobenzene
4-Nitrophenol
Pentachlorophenol
Phenol
Phorate
2-Picoline
Pyridine
Tetrachlorobenzene(s)
Tetrachlorophenol (s)
Toxaphene
Trichlorophenol (s)
2,4,5-TP (Silvex)
56-55-3
50-32-8
205-99-2
57-74-9
95-57-8
218-01-9
8001-58-9
94-75-7
105-67-9
25154-54-5
534-52-1
121-14-2
76-44-8
118-74-1
87-68-3
67-72-1
77-47-4
91-20-3
98-95-3
100-02-7
87-86-5
108-95-2
298-02-2
109-06-8
110-86-1
8001-35-2
93-72-1
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Acid
Base-neutral
Base-neutral and Acid
Acid
Base-neutral
Acid
Acid
Base-neutral
Acid
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Acid
Acid
Acid
Base-neutral
Base-neutral
Base-neutral
Base-neutral
Acid
Base-neutral
Acid
Acid
Chemical Abstract Services Registry Number,
3650A - 1
Revision 1
July 1992
-------
2.0 SUMMARY OF METHOD
2.1 The solvent extract from a prior solvent extraction method is shaken
•with water that is strongly basic. The acid analytes partition into the aqueous
layer, whereas, the basic and neutral compounds stay in the organic solvent. The
base/neutral fraction is concentrated and is then ready for further cleanup, if
necessary, or analysis. The aqueous layer is acidified and extracted with an
organic solvent. This extract is concentrated (if necessary) and is then ready
for analysis of the acid analytes.
3.0 INTERFERENCES
3.1 More extensive procedures than those outlined in this method may be
necessary for reagent purification.
3.2 A method blank must be run for the compounds of interest prior to
use of the method. The interferences must be below the method detection limit
before this method is applied to actual samples,
4.0 APPARATUS AND MATERIALS
4.1 Drying column - 20 mm ID Pyrex chromatographic column with Pyrex
glass wool at bottom, or equivalent.
NOTE: Fritted glass discs are difficult to clean after highly contaminated
extracts have been passed through them. Columns without frits are
recommended. Use a small pad of Pyrex glass wool to retain the
adsorbent. Prewash the glass wool pad with 50 mL of acetone
followed by 50 ml of elution solvent prior to packing the column
with adsorbent.
4.2 Kuderna-Danish (K-D) apparatus
4.2.1 Concentrator tube - 10 mi graduated (Kontes K570Q50-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of the
extracts.
4.2.2 Evaporation flask - 500 ml (K-570001-0500 or equivalent).
Attach to concentrator tube with springs, clamps, or equivalent.
4.2.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.2.4 Snyder column - Two ball micro (Kontes K569001-0219 or
equivalent).
tops.
4.2.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.3 Vials - Glass, 2 ml capacity with Teflon lined screw-caps or crimp
4.4 Water bath - Heated, concentric ring cover, temperature control of
± 2°C. Use this bath in a hood.
3650A - 2 Revision 1
July 1992
-------
4.5 Boiling chips - Solvent extracted, approximately 10/40 mesh (silicon
carbide or equivalent).
4.6 pH indicator paper - pH range including the desired extraction pH.
4.7 Separatory funnel - 125 ml.
4.8 Erlenmeyer flask - 125 ml.
5.0 REAGENTS
5.1 Reagent grade inorganic chemicals shall be used in all tests.
Unless otherwise indicated, it is intended that all inorganic 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.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sodium hydroxide, NaOH, (ION) - Dissolve 40 g of sodium hydroxide
in 100 ml of organic-free reagent water.
5.4 Sulfuric acid, H?S04, (1:1 v/v in water) - Slowly add 50 ml H2S04 to
50 ml of organic-free reagent water.
5.S Sodium sulfate (granular, anhydrous), Na2SO, - 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 is precleaned with methylene chloride,
a method blank must be analyzed, demonstrating that there is no interference from
the sodium sulfate.
5.6 Solvents:
\
5.6.1 Methylene chloride, CH2C12 - Pesticide quality or equivalent.
5.6.2 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.6.3 Methanol, CH3OH - Pesticide quality or equivalent.
5.6.4 Diethyl Ether, C2H5OC2H5 - Pesticide quality or equivalent.
Must be free of peroxides as indicated by test strips (EM Quant, or
equivalent). Procedures 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.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
3650A - 3 Revision 1
July 1992
-------
7.0 PROCEDURE
7.1 Place 10 mL of the solvent extract from a prior extraction procedure
into a 125 mL separatory funnel.
7.2 Add 20 mL of methylene chloride to the separatory funnel.
7.3 Slowly add 20 mL of prechilled organic-free reagent water which has
been previously adjusted to a pH of 12-13 with ION sodium hydroxide.
7.4 Seal and shake the separatory funnel for at least 2 minutes with
periodic venting to release excess pressure.
NOTE: Methylene chloride creates excessive pressure very rapidly;
therefore, initial venting should be done immediately after the
separatory funnel has been sealed and shaken once. The separatory
funnel should be vented into a hood to prevent unnecessary exposure
of the analyst to the organic vapor.
7.5 Allow the organic layer to separate from the aqueous phase for a
minimum of 10 minutes. If the emulsion interface between layers is more than
one-third the size of the solvent layer, the analyst must employ mechanical
techniques to complete the phase separation. The optimum technique depends upon
the sample, and may include stirring, filtration of the emulsion through glass
wool, centrifugation, or other physical methods.
7.6 Separate the aqueous phase and transfer it to a 125 ml Erlenmeyer
flask. Repeat the extraction two more times using 20 mL aliquots of dilute
sodium hydroxide (pH 12-13). Combine the aqueous extracts.
7.7 Water soluble organic acids and phenols will be primarily in the
aqueous phase. Base/neutral analytes will be in the methylene chloride. If the
analytes of interest are only in the aqueous phase, discard the methylene
chloride and proceed to Section 7.8. If the analytes of interest are only in the
methylene chloride, discard the aqueous phase and proceed to Section 7.10.
7.8 Externally cool the 125 ml Erlenmeyer flask with ice while adjusting
the aqueous phase to a pH of 1-2 with sulfuric acid (1:1). Quantitatively
transfer the cool aqueous phase to a clean 125 mL separatory funnel. Add 20 mL
of methylene chloride to the separatory funnel and shake for at least 2 minutes.
Allow the methylene chloride to separate from the aqueous phase and collect the
methylene chloride in an Erlenmeyer flask.
7.9 Add 20 mL of methylene chloride to the separatory funnel and extract
at pH 1-2 a second time. Perform a third extraction in the same manner combining
the extracts in the Erlenmeyer flask.
7.10 Assemble a Kuderna-Danish (K-D) concentrator (if necessary) by
attaching a 10 mL concentrator tube to a 500 mL evaporation flask.
7.11 Dry both acid and base/neutral fractions by passing them through a
drying column containing about 10 cm of anhydrous sodium sulfate. Collect the
dried fractions in K-D concentrators. Rinse the Erlenmeyer flasks which
3650A - 4 Revision 1
July 1992
-------
'contained the solvents and the columns with 20 ml of methylene chloride to
complete the quantitative transfer.
7.12 Concentrate both acid and base/neutral fractions as follows: Add
one or two boiling chips to the flask and attach a three ball macro-Snyder
column. Prewet the Snyder column by adding about 1 ml of methylene chloride to
the top of the column. Place the K-D apparatus on a hot water bath (80-90°C) so
that the concentrator tube is partially immersed in the warm water. Adjust 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.
When the apparent volume of liquid reaches 1 ml, remove the K-D apparatus from
the water bath and allow it to cool. Remove the Snyder column and rinse the
flask and its lower joints into the concentrator tube with 1-2 ml of methylene
chloride. Concentrate the extract to the final volume using either the micro-
Snyder column technique (7.12.1) or nitrogen blowdown technique (7.12.2).
7.12.1 Micro-Snyder Column Technique
7.12.1.1 Add another one or two boiling chips to the
concentrator tube and attach a two ball micro-Snyder column. Prewet
the column by adding 0.5 ml of methylene chloride to the top of the
column. Place the K-D apparatus in a hot water bath (80-90°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 5-10
minutes. 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 cool. Remove the Snyder column and rinse
the flask and its lower joints into the concentrator tube with 0.2
mL of methylene chloride. Adjust the final volume to 1 ml with
methylene chloride.
7.12.2 Nitrogen Blowdown Technique
7.12.2.1 Place the concentrator tube in a warm water bath
(35°C) and evaporate the solvent volume to 1.0-2.0 ml using a gentle
stream of clean, dry nitrogen (filtered through a column of
activated carbon).
CAUTION; Do not use plasticized tubing between the carbon
trap and the sample.
7.12.2.2 The internal wall of the concentrator tube must be
rinsed down several times with the appropriate solvent during the
operation. During evaporation, the tube solvent level must be
positioned to avoid condensation water. Under normal procedures,
the extract must not be allowed to become dry.
CAUTION; When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.13 The acid fraction is now ready for analysis. If the base/neutral
3650A - 5 Revision 1
July 1992
-------
fraction requires further cleanup by the alumina column cleanup for petroleum
waste (Method 3611), the solvent may have to be changed to hexane. If a solvent
exchange is required, momentarily remove the Snyder column, add approximately 5
ml of the exchange solvent and a new boiling chip, and reattach the Snyder
column. Concentrate the extract as described in Section 7.12.1.1, raising the
temperature of the water bath, if necessary, to maintain proper distillation.
When the apparent volume again reaches 1 ml, remove the K-D apparatus from the
water bath and allow it to drain and cool for at least 10 minutes. Repeat the
exchange 2 more times. If no further cleanup of the base/neutral extract is
required, it is also ready for analysis.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for general quality control procedures and
Method 3600 for cleanup procedures.
8.2 The analyst must demonstrate that the compounds of interest are
being quantitatively recovered before applying this method to actual samples.
8.3 For simples that are cleaned using this method, the associated
quality control samples must be processed through this cleanup method.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1- Test Methods; Methods for Organic Chemical Analysis of Municipal and
Industrial Mastewater; U.S. Environmental Protection Agency. Office of
Research and Development. Environmental Monitoring and Support Laboratory.
ORD Publication Offices of Center for Environmental Research Information:
Cincinnati, OH, 1982; EPA-600/4-82-057.
3650A - 6 Revision 1
July 1992
-------
METHOD 3650A
ACID-BASE PARTITION CLEANUP
START
'l I Place extract
or organic liquid
waste into
separator? funnel
7 2 Add methy.ene
chlorida
7.3 Add prechiiled
dilute sodium
? 4 Seal and shake
separate*')' funnel
7 S Allow
separa Iion of
organic layer f r ens
aqueous phase
S Complete phase
separation with
mechanica1
techniques
7 . 6 Tram for
aqueous phase to
flask; repeat
en traction twice;
combine aqueous
BKt racta
7 7 Discard aqueous
phase
Aqueous
7.? Discard o
phase
7.S Adjust pH .ith
sulfunc acid; t rani
far aquaous phaie tc
clean separatory fun
nel; add methylena
chloride; shake,
all01* phase separa-
tion; collect solven
phase in flash
7 10 Assemole K - D
appa ra tus
7 9 Perform 2 more
en tractions•
combine all
atttracts
3650A - 7
Revision 1
July 1992
-------
METHOD 3650A
(Continued)
7 11 Dry extracts,
collec t extracts in
K - D concentrator;
rinse flask wilh
methyletie chloride
? 12 Concentrate
both fractions
a 1 vent
Ana 1y ze
f ra c t i ana by
app r opr LSt te
de te r mma 14. ve
method
3650A - 8
Revision 1
July 1992
-------
METHOD 3660A
SULFUR CLEANUP
1.0 SCOPE AND APPLICATION
1.1 Elemental sulfur is encountered in many sediment samples (generally
specific to different areas in the country), marine algae, and some industrial
wastes. The solubility of sulfur in various solvents is very similar to the
organochlorine and organophosphorus pesticides. Therefore, the sulfur
interference follows along with the pesticides through the normal extraction and
cleanup techniques. In general, sulfur will usually elute entirely in Fraction
1 of the Florisil cleanup (Method 3620).
1.2 Sulfur will be quite evident in gas ehromatograms obtained from
electron capture detectors, flame photometric detectors operated in the sulfur
or phosphorous mode, and Coulson electrolytic conductivity detectors in the
sulfur mode. If the gas ehromatograph is operated at the normal conditions for
pesticide analysis, the sulfur interference can completely mask the region from
the solvent peak through Aldrin.
1.3 Three techniques for the elimination of sulfur are detailed within
this method: (1) the use of copper powder; (2) the use of mercury; and (3) the
use of tetrabutyl ammonium sulfite. Tetrabutylammonium sulfite causes the least
amount of degradation of a broad range of pesticides and organic compounds, while
copper and mercury may degrade organophosphorus and some organochlorine
pesticides.
2.0 SUMMARY OF METHOD
2.1 The sample to undergo cleanup is mixed with either copper, mercury,
or tetrabutylammonium (TBA) sulfite. The mixture is shaken and the extract is
removed from the sulfur cleanup reagent.
3.0 INTERFERENCES
3.1 Removal of sulfur using copper:
3.1.1 The copper must be very reactive. Therefore, all oxides of
copper must be removed so that the copper has a shiny, bright appearance.
3.1.2 The sample extract must be vigorously agitated with the
reactive copper for at least one minute.
4.0 APPARATUS AND MATERIALS
4.1 Mechanical shaker or mixer - Vortex Genie or equivalent.
4.2 Pipets, disposable - Pasteur type.
3660A - 1 Revision 1
July 1992
-------
4.3 Centrifuge tubes, calibrated - 12 ml.
4,4 Glass bottles or vials - 10 ml and 50 mLf with Teflon-lined screw
caps or crimp tops.
4.5 Kuderna-Danish (K-D) apparatus.
4.5,1 Concentrator tube - 10 ml graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.5.2 Evaporation flask - 500 ml (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
4.5.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4.5.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.5.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
5.0 REAGENTS
5.1 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.
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Nitric acid, HNOj, dilute.
5.4 Solvents
5.4.1 Acetone, CH3COCH3 - Pesticide quality or equivalent.
5.4.2 Hexane, C6H14 - Pesticide quality or equivalent.
5.4.3 2-Propanol, CH3CH(OH)CH3 - Pesticide quality or equivalent.
5.5 Copper powder - Remove oxides by treating with dilute nitric acid,
rinse with organic-free reagent water to remove all traces of acid, rinse with
acetone and dry under a stream of nitrogen. (Copper, fine granular Mallinckrodt
4649 or equivalent).
5.6 Mercury, triple distilled.
5.7 Tetrabutylammonium (TBA) sulfite reagent
3660A - 2 Revision 1
July 1992
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5.7.1 Tetrabutylammonium hydrogen sulfate, [CH3(CH2)3]4NHS04.
5.7.2 Sodium sulfite, Na2S03.
5.7.3 Prepare reagent by dissolving 3.39 g tetrabutylammonium
hydrogen sulfate in 100 ml organic-free reagent water. To remove
impurities, extract this solution three times with 20 ml portions of
hexane. Discard the hexane extracts, and add 25 g sodium sulfite to the
water solution. Store the resulting solution, which is saturated with
sodium sulfite, in an amber bottle with a Teflon-lined screw cap. This
solution can be stored at room temperature for at least one month.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Removal of sulfur using copper
7.1.1 Concentrate the sample to exactly 1.0 mL or other known
volume. Perform concentration using the Kuderna-Danish (K-D) Technique
(Method 3510, Sections 7.10.1 through 7.10.4).
CAUTION: When the volume of solvent is reduced below 1 mL,
semi volatile analytes may be lost.
7.1.2 If the sulfur concentration is such that crystallization
occurs, centrifuge to settle the crystals, and carefully draw off the
sample extract with a disposable pipet leaving the excess sulfur in the K-
D tube. Transfer 1.0 mL of the extract to a calibrated centrifuge tube.
7.1.3 Add approximately 2 g of cleaned copper powder (to the 0.5 mL
mark) to the centrifuge tube. Mix for at least 1 min on the mechanical
shaker.
7.1.4 Separate the extract from the copper by drawing off the
extract with a disposable pipet and transfer to a clean vial. The volume
remaining still represents 1.0 mL of extract.
NOTE; This separation is necessary to prevent further degradation of
the pesticides.
7.2 Removal of sulfur using mercury
NOTE; Mercury is a highly toxic metal. All operations involving mercury
should be performed in a hood. Prior to using mercury, it is
recommended that the analyst become acquainted with proper handling
and cleanup techniques associated with this metal.
7.2.1 Concentrate the sample extract to exactly 1.0 mL or other
3660A - 3 Revision 1
July 1992
-------
known volume. Perform concentration using the Kuderna-Danish (K-D)
Technique (Method 3510, Sections 7.10.1 through 7.10.4).
CAUTION: When the volume of solvent is reduced below 1 ml,
semi volatile analytes may be lost.
7.2.2 Pi pet 1.0 ml of the extract into a clean concentrator tube or
Teflon-sealed vial.
7.2.3 Add one to three drops of mercury to the vial and seal.
Agitate the contents of the vial for 15-30 sec. Prolonged shaking (2 hr)
may be required. If so, use a mechanical shaker.
7.2.4 Separate the sample from the mercury by drawing off the
extract with a disposable pipet and transfer to a clean vial.
7.3 Removal of sulfur using TBA sulfite
7.3.1 Concentrate the sample extract to exactly 1.0 ml or other
known volume. Perform concentration using the Kuderna-Danish (K-D)
Technique (Method 3510, Sections 7.10.1 through 7.10.4).
CAUTION: When the volume of solvent is reduced below 1 ml,
semivolatile analytes may be lost.
7.3.2 Transfer 1.0 ml of the extract to a 50 ml clear glass bottle
or vial with a Teflon-lined screw-cap. Rinse the concentrator tube with
1 ml of hexane, adding the rinsings to the 50 ml bottle.
7.3.3 Add 1.0 ml TBA sulfite reagent and 2 ml 2-propanol, cap the
bottle, and shake for at least 1 min. If the sample is colorless or if
the initial color is unchanged, and if clear crystals (precipitated sodium
sulfite) are observed, sufficient sodium sulfite is present. If the
precipitated sodium sulfite disappears, add more crystalline sodium
sulfite in approximately 0.100 g portions until a solid residue remains
after repeated shaking.
7.3.4 Add 5 ml organic free reagent water and shake for at least 1
iin. Allow the sample to stand for 5-10 min. Transfer the hexane layer
(top) to a concentrator tube and concentrate the extract to approximately
1.0 ml with the micro K-D Technique (Section 7.3.5) or the Nitrogen
Slowdown Technique (Section 7.3.6). Record the actual volume of the final
extract.
7.3.5 Micro-Snyder Column Technique
7.3.5.1 Add another one or two clean boiling chips 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 of the
column. Place the K-D apparatus in a hot 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 5-10 minutes. At the
proper rate of distillation the balls of the column will actively
3660A - 4 Revision 1
July 1992
-------
chatter, but the chambers will not flood. When the apparent volume
of liquid reaches 0.5 ml, remove the K-D apparatus from the water
bath and allow it to drain and cool for at least 10 minutes. Remove
the Snyder column and rinse the flask and its lower joints with
about 0.2 ml of solvent and add to the concentrator tube. Adjust
the final volume to approximately 1.0 ml with hexane.
7.3.6 Nitrogen Slowdown Technique
7.3.6.1 Place the concentrator tube in a warm water bath
(approximately 35°C) and evaporate the solvent volume to 1.0-2.0 ml,
using a gentle stream of clean, dry nitrogen (filtered through a
column of activated carbon).
CAUTION: Do not use plasticized tubing between the carbon
trap and the sample.
7.3.6.2 The internal wall of the tube must be rinsed down
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be positioned
to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
operating conditions, the extract should not be allowed to become
dry.
CAUTION: When the volume of solvent is reduced below 1 ml,
semi volatile analytes may be lost.
7.4 Analyze the cleaned up extracts by gas chromatography (see the
determinative methods, Section 4.3 of this chapter).
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3600 for cleanup procedures.
8.2 All reagents should be. checked prior to use to verify that
interferences do not exist.
9.0 METHOD PERFORMANCE
9.1 Table 1 indicates the effect of using copper and mercury to remove
sulfur on the recovery of certain pesticides.
10.0 REFERENCES
1. Loy, E.W., private communication.
2. Goerlitz, D.F. and L.M. Law, Bulletin for Environmental Contamination and
Toxicology, 6, 9 (1971).
3660A - 5 Revision 1
July 1992
-------
3. U.S. EPA Contract Laboratory Program, Statement of Work for Organic
Analysis, Revision, July 1985.
3660A - 6 Revision 1
July 1992
-------
Table 1.
EFFECT OF MERCURY AND COPPER ON PESTICIDES
Percent Recovery8 using:
Pesticide Mercury Copper
Aroclor 1254
Lindane
Heptachlor
Aldrin
Heptachlor epoxide
DDE
DDT
BHC
Dieldrin
Endrin
Chi orobenzi late
Malathion
Diazinon
Parathion
Ethion
Trithion
97.10
75.73
39.84
95.52
69.13
92.07
78.78
81.22
79.11
70.83
7.14
0.00
0.00
0.00
0.00
0.00
104.26
94.83
5.39
93.29
96.55
102.91
85.10
98.08
94.90
89.26
0.00
0.00
0.00
0.00
0.00
0.00
a Percent recoveries cited are averages based on duplicate analyses for all
compounds other than for Aldrin and BHC. For Aldrin, four and three
determinations were averaged to obtain the result for mercury and copper,
respectively. Recovery of BHC using copper is based on one analysis.
3660A - 7 Revision 1
July 1992
-------
METHOD 3660A
SULFUR CLEANUP
7.1.1
Concentrate
sample
extract,
7.1.2
Centrifuge
and draw off
sample
extract -
7,1.2
Transfer
extract to
centrifuge
tub*.
7.2.1
Concentrate
•ample
extract,
7.2.2 Pipat
extract into
concentrator
tube or vial -
7.2.3 Add
mercury,
agitate -
L
7.4.1
Concentrate
•ample
extract.
7.3,2
Transfer
extract to
centrifuge
tube.
7,3.3 Add
TBA-.ulfite
and
2-propanol.
agitate
3660A - 8
Revision 1
July 1992
-------
METHOD 3660A
continued
7
7.1.3 ftdd
copper
powder, mix.
7,2-4
Separate
sample from
mercury,
7.1,4
Separate
extract Irorr
copper.
'7.3-3 Add
more 3odium
sulfite;
shake.
J \nalyze entract
ling appropriate
determinativ
procedure.
3660A - 9
Revision 1
July 1992
-------
-------
METHOD 3665
SULFURIC ACID/PERMANGANATE CLEANUP
1.0 SCOPE AND APPLICATION
1.1 This method is suitable for the rigorous cleanup of sample extracts
prior to analysis for polychlorinated biphenyls. This method should be used
whenever elevated baselines or overly complex chromatograms prevent accurate
quantitation of PCBs. This method cannot be used to cleanup extracts for other
target analytes, as it will destroy most organic chemicals including the
pesticides Aldrin, Dieldrin, Endrin, Endosulfan (I and II), and Endosulfan
sulfate.
2.0 SUMMARY OF METHOD
2.1 An extract is solvent exchanged to hexane, then the hexane is
sequentially treated with (1) concentrated sulfuric acid and, if necessary, (2)
5% aqueous potassium permanganate. Appropriate caution must be taken with these
corrosive reagents.
2,2 Blanks and replicate analysis samples must be subjected to the same
cleanup as the samples associated with them.
2.3 It is important that all the extracts be exchanged to hexane before
initiating the following treatments.
3.0 INTERFERENCES
3.1 This technique will not destroy chlorinated benzenes, chlorinated
naphthalenes (Halowaxes), and a number of chlorinated pesticides.
4.0 APPARATUS
4.1 Syringe or Class A volumetric pipet, glass; 1.0, 2.0 and 5.0 ml.
4.2 Vials - 1, 2 and 10 mL, glass with Teflon lined screw caps or crimp
tops.
4.3 Kuderna-Danish (K-D) apparatus.
4.3.1 Concentrator tube - 10 mL graduated (Kontes K-570050-1025 or
equivalent). A ground glass stopper is used to prevent evaporation of
extracts.
4.3.2 Evaporation flask - 500 mL (Kontes K-570001-500 or
equivalent). Attach to concentrator tube with springs, clamps, or
equivalent.
3665 - 1 Revision 0
September 1994
-------
4.3.3 Snyder column - Three ball macro (Kontes K-503000-0121 or
equivalent).
4,3.4 Snyder column - Two ball micro (Kontes K-569001-0219 or
equivalent).
4.3.5 Springs - 1/2 inch (Kontes K-662750 or equivalent).
4.4 Vortex mixer.
5.0 REAGENTS
5.1 Reagent grade inorganic 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.
5.2 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.3 Sulfuric acid/Water, HjSQ^O, (1:1, v/v).
5.4 Hexane, CeH14 - Pesticide grade or equivalent.
5.5 Potassium permanganate, KMn04, 5 percent aqueous solution (w/v).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes, Sec.
4.1.
7.0 PROCEDURE
7.1 Sulfuric acid cleanup
7,1.1 Using a syringe or a volumetric pipet, transfer 1.0 or 2.0 mL
of the hexane extract to a 10 ml vial and, in a fume hood, carefully add
5 mL of the 1:1 sulfuric acid/water solution.
7.1.2 The volume of hexane extract used depends on the requirements
of the GC autosampler used by the laboratory. If the autosampler
functions reliably with 1 ml of sample volume, 1.0 mL of extract should be
used. If the autosampler requires more than 1 mL of sample volume, 2.0 mL
of extract should be used.
CAUTION: Make sure that there is no exothermic reaction nor
evolution of gas prior to proceeding.
3665 - 2 Revision 0
September 1994
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7.1.3 Cap the vial tightly and vortex for one minute. A vortex must
be visible in the vial.
CAUTION: Stop the vortexing immediately if the vial leaks, AVOID
SKIN CONTACT, SULFURIC ACID BURNS.
7.1.4 Allow the phases to separate for at least 1 minute. Examine
the top (hexane) layer; it should not be highly colored nor should it have
a visible emulsion or cloudiness.
7.1.5 If a clean phase separation is achieved, proceed to
Sec. 7.1.8.
7.1.6 If the hexane layer is colored or the emulsion persists for
several minutes, remove the sulfuric acid layer from the vial and dispose
of it properly. Add another 5 ml of the clean 1:1 sulfuric acid/water.
NOTE: Do not remove any hexane at this stage of the procedure.
7.1.7 Vortex the sample for one minute and allow the phases to
separate.
7.1.8 Transfer the hexane layer to a clean 10 ml vial.
7.1.9 Add an additional 1 ml of hexane to the sulfuric acid layer,
cap and shake. This second extraction is done to ensure quantitative
transfer of the PCBs and Toxaphene.
7.1.10 Remove the second hexane layer and combine with the
hexane from Sec. 7.1.8.
7.2 Permanganate cleanup
7.2.1 Add 5 ml of the 5 percent aqueous potassium permanganate
solution to the combined hexane fractions from 7.1.10.
CAUTION: Make sure that there is no exothermic reaction nor
evolution of gas prior to proceeding.
7.2.2 Cap the vial tightly and vortex for 1 minute. A vortex must
be visible in the vial.
CAUTION: Stop the vortexing immediately if the vial leaks. AVOID
SKIN CONTACT, POTASSIUM PERMANGANATE BURNS.
7.2.3 Allow the phases to separate for at least 1 minute. Examine
the top (hexane) layer, it should not be highly colored nor should it have
a visible emulsion or cloudiness.
7.2.4 If a clean phase separation is achieved, proceed to
Sec. 7.2.7.
3665 - 3 Revision 0
September 1994
-------
7,2.5 If the hexane layer is colored or the emulsion persists for
several minutes, remove the permanganate solution from the vial via a
glass pipette and dispose of it properly. Add another 5 ml of the clean
aqueous permanganate solution.
NOTE: Do not remove any hexane at this stage of the procedure.
7.2.6 Vortex the sample and allow the phases to separate.
7.2.7 Transfer the hexane layer to a clean 10 ml vial.
7.2.8 Add an additional 1 ml of hexane to the permanganate layer,
cap the vial securely and shake. This second extraction is done to ensure
quantitative transfer of the PCBs and Toxaphene..
7.2.9 Remove the second hexane layer and combine with the hexane
from Sec. 7.2.7.
7.3 Final preparation
7.3,1 Reduce the volume of the combined hexane layers to the
original volume (] or 2 ml) using the Kuderna-Oanish Technique
(Sec. 7.3,1.1).
7.3.1.1 Add one or two clean boiling chips to the flask
and attach a three ball Snyder column. Prewet the Snyder column by
adding about 1 mL of hexane to the top of the column. Place the K-D
apparatus on a hot water bath (15-20°C above the boiling point of
the solvent) 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 10-20 minutes. 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 1-2 ml,
remove the K-D apparatus from the water bath and allow it to drain
and cool for at least 10 minutes.
7.3.1.2 Remove the Snyder column and rinse the flask and
its lower joints into the concentrator tube with 1-2 mL of hexane.
The extract may be further concentrated by using either the micro
Snyder column technique (Sec. 7.3.2) or nitrogen blowdown technique
(Sec. 7.3.3).
7.3.2 Micro Snyder Column Technique
7.3.2.1 Add another one or two clean boiling chips 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 of the
column. Place the K-D apparatus in a hot 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 5-10 minutes. At the
3665 - 4 Revision 0
September 1994
-------
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 from the water
bath and allow it to drain and cool for at least 10 minutes. Remove
the Snyder column and rinse the flask and its lower joints with
about 0.2 ml of hexane and add to the concentrator tube. Adjust the
final volume to 1.0-2.0 mL, as required, with hexane.
7.3.3 Nitrogen Slowdown Technique
7.3.3,1 Place the concentrator tube in a warm water bath
(approximately 35°C) and evaporate the solvent volume to the
required level using a gentle stream of clean, dry nitrogen
(filtered through a column of activated carbon).
CAUTION: Do not use plastidzed tubing between the carbon
trap and the sample.
7.3.3.2 The internal wall of the tube must be rinsed down
several times with the appropriate solvent during the operation.
During evaporation, the solvent level in the tube must be positioned
to prevent water from condensing into the sample (i.e., the solvent
level should be below the level of the water bath). Under normal
operating conditions, the extract should not be allowed to become
dry.
7.3.4 Remove any remaining organochlorine pesticides from the
extracts using Florisil Column Cleanup (Method 3620) or Silica Gel Cleanup
(Method 3630).
7.3.5 The extracts obtained may now be analyzed for the target
analytes using the appropriate organic technique(s) (see Sec. 4.3 of this
Chapter). If analysis of the extract will not be performed immediately,
stopper the concentrator tube and store in a refrigerator. If the extract
will be stored longer than 2 days, it should be transferred to a vial with
a Teflon lined screw cap or crimp top, and labeled appropriately.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
9.0 METHOD PERFORMANCE
9.1 No performance data are currently available.
10.0 REFERENCES
None required.
3665 - 5 Revision 0
September 1994
-------
METHOD 3665
SULFURIC ACID/PERMANGANATE CLEANUP
St»rt
7.1.1 Carafullv
combtn* hsxane
with 1:1
H2SO4/H20
solution.
7.1.2
Tran»f»r th«
appropriate
volyntn to
vial.
7.1.3 - 7,1.4
Cap. vortex
and allow
phaaa
ovparetian.
7.1.8
Tranifar
h«x*n« layar
to clean yiei.
7.1.9 Add
haxana to
H2S04 layar,
cap and shake
7.1,10
Combing two
hexana levers.
7.1.6 Remove
and di»po««
H2S04 iclution,
add clean H2SO4
solution.
7.1.7 Cap,
vortsx, and
allow phasa
laparation.
7.2.1 Add
KMn04
sotution.
7.2.2 - 7.2.3
Cap, vort»x,
and allow
phase
separation.
/ 7.2.4 ta \.
f Dh«»« \ to w
t Mpvation )
>. clean? /
JYea
7.
Trai
h«xan
to cla
1
2.7
risfaf
an vni.
f
7.2.8 Add
haxane to
KMnO4 layar.
cap and ahaka.
\
r
7.2.9 Combine
two riaxan*
lay«r».
af
>.
7.2.5 Ramova
and diapote
add clean KMnO4
aolution.
V
7,2.6 Cap
vortex and
taparation.
7.3.1 - 7.3.3
Reduce volumn
using K-D
and/or nitrogen
^r
7.3.4 Ut«
M*tho« 3620 or
Method 3630 to
further remove
contaminant! .
7.3.5 Stopper
ants
refrig*rat«
for fMfthar
analyara.
Stop
3665 - 6
Revision 0
September 1994
-------
• METHOD 4010
SCREENING FOR PENTACHLOROPHENOL BY IMMUNOASSAY
1.0 SCOPE AND APPLICATION
1.1 Method 4010 is a procedure for screening solids such as soils,
sludges, and aqueous media such as waste water and leachates for
pentachlorophenol (PCP) (CAS Registry 87-86-5).
1.2 Method 4010 is recommended for screening samples to determine whether
PCP is likely to be present at concentrations above 0.5 ing/Kg for solids or
0.005 mg/L for aqueous samples. Method 4010 provides an estimate for the
concentration of PCP by comparison with a standard.
1.3 Using the test kits from which this method was developed, 95 % of
aqueous samples containing 2 ppb or less of PCPs will produce a negative result
in the 5 ppb test configuration. Also, 95 % of soil samples containing 125 ppb
or less of PCBs will produce a negative result in the 500 ppb test configuration.
1.4 In cases where the exact concentration of PCP is required, additional
techniques (i.e., gas chromatography (Method 8040} or gas chroraatography/mass
spectrometry (Method 8270)} should be used.
2.0 SUMMARY OF METHOD
2.1 Test kits are commercially available for this method. The
manufacturer's directions should be followed. In general, the method is
performed using a water sample or an extract of a soil sample. Sample and an
enzyme conjugate reagent are added to immobilized antibody. The enzyme conjugate
"competes" with PCP present in the sample for binding to immobilized anti-PCP
antibody. The test is interpreted by comparing the response produced by testing
a sample to the response produced by testing standard(s) simultaneously.
3.0 INTERFERENCES
3.1 Compounds that are chemically similar may cause a positive test (false
positive) for PCP. The test kit used in preparation of this method was evaluated
for interferences. Table 1 provides the concentration of compounds found to give
a false positive test at the indicated concentration.
3.2 Other compounds have been tested for cross reactivity with PCP, and
have been demonstrated to not interfere with the specific kit tested. Consult
the information provided by the manufacturer of the kit used for additional
information regarding cross reactivity with other compounds.
3.3 Storage and use temperatures may modify the method performance. Follow
the manufacturer's directions for storage and use.
4010-1 Revision 0
August 1993
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4.0 APPARATUS AND MATERIALS
4.1 PENTA RISc Test Kits (EnSys, Inc.), or equivalent. Each commercially
available test kit will supply or specify the apparatus and materials necessary
for successful completion of the test.
5.0 REAGENTS
5.1 Each commercially available test kit will supply or specify the
reagents necessary for successful completion of the test.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material to this chapter, Organic Analytes,
Section 4.1.
7.0 PROCEDURE
7.1 Follow the manufacturer's instructions for the test kit being used.
Those test kits used must meet or exceed the performance indicated in Tables 2-3.
8.0 QUALITY CONTROL
8.1 Follow the manufacturer's instructions for the test kit being used for
quality control procedures specific to the test kit used. Additionally, guidance
provided in Chapter One should be followed.
8.Z Use of replicate analyses, particularly when results indicate
concentrations near the action level, is recommended to refine information
gathered with the kit.
8.3 Do not use test kits past their expiration date.
8.4 Do not use tubes or reagents designated for use with other kits.
8.5 Use the test kits within their specified storage temperature and
operating temperature limits.
8.6 Method 4010 is intended for field or laboratory use. The appropriate
level of quality assurance should accompany the application of this method to
document data quality.
9.0 METHOD PERFORMANCE
9.1 This method has been applied to a series of groundwater, process
water, and wastewater samples from industries which use PCP, and the results
compared with 6C/MS determination of PCP (Method 8270). These results are
provided in Table 2. These results represent determinations by two laboratories,
4010-2 Revision 0
August 1993
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9.2 This method has been applied to a series of soils from industries
which use PCP and the results compared with GC/MS determination of PCP via Method
8270. These results are provided in Table 3. These results represent
determinations by two laboratories.
10.0 REFERENCES
1. J.P. Mapes, K.D. McKenzie, L.R. McClelland, S. Movassaghi, R.A. Reddy, R.L.
Allen, and S.B. Friedman, "Rapid, On-Site Screening Test for
Pentachlorophenol in Soil and Water - PENTA-RISc™", Ensys Inc., Research
Triangle Park, NC 27709
2. J.P. Mapes, K.D. McKenzie, L.R.
Allen, and S.B. Friedman,
Pentachlorophenol in Soil".
1992.
McClelland,
S. Movassaghi, R.A. Reddy, R.L.
"PENTA-RISc1" - An On-Site Immunoassay for
Bull. Environ. Contam. Toxicol., 49:334-341,
3. PENTA-RISc M Instructions for Use, Ensys Inc.
4010-3
Revision 0
August 1993
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Table 1
Cross Reactivity for PCPa
Compound
2,6-Dichlorophenol
2,4,6-Trichlorophenol
2, 4, 5-Trichl orophenol
2,3, 4-Tr i chl orophenol
2 , 3 , 5 , 6-Tetrachl orophenol
Tetrachl orohydroqui none
Concentration { nig/Kg }
in Soil to Cause a
False Positive for PCP
at 0.5 mg/Kg
700
16
100
400
1.2
500
Concentration (/ig/L)
in Water to Cause a
False Positive for PCP
at 5 fj.g/1
600
100
500
600
7
>1500
for PENTA RISc Test Kit (EnSys, Inc.)
4010-4
Revision 0
August 1993
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Table 2
Comparison of Immunoasssy" wtth fiC/MS
Water Matrix
Sample Type
grouri<3wster
process water
WHStewater
run-off
!|I
Screening Results (ppm) f| Concentration measured
0.005
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0.35
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2.9
O21
0.17
0.12
0.6
1.4
0.1
0.17
cO-1
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C.U96
0.064
0.086
2.1
0.073
0,026
0.006
0.169
0,239
3.190
0.114
0.3*6
1.1
13
4.3
Does screening test agree with
GC/MS determination?
rto
yes
yes
ires
yes
yes
no
yes
yes
no
yes
yes
yes
yes
yes
yes
yes
yes
no
yes
no
yes
rto
yes
no
no
yes
ye*
yes
ye*
> * screening test Indicates that the sample concentration Is greater than tne test concentration
< - screening test indicates that the sample concentration l& less than the test concentration
* tor PENTA BISe Test KM (EnSys. Inc.)
4010-5
Revision 0
August 1993
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Table 3
Comparison of immunosssay* with SC/MS
Soil Matrix
Screening Results (opm)
0.5
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3
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Coneentration measured fey QC/MS
HDD
se
0.31
D.T2
315
1,5
6.4
3
1.9
4E
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21
3.3
4
11
18
33
54
65
74
63
1.1
14.3
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1.4
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-------
TafileS
Continued
Screening Results {ppm)
0,5
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Concentration measured by GC/MS
117
56
2.5
3.5
143
nd
0,02
5
Does screening test agree wttti
QC/MS determination?
yes
yes
yes
no
yes
yes
yes
yes
> - screening test Indicates that the sample concentretlon is greater tften trie test concentration
< *• screening test indicates tnst the sample concentration is less then the test concentration
* for PENTA RIS£ Test Nt (EnSys. Inc.)
4010-7
Revision 0
August 1993
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METHOD 5030A
PURGE-AND-TRAP
1.0 SCOPE AND APPLICATION
1.1 This method describes sample preparation and extraction for the
analysis of volatile organics by a purge-and-trap procedure. The gas
chromatographic determinative steps are found in Methods 8010, 8015, 8020, 8021
and 8030. Although applicable to Methods 8240 and 8260, the purge-and-trap
procedure is already incorporated into Methods 8240 and 8260.
1.2 Method 5030 can be used for most volatile organic compounds that have
boiling points below 200°C and are insoluble or slightly soluble in water.
Volatile water-soluble compounds can be included in this analytical technique;
however, quantitation limits (by GC or GC/MS) are approximately ten times higher
because of poor purging efficiency. The method is also limited to compounds that
elute as sharp peaks from a GC column packed with graphitized carbon lightly
coated with a carbowax or a coated capillary column. Such compounds include low
molecular weight halogenated hydrocarbons, aromatics, ketones, nitriles,
acetates, acrylates, ethers, and sulfides.
1.3 Water samples can be analyzed directly for volatile organic compounds
by purge-and-trap extraction and gas chromatography. Higher concentrations of
these analytes in water can be determined by direct injection of the sample into
the chromatographic system.
1.4 This method also describes the preparation of water-miscible liquids,
non-water-miscible liquids, solids, wastes, and soils/sediments for analysis by
the purge-and-trap procedure.
2.0 SUMMARY OF METHOD
2.1 The purge-and-trap process: An inert gas is bubbled through the
solution at ambient temperature, and the volatile components are efficiently
transferred from the aqueous phase to the vapor phase. The vapor is swept
through a sorbent column where the volatile components are adsorbed. After
purging is completed, the sorbent column is heated and backflushed with inert gas
to desorb the components onto a gas chromatographic column.
2.2 If the sample introduction technique in Section 2.1 is not
applicable, a portion of the sample is dispersed in methanol to dissolve the
volatile organic constituents. A portion of the methanolic solution is combined
with water in a specially designed purging chamber. It is then analyzed by
purge-and-trap GC following the normal water method.
3.0 INTERFERENCES
3.1 Impurities in the purge gas, and from organic compounds out-gassing
from the plumbing ahead of the trap, account for the majority of contamination
problems. The analytical system must be demonstrated to be free from
5030A - 1 Revision 1
July 1992
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contamination under the conditions of the analysis by running laboratory reagent
blanks. The use of non-TFE plastic coating, non-TFE thread sealants, or flow
controllers with rubber components in the purging device should be avoided.
3.2 Samples can be contaminated by diffusion of volatile organics
(particularly methylene chloride and fluorocarbons) through the septum seal of
the sample vial during shipment and storage. A trip blank prepared from
organic-free reagent water and carried through sampling and handling protocols
serves as a check on such contamination.
3.3 Contamination by carryover can occur whenever high-concentration and
low-concentration samples are analyzed sequentially. Whenever an unusually
concentrated sample is analyzed, it should be followed by an analysis of
organic-free reagent water to check for cross-contamination. The trap and other
parts of the system are subject to contamination. Therefore, frequent bake-out
and purging of the entire system may be required.
3.4 The laboratory where volatile analysis is performed should be
completely free of solvents.
4.0 APPARATUS AND MATERIALS
4.1 Microsyringes - 10 pL, 25 /*L, 100 /iL, 250 /*!., 500 /^L, and 1,000 j*l.
These syringes should be equipped with a 20 gauge (0.006 in ID) needle having a
length sufficient to extend from the sample inlet to within 1 cm of the glass
frit in the purging device. The needle length will depend upon the dimensions
of the purging device employed.
4.2 Syringe valve - Two-way, with Luer ends (three each), if applicable
to the purging device.
4.3 Syringe - 5 ml, gas-tight with shutoff valve.
4.4 Analytical balance - 0.0001 g.
4.5 Top-loading balance - 0.1 g.
4.6 Glass scintillation vials - 20 ml, with screw-caps and Teflon Uners
or glass culture tubes with screw-caps and Teflon liners.
4.7 Volumetric flasks, Class A - 10 ml and 100 ml, with ground-glass
stoppers.
4.8 Vials - 2 ml, for GC autosampler.
4.9 Spatula - Stainless steel.
4.10 Disposable pipets - Pasteur.
4.11 Purge-and-trap device: The purge-and-trap device consists of three
separate pieces of equipment: the sample purger, the trap, and the desorber.
Several complete devices are commercially available.
5030A - 2 Revision 1
July 1992
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4.11.1 The recommended purging chamber is designed to accept 5
ml samples with a water column at least 3 cm deep. The gaseous headspace
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 sample purger, illustrated in Figure 1, meets these design
criteria. Alternate sample purge devices may be used, provided equivalent
performance is demonstrated.
4.11.2 The trap must be at least 25 cm long and have an inside
diameter of at least 0.105 in. Starting from the inlet, the trap must
contain the following amounts of adsorbents: 1/3 of 2,6-diphenylene oxide
polymer, 1/3 of silica gel, and 1/3 of coconut charcoal. It is
recommended that 1.0 cm of methyl silicone-coated packing be inserted at
the inlet to extend the life of the trap (see Figures 2 and 3). If it is
not necessary to analyze for dichlorodifluoromethane or other fluoro-
carbons of similar volatility, the charcoal can be eliminated and the
polymer increased to fill 2/3 of the trap. If only compounds boiling
above 35°C are to be analyzed, both the silica gel and charcoal can be
eliminated and the polymer increased to fill the entire trap. Before
initial use, the trap should be conditioned overnight at 180°C by
backflushing with an inert gas flow of at least 20 mL/min. Vent the trap
effluent to the hood, not to the analytical column. Prior to daily use,
the trap should be conditioned for 10 min at 180°C with backflushing. The
trap may be vented to the analytical column during daily conditioning;
however, the column must be run through the temperature program prior to
analysis of samples.
4.11.3 The desorber should be capable of rapidly heating the
trap to 180°C for desorption. The polymer section of the trap should not
be heated higher than 180°C, and the remaining sections should not exceed
220°C during bake-out mode. The desorber design illustrated in Figures 2
and 3 meet these criteria.
4.11.4 The purge-and-trap device may be assembled as a separate
unit or may be coupled to a gas chromatograph, as shown in Figures 4
and 5.
4.11.5 Trap Packing Materials
4.11.5.1 2,6-Diphenylene oxide polymer - 60/80 mesh,
chromatographic grade (Tenax GC or equivalent).
4.11.5.2 Methyl silicone packing - OV-1 (3%) on
Chromosorb-W, 60/80 mesh or equivalent.
4.11.5.3 Silica gel - 35/60 mesh, Davison, grade 15 or
equivalent.
4.11.5.4 Coconut charcoal - Prepare from Barnebey Cheney,
CA-580-26 lot #M-2649, or equivalent, by crushing through 26 mesh
screen.
5030A - 3 Revision 1
July 1992
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4.12 Heater or heated oil bath - capable of maintaining the purging
chamber to within 1°C, over a temperature range from ambient to 100°C.
5.0 REAGENTS
5.1 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Methanol, CH3OH - Pesticide quality or equivalent. Store away from
other solvents.
5.3 Reagent Tetraglyme - Reagent tetraglyme is defined as tetraglyme in
which interference is not observed at the method detection limit of the compounds
of interest.
5.3.1 Tetraglyme (tetraethylene glycol dimethyl ether, Aldrich #17,
240-5 or equivalent), CgH18Oc. Purify by treatment at reduced pressure in
a rotary evaporator. The tetraglyme should have a peroxide content of
less than 5 ppm as indicated by EM Quant Test Strips (available from
Scientific Products Co., Catalog No. P1126-8 or equivalent).
CAUTION; Glycol ethers are suspected carcinogens. All solvent
handling should be done in a hood while using proper
protective equipment to minimize exposure to liquid and
vapor.
Peroxides may be removed by passing the tetraglyme through a column
of activated alumina. The tetraglyme is placed in a round bottom flask
equipped with a standard taper joint, and the flask is affixed to a rotary
evaporator. The flask is immersed in a water bath at 90-100°C and a vacuum
is maintained at < 10 mm Hg for at least two hours using a two stage
mechanical pump. The vacuum system is equipped with an all glass trap,
which is maintained in a dry ice/methanol bath. Cool the tetraglyme to
ambient temperature and add 100 mg/L of 2,6-di-tert-butyl-4-methyl-phenol
to prevent peroxide formation. Store the tetraglyme in a tightly sealed
screw cap bottle in an area that is not contaminated by solvent vapors.
5.3.2 In order to demonstrate that all interfering volatiles have
been removed from the tetraglyme, an organic-free reagent water/tetraglyme
blank must be analyzed.
5.4 Polyethylene glycol, H(OCH2CH2)nOH. Free of interferences at the
detection limit of the analytes.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Refer to the introductory material to this chapter, Organic Analytes,
Section 4.1. Samples should be stored in capped bottles, with minimum headspace,
at 4°C or less.
5030A - 4 Revision 1
July 1992
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7.0 PROCEDURE
7.1 Initial calibration: Prior to using this introduction technique for
any GC method, the system must be calibrated. General calibration procedures are
discussed in Method 8000, while the specific determinative methods and Method
3500 give details on preparation of standards.
7.1.1 Assemble a purge-and-trap device that meets the specification
in Section 4.10. Condition the trap overnight at 180°C in the purge mode
with an inert gas flow of at least 20 mL/min. Prior to use, condition the
trap daily for 10 min while backflushing at 180°C with the column at 220°C.
7.1.2 Connect the purge-and-trap device to a gas chromatograph.
7.1.3 Prepare the final solutions containing the required
concentrations of calibration standards, including surrogate standards,
directly in the purging device. Add 5.0 ml of organic-free reagent water
to the purging device. The organic-free reagent water is added to the
purging device using a 5 ml glass syringe fitted with a 15 cm 20-gauge
needle. The needle is inserted through the sample inlet shown in
Figure 1. The internal diameter of the 14-gauge needle that forms the
sample inlet will permit insertion of the 20-gauge needle. Next, using a
10 /iL or 25 /xL micro-syringe equipped with a long needle (Section 4.1),
take a volume of the secondary dilution solution containing appropriate
concentrations of the calibration standards. Add the aliquot of
calibration solution directly to the organic-free reagent water in the
purging device by inserting the needle through the sample inlet. When
discharging the contents of the micro-syringe, be sure that the end of the
syringe needle is well beneath the surface of the organic-free reagent
water. Similarly, add 10 /xL of the internal standard solution. Close the
2-way syringe valve at the sample inlet.
7.1.4 Carry out the purge-and-trap analysis procedure using the
specific conditions given in Table 1.
7.1.5 Calculate response factors or calibration factors for each
analyte of interest using the procedure described in Method 8000.
7.1.6 The average RF must be calculated for each compound. A system
performance check should be made before this calibration curve is used.
If the purge-and-trap procedure is used with Method 8010, the following
five compounds are checked for a minimum average response factor:
chloromethane; 1,1-dichloroethane; bromoform; 1,1,2,2-tetrachloroethane;
and chlorobenzene. The minimum acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform). These compounds typically have RFs
of 0.4-0.6, and are used to check compound stability and to check for
degradation caused by contaminated lines or active sites in the system.
Examples of these occurrences are:
7.1.6.1 Chloromethane: This compound is the most likely
compound to be lost if the purge flow is too fast.
7.1.6.2 Bromoform: This compound is one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
5030A - 5 Revision 1
July 1992
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Cold spots and/or active sites in the transfer lines may adversely
affect response.
7.1.6.3 Tetrachloroethane and 1,1-dichloroethane: These
compounds are degraded by contaminated transfer lines in purge-and-
trap systems and/or active sites in trapping materials.
7.2 On-going calibration: Refer to Method 8000 for details on continuing
calibration.
7.3 Sample preparation
7.3.1 Water samples
7.3.1.1 Screening of the sample prior to purge-and-trap
analysis will provide guidance on whether sample dilution is
necessary and will prevent contamination of the purge-and-trap
system. Two screening techniques that can be utilized are: the use
of an automated headspace sampler (modified Method 3810), interfaced
to a gas chromatograph (GC), equipped with a photo ionization
detector (PID), in series with an electrolytic conductivity detector
(HECD); and extraction of the sample with hexadecane (Method 3820)
and analysis of the extract on a GC with a FID and/or an ECD.
7.3.1.2 All samples and standard solutions must be allowed
to warm to ambient temperature before analysis.
7.3.1.3 Assemble the purge-and-trap device. The operating
conditions for the GC are given in Section 7.0 of the specific
determinative method to be employed.
7.3.1.4 Daily GC calibration criteria must be met (Method
8000) before analyzing samples.
7.3.1.5 Adjust the purge gas flow rate (nitrogen or
helium) to that shown in Table 1, on the purge-and-trap device.
Optimize the flow rate to provide the best response for
chloromethane and bromoform, if these compounds are analytes.
Excessive flow rate reduces chloromethane response, whereas
insufficient flow reduces bromoform response.
7.3.1.6 Remove the plunger from a 5 ml syringe and attach
a closed syringe valve. Open the sample or standard bottle, which
has been allowed to come to ambient temperature, 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. This process of taking an aliquot destroys the
validity of the liquid sample for future analysis; therefore, if
there is only one VOA vial, the analyst should fill a second syringe
at this time to protect against possible loss of sample integrity.
This second sample is maintained only until such time when the
analyst has determined that the first sample has been analyzed
properly. Filling one 20 ml syringe would allow the use of only one
5030A - 6 Revision 1
July 1992
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syringe. If a second analysis is needed from a syringe, it must be
analyzed within 24 hr. Care must be taken to prevent air from
leaking into the syringe.
7,3,1.7 The following procedure is appropriate for
diluting purgeable samples. All steps must be performed without
delays until the diluted sample is in a gas-tight syringe.
7.3.1.7.1 Dilutions may be made in volumetric flasks
(10 mL to 100 ml). Select the volumetric flask that will
allow for the necessary dilution. Intermediate dilutions may
be necessary for extremely large dilutions.
7.3.1.7.2 Calculate the approximate volume of
organic-free reagent water to be added to the volumetric flask
selected and add slightly less than this quantity of organic-
free reagent water to the flask.
7.3.1.7.3 Inject the proper aliquot of samples from
the syringe prepared in Section 7.3.1.5 into the flask.
Aliquots of less than 1 ml are not recommended. Dilute the
sample to the mark with organic-free reagent water. Cap the
flask, invert, and shake three times. Repeat the above
procedure for additional dilutions.
7.3.1.7.4 Fill a I ml syringe with the diluted sample
as in Section 7.3.1.5.
7.3.1.8 Add 10.0 pi of surrogate spiking solution (found
in each determinative method, Section 5.0) and, if applicable, 10 /*L
of internal standard spiking solution through the valve bore of the
syringe; then close the valve. The surrogate and internal standards
may be mixed and added as a single spiking solution. Matrix spiking
solutions, if indicated, should be added (10 juL) to the sample at
this time.
7.3.1.9 Attach 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.
7.3.1.10 Close both valves and purge the^sample for the
time and at the temperature specified in Table 1.
7.3.1.11 At the conclusion of the purge time, attach the
trap to the chromatograph, adjust the device to the desorb mode, and
begin the gas chromatographic temperature program and GC data
acquisition. Concurrently, introduce the trapped materials to the
gas chromatographic column by rapidly heating the trap to 180°C
while backflushing the trap with inert gas between 20 and 60 mL/min
for the time specified in Table 1.
7.3.1.12 While the trap is being desorbed into the gas
chromatograph, empty the purging chamber. Wash the chamber with a
minimum of two 5 ml flushes of organic-free reagent water (or
5030A - 7 Revision 1
July 1992
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methanol followed by organic-free reagent water) to avoid carryover
of pollutant compounds into subsequent analyses.
7.3.1.13 After desorbing the sample, recondition the trap
by returning the purge-and-trap device to the purge mode. Wait 15
sec; 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 for Methods 8010, 8020, 8021, 8240 and 8260 and 210°C for
Methods 8015 and 8030. Trap temperatures up to 220°C may be
employed. However, the higher temperatures will shorten the useful
life of the trap. After approximately 7 min, 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.
7.3.1.14 If the initial analysis of a sample or a dilution
of the sample has a concentration of analytes that exceeds the
initial calibration range, the sample must be reanalyzed at a higher
dilution. When a sample is analyzed that has saturated response
from a compound, this analysis must be followed by a blank organic-
free reagent water analysis. If the blank analysis is not free of
interferences, the system must be decontaminated. Sample analysis
may not resume until a blank can be analyzed that is free of
interferences.
7.3.1.15 All dilutions should keep the response of the
major constituents (previously saturated peaks) in the upper half of
the linear range of the curve. Proceed to Method 8000 and the
specific determinative method for details on calculating analyte
response.
7.3.2 Water-miscible liquids:
7.3.2.1 Water-miscible liquids are analyzed as water
samples after first diluting them at least 50-fold with organic-free
reagent water.
7.3.2.2 Initial and serial dilutions can be prepared by
pipetting 2 ml of the sample into a 100 ml volumetric flask and
diluting to volume with organic-free reagent water. Transfer
immediately to a 5 mL gas-tight syringe.
7.3.2.3 Alternatively, prepare dilutions directly in a 5
ml syringe filled with organic-free reagent water by adding at least
20 jut, but not more than 100 juL of liquid sample. The sample is
ready for addition of surrogate and, if applicable, internal and
matrix spiking standards.
7.3.3 Sediment/soil and waste samples: It is highly recommended
that all samples of this type be screened prior to the purge-and-trap GC
analysis. These samples may contain percent quantities of purgeable
organics that will contaminate the purge-and-trap system, and require
extensive cleanup and instrument downtime. See Section 7.3.1.1 for
recommended screening techniques. Use the screening data to determine
whether to use the low-concentration method (0.005-1 mg/kg) or the high-
5030A - 8 Revision 1
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concentration method (>1 mg/kg).
7.3.3.1 Low-concentration method: This is designed for
samples containing individual purgeable compounds of <1 mg/kg. It
is limited to sediment/soil samples and waste that is of a similar
consistency (granular and porous). The low-concentration method is
based on purging a heated sediment/soil sample mixed with
organic-free reagent water containing the surrogate and, if
applicable, internal and matrix spiking standards. Analyze all
reagent blanks and standards under the same conditions as the
samples.
7.3.3.1.1 Use a 5 g sample if the expected
concentration is <0.1 mg/kg or a 1 g sample for expected
concentrations between 0.1 and 1 mg/kg.
7.3.3.1.2 The GC system should be set up as in
Section 7.0 of the specific determinative method. This should
be done prior to the preparation of the sample to avoid loss
of volatiles from standards and samples. A heated purge
calibration curve must be prepared and used for the
quantitation of all samples analyzed with the low-
concentration method. Follow the initial and daily
calibration instructions, except for the addition of a 40°C
purge temperature for Methods 8010, 8020, and 8021.
7.3.3.1.3 Remove the plunger from a 5 ml Luerlock type
syringe equipped with a syringe valve and fill until
overflowing with organic-free reagent water. Replace the
plunger and compress the reagent water to vent trapped air.
Adjust the volume to 5.0 ml. Add 10 pi each of surrogate
spiking solution and internal standard solution to the syringe
through the valve. (Surrogate spiking solution and internal
standard solution may be mixed together.) Matrix spiking
solutions, if indicated, should be added (10 jiL) to the sample
at this time.
7.3.3.1.4 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. Weigh the
amount determined in Section 7.3.3.1.1 into a tared purge
device. Note and record the actual weight to the nearest 0.1
9-
7.3.3.1.5 Determination of sample % dry weight - In
certain cases, sample results are desired based on dry weight
basis. When such data is desired, a portion of sample for
this determination should be weighed out at the same time as
the portion used for analytical determination.
WARNING: The drying oven should be contained in a
hood or vented. Significant laboratory
contamination may result from a heavily
5030A - 9 Revision 1
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contaminated hazardous waste sample.
7.3.3.1.5.1 Immediately after weighing the sample
for extraction, weigh 5-10 g of the sample into a tared
crucible. Determine the % dry weight of the sample by
drying overnight at 105°C. Allow to cool in a
desiccator before weighing:
% dry weight = g of dry sample x 100
g of sample
7.3.3.1.6 Add the spiked organic-free reagent water to
the purge device, which contains the weighed amount of sample,
and connect the device to the purge-and-trap system.
NOTE: Prior to the attachment of the purge device,
Sections 7.3,3.1.4 and 7.3,3.1.6 must be
performed rapidly and without interruption to
avoid loss of volatile organics. These steps
must be performed 1n a laboratory free of solvent
fumes.
7.3.3.1.7 Heat the sample to 40°C + 1°C (Methods 8010,
8020 and 8021) or to 85°C ± 26C (Methods~8015 and 8030} and
purge the sample for the time shown in Table 1.
7.3.3.1.8 Proceed with the analysis as outlined in
Sections 7.3.1.11-7.3.1.15. Use 5 ml of the same organic-free
reagent water as in the reagent blank. If saturated peaks
occurred or would occur if a 1 g sample were analyzed, the
high-concentration method must be followed.
7.3.3.1.9 For matrix spike analysis of
low-concentration sediment/soils, add 10 nL of the matrix
spike solution to 5 ml of organic-free reagent water (Section
7.3.3.1.3 ). The concentration for a 5 g sample would be
equivalent to 50 ng/kg of each matrix spike standard.
7.3.3.2 High-concentration method: The method is based on
extracting the sediment/soil with methanol. A waste sample is
either extracted or diluted, depending on its solubility in
methanol. Wastes (i.e. petroleum and coke wastes) that are
insoluble in methanol are diluted with reagent tetraglyme or
polyethylene glycol (PEG). An aliquot of the extract is added to
organic-free reagent water containing surrogate and, if applicable,
internal and matrix spiking standards. This is purged at the
temperatures indicated in Table 1. All samples with an expected
concentration of >1.0 mg/kg should be analyzed by this method.
7.3.3.2.1 The sample (for volatile organics) consists
of the entire contents of the sample container. Do not
discard any supernatant liquids. Mix the contents of the
sample container with a narrow metal spatula. For
sediment/soil and waste that are insoluble in methanol, weigh
5030A - 10 Revision 1
July 1992
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4 g (wet weight) of sample into a tared 20 ml vial. Use a
top-loading balance. Note and record the actual weight to 0.1
gram and determine the percent dry weight of the sample using
the procedure in Section 7.3.3.1.5. For waste that is soluble
in methanol, tetraglyme, or PEG, weigh 1 g (wet weight) into
a tared scintillation vial or culture tube or a 10 ml
volumetric flask. (If a vial or tube is used, it must be
calibrated prior to use. Pipet 10.0 ml of methanol into the
vial and mark the bottom of the meniscus. Discard this
solvent.)
7.3.3.2.2 For sediment/soil or solid waste, quickly
add 9.0 ml of appropriate solvent; then add 1.0 ml of the
surrogate spiking solution to the vial. For a solvent
miscible sample, dilute the sample to 10 ml with the
appropriate solvent after adding 1.0 ml of the surrogate
spiking solution. Cap and shake for 2 min.
NOTE: Sections 7.3.3.2.1 and 7.3.3.2.2 must be
performed rapidly and without interruption to
avoid loss of volatile organics. These steps
must be performed in a laboratory free from
solvent fumes.
7.3.3.2.3 Pipet approximately 1 ml of the extract into
a GC vial for storage, using a disposable pipet. The
remainder may be discarded. Transfer approximately 1 ml of
reagent methanol to a separate 6C vial for use as the method
blank for each set of samples. These extracts may be stored
at 4°C in the dark, prior to analysis.
7.3.3.2.4 The GC system should be set up as in
Section 7.0 of the specific determinative method. This should
be done prior to the addition of the methanol extract to
organic-free reagent water.
7.3.3.2.5 Table 2 can be used to determine the volume
of methanol extract to add to the 5 ml of organic-free reagent
water for analysis. If a screening procedure was followed,
use the estimated concentration to determine the appropriate
volume. Otherwise, estimate the concentration range of the
sample from the low-concentration analysis to determine the
appropriate volume. If the sample was submitted as a high-
concentration sample, start with 100 juL. All dilutions must
keep the response of the major constituents (previously
saturated peaks) in the upper half of the linear range of the
curve.
7.3.3,2.6 Remove the plunger from a 5.0 ml Luerlock
type syringe equipped with a syringe valve and fill until
overflowing with organic-free reagent water. Replace the
plunger and compress the water to vent trapped air. Adjust
the volume to 4.9 ml. Pull the plunger back to 5.0 ml to
allow volume for the addition of the sample extract and of
5030A - 11 Revision 1
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standards. Add 10 pL of Internal standard solution. Also add
the volume of methanol extract determined in Section 7.3.3.2.5
and a volume of methanol solvent to total 100 nl (excluding
methanol in standards).
7.3.3.2.7 Attach the syringe-syringe valve assembly to
the syringe valve on the purging device. Open the syringe
valve and inject the water/methanol sample into the purging
chamber.
7.3.3.2.8 Proceed with the analysis as outlined in the
specific determinative method. Analyze all reagent blanks on
the same instrument as that used for the samples. The
standards and blanks should also contain 100 juL of methanol
to simulate the sample conditions.
7.3.3.2.9 For a matrix spike in the high-concentration
sediment/soil samples, add 8.0 ml of methanol, 1.0 ml of
surrogate spike solution and 1.0 ml of matrix spike solution.
Add a 100 £iL aliquot of this extract to 5 ml of water for
purging (as per Section 7.3.3.2.6).
7.4 Sample analysis:
7.4.1 The samples prepared by this method may be analyzed by Methods
8010, 8015, 8020, 8021, 8030, 8240, and 8260. Refer to these methods for
appropriate analysis conditions.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 3500 for sample preparation procedures.
8.2 Before processing any samples, the analyst should demonstrate through
the analysis of a calibration blank that all glassware and reagents are
interference free. Each time a set of samples is extracted, or there is a change
in reagents, a method blank should be processed as a safeguard against chronic
laboratory contamination. The blanks should be carried through all stages of
the sample preparation and measurement.
8.3 Standard quality assurance practices should be used with this method.
Field duplicates should be collected to validate the precision of the sampling
technique. Laboratory replicates should be analyzed to validate the precision
of the analysis. Spiked samples should be carried through all stages of sample
preparation and measurement; they should be analyzed to validate the sensitivity
and accuracy of the analysis. If the spiked samples do not indicate sufficient
sensitivity to detect < 1 ng/g of the analytes in the sample, then the
sensitivity of the instrument should be increased, or the sample should be
subjected to additional cleanup.
5030A - 12 Revision 1
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9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
10.0 REFERENCES
1. U.S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for the
Analysis of Pollutants Under the Clean Water Act; Final Rule and Interim
Final Rule and Proposed Rule," October 26, 1984.
5030A - 13 Revision 1
July 1992
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TABLE 1
PURGE-AND-TRAP OPERATING PARAMETERS
Analysis Method
8010
8015
8020/8021
8030
Purge gas
Purge gas flow rate
(mL/min)
Purge time (min)
Purge temperature (°C)
Desorb temperature (°C)
Backflush inert gas flow
(mL/min)
Desorb time (min)
Nitrogen or Nitrogen or
Heli urn
40
11.0 ± 0,1
Ambient
180
20-60
4
Helium
20
15.0 ± 0.1
85 + 2
180
20-60
1.5
Nitrogen or Nitrogen or
Helium Helium
40
11.0 ± 0.1
Ambient
180
20-60
4
20
15.0 ± 0.1
85 ± 2
180
20-60
1.5
5030A - 14
Revision 1
July 1992
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TABLE 2
QUANTITY OF METHANOL EXTRACT REQUIRED FOR ANALYSIS OF
HIGH-CONCENTRATION SOILS/SEDIMENTS
Approximate Volume of
Concentration Range Methanol Extract8
500-10,000 pg/kg 100 pi
1,000-20,000 pg/kg SO ^L
5,000-100,000 ng/kg 10 j*L
25,000-500,000 ^9/kg 100 nl of 1/50 dilution b
Calculate appropriate dilution factor for concentrations exceeding this table,
aThe volume of methanol added to 5 mL of water being purged should be kept
constant. Therefore, add to the 5 mL syringe whatever volume of methanol is
necessary to maintain a volume of 100 j*L added to the syringe.
Dilute an aliquot of the methanol extract and then take 100 pi for analysis.
5030A - 15 Revision 1
July 1992
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Figure 1
Purging Chamber
OPTIONAL
FOAM TRAP
Inch O. D. Ixit
Into '4 Inch 0. 0.
Inttt
2-Way Synnot V«l*
17 cm. 20 Gcuot tynng*
6 mm 0. 0. ftubbtr Stptum
-IflmmO. D.
Inltt
)4 Inch 0. 0.
1'16lnct»0 D.
St*ml«u SIM:
Flow Control
Midium N»MHV
5030A - 16
Revision 1
July 1992
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Figure 2
Trap Packing and Construction for Method 8010
Procfdura
Construction
QiMiWool 8 mm I
Activattd
Charcoal
f
7.7 em
Grada IS
Sitic* 6*i
7.7 em
Tw>a» 7.7 em
3%OV-1
QlauWooi
>
ftttiittnct
Wirt Wr §pp«d
Solid
(Ooubtt Ljytr)
78/Foot +•
Rftiftanca
Wira Wrapptd
Solid
Lavt r)
• em
Comprwiion
Pining Nut
•nd P*rrult«
Thtrmoeouplt/
Controllfr
Sfnsor
ElKtronie
Control and
Pyromtttr
Tubing 25 em
0 105 In. 1,0,
0.125 In. 0.0
St»ml«« Stni
Trap Inlet
5030A - 17
Revision 1
July 1992
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Figure 3
Trap Packing and Construction for Methods 8020 and 8030
Picking Procedure
Construction
Glau Wool 5 mm
3% OV-1 1 cm ;;
Gf«i Wool 5 mm
%
I
k
i
Ttnax 23 cm
i
fej
Comprtsiion Pining Nut
•nd Ferrule*
14 Ft. 7fl/Foot Rtsittanc*
Wirt WnpBtd Solid
Th«rmocoupl«/Controll«r Senior
Eltctronic
Temperature
Control and
Pyromtttr
Tubing 25 cm
0.105 In. I.D.
0,125 In. O.D.
Stiinlen Stttl
T«p Inltt
5030A - 18
Revision 1
July 1992
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Figure 4
Purge-and-Trap System
Purge-Sorb Mode
For Method 8010, 8020, and 8030
CARRIER GAS
FLOW CONTROL
PRESSURE
REGULATOR
OPTIONAL *PORT COLUMN
SELECTION VALVE
PURGE OAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
UOUIO INJECTION PORTS
COLUMN OVEN
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
TRAP INLET
22*C
PURGING
DEVICE
NOTE
ALL LINES BETWEEN TRAP
AND GC SHOULD BE HEATED
TO«0*C
5030A - 19
Revision 1
July 1992
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Figure 5
Purge-and-Trap System
Desorb Mode
For Method 8010, 8020, and 8030
CAPMERGAS
FLOW CONTROL
PRESSURE
REGULATOR
UOWO INJECTION PORTS
COLUMN OVEN
OPTIONAL tPORT COLUMN
SELECTION VALVE
CONFIRMATORY COLUMN
TO DETECTOR
ANALYTICAL COLUMN
PURGE OAS
FLOW CONTROL
13X MOLECULAR
SIEVE FILTER
PURGING
DEVICE
NOTE
ALL LINES BETWEEN TRAP
AND GC SHOULD BE HEATED
TO WC.
5030A - 20
Revision 1
July 1992
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METHOD 5030A
PURGE-AND-TRAP
Start
7.1 Calibrate
CC system.
7.1.2 Assemble
purge-and-trap
device and
condilion trap.
7.1.2 Connect
t o gas
chromatograph.
71.3 Prepare
final
solutions.
7.1.4 Corry out
purge-and- trap
analysis.
7.1.5 Calculate
response or
calibration factors
for each analyte
(Method 8000) .
7.1.6
Calcula te
averafe RF
for each
compound ,
7
5030A - 21
Revision 1
July 1992
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METHOD 5030A
continued
7.3.3.1
Prepara
samples and
set-up CC
system.
7,3.3.1.4
Heigh sample
into tarad
davica.
7
Low concentration
Soil/sediment
High concentrati
Soil/sediment
7.3.3.1.5
Heigh anothar
sample and
datarmina %
dry Height.
7.3 3.1.6 Add
spiked raagant
water, connact
davica to
sys tarn .
7,3.3.1.7
Haat and
purga sample
7.3.1 Scraan
«ampla« prior to
purga-and-trap
analyaia, dilute
•atar miicibla
liquid*
7.3.1 Prapara
*ampl« and
purg-and- trap
davica.
7.3.1.7
Diluta
purgaabla
aamplaa .
7.3.1.8 Add
•urrogata and
intarnal spiking
aolutiona (if
indicated)
/
7
7.3.3.2 Add
ntethetnol
eHtract to
reagent water
for ana lysis .
7332 Set
up CC aystem.
7.33,26 Fill
syringe with
reagent water ,
vent air and
ad jua t vol ume .
7 3326 Add
internal
a tandard . and
methanol
extract
Analyze
acco rding to
determinative
method
7319
Injact aampla
into chamber,
purge
7 3.1.11
Deiorb trap
into CC.
7.3.1 13
Recondition
trap and
start gas
flow
7.3.1.13 Stop
gas flow and
cool trap for
next sample
Analyze
according to
determinative
method .
5030A - 22
Revision 1
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METHOD 5040A
ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN (VOST):
GAS CHROMATOGRAPHV/MASS SPECTROMETRY TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 Method 5040 was formerly Method 3720 in the Second Edition of this
manual.
1,2 This method covers the determination of volatile principal organic
hazardous constituents (POHCs), collected on Tenax and Tenax/charcoal sorbent
cartridges using a volatile organic sampling train, VOST (1), Much of the
description for purge-and-trap GC/MS analysis is described in Method 8240 of this
chapter. Because the majority of gas streams sampled using VOST will contain a
high concentration of water, the analytical method is based on the quantitative
thermal desorption of volatile POHCs from the Tenax and Tenax/charcoal traps and
analysis by purge-and-trap GC/MS. For the purposes of definition, volatile POHCs
are those POHCs with boiling points less than 100°C.
1.3 This method is applicable to the analysis of Tenax and Tenax/
charcoal cartridges used to collect volatile POHCs from wet stack gas effluents
from hazardous waste incinerators.
1.4 The sensitivity of the analytical method for a particular volatile
POHC depends on the level of interferences and the presence of detectable levels
of volatile POHCs in blanks. The desired target detection limit of the
analytical method is 0.1 ng/L (20 ng on a single pair of traps) for a particular
volatile POHC desorbed from either a single pair of Tenax and Tenax/charcoal
cartridges or by thermal desorption of up to six pairs of traps onto a single
pair of Tenax and Tenax/charcoal traps. The resulting single pair of traps is
then thermally desorbed and analyzed by purge-and-trap GC/MS.
1.5 This method is recommended for use only by experienced mass
spectroscopists or under the close supervision of such qualified persons.
2.0 SUMMARY OF METHOD
2.1 A schematic diagram of the analytical system is shown in Figure 1.
The contents of the sorbent cartridges are spiked with an internal standard and
thermally desorbed for 10 min at 180°C with organic-free nitrogen or helium gas
(at a flow rate of 40 mL/min), bubbled through 5 ml of organic-free reagent
water, and trapped on an analytical adsorbent trap. After the 10 min.
desorption, the analytical adsorbent trap is rapidly heated to 180°C, with the
carrier gas flow reversed so that the effluent flow from the analytical trap is
directed into the GC/MS. The volatile POHCs are separated by temperature
programmed gas ehromatography and detected by low-resolution mass spectrometry.
The concentrations of volatile POHCs are calculated using the internal standard
technique.
5040A - 1 Revision 1
September 1994
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3.0 INTERFERENCES
3.1 Refer to Methods 3500 and 3240.
APPARATUS AND MATERIALS
4,1 Thermal desorption unit:
4.1.1 The thermal desorption unit (for Inside/Inside VOST
cartridges, use Supelco "clamshell" heater; for Inside/Outside VOST
cartridges, user-fabricated unit is required) should be capable of
thermally desorbing the sorbent resin tubes. It should also be capable of
heating the tubes to 180 ± 10°C with flow of organic-free nitrogen or
helium through the tubes.
4.2 Purge-and-trap unit:
4.2.1 The purge-and-trap unit consists of three separate pieces of
equipment: the sample purger, trap, and the desorber. It should be
capable of meeting all requirements of Method 5030 for analysis of
purgeable organic compounds from water.
4.3 GC/MS system: As described in Method 8240.
5.0 REAGENTS
5.1 Organic-free reagent water. All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2 Methanol, CH3OH - Pesticide grade, or equivalent.
5.3 Analytical trap reagents:
5.3.1 2,6-Diphenylene oxide polymer: Tenax (60/80 mesh), chrornato-
graphic grade or equivalent.
5.3.2 Methyl silicone packing: 3% OV-1 on Chromosorb W (60/80 mesh)
or equivalent.
5.3.3 Silica gel: Davison Chemical (35/00 mesh), Grade 15, or
equivalent.
5.3.4 Charcoal: Petroleum-based (SKC Lot 104 or equivalent).
5.4 Stock standard solution:
5.4.1 Stock standard solutions will be prepared from pure standard
materials or purchased as certified solutions. The stock standards should
be prepared 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
5040A - 2 Revision 1
September 1994
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gas respirator should be used when the analyst handles high concentrations
of such materials.
5.4.2 Fresh stock standards should be prepared weekly for volatile
POHCs with boiling points of <35°C. All other standards must be replaced
monthly, or sooner if comparison with check standards indicates a problem.
5.5 Secondary dilution standards:
5.5.1 Using stock standard solutions, prepare, in rnethanol,
secondary dilution standards that contain the compounds of interest,
either singly or mixed together. The secondary dilution standards should
be prepared at concentrations such that the desorbed calibration standards
will bracket the working range of the analytical system.
5.6 4-Bromofluorobenzene (BFB) standard:
5.6.1 Prepare a 25 ng/juL solution of BFB in methanol.
5.7 Deuterated benzene:
5.7.1 Prepare a 25 ng/^L solution of benzene-d6 in methanol,
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Refer to Method 0030, Chapter Ten.
6.2 Sample trains obtained from the VOST should be analyzed within 2-6
weeks of sample collection.
7.0 PROCEDURE
7.1 Assembly of PTD device:
7.1.1 Assemble a purge-and-trap desorption device (PTD) that meets
all the requirements of Method 5030 (refer to Figure 1).
7.1.2 Connect the thermal desorption device to the PTD device.
Calibrate the PTD-SC/MS system using the internal standard technique.
7.2 Internal standard calibration procedure:
7.2.1 This approach requires the use of deuterated benzene as the
internal standard for these analyses. Other internal standards may be
proposed for use in certain situations. The important criteria for
choosing a particular compound as an internal standard are that it be
similar in analytical behavior to the compounds of interest and that it
can be demonstrated that the measurement of the internal standard be
unaffected by method or matrix interferences. Other internal standards
that have been used are ethylbenzene-d10 and, l-2-dichloroethane-d4. One
adds 50 ng of BFB to all sorbent cartridges (in addition to one or more
5040A - 3 Revision 1
September 1994
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internal standards) to provide continuous monitoring of the GC/MS
performance relative to BFB.
7.2.2 Prepare calibration standards at a minimum of three
concentration levels for each analyte of interest.
7.2.3 The calibration standards are prepared by spiking a blank
Tenax or Tenax/charcoal trap with a methanolic solution of the calibration
standards (including 50 ng of the internal standard, such as deuterated
benzene), using the flash evaporation technique. The flash evaporation
technique requires filling the needle of a 5.0 /iL syringe with clean
methanol and drawing air into the syringe to the 1.0 ^tL mark. This is
followed by drawing a methanolic solution of the calibration standards
(containing 25 M9//"L of the internal standard) to the 2.0 juL mark. The
glass traps should be attached to the injection port of a gas
chromatograph while maintaining the injector temperature at 160°C. The
carrier gas flow through the traps should be maintained at about 50
mL/min.
7.2.4 After directing the gas flow through the trap, the contents of
the syringe should be slowly expelled through the gas chromatograph
injection port over about 15 sec. After 25 sec have elapsed, the gas flow
through the trap should be shut off, the syringe removed, and the trap
analyzed by the PTD-GC/MS procedure outlined in Hethod 8240, The total
flow of gas through the traps during addition of calibration standards to
blank cartridges, or internal standards to sample cartridges, should be 25
ml or less.
7.2.5 Analyze each calibration standard for both Tenax and Tenax/
charcoal cartridges according to Section 7.3, Tabulate the area response
of the characteristic ions of each analyte against the concentration of
the internal standard and calculate the response factor (RF) for each
compound, using Equation 1.
RF = ASC1S/AISCS (1)
where:
A,. = Area of the characteristic ion for the analyte to be
measured.
AJS = Area of the characteristic ion for the internal
standard.
Cjs = Amount (ng) of the internal standard.
Cs = Amount {ng) of the volatile POHC in calibration
standard.
If the RF value over the working range is a constant (<10% RSD), the
RF can be ^ sumed 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, As/Ais versus RF.
5040A - 4 Revision 1
September 1994
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7.2.6 The working calibration curve or RF must be verified on each
working day by the measurement of one or more of the calibration
standards. If the response varies by more than ±25% for any analyte, a
new calibration standard must be prepared and analyzed for that analyte.
7.3 The schematic of the PTD-GC/MS system is shown in Figure 1. The
sample cartridge is placed in the thermal desorption apparatus (for Inside/
Inside VOST cartridges, use Supelco "clamshell" heater; for Inside/Outside VOST
cartridges, user fabricated unit is required) and desorbed in the purge-and-trap
system by heating to 180°C for 10 min at a flow rate of 40 inL/min. The desorbed
components pass into the bottom of the water column, are purged from the water,
and collected on the analytical adsorbent trap. After the 10 min desorption
period, the compounds are desorbed from the analytical adsorbent trap into the
GC/MS system according to the procedures described in Method 8240.
7.4 Qualitative analysis
7.4.1 The qualitative identification of compounds determined by this
method is based on retention time, and on comparison of the sample mass
spectrum, after background correction, with characteristic ions in a
reference mass spectrum. The reference mass spectrum must be generated by
the laboratory using the conditions of this method. The characteristic
ions from the reference mass spectrum are defined to be the three ions of
greatest relative intensity, or any ions over 30% relative intensity if
less than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.4.1.1 The intensities of the characteristic ions of a
compound maximize in the same scan or within one scan of each other.
Selection of a peak by a data system target compound search routine,
where the search is based on the presence of a target
chromatographic peak containing ions specific for the target
compound at a compound-specific retention time, will be accepted as
meeting this criterion.
7,4.1.2 The RRT of the sample component is within
±0.06 RRT units of the RRT of the standard component.
7.4.1.3 The relative intensities of the characteristic
ions agree within 30% of the relative intensities of these ions in
the reference spectrum. (Example: For an ion with an abundance of
50% in the reference spectrum, the corresponding abundance in a
sample spectrum can range between 20% and 80%.)
7.4.1.4 Structural isomers that produce very similar mass
spectra should be identified as individual isomers if they have
sufficiently different GC retention times. Sufficient GC resolution
is achieved if the height of the valley between two isomer peaks is
less than 25% of the sum of the two peak heights. Otherwise,
structural isomers are identified as isomeric pairs.
7.4.1.5 Identification is hampered when sample components
are not resolved chromatographically and produce mass spectra
5040A - 5 Revision 1
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containing ions contributed by more than one analyte. When gas
chromatographic peaks obviously represent more than one sample.
component (i.e., a. broadened peak with shoulder(s) or a valley
between two or more maxima), appropriate selection of analyte
spectra and background spectra is important. Examination of
extracted ion current profiles of appropriate ions can aid in the
selection of spectra, and in qualitative identification of
compounds. When analytes coelute (i.e., only one chromatographic
peak is apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by the
coeluting compound.
7.4.2 For samples containing components not associated with the
calibration standards, a library search may be made for the purpose of
tentative identification. The necessity to perform this type of
identification will be determined by the type of analyses being conducted.
Guidelines for making tentative identification are:
(1) Relative intensities of major ions in the reference spectrum
(ions > 10% of the most abundant ion) should be present 1n the sample
spectrum.
(2) The relative intensities of the major ions should agree within
± 20%. (Example: For an ion with an abundance of 50% in the standard
spectrum, the corresponding sample ion abundance must be between 30 and
70%),
(3) Molecular ions present in the reference spectrum should be
present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the reference
spectrum should be reviewed for possible background contamination or
presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the sample
spectrum should be reviewed for possible subtraction from the sample
spectrum because of background contamination or coeluting peaks. Data
system library reduction programs can sometimes create these
discrepancies.
Computer generated library search routines should not use
normalization routines that would misrepresent the library or unknown
spectra when compared to each other. Only after visual comparison of the
sample with the nearest library searches will the mass spectral
interpretation specialist assign a tentative identification.
7.5 Quantitative analysis
7.5.1 When an analyte has been qualitatively identified,
quantitation should be based on the integrated abundance from the EICP of
the primary characteristic ion chosen for that analyte. If the sample
produces an interference for the primary characteristic ion, a secondary
characteristic ion should be used.
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7.5.1.1 Using the internal standard calibration procedure,
the amount of analyte in the sample cartridge is calculated using
the response factor (RFJ determined in Section 7.2.5 and Equation 2,
Amount of POHC « A8Cis/AifiRF (2)
where:
As = Area of the characteristic ion for the analyte to be
measured.
Aj,, = Area for the characteristic ion of the internal
standard.
Cte = Amount (ng) of internal standard.
7.5.1.2 The choice of methods for evaluating data
collected using VOST for incinerator trial burns is a regulatory
decision. The procedures used extensively by one user are outlined
below.
7.5.1.3 The total amount of the POHCs of interest
collected on a pair of traps should be summed.
7.1.1.4 The observation of high concentrations of POHCs of
interest in blank cartridges indicates possible residual
contamination of the sorbent cartridges prior to shipment to and use
at the site. Data that fall in this category (especially data
indicating high concentrations of POHCs in blank sorbent cartridges)
should be qualified with regard to validity, and blank data should
be reported separately. The applicability of data of this type to
the determination of ORE is a regulatory decision. Continued
observation of high concentrations of POHCs in blank sorbent
cartridges indicates that procedures for cleanup, monitoring,
shipment, and storage of sorbent cartridges by a particular user be
investigated to eliminate this problem.
7.5.1.B If any internal standard recoveries, fall outside
the control limits established in Section 8.4, data for all analytes
determined for that cartridge(s) must be qualified with the
observation.
8,0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures and
Method 0030 for sample preparation procedures.
8.2 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 blank Tenax
and Tenax/charcoal cartridges spiked with the analytes of interest. The
laboratory is required to maintain performance records to define the quality of
5040A - 7 Revision I
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data that are generated. Ongoing performance checks must be compared with
established performance criteria to determine if results are within the expected
precision and accuracy limits of the method.
8.2,1 Before performing any analyses, the analyst must demonstrate
the ability to generate acceptable precision and accuracy with this
method. This ability is established as described in Section 7.2.
8.2.2 The laboratory must spike all Tenax and Tenax/charcoal
cartridges with the internal standard(s) to monitor continuing laboratory
performance. This procedure is described in Section 7.2,
8.3 To establish the ability to generate acceptable accuracy and
precision, the analyst must spike blank Tenax and Tenax/charcoal cartridges with
the analytes of interest at two concentrations in the working range.
8,3.1 The average response factor (RF) and the standard deviation
(s) for each must be calculated.
8.3.2 The average recovery and standard deviation must fall within
the expected range for determination of volatile POHCs using this method.
The expected range for recovery of volatile POHCs using this method is 50-
150%.
8.4 The analyst must calculate method performance criteria for the
internal standard(s).
8.4.1 Calculate upper and lower control limits for method
performances using the average area response (A) and standard
deviation(s) for internal standard:
Upper Control Limit (UCL) = A + 3s
Lower Control Limit (LCL) - A - 3s
The UCL and LCL can be used to construct control charts that are
useful in observing trends in performance. The control limits must be
replaced by method performance criteria as they become available from the
U.S. EPA.
8.5 The laboratory is required to spike all sample cartridges (Tenax and
Tenax/charcoal) with internal standard,
8.6 Each day, the analyst must demonstrate through analysis of blank
Tenax and Tenax/charcoal cartridges and organic-free reagent water that
interferences from the analytical system are under control.
8.7 The daily GC/MS performance tests required for this method are
described in Method 8240.
9.0 METHOD PERFORMANCE
9.1 Refer to the determinative methods for performance data.
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10.0 REFERENCES
1. Protocol for Collection and Analysis of Volatile POHC's Using VOST,
EPA/600/8-84-007, March 1984.
2. Validation of the Volatile Organic Sampling Train (VOST) Protocol.
Volumes I and II. EPA/600/4-86-014a, January 1986.
5040A - 9 Revision 1
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[ Flow During J
D
^\
N2 1/1}
m^ <•• «^M
Thermal
Desorption
tnomoer
Flov
GC
CH
D-i
Deiorptlon
t to
/MS
•* Flaw During ^
1 Adiorption I
j L>^JxIpxI|!>.
Frit ^fy r.T\ w
W T«""
1 T
/
Heated
Line
i (7.7cm)
[ @ Silica Gel (7.7cm)
(4J Charcoal (7.7cm)
Figure 1. Schematic diagram of trap desorpikin/analysis system.
5040A - 10
Revision 1
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METHOD 5040A
ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC SAMPLING TRAIN (VOST)
GAS CHROMATOGRAPHY/MASS SPECTROMETRY TECHNIQUE
Start
7,1,1 Assemble
purge and trap
deaorption
device.
7.1.2 Connect
thermal
deaorption
device;
calib. system.
7.2.1 Select
internal
standard.
7.2.3 Prepare
calibration
standards uaing
flash evaporat,
technique.
7.2.4 Diraci
g*a flow
through traps.
7.2.4 Expel
contanta of
•yringe through
GC injection
port.
7.2.4 Analyze
trap by P-T-0
GC/MS
procedure.
7.2.S Analyze
each ealib.
etandard for
both cartridges
(eee 7.3),
7.2.5 Tabulate
area response
and calculate
response factor.
7.2.8 Verify
response
factor each
day.
7.3 Place
sample
cartridge in
desorp. apparatus;
dvtorfa in P-T.
7.3 Deaorb
into GC/MS
ayatara.
7.4.1
Quantatively
identrfy
volatile POHCa.
7.5.1 lie*
primary
characteristic
ion for
quant itation.
7.6.1.1
Calculate
•mount of analyte
in aarnpla.
7.5; 1.3 Sym
amount of POHCt
of intareit for
each pair of
trapa.
7.S.1.4 Examine
blank* data for
aigni of raaidual
contamination.
7.6.1.S Compare
int. atd.
recoveries to
Section 8.4
control limit*.
Stop
5040A - 11
Revision 1
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\
-------
METHOD 5041
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
SAMPLING TRAIN fVOST]; WIDE-BORE CAPILLARY COLUMN TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 This method describes the analysis of volatile principal organic
hazardous constituents (POHCs) collected from the stack gas effluents of
hazardous waste incinerators using the VOST methodology (1). For a comprehensive
description of the VOST sampling methodology see Method 0030. The following
compounds may be determined by this lethod:
Compound Name
CAS No."
Acetone
Acrylonitrile
Benzene
Bromodichloromethane
Bromoformb
Bromomethane0
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chi orod i bromomethane
Chloroethane0
Chloroform
Chloromethane0
Di bromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans-l,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-1 , 3-Dichl oropropene
Ethyl benzene"
lodomethane
Methyl ene chloride
Styreneb
1,1,2, 2 -Tetrachl oroethaneb
Tetrachl oroethene
Toluene
67-64-1
107-13-1
71-43-2
75-27-4
75-25-2
74-83-9
75-15-0
56-23-5
108-90-7
124-48-1
75-00-3
67-66-3
74-87-3
74-95-3
75-35-3
107-06-2
75-35-4
156-60-5
78-87-5
10061-01-5
10061-02-6
100-41-4
74-88-4
75-09-2
100-42-5
79-34-5
127-18-4
108-88-3
(continued)
5041 - 1
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Compound Name CAS No.a
1,1,1-Trichloroethane 71-55-6
1,1,2-Trichloroethane 79-00-5
Trichloroethene 79-01-6
Trichlorofluoromethane 75-69-4
l,2,3-Trichloropropaneb 96-18-4
Vinyl chloride0 75-01-4
Xylenesb
* Chemical Abstract Services Registry Number.
b Boiling point of this compound is above 132°C, Hethod 0030 is not
appropriate for quantitative sampling of this analyte.
c Boiling point of this compound is below 30°C. Special precautions must
be taken when sampling for this analyte by Method 0030. Refer to Sec. 1.3 for
discussion.
1.2 This method is most successfully applied to the analysis of non-polar
organic compounds with boiling points between 30"C and 100°C, Data are applied
to the calculation of destruction and removal efficiency (ORE), with limitations
discussed below.
1.3 This method may be applied to analysis of many compounds which boil
above 1QO°C, but Method 0030 is always inappropriate for collection of compounds
with boiling points above 132°C. All target analytes with boiling points greater
than 132°C are so noted in the target analyte list presented in Sec. 1.1. Use
of Method 0030 for collection of compounds boiling between 100°C and 132°C is
often possible, and must be decided based on case by case inspection of
information such as sampling method collection efficiency, tube desorption
efficiency, and analytical method precision and bias. An organic compound with
a boiling point below 30°C may break through the sorbent under the conditions
used for sample collection. Quantitative values obtained for compounds with
boiling points below 30°C must be qualified, since the value obtained represents
a minimum value for the compound if breakthrough has occurred. In certain cases,
additional QC measures may have been taken during sampling very low boilers with
Method 0030. This information should be considered during the data
interpretation stage.
When Method 5041 is used for survey analyses, values for compounds boiling
above 132°C may be reported and qualified since the quantity obtained represents
a minimum value for the compound. These minimum values should not be used for
trial burn ORE calculations or to prove insignificant risk.
1.4 The VOST analytical methodology can be used to quantitate volatile
organic compounds that are insoluble or slightly soluble in water. When
volatile, water soluble compounds are included in the VOST organic compound
analyte list, quantitation limits can be expected to be approximately ten times
5041 - 2 Revision 0
September 1994
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higher than quantitation limits for water insoluble compounds (if the compounds
can be recovered at all) because the purging efficiency from water (and possibly
from Tenax-GC®) is poor.
1.5 Overall sensitivity of the method is dependent upon the level of
interferences encountered in the sample and the presence of detectable
concentrations of volatile POHCs in blanks. The target detection limit of this
method is 0.1 pg/m3 (ng/L) of flue gas, to permit calculation of a ORE equal to
or greater than 99.99% for volatile POHCs which may be present in the waste
stream at 100 ppm. The upper end of the range of applicability of this method
is limited by the dynamic range of the analytical instrumentation, the overall
loading of organic compounds on the exposed tubes, and breakthrough of the
volatile POHCs on the sorbent traps used to collect the sample. Table 1 presents
retention times and characteristic ions for volatile compounds which can be
determined by this method. Table 2 presents method detection limits for a range
of volatile compounds analyzed by the wide-bore VOST methodology.
1.6 The wide-bore VOST analytical methodology is restricted to use by,
or under the supervision of, analysts experienced in the use of sorbent media,
purge-and-trap systems, and gas chromatograph/mass spectrometers, and skilled in
the interpretation of mass spectra and their use as a quantitative tool.
2.0 SUMMARY OF METHOD
2.1 The sorbent tubes are thermally desorbed by heating and purging with
organic-free helium. The gaseous effluent from the tubes is bubbled through
pre-purged organic-free reagent water and trapped on an analytical sorbent trap
in a purge-and-trap unit (Figure 2). After desorption, the analytical sorbent
trap is heated rapidly and the gas flow from the analytical trap is directed to
the head of a wide-bore column under subambient conditions. The volatile organic
compounds desorbed from the analytical trap are separated by temperature
programmed high resolution gas chromatography and detected by continuously
scanning low resolution mass spectrometry (Figure 3). Concentrations of volatile
organic compounds are calculated from a multi-point calibration curve, using the
method of response factors.
3.0 INTERFERENCES
3.1 Sorbent tubes which are to be analyzed for volatile organic compounds
can be contaminated by diffusion of volatile organic compounds (particularly
Freon® refrigerants and common organic solvents) through the external container
(even through a Teflon® lined screw cap on a glass container) and the Swagelok®
sorbent tube caps during shipment and storage. The sorbent tubes can also be
contaminated if organic solvents are present in the analytical laboratory. The
use of blanks is essential to assess the extent of any contamination. Field
blanks must be prepared and taken to the field. The end caps of the tubes are
removed for the period of time required to exchange two pairs of traps on the
VOST sampling apparatus. The tubes are recapped and shipped and handled exactly
as the actual field samples are shipped and handled. At least one pair of field
blanks is included with each six pairs of sample cartridges collected.
5041 - 3 Revision 0
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3.2 At least one pair of blank cartridges (one Tenax-GC®, one
Tenax-GC®/charcoal) shall be included with shipment of cartridges to a hazardous
waste incinerator site as trip blanks. These trip blanks will be treated like
field blanks except that the end caps will not be removed during storage at the
site. This pair of traps will be analyzed to monitor potential contamination
which may occur during storage and shipment,
3.3 Analytical system blanks are required to demonstrate that
contamination of the purge-and-trap unit and the gas chromatograph/mass
spectrometer has not occurred or that, in the event of analysis of sorbent tubes
with very high concentrations of organic compounds,, no compound carryover is
occurring. Tenax® from the same preparation batch as the Tenax® used for field
sampling should be used in the preparation of the method (laboratory) blanks.
A sufficient number of cleaned Tenax® tubes from the same batch as the field
samples should be reserved in the laboratory for use as blanks.
3.4 Cross contamination can occur whenever low-concentration samples are
analyzed after high-concentration samples, or when several high-concentration
samples are analyzed sequentially. When an unusually concentrated sample is
analyzed, this analysis should be followed by a method blank to establish that
the analytical system is free of contamination. If analysis of a blank
demonstrates that the system is contaminated, an additional bake cycle should be
used. If the analytical system is still contaminated after additional baking,
routine system maintenance should be performed: the analytical trap should be
changed and conditioned, routine column maintenance should be performed (or
replacement of the column and conditioning of the new column, if necessary), and
bakeout of the ion source (or cleaning of the ion source and rods, if required).
After system maintenance has been performed, analysis of a blank is required to
demonstrate that the cleanliness of the system is acceptable.
3.5 Impurities in the purge gas and from organic compounds out-gassing
in tubing 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 analyzing two sets of clean, blank sorbent tubes with organic-
free reagent purge water as system blanks. The analytical system is acceptably
clean when these two sets of blank tubes show values for the analytes which are
within one standard deviation of the normal system blank. Use of plastic
coatings, non-Teflon® thread sealants, or flow controllers with rubber
components should be avoided.
3,6 VOST tubes are handled in the laboratory to spike standards and to
position the tubes within the desorption apparatus. When sorbent media are
handled in the laboratory atmosphere, contamination is possible if there are
organic solvents in use anywhere in the laboratory. It is therefore necessary
to make daily use of system blanks to monitor the cleanliness of the sorbents and
the absence of contamination from the analytical system. A single set of system
blank tubes shall be exposed to normal laboratory handling procedures and
analyzed as a sample. This sample should be within one standard deviation of
normal VOST tube blanks to demonstrate lack of contamination of the sorbent
media.
3.7 If the emission source has a high concentration of non-target organic
compounds (for example, hydrocarbons at concentrations of hundreds of ppm), the
5041 - 4 Revision 0
September 1994
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presence of these non-target compounds will interfere with the performance of the
VOST analytical methodology. If one or more of the compounds of interest
saturates the chromatographic and mass spectrometric instrumentation, no
quantitative calculations can be made and the tubes which have been sampled under
the same conditions will yield no valid data for any of the saturated compounds.
In the presence of a very high organic loading, even if the compounds of interest
are not saturated, the instrumentation is so saturated that the linear range has
been surpassed. When instrument saturation occurs, it is possible that compounds
of interest cannot even be identified correctly because a saturated mass
spectrometer may mis-assign masses. Even if compounds of interest can be
identified, accurate quantitative calculations are impossible at detector
saturation. No determination can be made at detector saturation, even if the
target compound itself is not saturated. At detector saturation, a negative bias
will be encountered in analytical measurements and no accurate calculation can
be made for the Destruction and Removal Efficiency if analytical values may be
biased negatively.
3.8 The recoveries of the surrogate compounds, which are spiked on the
VOST tubes immediately before analysis, should be monitored carefully as an
overall indicator of the performance of the methodology. Since the matrix of
stack emissions is so variable, only a general guideline for recovery of 50-150%
can be used for surrogates. The analyst cannot use the surrogate recoveries as
a guide for correction of compound recoveries. The surrogates are valuable only
as a general indicator of correct operation of the methodology. If surrogates
are not observed or if recovery of one or more of the surrogates is outside the
50-150% range, the VOST methodology is not operating correctly. The cause of the
failure in the methodology is not obvious. The matrix of stack emissions
contains large amounts of water, may be highly acidic, and may contain large
amounts of target and non-target organic compounds. Chemical and surface
interactions may be occurring on the tubes. If recoveries of surrogate compounds
are extremely low or surrogate compounds cannot even be identified in the
analytical process, then failure to observe an analyte may or may not imply that
the compound of interest has been removed from the emissions with a high degree
of efficiency (that is, the Destruction and Removal Efficiency for that analyte
is high).
4,0 APPARATUS AND MATERIALS
4.1 Tube desorption apparatus: Acceptable performance of the methodology
requires: 1) temperature regulation to ensure that tube temperature during
desorption is regulated to 180°C ± 10°; 2) good contact between tubes and the
heating apparatus to ensure that the sorbent bed is thoroughly and uniformly
heated to facilitate desorption of organic compounds; and 3) gas-tight
connections to the ends of the tubes to ensure flow of desorption gas through the
tubes without leakage during the heating/desorption process, A simple clamshell
heater which will hold tubes which are 3/4" in outer diameter will perform
acceptably as a desorption apparatus.
4.2 Purge-and-trap device: The purge-and-trap device consists of three
separate pieces of equipment: a sample purge vessel, an analytical trap, and a
desorber. Complete devices are commercially available from a variety of sources,
or the separate components may be assembled. The cartridge thermal desorption
5041 - 5 Revision 0
September 1994
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apparatus Is connected to the sample purge vessel by 1/8" Teflon® tubing
(unheated transfer line). The tubing which connects the desorption chamber to
the sample purge vessel should be as short as is practical.
4.2.1 The sample purge vessel is required to hold 5 ml of organic-
free reagent water, through which the gaseous effluent from the VOST tubes
is routed. The water column should be at least 3 cm deep. The gaseous
headspace between the water column and the analytical trap must have a
total volume of less than 15 ml. The purge gas roust pass through the
water column as finely divided bubbles with a diameter of less than 3 mm
at the origin. The sample purger shown in Figure 4 meets these
requirements. Alternate sample purging vessels may be used if equivalent
performance is demonstrated.
4.2.2 The analytical trap must be at least 25 cm and have an
internal diameter of at least 0.105 in. The analytical trap must contain
the following components:
2,6-diphenylene oxide polymer: 60/80 mesh, chromatograph grade
(Tenax-GC®, or equivalent)
methyl silicone packing: OV-1 (3%) on Chromosorb-W 60/80
mesh, or equivalent
silica gel: 35/60 mesh, Davison grade 15 or
equivalent
coconut charcoal: prepare from Barneby Cheney,
CA-580-26, or equivalent, by
crushing through 26 mesh
screen.
The proportions are: 1/3 Tenax-GC®, 1/3 silica gel, and 1/3
charcoal, with approximately 1.0 cm of methyl silicone packing. The
analytical trap should be conditioned for four hours at 180°C with gas flow
(10 mL/min) prior to use in sample analysis. During conditioning, the
effluent of the trap should not be vented to the analytical column. The
thermal desorption apparatus is connected to the injection system of the
mass spectrometer by a transfer line which is heated to 100°C.
4.2.3 The desorber must be capable of rapidly heating the analytical
trap to.!80°C for desorption. The polymer section of the trap should not
exceed 180°C, and the remaining sections should not exceed 220°C, during
bake-out mode.
4.3 Gas chromatograph/mass spectrometer/data system:
4.3.1 Gas chromatograph: An analytical system complete with a
temperature programmable oven with sub-ambient temperature capabilities
and all required accessories, including syringes, analytical columns, and
gases.
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4.3.2 Chromatographic column: 30 m x 0.53 mm ID wide-bore fused
silica capillary column, 3 IM film thickness, DB-524 or equivalent.
4.3.3 Mass spectrometer: capable of scanning from 35-260 amu every
second or less, using 70 eV (nominal) electron energy in the electron
ionization mode and producing a mass spectrum that meets all of the
criteria in Table 3 when 50 ng of 4-brontofluorobenzene (BFB) is injected
into the water in the purge vessel.
4.3.4 Gas chromatograph/mass spectrometer interface: Any gas
chromatograph to mass spectrometer interface that gives acceptable
calibration points at 50 ng or less per injection of each of the analytes,
and achieves the performance criteria for 4-bromofluorobenzene shown in
Table 3, may be used. If a glass jet separator is used with the wide-bore
column, a helium make-up flow of approximately 15 ml, introduced after the
end of the column and prior to the entrance of the effluent to the
separator, will be required for optimum performance.
4.3.5 Data system: A computer system that allows the continuous
acquisition and storage on machine readable media of all mass spectra
obtained throughout the duration of the Chromatographic program must be
interfaced to the mass spectrometer. The computer must have software that
allows searching any gas chromatographic/mass spectrometric data file for
ions of a specified mass and plotting such ion 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 the
integration of the ion abundances in any EICP between specified time or
scan number limits. The most recent version of the EPA/NIST Mass Spectral
Library should also be available.
4.4 Wrenches: 9/16", 1/2", 7/16", and 5/16".
4.5 Teflon® tubing: 1/8" diameter.
4.6 Syringes: 25 /iiL syringes (2), 10 ^L syringes (2).
4.7 Fittings: 1/4" nuts, 1/8" nuts, 1/16" nuts, 1/4" to 1/8" union, 1/4"
to 1/4" union, 1/4" to 1/16" union.
4.8 Adjustable stand to raise the level of the desorption unit, if
required.
4.9 Volumetric flasks: 5 ml, class A with ground glass stopper.
4.10 Injector port or equivalent, heated to 180°C for loading standards
onto VOST tubes prior to analysis.
4.11 Vials: 2 mL, with Teflon® lined screw caps or crimp tops.
4.12 Syringe: 5 ml, gas-tight with shutoff valve.
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5.0 REAGENTS
5.1 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,
5.2 Organic-free reagent water - All references to water in this method
refer to organic-free reagent water, as defined in Chapter One.
5.2.1 It is advisable to maintain the stock of organic-free reagent
water generated for use in the purge-and-trap apparatus with a continuous
stream of inert gas bubbled through the water. Continuous bubbling of the
inert gas maintains a positive pressure of inert gas above the water as a
safeguard against contamination.
5.3 Methanol, CH3OH. Pesticide quality or equivalent. To avoid
contamination with other laboratory solvents, it is advisable to maintain a
separate stock of methanol for the preparation of standards for VOST analysis and
to regulate the use of this methanol very carefully.
5.4 Stock standard solutions - Can be prepared from pure standard
materials or can be purchased as certified solutions. Stock standard solutions
must be prepared in high purity methanol. All preparation of standards should
take place in a hood, both to avoid contamination and to ensure safety of the
analyst preparing the standards.
5.4.1 Place about 4 ml of high purity methanol in a 5 ml volumetric
flask. Allow the flask to stand, unstoppered, for about 10 min, or until
all alcohol wetted surfaces have dried.
5.4.1.1 Add appropriate volumes of neat liquid chemicals
or certified solutions, using a syringe of the appropriate volume.
Liquid which is added to the volumetric flask must fall directly
into the alcohol without contacting the neck of the flask. Gaseous
standards can be purchased as methanol solutions from several
commercial vendors.
5.4.1.2 Dilute to volume with high purity methanol,
stopper, and then mix by inverting the flask several times. Calcu-
late concentration by the dilution of certified solutions or neat
chemicals.
5.4.2 Transfer the stock standard solution into a Teflon® sealed
screw cap bottle. An amber bottle may be used. Store, with minimal
headspace, at -10°C to -20°C, and protect from light.
5.4.3 Prepare fresh standards every two months for gases. Reactive
compounds such as styrene may need to be prepared more frequently. All
other standards must be replaced after six months, or sooner if comparison
with check standards indicates a problem.
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5.5 Secondary dilution standards: Using stock standard solutions,
prepare, in high purity methanol, secondary dilution standards containing the
compounds of interest, either singly or mixed together. Secondary dilution
standards must 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.
5.6 Surrogate standards: The recommended surrogates are toluene~ds,
4-bromofluorobenzene, and l»2-dichloroethane-d4. Other compounds may be used as
surrogate compounds, depending upon the requirements of the analysis. Surrogate
compounds are selected to span the elution range of the compounds of interest.
Isotopically labeled compounds are selected to preclude the observation of the
same compounds in the stack emissions. More than one surrogate is used so that
surrogate measurements can still be made even if analytical interferences with
one or more of the surrogate compounds are encountered. However, at least three
surrogate compounds should be used to monitor the performance of the methodology.
A stock surrogate compound solution in high purity methanol should be prepared
as described in Sec. 5.4, and a surrogate standard spiking solution should be
prepared from the stock at a concentration of 250 jLtg/10 ml in high purity
methanol. Each pair of VOST tubes (or each individual VOST tube, if the tubes
are analyzed separately) must be spiked with 10 pi of the surrogate spiking
solution prior to GC/MS analysis.
5.7 Internal standards: The recommended internal standards are
bromochloromethane, 1,4-difluorobenzene, and chlorobenzene-ds. Other compounds
may be used as internal standards as long as they have retention times similar
to the compounds being analyzed by GC/MS. The internal standards should be
distributed through the chromatographic elution range. Prepare internal standard
stock and secondary dilution standards in high purity methanol using the
procedures described in Sees. 5.2 and 5.3. The secondary dilution standard
should be prepared at a concentration of 25 mg/L of each of the internal standard
compounds. Addition of 10 pi of this internal standard solution to each pair
of VOST tubes (or to each VOST tube, if the tubes are analyzed individually) is
the equivalent of 250 ng total.
5.8 4-Bromofluorobenzene (BFB) standard; A standard solution containing
25 ng/juL of BFB in high purity methanol should be prepared for use as a tuning
standard.
5.9 Calibration standards: Calibration standards at a minimum of five
concentrations will be required from the secondary dilution of stock standards
(see Sees. 5.2 and 5,3). A range of concentrations for calibration can be
obtained by use of different volumes of a 50 mg/L methanol solution of the
calibration standards. One of the concentrations used should be at a
concentration near, but above, the method detection limit. The remaining
concentrations should correspond to the expected range of concentrations found
in field samples but should not exceed the linear range of the GC/MS analytical
system {a typical range for a calibration would be 10, 50, 100, 350, and 500 ng,
for example). Each calibration standard should contain each analyte for
detection by this method. Store calibration standards for one week only in a
vial with no headspace.
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5.10 Great care must be taken to maintain the integrity of all standard
solutions. All standards of volatile compounds in methanol must be stored at
-10° to -20°C in amber bottles with Teflon® lined screw caps or crimp tops. In
addition, careful attention must be paid to the use of syringes designated for
a specific purpose or for use with only a single standard solution since cross
contamination of volatile organic standards can occurs very readily.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Method 0030 for the VOST Sampling Methodology,
6.2 VOST samples are collected on paired cartridges. The first of the
pair of sorbent cartridges is packed with approximately 1,6 g of Tenax-GC®
resin. The second cartridge of the pair is packed with Tenax-GC® and petroleum
based charcoal (3:1 by volume; approximately 1 g of each). In sampling, the
emissions gas stream passes through the Tenax-GC® layer first and then through
the charcoal layer. The Tenax-GC® is cleaned and reused; charcoal is not reused
when tubes are prepared. Sorbent is cleaned and the tubes are packed. The tubes
are desorbed and subjected to a blank check prior to being sent to the field.
When the tubes are used for sampling (see Figure 5 for a schematic diagram of the
Volatile Organic Sampling Train (VOST)), cooling water is circulated to the
condensers and the temperature of the cooling water is maintained near 0°C. The
end caps of the sorbent cartridges are placed in a clean, screw capped glass
container during sample collection.
6,3 After the apparatus is leak checked, sample collection is
accomplished by opening the valve to the first condenser, turning on the pump,
and sampling at a rate of 1 liter/min for 20 minutes. The volume of sample for
any pair of traps should not exceed 20 liters. An alternative set of conditions
for sample collection requires sampling at a reduced flow rate, where the overall
volume of sample collected is 5 liters at a rate of 0.25 L/min for 20 minutes.
The 20 minute period is required for collecting an integrated sample.
6.4 Following collection of ZO liters of sample, the train is leak
checked a second time at the highest pressure drop encountered during the run to
minimize the chance of vacuum desorption of organics from the Tenax®.
6.5 The train is returned to atmospheric pressure and the two sorbent
cartridges are removed. The end caps are replaced and the cartridges are placed
in a sir "ible environment for storage and transport until analysis. The sample
is cons ared invalid if the leak test does not meet specifications.
6.6 A new pair of cartridges is placed in the VOST, the VOST is leak
checked, and the sample collection process is repeated until six pairs of traps
have been exposed.
6
exposure
stored
."* All sample cartridges are kept in coolers on cold packs after
e and during shipment. Upon receipt at the laboratory, the cartridges are
in a refrigerator at 4°C until analysis.
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7.0 PROCEDURE
7.1 Recommended operating conditions for cartridge desorber,
purge-and-trap unit, and gas chromatograph/mass spectrometer using the wide-bore
column are:
Cartridge Desorption Oven
Disorb Temperature
Desorb Time
Desorption Gas Flow
Desorption/Carrier Gas
Purge-and-Trap Concentrator
Analytical Trap Desorption Flow
Purge Temperature
Purge Time
Analytical Trap Desorb Temperature
Analytical Trap Desorb Time
Gas Chromatpgraph
Column
Carrier Gas Flow
Makeup Gas Flow
Injector Temperature
Transfer Oven Temperature
Initial Temperature
Initial Hold Time
Program Rate
Final Temperature
Final Hold Time
Mass Spectrometer
Manifold Temperature
Scan Rate
Mass Range
Electron Energy
Source Temperature
180°C
11 minutes
40 mL/min
Helium, Grade 5.0
2.5 mL/min helium
Ambient
11 minutes
180°C
5 minutes
DB-624, 0.53 mm ID x 30 m thick
film (3 ^m) fused silica capillary,
or equivalent
15 mL/min
15 mL/min
200°C
240°C
5°C
2 minutes
6°C/min
240°C
1 minute, or until elution ceases
105°C
1 sec/cycle
35-260 amu
70 eV (nominal)
According to
specifications
manufacturer's
7.2 Each GC/MS system must be hardware tuned to meet the criteria in
Table 3 for a 50 ng injection of 4-bromofluorobenzene (2 fj.1 injection of the BFB
standard solution into the water of the purge vessel). No analyses may be
initiated until the criteria presented in Table 3 are met.
7.3 Assemble a purge-and-trap device that meets the specifications in
Method 5030. Condition the analytical trap overnight at 180°C in the purge mode,
with an inert gas flow of at least 20 mL/min. Prior to use each day, condition
the trap for 10 minutes by backf lush ing at 18Q°C, with the column at 220°C.
7.4 Connect the purge-and-trap device to a gas chromatograph.
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7.5 Assemble a VOST tube desorption apparatus which meets the
requirements of Sec. 4.1.
7.6 Connect the VOST tube desorption apparatus to the purge-and-trap
unit.
7.7 Calibrate the instrument using the internal standard procedure, with
standards and calibration compounds spiked onto cleaned VOST tubes for
calibration.
7.7.1 Compounds in methanolic solution are spiked onto VOST tubes
using the flash evaporation technique. To perform flash evaporation, the
injector of a gas chromatograph or an equivalent piece of equipment is
required.
7.7.1.1 Prepare a syringe with the appropriate volume of
methanolic standard solution (either surrogates, internal standards,
or calibration compounds).
7.7.1.2 With the injector port heated to 180°C, and with
an inert gas flow of 10 mL/min through the injector port, connect
the paired VOST tubes (connected as in Figure 1, with gas flow in
the same direction as the sampling gas flow) to the injector port;
tighten with a wrench so that there is no leakage of gas. If
separate , tubes are being analyzed, an individual Tenax® or
Tenax®/charcoal tube is connected to the injector.
7.7.1.3 After directing the gas flow through the VOST
tubes, slowly inject the first standard solution over a period of 25
seconds. Wait for 5 sec before withdrawing the syringe from the
injector port.
7.7.1.4 Inject a second standard (if required) over a
period of 25 seconds and wait for 5 sec before withdrawing the
syringe from the injector port.
7.7.1.5 Repeat the sequence above as required until all of
the necessary compounds are spiked onto the VOST tubes.
7.7.1.6 Wait for 30 seconds, with gas flow, after the last
spike before disconnecting the tubes. The total time the tubes are
connected to the injector port with gas flow should not exceed 2.5
minutes. Total gas flow through the tubes during the spiking
process should not exceed 25 ml to prevent break through of adsorbed
compounds during the spiking process. To allow more time for
connecting and disconnecting tubes, an on/off valve may be installed
in the gas line to the injector port so that gas is not flowing
through the tubes during the connection/disconnection process.
7.8 Prepare the purge-and-trap unit with 5 ml of organic-free reagent
water in the purge vessel.
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7.9 Connect the paired VOST tubes to the gas lines in the tube desorption
unit. The tubes must be connected so that the gas flow during desorption will
be opposite to the flow of gas during sampling: i.e., the tube desorption gas
passes through the charcoal portion of the tube first. An on/off valve may be
installed in the gas line leading to the tube desorption unit in order to prevent
flow of gas through the tubes during the connection process,
7.10 Initiate tube desorption/purge and heating of the VOST tubes in the
desorption apparatus.
7.11 Set the oven of the gas chromatograph to subambient temperatures by
cooling with liquid nitrogen.
7.12 Prepare the GC/MS system for data acquisition.
7.13 At the conclusion of the tube/water purge time, attach the analytical
trap to the gas chromatograph, adjust the purge-and-trap device to the desorb
mode, and initiate the gas chromatographic program and the GC/MS data
acquisition. Concurrently, introduce the trapped materials to the gas
chromatographic column by rapidly heating the analytical trap to 180°C while
backflushing the trap with inert gas at 2.5 mL/min for 5 min. Initiate the
program for the gas chromatograph and simultaneously initiate data acquisition
on the GC/MS system.
7.14 While the analytical trap is being desorbed into the gas
chromatograph, empty the purging vessel. Wash the purging vessel with a minimum
of two 5 mL flushes of organic-free reagent water (or methanol followed by
organic-free reagent water) to avoid carryover of analytes into subsequent
analyses.
7.15 After the sample has been desorbed, recondition the analytical trap
by employing a bake cycle on the purge-and-trap unit. The analytical trap may
be baked at temperatures up to 220°C, However, extensive use of high
temperatures to recondition the trap will shorten the useful life of the
analytical trap. After approximately 11 minutes, terminate the trap bake and
cool the trap to ambient temperatures in preparation for the next sample. This
procedure is a convention for reasonable samples and should be adequate if the
concentration of contamination does not saturate the analytical system. If the
organic compound concentration is so high that the analytical system is saturated
beyond the point where even extended system bakeout is not sufficient to clean
the system, a more extensive system maintenance must be performed. To perform
extensive system maintenance, the analytical trap is replaced and the new trap
is conditioned. Maintenance is performed on the GC column by removing at least
one foot from the front end of the column. If the chromatography does not
recover after column maintenance, the chromatographic column must be replaced.
The ion source should be baked out and, if the bakeout is not sufficient to
restore mass spectrometric peak shape and sensitivity, the ion source and the
quadrupole rods must be cleaned.
7.16 Initial calibration for the analysis of VOST tubes; It is essential
that calibration be performed in the mode in which analysis will be performed.
If tubes are being analyzed as pairs, calibration standards should be prepared
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on paired tubes. If tubes are being analyzed individually, a calibration should
be performed on individual Tenax® only tubes and Tenax®/charcoal tubes.
7.16.1 Prepare the calibration standards by spiking VOST tubes
using the procedure described in Sec. 7.7.1. Spike each pair of VOST
tubes (or each of the individual tubes) immediately before analysis.
Perform the calibration analyses in order from low concentration to high
to minimize the compound carryover. Add 5.0 ml of organic-free reagent
water to the purging vessel. Initiate tube desorb/purge according to the
procedure described above.
7.16.2 Tabulate the area response of the characteristic primary
ions (Table 1} against concentration for each target compound, each
surrogate compound, and each internal standard. The first criterion for
quantitative analysis is correct identification of compounds. The
compounds must elute within ± 0.06 retention time units of the elution
time of the standard analyzed on the same analytical system on the day of
the analysis. The analytes should be quantitated relative to the closest
eluting internal standard, according to the scheme shown in Table 4.
Calculate response factors (RF) for each compound relative to the internal
standard shown in Table 4. The internal standard selected for the
calculation of RF is the internal standard that has a retention time
closest to the compound being measured. The RF is calculated as follows:
where:
Ax = area of the characteristic ion for the compound being
measured.
Ajs = area of the characteristic ion for the specific internal
standard.
Cis = concentration of the specific internal standard.
C,, = concentration of the compound being measured.
7.16.3 The average RF must be calculated for each compound. A
system performance check should be made before the calibration curve is
used. Five compounds (the System Performance Check Compounds, or SPCCs)
are checked for a minimum average response factor. These compounds are
chloromethane, 1,1-dichloroethane, bromoform, 1,1,2,2-tetrachloroethane,
and chlorobenzene. The minimum acceptable average RF for these compounds
should be 0.300 (0.250 for bromoform}. These compounds typically have RFs
of 0.4 - 0.6, and are used to check compound instability and check for
degradation caused by contaminated lines or active sites in the system.
Examples of these occurrences are:
7.16.3.1 Chloromethane: This compound is the most likely
compound to be lost if the purge flow is too fast.
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7.16.3,2 Bromoform: This compound is one of the compounds
most likely to be purged very poorly if the purge flow is too slow.
Cold spots and/or active sites in transfer lines may adversely
affect response. Response of the primary quantitation ion (m/z 173)
is directly affected by the tuning for 4-bromofluorobenzene at the
ions of masses 174 and 176, Increasing the ratio of ions 174 and 176
to mass 95 (the base peak of the mass spectrum of
bromofluorobenzene) may improve bromoform response.
7.16.3.3 1,1,2,2-Tetrachloroethane and 1,1-dichloroethane:
These compounds are degraded by contaminated transfer lines in
purge-and-trap systems and/or active sites in trapping materials.
7,16.4 Using the response factors from the initial calibration,
calculate the percent relative standard deviation (%RSD) for the
Calibration Check Compounds (CCCs).
%RSD = (SD/X) x 100
where:
%RSD
RF,
RF
SD
percent relative standard deviation
individual RF measurement
mean of 5 initial RFs for a compound (the 5 points
over the calibration range)
standard deviation of average RFs for a compound,
where SD is calculated:
SD =
The %RSD for each individual CCC should be less than 30 percent.
This criterion must be met in order for the individual calibration to be
valid. The CCCs are: 1,1-dichloroethene, chloroform, 1,2-dichloropropane,
toluene, ethylbenzene, and vinyl chloride.
7.17 Daily EC/MS Calibration
7.17.1 Prior to the analysis of samples, purge 50 ng of the
4-bromofluorobenzene standard. The resultant mass spectrum for the BFB
must meet all of the criteria given in Table 3 before sample analysis
begins. These criteria must be demonstrated every twelve hours of
operation.
7.17.2 The initial calibration curve (Sec. 7.16) for each compound
of interest must be checked and verified once every twelve hours of
analysis time. This verification is accomplished by analyzing a
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calibration standard that is at a concentration near the midpoint
concentration for the working range of the GC/MS and checking the SPCC
(Sec. 7.16.3} and CCC (Sec. 7.16.4).
7.17.3 System Performance Check Compounds (SPCCs): A system
performance check must be made each twelve hours of analysis. If the SPCC
criteria are met, a comparison of response factors is made for all
compounds. This is the same check that is applied during the initial
calibration. If the minimum response factors are not achieved, the system
must be evaluated, and corrective action must be taken before analysis is
allowed to begin. The minimum response factor for volatile SPCCs is 0.300
(0,250 for bromoform) . If these minimum response factors are not
achieved, some possible problems may be degradation of the standard
mixture, contamination of the injector port, contamination at the front
end of the analytical column, and active sites in the column or
chromatographic system. If the problem is active sites at the front end
of the analytical column, column maintenance (removal of approximately 1
foot from the front end of the column) may remedy the problem.
7.17.4 Calibration Check Compounds: After the system performance
check has been met, CCCs listed in Sec. 7.16.4 are used to check the
validity of the initial calibration. Calculate the percent difference
using the following equation:
- RFJ x 100
% Difference =
where:
RFj * average response factor from initial calibration
RFC = response factor from current calibration check standard.
If the percent difference for any compound is greater than 20, the
laboratory should consider this a warning limit. Benzene, toluene, and
styrene will have problems with response factors if Tenax® decomposition
occurs (either as a result of sampling exposure or temperature
degradation), since these compounds are decomposition products of Tenax®.
If the percent difference for each CCC is less than 25%, the initial
calibration is assumed to be valid. If the criterion of percent
difference less than 25% is not met for any one CCC, corrective action
MUST be taken. Problems similar to those listed under SPCCs could affect
this criterion. If a source of the problem cannot be determined after
corrective action is taken, a new five-point calibration curve MUST be
generated. The criteria for the CCCs MUST be met before quantitative
analysis can begin.
7.17.5 Internal standard responses and retention times in the
check calibration standard must be evaluated immediately after or during
data acquisition. If the retention time for any internal standard changes
by more than 30 seconds from the last check calibration (12 hr), thi
chroraatographic system must be inspected for malfunctions and corrections
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must be made, as required. A factor which may influence the retention
times of the internal standards on sample tubes is the level of overall
organic compound loading on the VOST tubes. If the VOST tubes are very
highly loaded with either a single compound or with multiple organic
compounds, retention times for standards and compounds of interest will be
affected. If the area for the primary ion of any of the internal
standards changes by a factor of two (-50% to +100%) from the last daily
calibration check, the gas chromatograph and mass spectrometer should be
inspected for malfunctions and corrections must be made, as appropriate.
If the level of organic loading of samples is high, areas for the primary
ions of both compounds of interest and standards will be adversely
affected. Calibration check standards should not be subject to variation,
since the concentrations of organic compounds on these samples are set to
be within the linear range of the instrumentation. If instrument
malfunction has occurred, analyses of samples performed under conditions
of malfunction may be invalidated.
7.18 GC/MS Analysis of Samples
7.18.1 Set up the cartridge desorption unit, purge-and-trap
unit, and GC/MS as described above.
7.18,2 BFB tuning criteria and daily GC/MS calibration check
criteria must be met before analyzing samples.
7.18.3 Adjust the helium purge gas flow rate (through the
cartridges and purge vessel) to approximately 40 mL/rrnn. Optimize the
flow rate to provide the best response for chloromethane and bromoform, if
these compounds are analytes. A flow rate which is too high reduces the
recovery of chloromethane, and an insufficient gas flow rate reduces the
recovery of bromoform.
7.18.4 The first analysis performed after the tuning check and
the calibration or daily calibration check is a method blank. The method
blank consists of clean VOST tubes (both Tenax® and Tenax«/charcoal) which
are spiked with surrogate compounds and internal standards according to
the procedure described in Sec. 7.7.1. The tubes which are used for the
method blanks should be from the same batch of sorbent as the sorbent used
for the field samples. After the tubes are cleaned and prepared for
shipment to the field, sufficient pairs of tubes should be retained from
the same batch in the laboratory to provide method blanks during the
analysis.
7.18.5 The organic-free reagent water for the purge vessel for
the analysis of each of the VOST samples should be supplied from the
laboratory inventory which is maintained with constant bubbling of inert
gas to avoid contamination.
7.18.6 If the analysis of a pair of VOST tubes has a
concentration of analytes that exceeds the initial calibration range, no
reanalysis of desorbed VOST tubes is possible. An additional calibration
point can be added to bracket the higher concentration encountered in the
samples so that the calibration database encompasses six or more points.
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Alternatively, the data may be flagged in the report as "extrapolated
beyond the upper range of the calibration." The use of the secondary ions
shown in Table 1 is permissible only in the case of interference with the
primary quantitation ion. Use of secondary ions to calculate compound
concentration in the case of saturation of the primary ion is not an
acceptable procedure, since a negative bias of an unpredictable magnitude
is introduced into the quantitative data when saturation of the mass
spectrum of a compound is encountered, If high organic loadings, either
of a single compound or of multiple compounds, are encountered, it is
vital that a method blank be analyzed prior to the analysis of another
sample to demonstrate that no compound carryover is occurring. If
concentrations of organic compounds are sufficiently high that carryover
problems are profound, extensive bakeout of the purge-and-trap unit will
be required. Complete replacement of the contaminated analytical trap,
with the associated requirement for conditioning the new trap, nay also be
required for VOST samples which show excessive concentrations of organic
compounds. Other measures which might be required for decontamination of
the analytical system include bakeout of the mass spectrometer,
replacement of the filament of the mass spectrometer, cleaning of the ion
source of the mass spectrometer, and/or (depending on the nature of the
contamination) maintenance of the chromatographic column or replacement of
the chromatographic column, with the associated requirement for
conditioning the new chromatographic column.
7.19 Data Interpretation
7.19.1 Qualitative analysis:
7.19.1.1 The qualitative identification of compounds
determined by this method is based on retention time, and on
comparison of the sample mass spectrum, after background correction,
with characteristic ions in a reference mass spectrum. The
reference mass spectrum must be generated by the laboratory using
the conditions of this method. The characteristic ions from the
reference mass spectrum are defined to be the three ions of greatest
relative intensity, or any ions over 30% relative intensity if less
than three such ions occur in the reference spectrum. Compounds
should be identified as present when the criteria below are met.
7.19.1.1.1 The intensities of the characteristic ions
of a compound maximize in the same scan or within one scan of
each other. Selection of a peak by a data system target
compound search routine where the search is based on the
presence of a target chromatographic peak containing ions
specific for the target compound at a compound specific
retention time will be accepted as meeting this criterion.
7.19.1.1.2 The RRT of the sample component is + 0.06
RRT units of the RRT of the standard component.
7.19.1.1.3 The relative intensities of the
characteristic ions agree within 30% of the relative
intensities of these ions in the reference spectrum.
(Example: For an ion with an abundance of 50% in the
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reference spectrum, the corresponding abundance in a sample
spectrum can range between 20% and 80%.}
7.19.1,1,4 Structural isomers that produce very similar
mass spectra should be identified as individual isomers if
they have sufficiently different GC retention times.
Sufficient GC resolution is achieved if the height of the
valley between two isomer peaks is less than 25% of the sum of
the two peak heights. Otherwise, structural isomers are
identified as isomeric pairs.
7.19.1.1.5 Identification is hampered when sample
components are not resolved chromatographically and produce
mass spectra containing ions contributed by more than one
analyte. When gas chromatographic peaks obviously represent
more than one sample component (i.e., a broadened peak with
shoulder(s) or a valley between two or more maxima),
appropriate selection of analyte spectra and background
spectra is important. Examination of extracted ion current
profiles of appropriate ions can aid in the selection of
spectra, and in qualitative identification of compounds. When
analytes coelute (i.e., only one chromatographic peak is
apparent), the identification criteria can be met, but each
analyte spectrum will contain extraneous ions contributed by
the coeluting compound.
7.19.1.2 For samples containing components not associated
with the calibration standards, a library search may be made for the
purpose of tentative identification. The necessity to perform this
type of identification will be determined by the type of analyses
being conducted. Guidelines for making tentative identification
are:
(1) Relative intensities of major ions in the reference
spectrum (ions > 10% of the most abundant ion) should be present in
the sample spectrum.
(2) The relative intensities of the major ions should agree
within + 20%. (Example: For an ion with an abundance of 50% in the
standard spectrum, the corresponding sample ion abundance must be
between 30 and 70%).
(3) Molecular ions present in the reference spectrum should
be present in the sample spectrum.
(4) Ions present in the sample spectrum but not in the
reference spectrum should be reviewed for possible background
contamination or presence of coeluting compounds.
(5) Ions present in the reference spectrum but not in the
sample spectrum should be reviewed for possible subtraction from the
sample spectrum because of background contamination or coeluting
peaks. Data system library reduction programs can sometimes create
these discrepancies.
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-------
Computer generated library search routines should not use
normalization routines that would misrepresent the library or
unknown spectra when compared to each other. Only after visual
comparison of sample with the nearest library searches will the mass
spectral interpretation specialist assign a tentative
identification.
7.19.2 Quantitative analysis:
7.19,2,1 When a compound has been identified, the
quantitative analysis of that compound will be based on the
integrated abundance from the extracted ion current profile of the
primary characteristic ion for that compound (Table 1). In the
event that there is interference with the primary ion so that
quantitative measurements cannot be made, a secondary ion may be
used.
NOTE: Use of a secondary ion to perform quantitative
calculations in the event of the saturation of the
primary ion is not an acceptable procedure because of
the unpredictable extent of the negative bias which is
introduced. Quantitative calculations are performed
using the internal standard technique. The internal
standard used to perform quantitative calculations shall
be the internal standard nearest the retention time of
a given analyte (see Table 4).
7.19.2.2 Calculate the amount of each identified analyte
from the VOST tubes as follows:
Amount (ng) = (AECis)/(AisRF)
where:
A,. = area of the characteristic ion for the analyte to be
measured.
Ais = area of the characteristic ion of the internal standard,
Cjs = amount (ng} of the internal standard.
7,19.2.3 The choice of methods for evaluating data
collected using the VOST methodology for incinerator trial burns is
a regulatory decision. Various procedures are used to decide
whether blank correction should be performed and how blank
correction should be performed. Regulatory agencies to which VOST
data are submitted also vary in their preferences for data which are
or which are not blank corrected.
7.19.2.4 The total amount of the PQHCs of interest
collected on a pair of traps should be summed.
5041 - 20 Revision 0
September 1994
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7.19,2,5 The occurrence of high concentrations of analytes
on method blank cartridges indicates possible residual contamination
of sorbent cartridges prior to shipment and use at the sampling
site. Data with high associated blank values must be qualified with
respect to validity, and all blank data should be reported
separately. No blank corrections should be made in this case.
Whether or not data of this type can be applied to the determination
of destruction and removal efficiency is a regulatory decision.
Continued observation of high concentrations of analytes on blank
sorbent cartridges indicates that procedures for cleanup and quality
control for the sampling tubes are inadequate. Corrective action
MUST be applied to tube preparation and monitoring procedures to
maintain method blank concentrations below detection limits for
analytes.
7.19.2.6 Where applicable, an estimate of concentration for
noncalibrated components in the sample may be made. The formulae
for quantitative calculations presented above should be used with
the following modifications: The areas A,, and Ais should be from the
total ion chromatograms, and the Response Factor for the
noncalibrated compound should be assumed to be 1. The nearest
eluting internal standard free from interferences in the total ion
chromatogram should be used to determine the concentration. The
concentration which is obtained should be reported indicating: (1)
that the value is an estimate; and (2) which internal standard was
used.
7.19.2.7 If any internal standard recoveries fall outside
the control limits established in Sec. 8.4, data for all analytes
determined for that cartridge(s) must be qualified .with the
observation. Report results without correction for surrogate
compound recovery data. When duplicates are analyzed, report the
data obtained with the sample results.
8.0 QUALITY CONTROL
8.1 Each laboratory that uses these methods is required to operate a
formal quality control program. The minimum quality control requirements are
specified in Chapter One. In addition, this program should consist of an initial
demonstration of laboratory capability and an ongoing analysis of check samples
to evaluate and document data quality. The laboratory must maintain records to
document the quality of the data 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 sample
analyses indicate atypical method performance, a quality control check standard
(spiked method blank) must be analyzed to confirm that the measurements were
performed in an in-control mode of instrument operation.
8.2 Before processing any samples, the analyst should demonstrate,
through the analysis of a method blank (laboratory blank sorbent tubes, reagent
water purge) that interferences from the analytical system, glassware, sorbent
tube preparation, and reagents are under control. Each time a new batch of
5041 - 21 Revision 0
September 1994
-------
sorbent tubes is analyzed, a method blank should be processed as a safeguard
against chronic laboratory contamination. Blank tubes which have been carried
through all the stages of sorbent preparation and handling should be used in the
analysis.
8.3 The experience of the analyst performing the GC/MS analyses is
invaluable to the success of the analytical methods. Each day that the analysis
is performed, the daily calibration check standard should be evaluated to
determine if the chromatographic and tube desorption systems are operating
properly. Questions that should be asked are: Do the peaks look normal? Is the
system response obtained comparable to the response from previous calibrations?
Careful examination of the chromatogram of the calibration standard can indicate
whether column maintenance is required or whether the column is still usable,
whether there are leaks in the system, whether the injector septum requires
replacing, etc. If changes are made to the system (such as change of a column),
a calibration check must be carried out and a new multipoint calibration must be
generated.
8.4 Required instrument quality control is found in the following
sections:
8.4.1 The mass spectrometer must be tuned to meet the specifications
for 4-bromofluorobenzene in Sec. 7.2 {Table 3).
8J4.2 An initial calibration of the tube desorption/purge-and-trap/
GC/MS must be performed as specified in Sec. 7.7.
8.4.3 The GC/MS system must meet the SPCC criteria specified in Sec.
7.16.3 and the CCC criteria in Sec. 7.16.4 each twelve hours of instrument
operation.
8.5 To establish the ability to generate acceptable accuracy and
precision, the analyst must perform the following operations.
8.5.1 A quality control (QC) check sample concentrate is required
containing each analyte at a concentration of 10 mg/L in high purity
methanol. The QC check sample concentrate may be prepared from pure
standard materials or purchased as certified solutions. If the QC check
sample concentrate is prepared by the laboratory, the QC check sample
concentrate must be prepared using stock standards prepared independently
from the stock standards used for calibration.
8.5.2 Spike four pairs of cleaned, prepared VOST tubes with 10 /uL
of the QC check sample concentrate and analyze these spiked VOST tubes
according to the mathod beginning in Sec. 7.0.
8.5.3 Calculate the average recovery (X) in ng and the standard
deviation of the recovery (s) in ng for each analyte using the results of
the four analyses.
8.5.4 The average recovery and standard deviation must fall within
the expected range for determination of volatile organic compounds using
the VOST analytical methodology. The expected range for recovery of
5041 - 22 Revision 0
September 1994
-------
volatile organic compounds using this method is 50-150%. Standard
deviation will be compound dependent, but should, in general, range from
15 to 30 ng. More detailed method performance criteria must be generated
from historical records in the laboratory or from interlaboratory studies
coordinated by the Environmental Protection Agency. Since the additional
steps of sorbent tube spiking and desorption are superimposed upon the
methodology of Method 8260, direct transposition of Method 8260 criteria
is questionable. If the recovery and standard deviation for all analytes
meet the acceptance criteria, the system performance is acceptable and the
analysis of field samples may begin. If any individual standard deviation
exceeds the precision limit or any individual recovery falls outside the
range for accuracy, then the system performance is unacceptable for that
analyte.
NOTE: The large number of analytes listed in Table 1 presents a
substantial probability that one or more will fail at least
one of the acceptance criteria when all analytes for this
method are determined.
8,5.5 When one or more of the analytes tested fails at least one of
the acceptance criteria, the analyst must proceed according to one of the
alternatives below.
8.5.5.1 Locate and correct the source of any problem with
the methodology and repeat the test for all the analytes beginning
with Sec. 8.5.2.
8.5.5.2 Beginning with Sec. 8.5.2, repeat the test only
for those analytes that have failed to meet acceptance criteria.
Repeated failure, however, will confirm a general problem either
with the measurement system or with the applicability of the
methodology to the particular analyte (especially if the analyte in
question is not listed in Table 1). If the problem is identified as
originating in the measurement system, locate and correct the source
of the problem and repeat the test for all compounds of interest
beginning with Sec. 8.5.2.
8.6 To determine acceptable accuracy and precision limits for surrogate
standards, the following procedure should be performed.
8.6.1 For each sample analyzed, calculate the percent recovery of
each surrogate compound in the sample.
8.6.2 Once a minimum of thirty samples has been analyzed, calculate
the average percent recovery (p) and the standard deviation of the percent
recovery (s) for each of the surrogate compounds.
8.6.3 Calculate the upper and lower control limits for method
performance for each surrogate standard. This calculation is performed as
follows:
Upper Control Limit (UCL) = p 4- 3s
Lower Control Limit (LCL) = p - 3s
5041 - 23 Revision 0
September 1994
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For reference, the comparable control limits for recovery of the
surrogate compounds from water and soil in Method 8240 are:
4-Bromofluorobenzene Water: 86-115% Soil: 74-121%
I,2-Dichloroethane-d4 Water: 76-114% Soil: 70-121%
Toluene-dg Water: 88-110% Soil: 81-117%
The control limits for the VOST methodology would be expected to be
similar, but exact data are not presently available. Individual laboratory
control limits can be established by the analysis of replicate samples.
8.6.4 If surrogate recovery is not within the limits established by
the laboratory, the following procedures are required: (1) Verify that
there are no errors in calculations, preparation of surrogate spiking
solutions, and preparation of internal standard spiking solutions. Also,
verify that instrument performance criteria have been met, (2) Recalculate
the data and/or analyze a replicate sample, if replicates are available.
(3) If all instrument performance criteria are met and recovery of
surrogates from spiked blank VOST tubes (analysis of a method blank) is
acceptable, the problem is due to the matrix. Emissions samples may be
highly acidic and may be highly loaded with target and non target organic
compounds. Both of these conditions will- affect the ability to recover
surrogate compounds which are spiked on the field samples. The surrogate
compound recovery is thus a valuable indicator of the interactions of
sampled compounds with the matrix. If surrogates spiked immediately
before analysis cannot be observed with acceptable recovery, the
implications for target organic analytes which have been sampled in the
field must be assessed very carefully. If chemical or other interactions
are occurring on the exposed tubes, the failure to observe an analyte may
not necessarily imply that the Destruction and Removal Efficiency for that
analyte is high.
8.7 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 analyzed. 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 a different ionization mode using a mass spectrometer may
be used, if replicate samples showing the same compound are available. Whenever
possible, the laboratory should analyze standard reference materials and
participate in relevant performance evaluation studies.
9.0 METHOD PERFORMANCE
9.1 The method detection limit (MDL) is defined in Chapter One. The MDL
concentrations listed in Table 2 were obtained using cleaned blanked VOST tubes
and reagent water. Similar results have been achieved with field samples. The
MDL actually achieved in a given analysis will vary depending upon instrument
sensitivity and the effects of the matrix. Preliminary spiking studies indicate
that under these conditions, the method detection limit for spiked compounds 1n
extremely complex matrices may be larger by a factor of 500-1000.
5041 - 24 Revision 0
September 1994
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10.0 REFERENCES
1. Protocol for Collection and Analysis of Volatile POHCs Using VOST.
EPA/600/8-84-007, March, 1984.
2. Validation of the Volatile Organic Sampling Train (VOST) Protocol,
Volumes I and II. EPA/600/4-86-014A, January, 1986.
3, U. S. EPA 40 CFR Part 136, "Guidelines Establishing Test Procedures for
Analysis of Pollutants Under the Clean Water Act, Method 624," October 26,
1984.
4. Bellar, T. A., and J. J. Lichtenberg, J. Amer. Water Works Assoc., 66(12),
739-744, 1974.
5. Bellar, T. A., and J. J. Lichtenberg, "Semi-Automated Headspace Analysis
of Drinking Waters and Industrial Waters for Purgeable Volatile Organic
Compounds," in Van Hall, ed., Measurement of Organic Pollutants in Hater
and Wastewater, ASTM STP 686, pp 108-129, 1979.
5041 - 25 Revision 0
September 1994
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TABLE 1.
RETENTION TIMES AND CHARACTERISTIC IONS FOR VOLATILE COMPOUNDS
WHICH CAN BE ANALYZED BY METHOD 5041
Retention
Compound Time (min)
Acetone
Acrylonitrile
Benzene
Bromochl oromethane
Bromodi chl oromethane
4-Bromofluorobenzene
Bromoform
Bromomethane
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chlorodibromomethane
Chloroethane
Chloroform
Chloromethane
Dibromomethane
1,1-Dichloroethane
1,2-Dichloroethane
1,1-Dichloroethene
trans -1,2-Dichloroethene
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans- 1 , 3 -Di chl oropropene
1 ,4-Difluorobenzene
Ethyl benzene
lodomethane
Methyl ene chloride
Styrene
1,1,2. V -Tetrachl oroethane
Tetrat oroet^rne
Toluer
1,1,1 chloroethane
1,1,2- ? i chl oroethane
Trichloroethene
Tri chl orof 1 uoromethane
1 ,2,3-Trichloropropane
Vinyl chloride
Xylenes*
7.1
8.6
13.3
12.0
16.0
23.4
22.5
4.1
7.1
12.6
20.5
19.3
4.2
12.2
3.0
15.4
10,0
13.3
6.4
8.6
15.2
17.0
18.2
14.2
21.1
7.0
8.1
22.3
24.0
18.6
17.4
12.4
18.4
14.5
5.1
24.0
3.2
22.2
Primary Ion
Mass
43
53
78
128
83
95
173
94
76
117
112
129
64
83
50
93
63
62
96
96
63
75
75
114
106
142
84
104
83
164
92
97
97
130
101
75
62
106
Secondary Ion(s)
Mass(es)
58
52, 51
52, 77
49, 130, 51
85, 129
174, 176
171, 175, 252
96, 79
78
119, 121
114, 77
208, 206
66, 49
85, 47
52, 49
174, 95
65, 83
64, 98
61, 98
61, 98
62, 41
77, 39
77, 39
63, 88
91
127, 141
49, 51, 86
78, 103
85, 131, 133
129, 131, 166
91, 65
99, 117
83, 85, 99
95, 97, 132
103, 66
110, 77, 61
64, 61
91
The retention time given is for m- and p-xylene, which coelute on the wide-bore
column. o-Xylene elutes approximately 50 seconds later.
5041 - 26
Revision 0
September 1994
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TABLE 2.
PRELIMINARY METHOD DETECTION LIMITS AND BOILING POINTS
FOR VOLATILE ORGANICS ANALYZED BY METHOD 5041*
Compound
Chloromethane
Bromomethane
Vinyl chloride
Chloroethane
Methylene chloride
Acetone
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
trans-l,2-Dichloroethene
Chloroform
1,2-Dichloroethane
1,1,1-Tri chloroethane
Carbon tetrachloride
Bromodichloromethane
1,1,2,2-Tetrachloroethane"
1,2-Dichloropropane
trans- 1 , 3 -Di chl oropropene
Trichloroethene
Dibromochloromethane
1,1,2-Trichloroethane
Benzene
cis-1 , 3-Dichl oropropene
Bromoform""
Tetrachl oroethene
Toluene
Chlorobenzene^
Ethyl benzene"
Styrene"
Trichlorofl uoromethane
lodomethane
Acryloni trile
Dibromomethane
1,2,3-Trichloropropane**
total Xylenes"
CAS Number
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-35-3
156-60-5
67-66-3
107-06-2
71-55-6
56-23-5
75-27-4
79-34-5
78-87-5
10061-02-6
79-01-6
124-48-1
79-00-5
71-43-2
10061-01-5
75-25-2
127-18-4
108-88-3
108-90-7
100-41-4
100-42-5
75-69-4
74-88-4
107-13-1
74-95-3
96-18-4
Detection
Limit, ng
58
26
14
21
9
35
11
14
12
11
11
13
8
8
11
23
12
17
11
21
26
26
27
26
11
15
15
21
46
17
9
13
14
37
22
Boiling
Point, °t
-24
4
-13
13
40
56
46
32
57
48
62
83
74
77
88
146
95
112
87
122
114
80
112
150
121
111
132
136
145
24
43
78
97
157
138-144
* The method detection limit (HDL) 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. The detection limits cited above were
determined according to Title 40 CFR, Part 136, Appendix B, using standards spiked
onto clean VOST tubes. Since clean VOST tubes were used, the values cited above
represent the best that the methodology can achieve. The presence of an emissions
matrix will affect the ability of the methodology to perform at its optimum level.
** Not appropriate for quantitative sampling by Method 0030.
5041 - 27
Revision 0
September 1994
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TABLE 3.
KEY ION ABUNDANCE CRITERIA FOR 4-BROMQFLUOROBENZENE
Mass Ion Abundance Criteria
50 15 to 40% of mass 95
75 30 to 60% of mass 95
95 base peak, 100% relative abundance
96 5 to 9% of mass 95
173 less than 2% of mass 174
174 greater than 50% of mass 95
175 5 to 9% of mass 174
176 greater than 95%, but less than 101% of mass 174
177 5 to 9% of mass 176
5041 - 28 Revision 0
September 1994
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TABLE 4.
VOLATILE INTERNAL STANDARDS WITH CORRESPONDING ANALYTES
ASSIGNED FOR QUANT RATION
Bromochlpromethane
Acetone
Acrylonitrile
Bromomethane
Carbon distil fide
Chloroethane
Chloroform
Chloromethane
1,1-Dichloroethane
1,2-Dichloroethane
l,2-Dichloroethane-d4 (surrogate)
1,1-Dichloroethene
Trichloroethene
trans-1,2-Dichloroethene
lodomethane
Methylene chloride
Tri chlorof1uoromethane
Vinyl chloride
1,4-Di f1uorobenzene
Benzene
Bromodi chloromethane
Brotnoform
Carbon tetrachloride
Chlorodibromomethane
Dibromomethane
1,2-Dichloropropane
cis-l,3-Dichloropropene
trans-1,3-Dichlcropropene
1,1,1-Tri chloroethane
1,1,2-Tr1chloroethane
Ch1orobenzene-d5
4-Bromofluorobenzene (surrogate)
Chlorobenzene
Ethyl benzene
Styrene
1,1,2,2-Tetrach1oroethane
Tetrachloroethene
Toluene
Toluene-d8 (surrogate)
1,2,3-Tri chloropropane
Xylenes
5041 - 29
Revision 0
September 1994
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Ol
een
o •-«
O)
oe
o.
01
o
o
s-
o
o
en
a
en
o
in
OJ
s_
i i
© 0
-------
Cartridge Oesorplion Unit
1/8" Teflon Tubing
Stand to Raise
Clam Shell Oven
Figure 2. Cartridge Desorption Unit with Purge and Trap Unit
5041 - 31
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September 1994
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Tube
Desorption
Unit
Purge and Trap
Apparatus
Gas
Chromalograph
Interface
Mass
Spectrometer
i
| Polo System j
Storage Media
lor Archive
Figure 3. Schematic Diagram of Overall Analytical System
5041 - 32
Revision 0
September 1994
-------
Water nil Line
Sin»«red Class frit
Gas Flow
Figure 4. Sample Purge Vessel
5041 - 33
Revision 0
September 1994
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Slack
(or l«il system)
Condenialt
Trap
Impingcr
Silica Gel
Vacuum
.Indicator
Cxhauil
Figure 5. Schematic of Volatile Organic Sampling Train (VOST)
5041 - 34
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September 1994
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METHOD 5041
PROTOCOL FOR ANALYSIS OF SORBENT CARTRIDGES FROM VOLATILE ORGANIC
SAMPLING TRAIN: WIDE-BORE CAPILLARY COLUMN TECHNIQUE
( Start J
1
r
7.1 Condition* for
cartridge
deeorption oven,
purge-and-trap
concentrator, GC,
•nd MS.
1
7.2 Daily, tuna
the GC/MS with
BFB and check
calibration curve
(a*e Section 7.17).
^
i
7.3 - 7.6
Assemble the
ayatem.
1
r
7.7.1 Calibrate the
instrument eyatem
Ljiing th* internal ltd.
procedure. Std». and
calibration compound*
are epiked into cleaned
VOST tube* uaing th*
flaah evaporation
technique.
1
f
7.8 Prep th*
purge-and-trap
unit with 6 ml
organic-free
reagent water.
1
7.9 C<
paired
tubee
gai Mr
a»*or
f
Miiiaet
VOST
to the
ea lor
ition.
. fc
7.10 Initiate
tube deaorption/
purge and
heating.
,
.
7.11 Sat th* GC
oven to »ubambient
temperature
with liquid
nitroflsn.
^
T
7.12 Prep the
GC/MS ayitem
for date
aquieition.
J
f
7.13 After the tube/
water purge time,
attach the
analytical trap to
the GC/MS for
daaorpttort.
^
r
7.14 Waah purging
veaiel with two
S mi flua hea of
organic-free
reagent water.
1
r
7. IE Recondition th*
enalytical trap by
making it cut ml
tempi up to 220 C for
11 min. Trap replacement
may be naceeaory
if th* analytical trap
i* aatu rated beyond
cleanup.
1
r
7.18.1 Prep
calibration atde.
at in 7.7.1. Add
water to veeiel
and deaorb.
, ,. fr
7.16.2
Tabulate the
area re»pon»e
of ell compounds
of interest.
V
7.16.3
Calculate the
average RF for
each compound
of intereet.
1 r
7.16.4 Calculate
the %RSD
for the CCC*.
The %RSO must
be <30%.
v
7.18 GC/MS
anelyei« of
aemplea.
ir
7.13.1 Qualitative
anelyai* of data
and ident. guideline*
of compounds.
i r
7.19.2 Quantitative
anelyei* of data for
the compound* of
interest.
1 r
/ Stop J
5041 - 35
Revision 0
September 1994
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-------
METHOD 5050
BOMB PREPARATION METHOD FOR SOLID WASTE
1.0 SCOPE AND APPLICATION
1.1 This method describes the sample preparation steps necessary to
determine total chlorine in solid waste and virgin and used oils, fuels and
related materials, including: crankcase, hydraulic, diesel, lubricating and fuel
oils, and kerosene by bomb oxidation and titration or ion chromatography.
Depending on the analytical finish chosen, other halogens (bromine and fluorine)
and other elements (sulfur and nitrogen) may also be determined.
1.2 The applicable range of this method varies depending on the
analytical finish chosen. In general, levels as low as 500 jug/g chlorine in the
original oil sample can be determined. The upper range can be extended to
percentage levels by dilution of the combustate.
1.3 This standard may involve hazardous materials, operations, and
equipment. This standard does not purport to address all of the safety problems
associated with its use. It is the responsibility of the user of this standard
to establish appropriate safety and health practices and determine the
applicability of regulatory limitations prior to use. Specific safety statements
are given in Section 3.0.
2.0 SUMMARY OF METHOD
2.1 The sample is oxidized by combustion in a bomb containing oxygen
under pressure. The liberated halogen compounds are absorbed in a sodium
carbonate/sodium bicarbonate solution. Approximately 30 to 40 minutes are
required to prepare a sample by this method. Samples with a high water content
(> 25%) may not combust efficiently and may require the addition of a mineral oil
to facilitate combustion. Complete combustion is still not guaranteed for such
samples.
2.2 The bomb combustate solution can then be analyzed for the following
elements as their anion species by one or more of the following methods:
Method Title
9252 Chloride (Titrimetric, Mercuric Nitrate)
9253 Chloride (Titrimetric, Silver Nitrate)
9056 Inorganic Anions by Ion Chromatography (Chloride, Sulfate,
Nitrate, Phosphate, Fluoride, Bromide)
5050 - 1 Revision 0
September 1994
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NOTE: Strict adherence to all of the provisions prescribed hereinafter
ensures against explosive rupture of the bomb, or a blowout, provided the
bomb is of proper design and construction and in good mechanical
condition. It is desirable, however, that the bomb be enclosed in a
shield of steel plate at least 1/2 in. (12.7 mm) thick, or equivalent
protection be provided against unforeseeable contingencies.
3.0 INTERFERENCES
3.1 Samples with very high water content (> 25%) may not combust
efficiently and may require the addition of a mineral oil to facilitate
combustion.
3.2 To determine total nitrogen in samples, the bombs must first be
purged of ambient air. Otherwise, nitrogen results will be biased high.
4.0 APPARATUS AND MATERIALS
4.1 Bomb, having a capacity of not less than 300 ml, so constructed
that it will not leak during the test, and that quantitative recovery of the
liquids from the bomb may be readily achieved. The inner surface of the bomb may
be made of stainless steel or any other material that will not be affected by the
combustion process or products. Materials used in the bomb assembly, such as the
head gasket and lead-wire insulation, shall be resistant to heat and chemical
action and shall not undergo any reaction that will affect the chlorine content
of the sample in the bomb.
4.2 Sample cup, platinum or stainless steel, 24 mm in outside diameter
at the bottom, 27 mm in outside diameter at the top, 12 mm in height outside, and
weighing 10 to 11 g.
4.3 Firing wire, platinum or stainless steel, approximately No. 26 B
& S gage.
4.4 Ignition circuit, capable of supplying sufficient current to ignite
the nylon thread or cotton wicking without melting the wire.
NOTE: The switch in the ignition circuit shall be of the type that remains
open, except when held in closed position by the operator.
4.5 Nylon sewing thread, or Cotton Wicking, white.
4.6 Funnel, to fit a 100-mL volumetric flask.
4.7 Class A volumetric flasks, 100-mL, one per sample.
4.8 Syringe, 5- or 10-mL disposable plastic or glass.
4.9 Apparatus for specific analysis methods are given in the methods.
4.10 Analytical balance: capable of weighing to 0.0001 g.
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5.0 REAGENTS
5.1 Purity of reagents. 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.
5,2 Reagent water. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Oxygen. Free of combustible material and halogen compounds,
available at a pressure of 40 atra.
WARNING: Oxygen vigorously accelerates combustion (see Appendix Al.l)
5.4 Sodium bicarbonate/sodium carbonate solution. Dissolve 2.5200 g
NaHC03 and 2.5440 g Na2C03 in reagent water and dilute to 1 L.
5.5 White oil. Refined.
5.6 Reagents'and materials for specific analysis methods are given in
the methods.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine.
6.2 Ensure that the portion of the sample used for the test is repre-
sentative of the sample.
6.3 To minimize losses of volatile halogenated solvents that may be
present in the sample, keep the field and laboratory samples as free of headspace
as possible.
6.4 Because used oils may contain toxic and/or carcinogenic substances
appropriate field and laboratory safety procedures should be followed.
7.0 PROCEDURE
7.1 Sample Preparation
7.1.1 Preparation of bomb and sample. Cut a piece of firing wire
approximately 100 mm in length and attach the free ends to the terminals.
Arrange the wire so that it will be just above and not touching the sample
cup. Loop a cotton thread around the wire so that the ends will extend
into the sampling cup. Pipet 10 mL of the NaHCO.j/Na2C03 solution into the
bomb, wetting the sides. Take an aliquot of the oil sample of approxi-
mately 0.5 g using a 5- or 10-mL disposable plastic syringe, and place in
the sample cup. The actual sample weight is determined by the difference
5050 - 3 Revision 0
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between the weight of the empty and filled syringe. Do not use more than
1 g of sample.
NOTE: After repeated use of the bomb for chlorine determination,
a film may be noticed on the inner surface. This dullness should
be removed by periodic polishing of the bomb. A satisfactory
method for doing this is to rotate the bomb in a lathe at about
300 rpm and polish the inside surface with Grit No. 2/0 or
equivalent paper1 coated with a light machine oil to prevent
cutting, and then with a paste of grit-free chromic oxide2 and
water. This procedure will remove all but very deep pits and put
a high polish on the surface. Before using the bomb, it should
be washed with soap and water to remove oil or paste left from the
polishing operation. Bombs with porous or pitted surfaces should
never be used because of the tendency to retain chlorine from
sample to sample.
NOTE: If the sample is not readily combustible, other
nonvolatile, chlorine-free combustible diluents such as white oil
may be employed. However, the combined weight of sample and
nonvolatile diluent shall not exceed 1 g. Some solid additives
are relatively insoluble but may be satisfactorily burned when
covered with a layer of white oil.
NOTE: The practice of alternately running samples high and low
in chlorine content should be avoided whenever possible. It is
difficult to rinse the last traces of chlorine from the walls of
the bomb, and the tendency for residual chlorine to carry over
from sample to sample has been observed in a number of
laboratories. When a sample high in chlorine has preceded one low
in chlorine content, the test on the low-chlorine sample should
be repeated, and one or both of the low values thus obtained
should be considered suspect if they do not agree within the
limits of repeatability of this method.
NOTE: Do not use more than 1 g total of sample and white oil or
other chlorine-free combustible material. Use of excess amounts
of these materials could cause a buildup of dangerously high
pressure and possible rupture of the bomb.
7.1.2 Addition of oxygen. Place the sample cup in position
and arrange the thread so that the end dips into the sample. Assemble the
bomb and tighten the cover securely. Admit oxygen slowly (to avoid
blowing the oil from the cup) until a pressure is reached as indicated in
Table 1.
NOTE: Do not add oxygen or ignite the sample if the bomb has been
jarred, dropped, or tiled.
"'Emery Polishing Paper grit No. 2/0 may be purchased from the Behr-Manning
Co., Troy, NY.
2Chromic oxide may be purchased from J.T. Baker & Co., PhiTiipsburg, NJ.
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7,1.3 Combustion. Immerse the bomb in a cold water bath.
Connect the terminals to the open electrical circuit. Close the circuit
to ignite the sample. Remove the bomb from the bath after immersion for
at least 10 minutes. Release the pressure at a slow, uniform rate such
that the operation requires at least 1 min. Open the bomb and examine the
contents. If traces of unburned oil or sooty deposits are found, discard
the determination, and thoroughly clean the bomb before using it again.
7.1.4 Collection of halogen solution. Using reagent water and
a funnel, thoroughly rinse the interior of the bomb, the sample cup, the
terminals, and the inner surface of the bomb cover into a IQQ-mL
volumetric flask. Dilute to the mark with reagent water.
7.1.5 Cleaning procedure for bomb and sample cup. Remove any
residual fuse wire from the terminals and the cup. Using hot water, rinse
the interior of the bomb, the sample cup, the terminals, and the inner
surface of the bomb cover. (If any residue remains, first scrub the bomb
with Alconox solution). Copiously rinse the bomb, cover, and cup with
reagent water.
7.2 Sample Analysis. Analyze the combustate for chlorine or other
halogens using the methods listed in Step 2.2. It may be necessary to dilute the
samples so that the concentration will fall within the range of standards.
7.3 Calculations. Calculate the concentrations of each element
detected in the sample according to the following equation:
Ccom * Vcom x DF (1)
C,
o
where:
C0 = concentration of element in the sample,
CCom = concentration of element in the combustate,
Vcom = total volume of combustate, ml
DF = dilution factor
W0 = weight of sample combusted, g.
Report the concentration of each element detected in the sample in
micrograms per gram.
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Example: A 0.5-g oil sample was combusted, yielding 10 ml of combustate.
The combustate was diluted to 100 ml total volume and analyzed for chloride,
which was measured to be 5 ^g/ml. The concentration of chlorine in the original
sample is then calculated as shown below:
5 ug x (10 ml) x (10)
C0 = ml (2)
0.5 g
C0 = 1,000 M (3)
g
8.0 QUALITY CONTROL
8,1 Refer to Chapter One for specific quality control procedures.
8.2 One sample in ten should be bombed twice. The results should agree
to within 10%, expressed as the relative percent difference of the results.
8.3 Analyze matrix spike and matrix spike duplicates - spike samples with
the elements of interest at a level commensurate with the levels being
determined. The spiked compounds should be similar to those expected in the
sample. Any sample suspected of containing > 25% water should also be spiked
with organic chlorine.
8.4 For higher levels (e.g., percent levels), spiking may be
inappropriate. For these cases, samples of known composition should be
combusted. The results should agree to within 10% of the expected result.
8.5 Quality control for the analytical method(s) of choice should be
followed.
9.0 PERFORMANCE
See analytical methods referenced in Step 2.2.
10.0 REFERENCES
1. ASTH Method D 808-81, Standard Test Method for Chlorine in New and Used
Petroleum Products (Bomb Method). 1988 Annual Book of ASTM Standards. Volume
05.01 Petroleum Products and Lubricants.
2. Gaskill, A.; Estes, E. D.; Hardison, D. L.; and Myers, L. E. Validation
of Methods for Determining Chlorine in Used Oils and Oil Fuels. Prepared for
U.S. Environmental Protection Agency, Office of Solid Waste. EPA Contract No.
58-01-7075, WA 80. July 1988.
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TABLE 1.
GAGE PRESSURES
Capacity of bomb, ml
Minimum
gage
pressure8, atm
Maximum
gage
pressure8
atm
300 to 350
350 to 400
400 to 450
450 to 500
38
35
30
27
40
37
32
29
"The minimum pressures are specified to provide sufficient oxygen for complete
combustion, and the maximum pressures represent a safety requirement. Refer to
manufacturers' specifications for appropriate gage pressure, which may be lower
than those listed here.
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APPENDIX
Al. PRECAUTIONARY STATEMENTS
Al.'l Oxygen
Warning—Oxygen vigorously accelerates combustion.
Keep oil and grease away. Do not use oil or grease on regulators, gages,
or control equipment.
Use only with equipment conditioned for oxygen service by careful cleaning
to remove oil, grease, and other combustibles.
Keep combustibles away from oxygen and eliminate ignition sources.
Keep surfaces clean to prevent ignition or explosion, or both, on contact
with oxygen.
Always use a pressure regulator. Release regulator tension before opening
cylinder valve.
All equipment and containers used must be suitable and recommended for
oxygen service.
Never attempt to transfer oxygen from cylinder in which it is received to
any other cylinder. Do not mix gases in cylinders.
Do not drop cylinder. Make sure cylinder is secured at all times.
Keep cylinder valve closed when not in use.
Stand away from outlet when opening cylinder valve.
For technical use only. Do not use for inhalation purposes.
Keep cylinder out of sun and away from heat.
Keep cylinders from corrosive environment.
Do not use cylinder without label.
Do not use dented or damaged cylinders.
See Compressed Gas Association booklets G-4 and G4.1 for details of safe
practice in the use of oxygen.
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METHOD 5050
BOMB PREPARATION METHOD FOR SOLID WASTE
START
1
? 1 I Prepare bcmb
and sample
I
71.2 Slowly add
oxygen to aampie
CUJ3
I
7 1.3 Ifnttterse bomb
in cold wa LET ;
ignite sample ;
remove bomb f r om
*ta ter ; release
pressure, open bocnb
1
1 1 4 Hir.a e bomb ,
sample cup,
terminals . and bomb
covet **ith water
1 . 1 . S Hinate bomb .
sample cup ,
terminals , and bomb
cover with ha I
wa ter
1
7 2 Analyze
cstfibuj ta t«
1
? 3 Calculate
can cert tra lion of
each element
detected
1
C - )
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METHOD 6020
INDUCTIVELY COUPLED PLASMA - MASS SPECTROMETRY
1.0 SCOPE AND APPLICATION
1.1 Inductively coupled plasma-mass spectrometry (ICP-MS) is applicable
to the determination of sub-^g/L concentrations of a large number of elements in
water samples and in waste extracts or digests [1,2]. When dissolved
constituents are required, samples must be filtered and acid-preserved prior to
analysis. No digestion is required prior to analysis for dissolved elements in
water samples. Acid digestion prior to filtration and analysis is required for
groundwater, aqueous samples, industrial wastes, soils, sludges, sediments, and
other solid wastes for which total (acid-leachable) elements are required.
1.2 ICP-MS has been applied to the determination of over 60 elements in
various matrices. Analytes for which EPA has demonstrated the acceptability of
Hethod 6020 in a multi-laboratory study on solid wastes are listed in Table 1.
Acceptability of the method for an element was based upon the multi-laboratory
performance compared with that of either furnace atomic absorption spectroscopy
or inductively coupled plasma-atomic emission spectroscopy. It should be noted
that the multi-laboratory study was conducted in 1986. Multi-laboratory
performance data for the listed elements (and others) are provided in Section 9.
Instrument detection limits, sensitivities, and linear ranges will vary with the
matrices, instrumentation, and operating conditions. In relatively simple
matrices, detection limits will generally be below 0.02//g/L.
1.3 If Method 6020 is used to determine any analyte not listed in Table
1, it is the responsibility of the analyst to demonstrate the accuracy and
precision of the Method in the waste to be analyzed. The analyst is always
required to monitor potential sources of interferences and take appropriate
action to ensure data of known quality (see Section 8.4).
1.4 Use of this method is restricted to spectroscopists who are
knowledgeable in the recognition and in the correction of spectral, chemical, and
physical interferences in ICP-MS.
1.5 An appropriate internal standard is required for each analyte
determined by ICP-MS. Recommended internal standards are 6Li, 45Sc, 89Y, 103Rh,
mln, 159Tb, 165Ho, and 209Bi. The lithium internal standard should have an
enriched abundance of 6Li, so that interference from lithium native to the sample
is minimized. Other elements may need to be used as internal standards when
samples contain significant amounts of the recommended internal standards.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, samples which require total ("acid-leachable")
values must be digested using appropriate sample preparation methods (such as
Methods 3005 - 3051).
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2,2 Method 6020 describes the multi-elemental determination of analytes
by ICP-MS. The method measures ions produced by a radio-frequency inductively
coupled plasma. Analyte species originating in a liquid are nebulized and the
resulting aerosol transported by argon gas into the plasma torch. The ions
produced are entrained in the plasma gas and introduced, by means of an
interface, into a mass spectrometer. The ions produced in the plasma are sorted
according to their mass-to-charge ratios and quantified with a channel electron
multiplier. Interferences must be assessed and valid corrections applied or the
data flagged to indicate problems. Interference correction must include
compensation for background ions contributed by the plasma gas, reagents, and
constituents of the sample matrix.
3.0 INTERFERENCES
3.1 Isobaric elemental interferences in ICP-MS are caused by isotopes of
different elements forming atomic ions with the same nominal mass-to-charge ratio
(m/z). A data system must be used to correct for these interferences. This
involves determining the signal for another isotope of the interfering element
and subtracting the appropriate signal from the analyte isotope signal. Since
commercial ICP-MS instruments nominally provide unit resolution at 10% of the
peak height, very high ion currents at adjacent masses can also contribute to ion
signals at the mass of.interest. Although this type of interference is uncommon,
it is not easily corrected, and samples exhibiting a significant problem of this
type could require resolution improvement, matrix separation, or analysis using
another verified and documented isoptope, or use of another method.
3.2 Isobaric molecular and doubly-charged ion interferences in ICP-MS are
caused by ions consisting of more than one atom or charge, respectively. Most
isobaric interferences that could affect ICP-MS determinations have been
identified in the literature [3,4]. Examples include ArCl* ions on the 7SAs
signal and MoO* ions on the cadmium isotopes. While the approach used to
correct for molecular isobaric interferences is demonstrated below using the
natural isotope abundances from the literature [5], the most precise coefficients
for an instrument can be determined from the ratio of the net isotope signals
observed for a standard solution at a concentration providing suitable (<1
percent) counting statistics. Because the 35C1 natural abundance of 75.77
percent is 3.13 times the 37C1 abundance of 24.23 percent, the chloride
correction for arsenic can be calculated (approximately) as follows (where the
^Ar37^* contribution at m/z 75 is a negligible 0.06 percent of the *°Ar35Cl +
signal):
corrected arsenic signal (using natural isotopes abundances for
coefficient approximations) =
(m/z 75 signal) - (3.13) (m/z 77 signal) 4 (2.73) (m/z 82 signal),
(where the final term adjusts for any selenium contribution at 77 m/z),
NOTE: Arsenic values can be biased high by this type of equation when the
net signal at m/z 82 is caused by ions other than Se+, (e.g., 81BrH+' from
bromine wastes [6]).
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Similarly,
corrected cadmium signal (using natural isotopes abundances for
coefficient approximations) =
(m/z 114 signal) - (O.OZ7)(m/z 118 signal) - (1.63)(m/z 108 signal),
(where last 2 terms adjust for any tin or MoO+ contributions at m/z 114).
NOTE: Cadmium values will be biased low by this type of equation when
8ZZrO* ions contribute at m/z 108, but use of m/z 111 for Cd is even
subject to direct (94ZrOH4) and indirect (BOZrQ*) additive interferences
when Zr is present.
NOTE: As for the arsenic equation above, the coefficients in the Cd
equation are ONLY illustrative. The most appropriate coefficients for an
instrument can be determined from the ratio of the net isotope signals
observed for a standard solution at a concentration providing suitable (<1
percent) counting precision.
The^accuracy of these types of equations is based upon the constancy of the
OBSERVED isotopic ratios for the interfering species. Corrections that presume
a constant fraction of a molecular ion relative to the "parent" ion have not been
found [7] to be reliable, e.g., oxide levels can vary. If a correction for an
oxide ion is based upon the ratio of parent-to-oxide ion intensities, the
correction must be adjusted for the degree of oxide formation by the use of an
appropriate oxide internal standard previously demonstrated to form a similar
level of oxide as the interferant. This type of correction has been reported [7]
for oxide-ion corrections using ThO+/Th+ for the determination of rare earth
elements. The use of aerosol desolvation and/or mixed plasmas have been shown
to greatly reduce molecular interferences [8]. These techniques can be used
provided that method detection limits, accuracy, and precision requirements for
analysis of the samples can be met.
3.3 Physical interferences are associated with the sample nebulization and
transport processes as well as with ion-transmission efficiencies. Nebulization
and transport processes can be affected if a matrix component causes a change in
surface tension or viscosity. Changes in matrix composition can cause
significant signal suppression or enhancement [9]. Dissolved solids can deposit
on the nebulizer tip of a pneumatic nebulizer and on the interface skimmers
(reducing the orifice size and the instrument performance). Total solid levels
below 0.2% (2,000 mg/L) have been currently recommended [10] to minimize solid
deposition. An internal standard can be used to correct for physical
interferences, if it is carefully matched to the analyte so that the two elements
are similarly affected by matrix changes [11]. When the intensity level of an
internal standard is less than 30 percent or greater than 120 percent of the
intensity of the first standard used during calibration, the sample must be
reanalyzed after a fivefold (1+4) or greater dilution has been performed.
3.4 Memory interferences can occur when there are large concentration
differences between samples or standards which are analyzed sequentially. Sample
6020-3 Revision 0
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deposition on the sampler and skimmer cones, spray chamber design, and the type
of nebulizer affect the extent of the memory interferences which are observed.
The rinse period between samples must be long enough to eliminate significant
memory interference.
4,0 APPARATUS AND MATERIALS
4.1 Inductively coupled plasma-mass spectrometer:
4.1.1 A system capable of providing resolution, better than or
equal to amu at 10% peak height is required. The system must have a mass
range from at least 6 to 240 amu and a data system that allows corrections
for isobaric interferences and the application of the internal standard
technique. Use of a mass-flow controller for the nebulizer argon and a
peristaltic pump for the sample solution are recommended.
4.1.2 Argon gas supply: high-purity grade (99.99%).
i.O REAGENTS
5.1 Acids used in the preparation of standards and for sample processing
must be of high purity. Redistilled acids are recommended because of the high
sensitivity of ICP-MS. Nitric acid at less than 2 per cent (v/v) is required for
ICP-MS to minimize damage to the interface and to minimize isobaric molecular-ion
interferences with the analytes. Many more molecular-ion interferences are
observed on the analytes when hydrochloric and sulfuric acids are used [3,4].
Concentrations of antimony and silver between 50-500 //g/L require 1% (v/v) HC1
for stability; for concentrations above 500 //g/L Ag, additional HC1 will be
needed.
5.2 Reagent water: All references to water in the method refer to reagent
water unless otherwise specified. Refer to Chapter One for a definition of
reagent water.
5.3 Standard stock solutions may be purchased or prepared from ultra-high
purit1 grade chemicals or metals (99.99 or greater purity }. See Method 6010A,
Sect 5.3, for instructions on preparing standard solutions from solids.
5.3.1 Bismuth internal standard solution, stock, 1 ml = 100 /jg Bi:
Dissolve 0.1115 g Bi203 in a minimum amount of dilute HN03. Add 10 ml
cone. HN03 and dilute to 1,000 mi. with reagent water.
5.3.2 Holmium internal standard solution, stock, 1 ml = 100//g Ho:
uissolve 0.1757 g Ho2(C03)2-5H20 in 10 ml reagent water and 10 ml HN03.
After dissolution is complete, warm the solution to degas. Add 10 ml
cone. HN03 and dilute to 1,000 ml with reagent water.
5.3.3 Indium internal standard solution, stock, 1 ml = 100 //g In:
Dissolve 0.1000 g indium metal in 10 ml cone. HN03. Dilute to 1,000 ml
with reagent water.
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5.3.4 Lithium internal standard solution, stock, 1 ml = 100 fjg 6Li:
Dissolve 0.6312 g 95-atom-% 6Li, Li2COa in 10 ml of reagent water and 10 ml
HN03. After dissolution is complete, warm the solution to degas. Add
10 ml cone. HN03 and dilute to 1,000 ml with reagent water.
5.3.5 Rhodium internal standard solution, stock, 1 ml = 100 //g Rh:
Dissolve 0.3593 g ammonium hexachlororhodate (II!) {NH4)3RhCl6 in 10 mL
reagent water. Add 100 ml cone. HC1 and dilute to 1,000 ml with reagent
water.
5.3.6 Scandium internal standard solution, stock, 1 raL = 100//g Sc:
Dissolve 0.15343 g Scz03 in 10 ml (1+1) hot HN03. Add 5 ml cone. HN03 and
dilute to 1,000 ml with reagent water.
5.3.7 Terbium internal standard solution, stock, 1 ml = 100 //g Tb:
Dissolve 0.1828 g Tb2(C03)3-5H20 in 10 ml (1+1) HN03. After dissolution is
complete, warm the solution to degas. Add 5 ml cone. HN03 and dilute to
1,000.ml with reagent water.
5.3.8 Yttrium internal standard solution, stock, 1 ml = 100 f/q Y:
Dissolve 0.2316 g Y2(C03)3.3H20 in 10 ml (1+1) HN03. Add 5 ml cone. HN03
and dilute to 1,000 ml with reagent water.
5.3.9 Titanium solution, stock, 1 mL = 100 ^g T1: Dissolve 0.4133 g
(NH4)2TiFe in reagent water. Add 2 drops cone. HF and dilute to 1,000 ml
with reagent water.
5.3.10 Molybdenum solution, stock, 1 mL = 100 fjg Mo: Dissolve
0.2043 g (NH4)2Mo04 in reagent water. Dilute to 1,000 mL with reagent
water.
5.4 Mixed calibration standard solutions are prepared by diluting the
stock-standard solutions to levels in the linear range for the instrument in a
solvent consisting of 1 percent (v/v) HN03 in reagent water. The calibration
standard solutions must contain a suitable concentration of an appropriate
internal standard for each analyte. Internal standards may be added on-line at
the time of analysis using a second channel of the peristaltic pump and an
appropriate mixing manifold.) Generally, an internal standard should be no more
than 50 amu removed from the analyte. Recommended internal standards include
eLi, 45Sc, 89Y, 103Rh, 115In, 159Tb, ^Ho, and 209Bi. Prior to preparing the mixed
standards, each stock solution must be analyzed separately to determine possible
spectral interferences or the presence of impurities. Care must be taken when
preparing the mixed standards that the elements are compatible and stable.
Transfer the mixed standard solutions to freshly acid-cleaned FEP fluorocarbon
bottles for storage. Fresh mixed standards must be prepared as needed with the
realization that concentrations can change on aging. Calibration standards must
be initially verified using a quality control standard (see Section 5.7) and
monitored weekly for stability.
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5.5 Blanks: Three types of blanks are required for the analysis. The
calibration blank is used in establishing the calibration curve. The
preparation blank is used to monitor for possible contamination resulting from
the sample preparation procedure. The rinse blank is used to flush the system
between all samples and standards.
5.5,1 The calibration blank consists of the same concentration(s)
of the same acid(s) used to prepare the final dilution of the calibrating
solutions of the analytes [often 1 percent HN03 (v/v) in reagent water]
along with the selected concentrations of internal standards such that
there is an appropriate internal standard element for each of the
analytes. Use of HC1 for antimony and silver is cited in Section 5.1
5.5.2 The preparation (or reagent) blank must be carried through
the complete preparation procedure and contain the same volumes of
reagents as the sample solutions.
5.5.3 The rinse blank consists of 1 to 2 percent HN03 (v/v) in
reagent water. Prepare a sufficient quantity to flush the system between
standards and samples.
NOTE: The ICS solutions in Table 2 are intended to evaluate
corrections for known interferences on only the analytes in Table 1.
If Method 6020 is used to determine an element not listed in Table
1, it is the responsibility of the analyst to modify the ICS
solutions, or prepare an alternative ICS solution, to allow adequate
verification of correction of interferences on the unlisted element
(see section 8.4).
5.6 The interference check solution (ICS) is prepared to contain known
concentrations of interfering elements that will demonstrate the magnitude of
interferences and provide an adequate test of any corrections. Chloride in the
ICS provides a means to evaluate software corrections for chloride-related
interferences such as 35C1160* on 51V+ and 40Ar35Cl + on 75As*. Iron is used to
demonstrate adequate resolution of the spectrometer for the determination of
manganese. Holybdenum serves to indicate oxide effects on cadmium isotopes. The
other components are present to evaluate the ability of the measurement system
to correct for various molecular-ion isobaric interferences. The ICS is used to
verify that the interference levels are corrected by the data system within
quality control limits.
5.6.1 These solutions must be prepared from ultra-pure reagents.
They can be obtained commercially or prepared by the following procedure.
5.6.1.1 Mixed ICS solution I may be prepared by adding
13.903 g A1(N03)3-9H20S 2.498 g CaC03 (dried at 180 C for 1 h before
weighing), 1.000 g Fe, 1.658 g MgO, 2.305 g Na2C03, and 1.767 g K2C03
to 25 ml of reagent water. Slowly add 40 ml of (1+1) HN03. After
dissolution is complete, warm the solution to degas. Cool and
dilute to 1,000 ml with reagent water.
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5.6.1.2 Mixed ICS solution II may be prepared by slowly
adding 7.444 g 85 % H3P04, 6.373 g 96% H2S04, 40.024 g 37% HC1, and
10.664 g citric acid C607Ha to 100 ml of reagent water. Dilute to
1,000 ml with reagent water.
5.6.1.3 Mixed ICS solution III may be prepared by adding
1.00 ml each of IDO-jug/mL arsenic, cadmium, chromium, cobalt,
copper, manganese, nickel, silver, and zinc stock solutions to about
50 ml reagent water. Add 2.0 ml concentrated HN03, and dilute to
100.0 ml with reagent water.
5.6.1.4 Working ICS Solutions
5.6.1.4.1 ICS-A may be prepared by adding 10.0 ml of
mixed ICS solution I (5.7.1.1), 2.0 ml each of IQO-fjg/ml
titanium stock solution (5.3.9) and molybdenum stock solution
(5.3.10), and 5.0 ml of mixed ICS solution II (5.7.1.2).
Dilute to 100 ml with reagent water. ICS solution A must be
prepared fresh weekly.
5.6.1.4.2 ICS-AB may be prepared by adding 10.0 ml of
mixed ICS solution I (5.7.1.1), 2.0 ml each of 100-#g/iL
titanium stock solution (5.3.9) and molybdenum stock solution
(5.3.10), 5.0 ml of mixed ICS solution II (5.7.1.2), and
2.0 ml of Mixed ICS solution III (5.7.1.3). Dilute to 100 mL
with reagent water. Although the ICS solution AB must be
prepared fresh weekly, the analyst should be aware that the
solution may precipitate silver more quickly.
5.7 The quality control standard is the initial calibration verification
solution (ICV), which must be prepared in the same acid matrix as the calibration
standards. This solution must be an independent standard near the midpoint of
the linear range at a concentration other than that used for instrument
calibration. An independent standard is defined as a standard composed of the
analytes from a source different from those used in the standards for instrument
calibration.
5.8 Mass spectrometer tuning solution, A solution containing elements
representing all of the mass regions of interest (for example, 10//g/L of Li, Co,
In, and Tl) must be prepared to verify that the resolution and mass calibration
of the instrument are within the required specifications (see Section 7.5). This
solution is also used to verify that the instrument has reached thermal stability
(See Section 7.4).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Sample collection procedures should address the considerations
described in Chapter Nine of this Manual.
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6.2 See the introductory material in Chapter Three, Inorganic Analytes,
Sections 3.1,3 for information on sample handling and preservation. Only
polyethylene or fluorocarbon {TFE or PFA) containers are recommended for use in
Method 6020.
7.0 PROCEDURE
7.1 Solubilization and digestion procedures are presented in the Sample
Preparation Methods (e.g., Methods 3005 - 3051).
7.2 Initiate appropriate operating configuration of the instruments
computer according to the instrument manufacturer's instructions.
7.3 Set up the instrument with the proper operating parameters according
to the instrument manufacturer's instructions.
7,4 Operating conditions: The analyst should follow the instructions
provided by the instrument manufacturer. Allow at least 30 minutes for the
instrument to equilibrate before analyzing any samples. This must be verified
by analyzing a tuning solution (Section 5.8) at least four times with relative
standard deviations of < 5% for the analytes contained in the tuning solution.
NOTE: Precautions must be taken to protect the channel electron
multiplier from high ion currents. The channel electron multiplier
suffers from fatigue after being exposed to high ion currents. This
fatigue can last from several seconds to hours depending on the
extent of exposure. During this time period, response factors are
constantly changing, which invalidates the calibration curve, causes
instability, and invalidates sample analyses.
7.5 Conduct mass calibration and resolution checks in the mass regions of
interest. The mass calibration and resolution parameters are required criteria
which must be met prior to any samples being analyzed. If the mass calibration
differs more than 0.1 amu from the true value, then the mass calibration must be
adjusted to the correct value. The resolution must also be verified to be less
than 0.9 amu full width at 10 percent peak height,
7.6 Calibrate the instrument for the analytes of interest (recommended
isotopes for the analytes in Table 1 are provided in Table 3), using the
calibration blank and at least a single initial calibration standard according
to the instrument manufacturer's procedure. Flush the system with the rinse
blank (5.5.3) between each standard solution. Use the average of at leastthree
integrations for both calibration and sample analyses.
7.7 All masses which could affect data quality should be monitored to
determine potential effects from matrix components on the analyte peaks. The
recommended isotopes to be monitored are liste in Table 3.
7.8 Immediately after the calibration has been established, the
calibration must be verified and documented for every analyte by the analysis of
the calibration verification solution (Section 5.7). When measurements exceed
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±, 10% of the accepted value, the analyses must be terminated, the problem
corrected, the instrument recalibrated, and the new calibration verified. Any
samples analyzed under an out-of-control calibration must be reanalyzed. During
the course of an analytical run, the instrument may be "resloped" or recalibrated
to correct for instrument drift. A recalibration must then be followed
immediately by a new analysis of a CCV and CCB before any further samples may be
analyzed.
7.9 Flush the system with the rinse blank solution (5.5.3) until the
signal levels return to the method's levels of quantitation (usually about 30
seconds) before the analysis of each sample (see Section 7.7). Nebulize each
sample until a steady-state signal is achieved (usually about 30 seconds) prior
to collecting data. Analyze the calibration verification solution (Section 5.6)
and the calibration blank (Section 5.5.1) at a frequency of at least once every
10 analytical samples. Flow-injection systems may be used as long as they can
meet the performance criteria of this method.
7.10 Dilute and reanalyze samples that are more concentrated than the
linear range for an analyte (or species needed for a correction) or measure an
alternate less-abundant isotope. The linearity at the alternate mass must be
confirmed by appropriate calibration (see Sec. 7.6 and 7.8).
7.11 Calculations: The quantitative values shall be reported in
appropriate units, such as micrograms per liter U/g/L) for aqueous samples and
milligrams per kilogram (mg/kg) for solid samples. If dilutions were performed,
the appropriate corrections must be applied to the sample values.
7.11.1 If appropriate, or required, calculate results for solids on
a dry-weight basis as follows:
(1) A separate determination of percent solids must be
performed.
(2) The concentrations determined in the digest are to be
reported on the basis of the dry weight of the sample.
Concentration (dry weight)(mg/kg) = §-^-f
W A, «9
Where,
C = Digest Concentration (mg/L)
V = Final volume in liters after sample preparation
W = Weight in kg of wet sample
= % Solids
100
Calculations should include appropriate interference corrections (see
Section 3.2 for examples), internal-standard normalization, and the
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summation of signals at 206, 207, and 208 m/z for lead (to compensate for
any differences in the abundances of these isotopes between samples and
standards),
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and be available for
easy reference or inspection.
8.2 Instrument Detection Limits (IDLs) in #g/L can be estimated by
calculating the average of the standard deviations of the three runs on three
non-consecutive days from the analysis of a reagent blank solution with seven
consecutive measurements per day. Each measurement must be performed as though
it were a separate analytical sample (i.e., each measurement must be followed by
a rinse and/or any other procedure normally performed between the analysis of
separate samples). IDLs must be determined at least every three months and kept
with the instrument log book. Refer to Chapter One for additional guidance.
8.3 The intensities of all internal standards must be monitored for every
analysis. When the intensity of any internal standard fails to fall between 30
and 120 percent of the intensity of that internal standard in the initial
calibration standard, the following procedure is followed. The sample must be
diluted fivefold (1+4) and reanalyzed with the addition of appropriate amounts
of internal standards. This procedure must be repeated until the internal -
standard intensities fall within the prescribed window. The intensity levels of
the internal standards for the calibration blank {Section 5.5.1) and instrument
check standard (Section 5.6) must agree within ± 20 percent of the intensity
level of the internal standard of the original calibration solution. If they do
not agree, terminate the analysis, correct the problem, recalibrate, verify the
new calibration, and reanalyze the affected samples.
8.4 To obtain analyte data of known quality, it is necessary to measure
more than the analytes of interest in order to apply corrections or to determine
whether interference corrections are necessary. If the concentrations of
interference sources (such as C, Cl, Mo, Zr, W) are such that, at the correction
factor, the analyte is less than the limit of quantification and the
concentration of interferents are insignificant, then the data may go
uncorrected. Note that monitoring the interference sources does not necessarily
require monitoring the interferant itself, but that a molecular species may be
monitored to indicate the presence of the interferent. When correcttion
equations are used, all QC criteria must also be met. Extensive QC for
interference corrections are required at all times. The monitored masses must
include those elements whose hydrogen, oxygen, hydroxyl, chlorine, nitrogen,
carbon and sulfur molecular ions could impact the analytes of interest.
Unsuspected interferences may be detected by adding pure major matrix components
to a sample to observe any impact on the analyte signals. When an interference
source is present, the sample elements impacted must be flagged to indicate (a)
the percentage interference correction applied to the data or (b) an uncorrected
interference by virtue of the elemental equation used for quantitation. The
isotope proportions for an element or molecular-ion cluster provide information
useful for quality assurance.
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NOTE: Only isobaric elemental, molecular, and doubly charged Interference
corrections which use the observed isotopic-response ratios or parent-to-
oxide ratios (provided an oxide internal standard is used as described in
Section 3.2) for each instrument system are acceptable corrections for use
in Method 6020.
8.5 Dilution Test: If the analyte concentration is within the linear
dynamic range of the instrument and sufficiently high (minimally, a factor of at
least 100 times greater than the concentration in the reagent blank, refer to
Section 5,5.2), an analysis of a fivefold (1+4} dilution must agree within ± 10%
of the original determination. If not, an interference effect must be suspected.
One dilution test must be included for each twenty samples (or less) of each
matrix in a batch.
8.6 Post-Digestion Spike Addition: An analyte spike added to a portion
of a prepared sample, or its dilution, should be recovered to within 75 to 125
percent of the known value or within the laboratory derived acceptance criteria.
The spike addition should be based on the indigenous concentration of each
element of interest in the sample. If the spike is not recovered within the
specified limits, the sample must be diluted and reanalyzed to compensate for the
matrix effect. Results must agree to within 10% of the original determination.
The use of a standard-addition analysis procedure may also be used to compensate
for this effect (Refer to Method 7000).
8.7 A Laboratory Control Sample (LCS) should be analyzed for each analyte
using the same sample preparations, analytical methods and QA/QC procedures
employed for the test samples. One LCS should be prepared and analyzed for each
sample batch at a frequency of one LCS for each 20 samples or less.
8.8 Check the instrument calibration by analyzing appropriate quality
control solutions as follows:
8.8.1 Check instrument calibration using a calibration blank
(Section 5.5.1) and the initial calibration verification solution
(Sections 5.7 and 7.9).
8.8.2 Verify calibration at a frequency of every 10 analytical
samples with the instrument check standard (Section 5.6) and the
calibration blank (Section 5.5.1). These solutions must also be analyzed
for each analyte at the beginning of the analysis and after the last
sample.
8,8.3 The results of the initial calibration verification solution
and the instrument check standard must agree within ± 10% of the expected
value. If not, terminate the analysis, correct the problem, and
recalibrate the instrument. Any sample analyzed under an out-of-control
calibration must be reanalyzed . '
8.8.4 The results of the calibration blank must be less than 3
times the current IOL for each element. If this is not the case, the
reason for the out-of-control condition must be found and corrected, and
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affected samples must be reanalyzed. If the laboratory consistently has
concentrations greater than 3 times the IDL, the IDL may be indicative of
an estimated IDL and should be re-evaluated.
8.9 Verify the magnitude of elemental and molecular-ion isobaric
interferences and the adequacy of any corrections at the beginning of an
analytical run or once every 12 hours, whichever is more frequent. Do this by
analyzing the interference check solutions A and AB. The analyst should be aware
that precipitation from solution AB may occur with some elements, specifically
silver. Refer to Section 3.0 for a discussion on interferences and potential
solutions to those interferences if additional guidance is needed.
8.10 Analyze one duplicate sample for every matrix in a batch at a
frequency of one matrix duplicate for every 20 samples.
8.10,1 The relative percent difference (RPD) between duplicate
determinations must be calculated as follows:
ID, - D2 I
RPD = x 100
(0, + D2)/2
where:
RPD = relative percent difference.
D, « first sample value.
D2 = second sample value (duplicate)
A control limit of 20% RPD should not be exceeded for analyte values
greater than 100 times the instrumental detection limit. If this limit is
exceeded, the reason for the out-of-control situation must be found and
corrected, and any samples analyzed during the out-of-control condition
must be reanalyzed.
9.0 METHOD PERFORMANCE
9.1 In an EPA multi-laboratory study, 10 laboratories applied the
IC.-'-MS technique to both aqueous and solid samples. TABLE 4 summarizes the
method performance data for aqueous samples. Performance data for solid samples
is provided in TABLE 5.
10.0 REFERENCES
1. Horlick, 6., et al., Spectrochim. Acta 40B, 1555 (1985).
2. Gray, A.L., Spectrochim. Acta 40B, 1525 (1985); 41B, 151 (1986).
3. Tan, S.H., and Horlick, G., Appl. Spectrosc. 40, 445 (1986).
4. Vaughan, M.A., and Horlick, G., Appl. Spectrosc. 40, 434 (1986).
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5. Holden, N.E., "Table of the Isotopes," in Lide, O.R,? Ed., CRC Handbook of
Chemistry and Physics, 74th Ed., CRC Press, Boca Raton, FL, 1993.
6. Hinners, T.A., Heithmar, E., Rissmann, E., and Smith, 0., Winter Conference
on Plasma Spectrochemistry, Abstract THP18; p. 237, San Diego, CA (1994).
7. Lichte, F.E., et al., Anal. Chem. 59, 1150 (1987).
8. Evans E.H., and Ebdon, 1., J. Anal. At. Spectrom. 4, 299 (1989).
9. Beauchemin, D., et al., Spectrochim. Acta 42B, 467 (1987).
10. Houk, R.S., Anal. Chem. 58, 97A (1986).
11. Thompson, O.J., and Houk, R.S., Appl. Spectrosc. 41, 801 (1987).
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TABLE 1. ELEMENTS APPROVED FOR ICP-MS DETERMINATION
Element CAS* #
Aluminum 7429-90-5
Antimony 7440-36-0
Arsenic 7440-38-2
Barium 7440-39-3
Beryllium 7440-41-7
Cadmium 7440-43-9
Chromium 7440-47-3
Cobalt 7440-48-4
Copper 7440-50-8
Lead 7439-92-1
Manganese 7439-96-5
Nickel 7440-02-0
Silver 7440-22-4
Thallium 7440-28-0
Zinc 7440-66-6
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TABLE 2. RECOMMENDED INTERFERENCE CHECK SAMPLE COMPONENTS AND CONCENTRATIONS
Solution
component
Al
Ca
Fe
Mg
Na
P
K
S
C
Cl
Mo
Ti
As
Cd
Cr
Co
Cu
Nn
N1
Ag
Zn
Solution A
Concentration (mg/L)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
200.0
1000.0
2.0
2.0
0.0
0.0
0,0
0.0
0.0
0.0
0.0
0.0
0.0
Solution AB
Concentration (mg/L)
100.0
100.0
100.0
100.0
100.0
100.0
100.0
100.0
200.0
1000.0
2.0
2.0
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
0.0200
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TABLE 3. RECOMMENDED ISOTOPES FOR SELECTED ELEMENTS
Mass Element of interest
27 AT umi num
121, 123 Antimony
75 Arsenic
138, 137, 136, 135, 134 Barium
9 Beryl 1i urn
209 Bismuth (IS)
114. 112, 111. 110, 113, 116, 106 Cadmium
42, 43, 44. 46, 48 Calcium (I)
35, 37, (77, 82)a Chlorine (I)
52, 53. 50, 54 Chromium
59 Cobalt
63, 65 Copper
165 Hoi mi urn (IS)
115, 113 Indium (IS)
56, 14, 57, 58 Iron (I)
139 Lanthanum (I)
208, 207, 206, 204 Lead
6*77 Lithium (IS)
24, 25, 26 Magnesium (I)
55 Manganese
98, 96, 92, 97, 94, (108)a Molybdenum (I)
58, 60, 62, 6J.> 64 Nickel
38 Potassium (I)
103 Rhodium (IS)
45 Scandium (IS)
107, 109 Silver
23 Sodium (I)
159 Terbium (IS)
205. 203 Thallium
120, 118 Tin (I)
89 Yttrium (IS)
64, 66, !l> !Z» 70 Zinc
NOTE: Method 6020 is recommended for only those analytes listed in Table
1. Other elements are included in this table because they are potential
interferents (labeled I) in the determination of recommended analytes, or because
they are commonly used internal standards (labeled IS). Isotopes are listed in
descending order of natural abundance. The most generally useful isotopes are
underlined and in boldface, although certain matrices may require the use of
alternative isotopes. a These masses are also useful for interference correction
(Section 3.2). b Internal standard must be enriched in the 6Li isotope. This
minimizes interference from indigenous lithium.
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TABLE 4,
SOLUTIONS
ICP-MS MULTI-LABORATORY PRECISION AND ACCURACY DATA FOR AQUEOUS
Element
Comparability8
Range
%RSD
Range
Nb Sc
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
95 - 100
d
97 - 114
91 - 99
103 - 107
98 - 102
99 - 107
95 - 105
101 - 104
85 - 101
91 - 900
71 - 137
98 - 102
95 - 101
98 - 101
101 - 114
102 - 107
104 - 105
82 - 104
88 - 97
107 - 142
93 - 102
11 - 14
5.0 - 7.6
7.1 - 48
4.3 - 9.0
8,6 - 14
4.6 - 7.2
5.7 - 23
13 - 27
8.2 - 8.5
6.1 - 27
11 - 150
11
10
8.8
6.1
23
15
15
6.7
9.9 - 19
15 - 25
5.2 - 7.7
24 - 43
9.7 - 12
23 - 68
6.8 - 17
14 - 14
16 - 16
12 - 14
16 - 16
13 - 14
18 - 20
17 - 18
16 - 18
18 - 18
17 - 18
10 - 12
17 - 18
16 - 16
18 - 18
18 - 18
11 - 12
12 - 12
13 - 16
9 - 10
18 - 18
8 - 13
16 - 18
4
3
4
5
3
3
5
4
3
5
5
6
5
4
2
5
3
2
5
3
3
a Comparability refers to the percent agreement of mean ICP-MS values to those
of the reference technique. b N is the range of the number of ICP-MS
measurements where the analyte values exceed the limit of quantitation (3.3 times
the average IOL value). c S is the number of samples with results greater
than the limit of quantitation. d No comparability values are provided for
antimony because of evidence that the reference data is affected by an
interference.
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TABLE 5. ICP-MS HULTI-LABORATORY PRECISION AND ACCURACY DATA FOR SOLID MATRICES
Element
Comparability3
Range
%RSD
Range Nb
Sc
Aluminum
Antimony
Arsenic
Barium
Beryllium
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Nickel
Potassium
Selenium
Silver
Sodium
Thai1i urn
Vanadium
Zinc
83 - 101
d
79 - 102
100 - 102
50 - 87
93 - 100
95 - 109
77 - 98
43 - 102
90 - 109
87 - 99
90 - 104
89 - 111
80 - 108
87 - 117
97 - 137
81
43 - 112
100 - 146
91
83 - 147
84 - 124
11 - 39
12 - 21
12 - 23
4.3 - 17
19 - 34
6.2 - 25
4.1 - 27
11 - 32
15 - 30
9.0 - 25
6.7 - 21
5.9 - 28
7.6 - 37
11 - 40
9.2 - 29
11 - 62
39
12 - 33
14 - 77
33
20 - 70
14 - 42
13 - 14
15 - 16
16 - 16
15 - 16
12 - 14
19 - 20
15 - 17
17 - 18
17 - 18
18 - 18
12 - 12
15 - 18
15 - 16
16 - 18
16 - 18
10 - 12
12
15 - 15
8 - 10
18
6 - 14
18 - 18
7
2
7
7
5
5
7
7
6
7
7
7
7
7
7
5
1
3
5
1
7
7
a Comparability refers to the percent agreement of mean ICP-MS values to those
of the reference technique. N is the range of the number of ICP-MS
measurements where the analyte values exceed the limit of quantitation (3,3 times
the average IDL value). c S is the number of samples with results greater
than the limit of quantitation. d No comparability values are provided for
antimony because of evidence that the reference data is affected by an
interference.
6020-18
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HETHOD 6020
INDUCTIVELY COUPLED PLASMA - HASS SPECTROMETRY
7,1 Ainlyi.
by M*tko«
Method 6010,
«ll,_ni
7.1 Un
M«iwd aoto.
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METHOD 7060A
ARSENIC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7060 Is an atomic absorption procedure approved for
determining the concentration of arsenic in wastes, mobility procedure extracts,
soils, and ground water. All samples must be subjected to an appropriate
dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7060, samples must be prepared in order
to convert organic forms of arsenic to inorganic forms, to minimize organic
interferences, and to convert the sample to a suitable solution for analysis.
The sample preparation procedure varies depending on the sample matrix. Aqueous
samples are subjected to the acid digestion procedure described in this method.
Sludge samples are prepared using the procedure described in Method 3050.
2.2 Following the appropriate dissolution of the sample, a representative
aliquot of the digestate is spiked with a nickel nitrate solution and is placed
manually or by means of an automatic sampler into a graphite tube furnace. The
sample aliquot is then slowly evaporated to dryness, charred (ashed), and
atomized. The absorption of hollow cathode or EDL radiation during atomization
will be proportional to the arsenic concentration. Other modifiers may be used
in place of nickel nitrate if the analyst documents the chemical and
concentration used.
2.3 The typical detection limit for water samples using this method is
1 ug/L. This detection limit may not be achievable when analyzing waste samples.
3.0 INTERFERENCES
3.1 Elemental arsenic and many of its compounds are volatile; therefore,
samples may be subject to losses of arsenic during sample preparation. Spike
samples and relevant standard reference materials should be processed to
determine if the chosen dissolution method is appropriate.
3.2 Likewise, caution must be employed during the selection of
temperature and times for the dry and char (ash) cycles. A matrix modifier such
as nickel nitrate must be added to all digestates prior to analysis to minimize
volatilization losses during drying and ashing.
3.3 In addition to the normal interferences experienced during graphite
furnace analysis, arsenic analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Arsenic
analysis is particularly susceptible to these problems because of its low
analytical wavelength (193.7 nm). Simultaneous background correction must be
employed to avoid erroneously high results. Aluminum is a severe positive
interferent in the analysis of arsenic, especially using D2 arc background
7060A - 1 Revision 1
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correction. Although Zeeman background correction is very useful in this
situation, use of any appropriate background correction technique is acceptable.
3.4 If the analyte is not completely volatilized and removed from the
furnace during atomization, memory effects will occur. If this situation is
detected by means of blank burns, the tube should be cleaned by operating the
furnace at full power at regular intervals in the analytical scheme.
4.0 APPARATUS AND MATERIALS
4.1 Griffin beaker or equivalent: 250 ml.
4.2 Class A Volumetric flasks: 10-mL.
4.3 Atomic absorption spectrophotometer: Single or dual channel, single-
or double-beam instrument having a grating monochromator, photo-multiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm, and provisions
for simultaneous background correction and interfacing with a suitable recording
device.
4,4 Arsenic hollow cathode lamp, or electrodeless discharge lamp (EDL):
EDLs provide better sensitivity for arsenic analysis.
4.5 Graphite furnace: Any graphite furnace device with the appropriate
temperature and timing controls.
4.6 Data systems recorder: A recorder is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, incomplete atomization, losses during charring,
changes in sensitivity, etc., can easily be recognized.
4.7 Pipets: Microliter with disposable tips. Sizes can range from
5 to 1,000 uL, as required.
5.0 REAGENTS
5.1 Reagent water: Water should be monitored for impurities.
All references to water will refer to reagent water.
5.2 Concentrated nitric acid: Acid should be analyzed to determine levels
of impurities. If a method blank using the acid is
-------
5.5 Nickel nitrate solution (5%): Dissolve 24.780 g of ACS reagent grade
Ni(N03)2"6H20 or equivalent in reagent water and dilute to 100 ml.
5.6 Nickel nitrate solution (1%): Dilute 20 ml of the 5% nickel nitrate
to 100 ml with reagent water.
5.7 Arsenic working standards: Prepare dilutions of the stock solution
to be used as calibration standards at the time of the analysis. Withdraw
appropriate aliquots of the stock solution, add concentrated HN03, 30% H202, and
5% nickel nitrate solution or other appropriate matrix modifier. Amounts added
should be representative of the concentrations found in the samples. Dilute to
100 ml with reagent water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
reagent water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile arsenic compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid and
refrigerated prior to analysis.
6.5 Although waste samples do not need to be refrigerated sample handling
and storage must comply with the minimum requirements established in Chapter One.
7.0 PROCEDURE
7.1 Sample preparation: Aqueous samples should be prepared in the manner
described in Paragraphs 7.1.1-7.1.3. Sludge-type samples should be prepared
according to Method 3050A. The applicability of a sample-preparation technique
to a new matrix type must be demonstrated by analyzing spiked samples and/or
relevant standard reference materials.
7.1.1 Transfer a known volume of well-mixed sample to a 250-mL
Griffin beaker or equivalent; add 2 mL of 30% H202 and sufficient
concentrated HN03 to result in an acid concentration of 1% (v/v). Heat,
until digestion is complete, at 95°C or until the volume is slightly less
than 50 mL.
7.1.2 Cool, transfer to a volumetric flask, and bring back to 50
mL with reagent water.
7.1.3 Pipet 5 mL of this digested solution into a 10-mL volumetric
flask, add 1 mL of the 1% nickel nitrate solution or other appropriate
matrix modifier, and dilute to 10 mL with reagent water. The sample is
now ready for injection into the furnace.
7060A - 3 Revision 1
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7.2 The 193.7-nm wavelength line and a background correction system are
required. Follow the manufacturer's suggestions for all other spectrophotoraeter
parameters.
7.3 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Because temperature-sensing mechanisms and temperature
controllers can vary between instruments or with time, the validity of the
furnace parameters must be periodically confirmed by systematically altering the
furnace parameters while analyzing a standard. In this manner, losses of analyte
due to overly high temperature settings or losses in sensitivity due to less than
optimum settings can be minimized. Similar verification of furnace parameters
may be required for complex sample matrices.
7.4 Inject a measured microliter aliquot of sample into the furnace and
atomize. If the concentration found is greater than the highest standard, the
sample should be diluted in the same acid matrix and reanalyzed. The use of
multiple injections can improve accuracy and help detect furnace pipetting
errors.
8.0 QUALITY CONTROL
8.1 Refer to section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 206.2 of Methods
for Cnemical Analysis of Water and Wastes.
9.2 The optimal concentration range for aqueous samples using this method
is 5-100 ug/L. Concentration ranges for non-aqueous samples will vary with
matrix type.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 206.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7060A - 4 Revision 1
September 1994
\
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TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Contaminated soil 3050 2.0, 1.8 ug/g
Oily soil 3050 3.3, 3.8 ug/g
NBS SRM 1646 Estuarine sediment 3050 8.1, 8.33 ug/ga
Emission control dust 3050 430, 350 ug/g
aBias of -30 and -28% from expected, respectively.
7060A - 5 Revision 1
Septenfcer 1994
-------
METHOD 7060A
ARSENIC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
7.1.1 Tran.f.r
• upli to
baakic.arfd H«0,
mat ease. HHO.,
7 . 1 Pr«pmr<
accord ing te
M*thod 3050
7060A - 6
Revision 1
Septenter 1994
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METHOD 7062
ANTIMONY AND ARSENIC (ATOMIC ABSORPTION. BOROHYDRIDE REDUCTION)
1,0 SCOPE AND APPLICATION
1,1 Method 7062 1s an atomic absorption procedure for determining 1
to 400//g/L concentrations of antimony and arsenic in wastes, mobility procedure
extracts, soils, and ground water. Method 7062 is approved for sample matrices
that contain up to a total of 4000 mg/L concentrations of cobalt, copper, iron,
mercury, or nickel. A solid sample can contain up to 40% by weight of the
interferents before exceeding 4000 mg/L in a digested sample. All samples
including aqueous matrices must be subjected to an appropriate dissolution step
prior to analysis. Spiked samples and relevant standard reference materials are
used to determine the applicability of the method to a given waste.
2.0 SUMMARY OF METHOD
2.1 Samples are prepared according to the nitric add digestion procedure
described in Method 3010 for aqueous and extract samples and the
nitric/peroxide/hydrochloric acid digestion procedure described in Method 3050
(furnace AA option) for sediments, soils, and sludges. Excess peroxide is
removed by evaporating samples to near dryness at the end of the digestion
followed by degassing the samples upon addition of urea. L-cysteine is then
added as a masking agent. Next, the antimony and arsenic in the digest are
reduced to the trivalent forms with potassium iodide. The trivalent antimony and
arsenic are then converted to volatile hydrides using hydrogen produced from the
reaction of the acidified sample with sodium borohydride in a continuous-flow
hydride generator.
2.2 The volatile hydrides are swept into, and decompose in, a heated
quartz cell located in the optical path of an atomic absorption
spectrophotometer. The resulting absorption of the lamp radiation is
proportional to the arsenic or antimony concentration.
2.3 The typical detection limit for this method is 1.0 fjg/L.
3.0 INTERFERENCES
3.1 Very high (>4000 mg/L) concentrations of cobalt, copper, iron,
mercury, and nickel can cause analytical interferences through precipitation as
reduced metals and associated blockage of transfer lines and fittings.
3.2 Traces of peroxides left following the sample work-up can result in
analytical interferences. Peroxides must be removed by evaporating each sample
to near dryness followed by reaction with urea and allowing sufficient time for
degassing before analysis (see Sections 7.1 and 7.2).
7062-1 Revision 0
September 1994
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3.3 Even after acid digestion, organic compounds will remain in the
sap "•. These flame gases and these organic compounds can absorb at the
ant ical wavelengths and background correction must be used.
4.0 APPARATUS AND MATERIALS
4.1 Electric hot plate: Large enough to hold at least several 100 mL
Pyrex digestion beakers.
4.2 A continuous-flow hydride generator: A commercially available
continuous-flow sodium borohydride/HCl hydride generator or a generator
constructed similarly to that shown in Figure 1 (P. S. Analytical or equivalent).
4.2,1 Peristaltic Pump: A four-channel, variable-speed peristaltic
pump to permit regulation of liquid-stream flow rates (Ismatec Reglo-100
or equivalent). Pump speed and tubing diameters should be adjusted to
provide the following flow rates: sample/blank flow = 4.2 ml/min;
borohydride flow =2.1 mL/min; and potassium iodide flow = 0.5 mL/min.
4.2.2 Sampling Valve (optional): A sampling valve (found in the
P. S. Analytical Hydride Generation System or equivalent) that allows
switching between samples and blanks (rinse solution) without introduction
of air into the system will provide more signal stability.
4.2.3 Transfer Tubing and Connectors: Transfer tubing (1 mm I.D.),
mixing T's, and connectors are made of a fluorocarbon (PFA or TFM) and are
of compatible sizes to form tight, leak-proof connections (Latchat,
Technicon, etc. flow injection apparatus accessories or equivalent).
4.2.4 Mixing Coil: A 20-turn coil made by wrapping transfer tubing
around a 1-cm diameter by 5-cm long plastic or glass rod (see Figure 1).
4.2.5 Mixing Coil Heater, if appropriate: A 250-mL Erlenmeyer
flask containing 100 ml of water heated to boiling on a dedicatee one-
beaker hotplate (Corning PC-35 or equivalent). The mixing coil in 4.2.4
is immersed in the boiling water to speed kinetics of the hydride forming
reactions and increase solubility of interfering reduced metal
precipitat
4.2.6 Gas-Liquid Separator: A glass apparatus for collecting and
separating liquid and gaseous products (P.T. Analytical accessory or
equivalent) which allows the liquid fraction to drain to waste and gaseous
products above the liquid to be swept by a regulated carrier gas (argon)
out of the cell for analysis. To avoid undue carrier gas dilution, the
gas volume above the liquid should not exceed 20 mL. See Figure 1 for an
acceptable separator shape.
4.2.7 Condenser: Moisture picked up by the carrier gas must be
removed before encountering the hot absorbance cell. The moist carrier
gas with the hydrides is dried by passing the gasses through a small (< 25
7062-2 Revision 0
September 1994
-------
ml) volume condenser coil (Ace Glass Model 6020-02 or equivalent) that is
cooled to 5°C by a water chiller (Neslab RTE-110 or equivalent). Cool tap-
water in place of a chiller is acceptable.
4.2.8 Flow Meter/Regulator: A meter capable of regulating up to 1
L/min of argon carrier gas is recommended.
4.3 Absorbance Cell: A 17 cm or longer quartz tube T-cell {windowless is
strongly suggested) is recommended, as shown in Figure 1 (Varian Model V6A-76
accessory or equivalent). The cell is held in place by a holder that positions
the cell about 1 cm over a conventional AA air-acetylene burner head. In
operation, the cell is heated to around 900°C.
4.4 Atomic absorption spectrophotometer: Single or dual channel, single-
or double-beam instrument having a grating monochrotnator, photomultiplier
detector, adjustable slits, a wavelength range of 190 to 800 nm» and provisions
for interfacing with an appropriate recording device.
4.5 Burner: As recommended by the particular instrument manufacturer for
an air-acetylene flame. An appropriate mounting bracket attached to the burner
that suspends the quartz absorbance cell between 1 and 2 cm above the burner slot
is required.
4.6 Antimony and arsenic hollow cathode lamps or antimony and arsenic
electrodeless discharge lamps and power supply. Super-charged hollow-cathode
lamps or EDL lamps are recommended for maximum sensitivity.
4.7 Strip-chart recorder (optional): Connect to output of
spectrophotometer.
5.0 REAGENTS
5.1 Reagent water: Water must be monitored for impurities. Refer to
Chapter 1 for definition of Reagent water.
5.2 Concentrated nitric acid (HN03): Acid must be analyzed to determine
levels of impurities. If a method blank is
-------
QUARTZ CELL
* ft OUR HE ft
TO
CHlLLEft
CONDENSER—-»
MIXING
TCE*
•ftSSLIQUID
SEPARATOR
iMBlSCONHtCTCOl
I OURINO S«'tA I
VALUE
(SAHPLIHO)
THERMOHfTER
>_—* OR«IM
20 TORM COIL
(TEPLON)
«*!.*•
CtLANN}
Figure 1. Continuous-flow sodium borohydride/hydride generator apparatus set-up
and an AAS sample introduction system.
7052-4
Revision 0
Septarber 1994
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5.6 Urea (H2NCONH2): A 5.00-g portion of reagent grade urea must be added
to a 25-mL aliquot of each sample for removal of excess peroxide through
degassing (see Section 7,2),
5.7 L-cysteine (C6H12N204S2): A 1.00-g portion of reagent grade L-cystine
must be added to a 25-mL aliquot of each sample for masking the effects of
suppressing transition metals (see Section 7.2).
5.8 20% Potassium iodide (1(1): A 20% KI solution (20 g reagent-grade KI
dissolved and brought to volume in 100 ml reagent water) must be prepared for
reduction of antimony and arsenic to their +3 valence states.
5.9 4% Sodium borohydride (NaBH4): A 4% sodium borohydride solution (20
g reagent-grade NaBH4 plus 2 g sodium hydroxide dissolved in 500 ml of reagent
water) must be prepared for conversion of the antimony and arsenic to their
hydrides,
5.10 Analyte solutions:
5.10.1 Antimony and arsenic stock standard solution (1,000 mg/L):
Either procure certified aqueous standards from a supplier and verify by
comparison with a second standard, or dissolve 1.197 g of antimony
trioxide Sb203 and 1.320 g of arsenic trioxide As203 in 100 ml of reagent
water containing 4 g NaOH. Acidify the solution with 20 ml concentrated
HN03 and dilute to 1 liter.
5.10,2 Intermediate antimony and arsenic solution: Pi pet 1 ml
stock antimony and arsenic solution into a 100-mL volumetric flask and
bring to volume with reagent water containing 1.5 ml concentrated
HNOg/liter (1 ml = 10 //g each of Sb and As).
5.10.3 Standard antimony and arsenic solution: Pi pet 10 ml
intermediate antimony and arsenic solution into a 100-mL volumetric flask
and bring to volume with reagent water containing 1.5 mL concentrated
HNO-j/liter (1 ml - 1 #g each of Sb and As).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual,
6.2 All sample containers must be prewashed with detergents, acids, and
reagent water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile antimony and arsenic compounds are
suspected to be present in the samples.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric acid.
7062-5 Revision 0
September 1994
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6.5 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Place a 100-mL portion of an aqueous sample or extract or 1.000 g of
a dried solid sample in a 250-mL digestion beaker. Digest aqueous samples and
extracts according to Method 3010. Digest solid samples according to Method 3050
{furnace M option) with the following modifications: add 5 ml of concentrated
hydrochloric acid just prior to the final volume reduction stage to aid in
antimony recovery; the final volume reduction should be to less than 5 ml but not
to dryness to adequately remove excess hydrogen peroxide (see note). After
dilution to volume, further dilution with diluent may be necessary if analytes
are known to exceed 400 f/g/L or if interferents are expected to exceed 4000 mg/L
in the digestate.
Note: For solid digestions, the volume reduction stage is critical
to obtain accurate data, especially for arsenic. Close monitoring
of each sample is necessary when this critical stage is reached.
7,2 Prepare samples for hydride analysis by adding 5.00 g urea, 1.00 g L-
cysteine, and 20 ml concentrated HC1 to a 25-mL aliquot of digested sample in a
50-mL volumetric flask. Heat in a water bath until the L-cysteine has dissolved
and effervescence has subsided (At least 30 minutes is suggested. If
effervescense is still seen, repeat step 7.1 with more volume reduction,}. Bring
flask to volume with reagent water before analyzing. A 1:1 dilution correction
must be made in the final concentration calculations.
7.3 Prepare working standards from the standard antimony and arsenic
solution. Transfer 0, 0.5, -1.0, 1.5, 2.0, and 2.5 mL of standard to 100-mL
volumetric flasks and bring to volume with diluent. These concentrations will
be 0, 5, 10, 15, 20, and 25 fjg Sb and As/liter.
7.4 If EP extracts (Method 1310} are being analyzed for arsenic, the
method of standard additions must be used. Spike appropriate amounts of
intermediate or standard antimony and arsenic solution to three 25 ml aliquots
of each unknown. Spiking volumes should be kept less than 0.250 ml to avoid
excessive spiking dilution errors.
7.5 Set up instrumentation and hydride generation apparatus and fill
reagent containers. The sample and blank flows should be set around 4.2 mL/min,
the borohydride flow around 2.1 mL/min, and the potassium iodide flow around 0.5
mL/min. The argon carrier gas flow is adjusted to about 200 mL/min. For the AA,
use the 217.6-nm wavelength and 0.7-nm slit width (or manufacturer's recommended
slit-width} without background correction if analyzing for antimony. Use the
193.7-nm wavelength and 0.7-nm slit width (or manufacturer's recommended slit-
width) with background correction for the analysis of arsenic. Begin all flows
and allow 10 minutes for warm-up.
7062-6 Revision 0
September 1994
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7,6 Place sample feed line into a prepared sample solution and start pump
to begin hydride generation. Wait for a maximum steady-state signal on the
strip-chart recorder or output meter. Switch to blank sample and watch for
signal to decline to baseline before switching to the next sample and beginning
the next analysis. Run standards first (low to high), then unknowns. Include
appropriate QA/QC solutions, as required. Prepare calioration curves and convert
absorbances to concentration. If a heating coil is not being used, KI must be
added to the samples and heated for thirty minutes to ensure reduction.
CAUTION: The hydrides of antimony and arsenic are very toxic.
Precautions must be taken to avoid inhaling the gas,
7.7 If the method of standard additions was employed, plot the measured
concentration of the spiked samples and unspiked sample versus the spiked
concentrations. The spiked concentration axis intercept will be the method of
standard additions concentration. If the plot does not result in a straight
line, a nonlinear interference is present. This problem can sometimes be
overcome by dilution or addition of other reagents if there is some knowledge
about the waste. If the method of standard additions was not required, then the
concentration is determined from a standard calibration curve.
8.0 QUALITY CONTROL
8.1 See section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The relative standard deviations obtained by a single laboratory for
7 replicates of a contaminated soil were 18% for antimony at 9.1 ug/L in solution
and 4.6% for arsenic at 68 ug/L in solution. The average percent recovery of the
analysis of an 8 jjg/L spike on ten different samples is 103.7% for arsenic and
95.6% for antimony.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-60Q/4-82r055,
December 1982, Method 206.3.
2. "Evaluation of Hydride Atomic Absorption Methods for Antimony, Arsenic,
Selenium, and Tin", an EMSL-LV internal report under Contract 68-03-3249,
Job Order 70.16, prepared for T. A, Hinners by D. E. Dobb, and J, D.
Lindner of Lockheed Engineering and Sciences Co., and L. V. Beach of the
Varian Corporation.
7062-7 Revision 0
September 1994
\
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METHOD 7062
ANTIHONY AND ARSENIC (ATOMIC ABSORPTION, BORQHYDRIDE REDUCTION)
7.1 Use Method
3050 (furnace A A
option) to digest
1.0 g sample.
7.1 U*B
Method 3O10
to dig«*I 100
ml »amplo.
7.1 Add
o nc»ntret»d
HCI.
7.1 Do final
volume
reduction end
dilution, ec
described.
Vee
7.1 Fyrthir
dilute with
diluent.
7.2 Add to
aliquot urea;
L-cysteine, HCI:
heat H2O bath;
bring to volume.
7.3 Prepare
standards from
•tindard (tock
solutions ot Sb
and As.
7.4 Use the
method of
etandard
addition* on EP
extracts, only.
7.B - 7.6 Analyze
the sample
mine hydride
gene ration
apparatug.
7.E -7.8 Analyze
the aampl*
using hydride
generation
appantua.
7.6 • 7.7 Determine
Sb and Ac cane,
from ttandtrd
calibration
curve.
7.7 Determine
Sb and As
concentrations
by Method of
Standard Additions,
Stop
7062-8
Revision 0
Septarter 1994
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METHOD 7080A
BARIUH (ATOMIC ABSORPTION, DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2,0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 High hollow cathode current settings and a narrow spectral band pass
must be used, because both barium and calcium emit strongly at barium's
analytical wavelength.
3.3 Barium undergoes significant ionization in the nitrous oxide/
acetylene flame, resulting in a significant decrease in sensitivity. All
samples and standards must contain a ionization suppressant. The type of
suppressant and concentration used must be documented.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Barium hollow cathode lamp.
4.2.2 Wavelength: 553.6 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Nitrous oxide,
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards:
5.2.1 Stock solution: Dissolve 1.7787 g barium chloride
(BaCl2'2H20) analytical reagent grade in reagent water and dilute to 1
liter (1000 mg/L). Alternatively, procure a certified standard front a
supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
7080A - 1 Revision 1
Septenter 1994
-------
should be prepared using the same type of acid and at the sane
concentration as will result in the sample to be analyzed after
processing. All calibration standards and samples should contain the
ionization suppressant.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7,0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample are
given in Chapter Three, Section 3.2.
7.2 See Method 7000, Section 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 1-20 mg/L with a wavelength of 553.6 nrn.
Sensitivity: 0.4 mg/L.
Detection limit: 0.1 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic waste
effluent, digested with Method 3010, at concentrations of 0.4 and 2 mg Ba/L gave
standard deviations of ±0.043 and +0.13, respectively. Recoveries at these
levels were 94% and 113%, respectively.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 198E, Method 208.1.
7080A - 2 Revision 1
September 1994
\
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METHOD 7080A
BARIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
( Start ]
5.2 Prepare
standard *.
7.1 For cample
preparation see
Chapter 3, Section
3.2.
7.2 Analyze using
Method 7000
Section 7,2.
( Stop J
7080A - 3
Revision 1
September 1994
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-------
METHOD 7131A
CADMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, cadmium analysis can suffer from severe nonspecific absorption
and light scattering caused by matrix components during atomization. Simultaneous
background correction 1s required to avoid erroneously high results.
3.3 Excess chloride may cause premature volatilization of cadmium.
Ammonium phosphate used as a matrix modifier minimizes this loss. Other
modifiers may be used as long as it is documented with the type of suppressant
and concentration.
3.4 Many plastic pipet tips (yellow) contain cadmium. Use "cadmium-
free" tips.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125°C.
4.2.2 Ashing time and temp: 30 sec at 500°C.
4.2.3 Atomizing time and temp: 10 sec at 1900°C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 228.8 nm,
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular instrument manufacturer.
7131A - 1 Revision 1
September 1994
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NOTE: The above concentration values and instrument conditions are
for a Perkin-Elmer HGA-2100, based on the use of a 20-uL injection,
continuous-flow purge gas, and nonpyrolytic graphite. Smaller sizes
of furnace devices or those employing faster rates of atomization
can be operated using lower atomization temperatures for shorter
tiie periods than the above-recommended settings.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards:
5.2.1 Stock solution: Dissolve 1.000 g of cadmium metal
(analytical reagent grade) in 20 ml of 1:1 HN03 and dilute to 1 liter with
reagent water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock cadmium solution to be used
as calibration standards at the time of analysis. To each 100 ml of
standard and sample alike add 2.0 ml of the ammonium phosphate solution.
The calibration standards should be prepared to contain 0.5% (v/v) HN03.
5.2.3 Ammonium phosphate solution (40%); Dissolve 40 g of
ammonium phosphate, (NH4)2HP04 (analytical reagent grade), in reagent water
and dilute to 100 ml,
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation,
7.0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample are
provide-: 'n Chapter Three, Section 3.2.
7;2 See Method 7000, Section 7.3, Furnace Procedure. The calculation is
provider i Method 7000, Section 7.4.
8.0 QUi-,-.TY CONTROL
8.1 Refer to Section 8.0 of Method 7000 .
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 213.2 of Methods
for Chemical Analysis of Water and Wastes.
7131A - 2 Revision 1
September 1994
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9.2 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.5-10 ug/L.
Detection limit: 0.1 ug/L.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 213.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7131A - 3 Revision 1
September 1994
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Lagoon soil 3050 0.10, 0.095 ug/g
NBS SRM 1646 Estuarine sediment 3050 0.35 ug/g"
Solvent extract of oily waste 3030 1.39, 1.09 ug/L
"Bias of -3% from expected value.
7131A - 4 Revision 1
September 1994
\
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METHOD 7131A
CADMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1
f
5.2 Prepare
standards.
^
f
7. 1 For sample
preparation see
Chapter 3, Saciion
3.2.
^
f
7.2 Analyze using
Method 7000
Section 7.3.
1
f
I Stop J
7131A - 5
Revision 1
September 1994
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METHOD 7470A
MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7470 is a cold-vapor atomic absorption procedure approved for
determining the concentration of mercury in mobility-procedure extracts, aqueous
wastes, and ground waters. (Method 7470 can also be used for analyzing certain
solid and sludge-type wastes; however, Method 7471 is usually the method of
choice for these waste types.) All samples must be subjected to an appropriate
dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, the liquid samples must be prepared according to
the procedure discussed in this method.
2.2 Method 7470, a cold-vapor atomic absorption technique, is based on
the absorption of radiation at 253.7-nm by mercury vapor. The mercury is reduced
to the elemental state and aerated from solution in a closed system. The mercury
vapor passes through a cell positioned in the light path of an atomic absorption
spectrophotometer. Absorbance (peak height) is measured as a function of mercury
concentration.
2.3 The typical detection limit for this method is 0.0002 mg/L.
3.0 INTERFERENCES
3.1 Potassium permanganate is added to eliminate possible interference
from sulfide. Concentrations as high as 20 mg/L of sulfide as sodium sulfide do
not interfere with the recovery of added inorganic mercury from reagent water.
3.2 Copper has also been reported to interfere; however, copper concen-
trations as high as 10 mg/L had no effect on recovery of mercury from spiked
samples.
3.3 Seawaters, brines, and industrial effluents high in chlorides require
additional permanganate (as much as 25 ml) because, during the oxidation step,
chlorides are converted to free chlorine, which also absorbs radiation of 253.7
nm. Care must therefore be taken to ensure that free chlorine is absent before
the mercury is reduced and swept into the cell. This may be accomplished by
using an excess of hydroxylamine sulfate reagent (2.5 ml). In addition, the dead
air space in the BOD bottle must be purged before adding stannous sulfate. Both
inorganic and organic mercury spikes have been quantitatively recovered from
seawater by using this technique.
3.4 Certain volatile organic materials that absorb at this wavelength may
also cause interference. A preliminary run without reagents should determine if
this type of interference is present.
7470A - 1 Revision 1
September 1994
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4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer or equivalent: Any atomic
absorption unit with an open sample presentation area in which to mount the
absorption cell is suitable. Instrument settings recommended by the particular
manufacturer should be followed. Instruments designed specifically for the
measurement of mercury us~ -2 the cold-vapor technique are commercially available
and may be substituted for the atomic absorption speetrophotometer.
4.2 Mercury hollow cathode lamp or electrode!ess discharge lamp.
4.3 Recorder: Any multirange variable-speed recorder that is compatible
with the UV detection system is suitable.
4.4 Absorption cell: Standard spectrophotometer cells 10 cm long with
quartz end windows may be used. Suitable cells may be constructed from Plexiglas
tubing, 1 in. O.D. x 4.5 in. The ends are ground perpendicular to the
longitudinal axis, and quartz windows (1 in. diameter x 1/16 in. thickness) are
cemented in place. The cell is strapped to a burner for support and aligned in
the light beam by use of two 2-in. x 2-in. cards. One-in.-diameter holes are cut
in the middle of each card. The cards are then placed over each end of the cell.
The cell is then positioned and adjusted vertically and horizontally to give the
maximum transmittance.
4.5 Air pump: Any peristaltic pump capable of delivering 1 liter air/min
may be used. A Masterflex pump with electronic speed control has been found to
be satisfactory.
4.6 Flowmeter: Capable of measuring an air flow of 1 liter/min.
4.7 Aeration tubing: A straight glass frit with a coarse porosity. Tygon
tubing is used for passage of the mercury vapor from the sample bottle to the
absorption cell and return.
4.8 Drying tube: 6-in. x 3/4-in.-diameter tube containing 20 g of mag-
nesium perchlorate or a small reading lamp with 60-W bulb which may be used to
prevent condensation of moisture inside the cell. The lamp should be positioned
to shine on the absorption cell so that the air temperature in the cell is about
10°C above ambient.
4 The cold-vapor generator is assembled as shown in Figure 1 of
referenc 1 or according to the instrument manufacturers instructions. The
apparatus shown in Figure 1 is a closed system. An open system, where the
mercury vapor is passed through the absorption cell only once, may be used
instead of the closed system. Because mercury vapor is toxic, precaution must
be taken to avoid its inhalation. Therefore, a bypass has been included in the
system either to vent the mercury vapor into an exhaust hood or to pass the vapor
through some absorbing medium, such as:
1. Equal volumes of 0.1 M KMn04 and 10% H2S04; or
2. 0.25% Iodine in a 3% KI solution.
7470A - 2 Revision 1
September 1994
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A specially treated charcoal that will adsorb mercury vapor is also
available from Barnebey and Cheney, East 8th Avenue and North Cassidy
Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22.
4.10 Hot plate or equivalent - Adjustable and capable of maintaining a
temperature of 90-95°C.
4.11 Graduated cylinder or equivalent.
5.0 REAGENTS
5.1 Reagent Water: Reagent water will be interference free. All
references to water in this method will refer to reagent water unless otherwise
specified.
5.2 Sulfuric acid (HZS04), concentrated: Reagent grade.
5.3 Sulfuric acid, 0.5 N: Dilute 14.0 ml of concentrated sulfuric acid
to 1.0 liter.
5.4 Nitric add (HNQ3}» concentrated: Reagent grade of low mercury
content. If a high reagent blank is obtained, it may be necessary to distill the
nitric acid.
5.5 Stannous sulfate: Add 25 g stannous sulfate to 250 ml of 0.5 N
H2S04. This mixture is a suspension and should be stirred continuously during
use. {Stannous chloride may be used in place of stannous sulfate.)
5.6 Sodium chloride-hydroxylamine sulfate solution: Dissolve 12 g of
sodium chloride and 12 g of hydroxylamine sulfate in reagent water and dilute to
100 mL. (Hydroxylamine hydrochloride may be used in place of hydroxylamine
sulfate.}
5.7 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate in 100 ml of reagent water.
5.8 Potassium persulfate, 5% solution (w/v): Dissolve 5 g of potassium
persulfate in 100 ml of reagent water.
5.9 Stock mercury solution: Dissolve 0.1354 g of mercuric chloride in
75 ml of reagent water. Add 10 ml of concentrated HN03 and adjust the volume to
100.0 ml (1 ml = 1 mg Hg). Stock solutions may also be purchased.
5.10 Mercury working standard: Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 ug per mL. This
working standard and the dilutions of the stock mercury solution should be
prepared fresh daily. Acidity of the working standard should be maintained at
0.15% nitric acid. This acid should be added to the flask, as needed, before
addition of the aliquot.
7470A - 3 Revision 1
September 1994
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6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6,1 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
reagent water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH <2 with HN03. The
suggested maximum holding times for mercury is 28 days.
6.4 Nonaqueous samples shall be refrigerated, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation: Transfer 100 mL, or an aliquot diluted to
100 mL, containing <1.0 g of mercury, to a 300-mL BOO bottle or equivalent. Add
5 mL of H2S04 and 2.5 mL of concentrated HNQ3, mixing after each addition. Add
15 mL of potassium permanganate solution to each sample bottle. Sewage samples
way require additional permanganate. Ensure that equal amounts of permanganate
are added to standards and blanks. Shake and add additional portions of
potassium permanganate solution, if necessary, until the purple color persists
for at least 15 rain. Add 8 mL of potassium persulfate to each bottle and heat
for 2 hr in a water bath maintained at 95°C. Cool and add 6 mL of sodium
chloride-hydroxylamlne sulfate to reduce the excess permanganate. After a delay
of at least 30 sec, add 5 n»L of stannous sulfate, immediately attach the bottle
to the aeration apparatus, and continue as described in Paragraph 7.3.
7.2 Standard preparation: Transfer 0-, 0.5-, 1.0-, 2.0-, 5.0-, and 10.0-
mL aliquots of the mercury working standard, containing 0-1.0 ug of mercury, to
a series of 300-mL BOD bottles. Add enough reagent water to each bottle to make
a total volume of 100 raL. Mix thoroughly and add 5 mL of concentrated H2S04 and
2.5 raL of concentrated HN03 to each bottle. Add 15 mL of KMn04 solution to each
bottle and allow to stand at least 15 min. Add 8 mL of potassium persulfate to
each bottle and heat for 2 hr in a water bath maintained at 95°C, Cool and add
6 mL of sodium chloride-hydroxylamine sulfate solution to reduce the excess
permanganate. When the solution has been decolorized, wait 30 sec, add 5 mL of
the stannous sulfate solution, immediately attach the bottle to the aeration
apparatus, and continue as described in Paragraph 7.3.
7.3 Analysis: At this point the sample is allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of 1 liter/min, is allowed to run continuously. The
absorbance will increase and reach a maximum within 30 sec. As soon as the
recorder pen levels off (approximately 1 min), open the bypass valve and continue
the aeration until the absorbance returns to its minimum value. Close the bypass
valve, remove the stopper and frit from the BOD bottle, and continue the
aeration. Because of instrument variation refer to the manufacturers recommended
operating conditions when using this method.
7470A - 4 Revision 1
September 1994
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7.4 Construct a calibration curve by plotting the absorbances of stan-
dards versus micrograms of mercury. Determine the peak height of the unknown
from the chart and read the mercury value from the standard curve. Duplicates,
spiked samples, and check standards should be routinely analyzed.
7.5 Calculate metal concentrations (1) by the method of standard
additions, or (2) from a calibration curve. All dilution or concentration
factors must be taken into account. Concentrations reported for multiphased or
wet samples must be appropriately qualified (e.g., 5 ug/g dry weight).
8.0 QUALITY CONTROL
8.1 Refer to section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 245.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 245.1.
7470A - 5 Revision 1
Septenber 1994
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METHOD 7470A
HERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
Sample Preparation
Standard Preparation
7.1 Tr*nif*r aliquot
to bottla, add HjSO^
and HNO& and mix.
7,2 Tranafar aliquot
of (ha Hfl working
atandard to
battla.
7.1 Add KMnO*
and ahaka.
7.2 Add raagant
water, mix, add
eoncantratad
7.1 Add mora
parmanganai*
if nac*«aary.
I No
7.1 Add
pota**ium
pftraulfatt, hail
for 2 Hr>.t cool.
7.2 Add KMn04
pota»aium
paraulfati, haai
for 2 hr». and cool.
7.2 Add aodium
cltiorid«-
hydroxylanrtino
•ulfat«. wait 30
**condc.
7.1 Add aodium
cMorid*-
hydroxylMnina
•utfato, wait 30
•aeonds.
7.1 Add atannoua
•ulfata, attach
to aeration
apparatui.
7.3 Analyza
•ampla.
7.2 Add §1 an no in
aulfata, atiach
to aaration
apparatus.
7.4 Conatruct
calibraition
eurva, datarmrna
paak bvight and
HO valtia.
7.4 Routinaly
analvx* dupticant,
apikad aamplaa.
7.5 Caleulat*
matal
concantration*.
| Stop J
7470A - 6
Revision 1
Septerber 1994
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METHOD 7471A
MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0 SCOPE AND APPLICATION
I.I Method 7471 is approved for measuring total mercury (organic and
inorganic) in soils, sediments, bottom deposits, and sludge-type materials. All
samples must be subjected to an appropriate dissolution step prior to analysis.
If this dissolution procedure is not sufficient to dissolve a specific matrix
type or sample, then this method is not applicable for that matrix.
2.0 SUMMARY OF METHOD
2,1 Prior to analysis, the solid or semi-solid samples must be prepared
according to the procedures discussed in this method.
2.2 Method 7471, a cold-vapor atomic absorption method, is based on the
absorption of radiation at the 253.7-nm wavelength by mercury vapor. The mercury
is reduced to the elemental state and aerated from solution in a closed system.
The mercury vapor passes through a cell positioned in the light path of an atomic
absorption spectrophotometer. Absorbance (peak height) is measured as a function
of mercury concentration.
2.3 The typical instrument detection limit (IDL) for this |