United States
Environmental Protection
Agency
Office of Solid Waste
and Emergency Response
Washington, DC 20460
November 1986
SW-846
Third Edition
Solid Waste
&EPA Test Methods
for Evaluating Solid Waste
Volume 1C: Laboratory Manual
Physical/Chemical Methods
*
-------
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.
-------
TABLE OF. CONTENTS
VOLUME ONE
SECTION A
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS
PART I METHODS FOR ANALYTES AND PROPERTIES
CHAPTER ONE -- QUALITY CONTROL
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) Spectrbscopy
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 and
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 Analyses by, Graphite-Furnace Atomic
Absorption (GFAA) Spectroscopy ' .' ,,'.%''
Dissolution Procedure for Oils, Greases, 'ojr|Waxes
Acid Digestion .of Sediments, SI udges,-,ancl ffpils
Microwave Assisted'Acid Digestion of-.Se.d\menjts,. Sludges,
Soils, and Oils , ' f:^*ซv.-
3.3 Methods for Determination of Meta'ls
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:
Method 7610:
Method 7740:
'iff.
Inductively Coupled Plasma-Atomic Emission Spectroscopy
Inductively Coupled Plasma - Mass Speetfometry
Atomic Absorption Methods . >'''t; '-..
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration) , r- c*. .,_ -^ ,
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)
Beryllium (AA, Direct Aspiration)
Beryllium (AA, Furnace Technique) --
Cadmium (AA, Direct Aspiration) .
Cadmium (AA, Furnace Technique) !.
Calcium (AA, Direct Aspiration,) ..',,.. ^
Chromium (AA, Direct Aspiration) 4^
Chromium (AA, Furnace Technique) . .-.. :, ,
Chromium, Hexavalent (Coprecipitation) v-,V* i
Chromium, Hexavalent (Colorimetric) . ..-;'',
Chromium, Hexavalent (Delation/Extraction) ..V,
Chromium, Hexavalent (Differential Pulse Polar9,gf.aphy)
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
-------
Hethod 7741A: Selenium (AA, Gasebus Hydride)
Method 7742: Seleniuitt (AA, Borohydride Reduction)
Method 7760A: $:ilvef"(AA, Direct Aspiration)
Hethod 7761: Silver (AA, Furnace Technique)
Method 7770^ Sodium (AA,rDirect 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 revisipn^onje
(the method has been revised once). A suffix of "B" in the method
number indicates revision two (the method has been revised tw1ceL;vIn
order to properly document the method used for analysis, the effltlte
method number Including the suffix letter designation (e.g., A/pj
must be Identified by the analyst. A method reference found wVj
the RCRA regulations and the text of SW-846 methods and chapter
refers, to the latest promulgated revision of the method, even thoii
:;i'the method number does not include the appropriate letter suffix..*
CONTENTS - 3 Revision 2
September 1994
-------
VOLUME ONE
SECTION B
DISCLAIMER
ABSTRACT '
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS
CHAPTER ONE. REPRINTED -- QUALITY CONTROL
.. '*
!..(ฃ' Introduction .;. ฐ Vl
2.0 " QA Project Plan it .
3.0...., Field Operations ' ,
4.0% Laboratory Operations *?r v v
5.0 Definitions /r r ''.'t
6".0 .'References
-"*'' -. '.
CHAPTER FOUR..- ORGANIC ANALYTES : :
4.1 Sampling Considerations r"
4.2 Sample Preparation Methods
t
.,.,4.2.1 Extractions and Preparations '-
'. .-" 'r- '3M
Method 3500A: Organic Extraction and Sample Preparation
?- .-Method 3510B: Separatory Funnel Liquid-Liquid Extraction
'Method 3520B: Continuous Liquid-Liquid Extraction
Method 3540B: Soxhlet Extraction
" Mejthod 3541: Automated Soxtilet Extraction 5
Method 3550A: Ultrasonic Extraction
Method 3580A: Waste Dilution ;]
Method 5030A: Purge-and-Trap '.; ''; 's
Method 5040A: Analysis of Sorbent Cartridges from1--Volatile Organic
} . Sampling Train (VOST): Gas -Chromatogfaphy/Mass
Spectrometry Technique
Method 5041: Protocol for Analysis of Sorbent Cartridges from
_r ^ Volatile Organic Sampling Train
!r ' ' 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 8010B:
Method 8011:
Method 8015A:
Method 8020A:
Method 8021A:
Method
Method
Method
Method
Method
Method
8030A:
8031:
8032:
8040A:
8060:
8061:
Method 8070:
Method 8080A:
Method 8081:
Method 8090:
Method 8100:
sMethod 8110:
Method 8120A:
Method 8121:
Method 8140:
Method 8141A:
r
Method 8150B:
Method. 8151 :
by
Gas Chromatography ' - --
Halogenated Volatile Organics by Gas Chromatography
1,2-Dibromoethane and l,2-Dibromo-3-chloropropaTie
Microextraction and Gas Chromatography .1
Nonhalogenated Volatile Organics by Gas Chr.bitiatography
Aromatic Volatile Organics by Gas ChromatogHphyr
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 ChromatogVaphy with
Electron Capture Detection (GC/ECD)
Nitrosamines by Gas Chromatography ;;
Organochlorine Pesticides and PolychlorinateU Biphenyls
by Gas Chromatography .
Organochlorine Pesticides and PCBs as Aropl'ors by Gas
Chromatography: Capillary Column Techniqu"e\!
Nitroaromatics and Cyclic Ketones ;:1,
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
CONTENTS - 5
Revision 2
September 1994
-------
4.3.2 Gas Chromatographic/Mass, Spectroscopic Methods .,.
Method 824QB: Volatile Organic Compounds by Gas Chromatography/Mass
Spectrometry (GC/MS)
Method 8250A: SemlvolatHe Organic Compounds by Gas
Chromatography/Mass Spectrometry (GC/MS)^ <
Method 8260A: Volatile Organic Compounds by Gas Chromatography/Mass
Spectrometry.(GC/MS): Capillary Column Technique
Method 8270B: Semivolatile Organic Compounds by Gas
Chromatography/Mass Spectrometry (G,C/MS): Capillary
Column Technique "" "
Method 8280: The Analysis of Polychlorinated Dibenzo-p-Dioxins and
Polychlorinated Dibenzofurans
Appendix A: Signal-to-Noise Determination Methods
Appendix B: Recommended Safety and Handling Procedures for
PCDDs/PCOFs
Method 8290: Polychlorinated Dibenzodioxins (PCDDs) and
Polychlorinated Dibenzofurans (PCDFs) by High'-Resolution
5f ., Gas Chromatography/High-Resolutipn Mass Spectrometry
,!; (HRGC/HRMS) ; ''.,," '"^'' i
..Appendix A: Procedures for the Collection, Handling,
V, . Analysis, and Reporting ,of Wipe Tests Performed
-.ฃ,' within the Laboratory '" ^ i
'>- . , r. *
4.3.3 High Performance Liquid Chromatographic Methods . "!' |
Method 8310: Polynuclear Aromatic Hydrocarbons * \
Method 8315: Determination of Carbonyl Compounds by High Performance
Liquid Chromatography (HPLC)
Appendix A: Recrystallization of 2,4-Dinitrophenylhydrazine
(DNPH)
Method 8316: Acrylamide, Acrylonitrile and Acrolein by High
Performance Liquid Chromatography (HPLC)
Method 8318: N-Methylcarbamates by High Performance Liquid
Chromatography (HPLC)
Method 8321: Solvent Extractable Non-Volatile Compounds by High
Performance Liquid Chromatography/Thermospray/Mass
Spectrometry (HPLC/TSP/MS) or Ultraviolet (UV) Detection
Method 8330: Nitroaromatics and Nitramines by High Performance Liquid
Chromatography (HPLC)
Method 8331: Tetrazene by Reverse Phase High Performance Liquid
Chromatography (HPLC)
4.3.4 Fourier Transform Infrared Methods
Method 8410: Gas Chromatography/Fourier Transform Infrared (GC/FT-IR)
Spectrometry for Semivolatile 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
v Organics "
Method 4010: "' Screening for Pentachlorophenol by Immunoassay
Method 8275: Thermal Chromatography/Mass Spectrometry (TC/MS) for
"" Screening'Semivolatile Organic Compounds
J .. -. "*<>!
APPENDIX -- COMPANY REFERENCES
A suffix'of "A*Mn 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?
'
Dr.,;).
CONTENTS - 7 Revision 2
September 1994
-------
VOLUME ONE
SECTION C
DISCLAIMER
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE ,-.
CHAPTER ONE. REPRINTED -- QUALITY CONTROL
1.0 Introduction
2.0 QA Project Plan
3.0 Field Operations
4.0 Laboratory Operations
5.0 Definitions
6.0 References
CHAPTER FIVE -- MISCELLANEOUS TEST METHODS
Method
Method
Method
Method
Method
Method
Method
5050:
9010A:
9012:
9013:
9020B:
9021:
9022:
Method 9030A:
Method 9031:
Method 9035:
Method 9036:
Method 9038:
Method 9056:
Method 9060:
Method 9065:
Method 9066:
Method 9067:
Method 9070:
Method 9071A:
Method 9075:
Method 9076:
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
ID
Sulfate (Turbidimetric)
Determination of Inorganic Anions by Ion Chromatography
Total Organic Carbon . - r;.
Phenolics (Spectrophotometric, Manual 4--AAP'-':with
Distillation) , T
Phenolics (Colorimetric, Automated 4-^AP with
Distillation) rr
Phenolics (Spectrophotometric, MBTH with Distillation)
Total Recoverable Oil & Grease (Gravimetric, Separatory
Funnel Extraction)
Oil and Grease Extraction Method for Sludge and Sediment
Samples . ^
Test Method for Total Chlorine in New and Used Petroleum
Products by X-Ray Fluorescence Spectrometry (XRF)
Test Method for Total Chlorine in New and Used Petroleum
Products by Oxidative Combustion and Microcoulometry
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 9045B:
. ... Method 9050:
. " '' Method 9080:
,' Method 9081:
Method 9090A:
Method 9095:
Method 9096:
Appendix A:
Method 9100:
Method 9310:
... P7 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 Membrane 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 Ignilability
712 " 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 DETERMINING CHARACTERISTICS
8.1 Ignitability
Method 1010: Pensky-Martens Closed-Cup Method for Determining
Ignitability
Method 1020A: Setaflash Closed-Cup Method for Determining Ignitability
8.2 Corrosivity
Method 1110: Corrosivity Toward Steel
8.3 Reactivity
8.4 Toxicity
Method 1310A: Extraction Procedure (EP) .Toxicity Test Method and
Structural Integrity Test ,;'),
Method 1311: Toxicity Characteristic Leaching Procedure ;; r'
APPENDIX -- COMPANY REFERENCES ]'b
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.Q> QA Project Plan
3Vt)J Field Operations
4.0 Laboratory Operations
5.0 Definitions
6.0 References
PART III SAMPLING
CHAPTER NINE -- SAMPLING PLAN
i9.1 Design and Development
9.2 Implementation
CHAPTER TEN -- SAMPLING METHODS
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 WATER MONITORING
11.1 Background and Objectives
11.2 Relationship to the Regulations and to Other Documents
11.3 Revisions and Additions
11.4 Acceptable Designs and Practices
11.5 Unacceptable Designs and Practices
CHAPTER TWELVE -- LAND TREATMENT MONITORING
12.1 Background
12.2 Treatment Zone
12.3 Regulatory Definition
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
I'.i
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 - 12
Revision 2
September 1994
-------
SH-846 METHOD STATUS TABLE
September 1994
METH NO.
THIRD ED
DATED
9/86
0010
0020
0030
1010
1020
J
i :;
i 1110
. i
!
\
1310
"
'
METH NO.
FINAL
UPDATE I
DATED
7/92
** ~
*" ~
*~
1020A
~ ~
1310A
1311
"
METH NO.
FINAL
UPDT. II
DATED
9/94
~ **
~ *
~ *
~ **
~ "
~ "
"'
1312
METHOD TITLE
Modified Method 5
Sampling Train
Source Assessment
Sampling System
(SASS)
Volatile Organic
Sampling Train
Pensky-Martens
Closed-Cup Method
for Determining
Ignitability
Setaflash Closed-Cup
Method for
Determining
Ignitability
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.11
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
-------
SU-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
1320
1330
3005
3010
~ ~*
3020
3040
3050
METH NO.
FINAL
UPDATE I
DATED
7/92
~ *"
1330A
3005A
3010A
_ .1
3020A
~
3050A
METH NO.
FINAL
UPDT. II
DATED
9/94
"
"
3015
V V
"
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
133QA
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 HETHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
v'
3500
'. S
,1 r
3510
i
3520
3540
S
3550
3580
3600
HETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
3500A
3510A
3520A
3540A
~ ~
~ ~
3580A
3600A
NETH NO.
FINAL
UPDT. II
DATED
9/94
3051
~ ~
3510B
3520B
3540B
3541
3550A
~ ~
3600B
NETHOD 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
NETHOD
3051
Rev 0
9/94
3500A
Rev 1
7/92
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
-------
SU-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
3610
3611
3620
3630
3640
3650
3660
~ ~
3810
HETH NO.
FINAL
UPDATE I
DATED
7/92
3610A
3611A
3620A
3630A
~ "
3650A
3660A
~ ~
"
METH NO.
FINAL
UPDT. II
DATED
9/94
"
*
"
3630B
3640A
~ ~
*"
3665
"
METHOD TITLE
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
Acid/Permanganate
Cleanup
Headspace
SW-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
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
3820
5030
5040
. i
~
6010
HETH NO.
FINAL
UPDATE I
DATED
7/92
~ *"
5030A
~
6010A
HETH NO.
FINAL
UPDT. II
DATED
9/94
"
4010
(Update
IIA,
dated
8/93)
*~ ~
5040A
5041
5050
"
HETHOD TITLE
Hexadecane
Extraction and
Screening of
Purgeable Organics
Screening for
Pentachlorophenol
by Immunoassay
Purge-and-Trap
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST): Gas
Chromatography/Mass
Spectrometry
Technique
Protocol for
Analysis of Sorbent
Cartridges from
Volatile Organic
Sampling Train
(VOST): Wide-bore
Capillary Column
Technique
Bomb Preparation
Method for Solid
Waste
Inductively Coupled
Plasma-Atomic
Emission
Spectroscopy
SW-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
HETHOD
3820
Rev 0
9/86
4010
Rev 0
8/93
5030A
Rev 1
7/92
5040A
Rev 1
9/94
5041
Rev 0
9/94
5050
Rev 0
9/94
6010A
Rev 1
7/92
-------
SW-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
"* ~
ff
"
"
7061A
"
"
NETH NO.
FINAL
UPDT. II
DATED
9/94
6020
~ ~
~
V ซ
'"
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 I
7/92
7020
Rev 0
9/86
7040
Rev 0
9/86
7041
Rev 0
9/86
7060A
Rev 1
9/94
7061 A
Rev 1
7/92
7062
Rev 0
9/94
7080A
Rev 1
9/94
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
j
7090
7091
7130
7131
7140
7190
f
7191
7195
HETH NO.
FINAL
UPDATE I
DATED
7/92
7081
~
~ ~
~ ~
_ *
" ~
~
~ ~
~
HETH NO.
FINAL
UPDT. II
DATED
9/94
~ "
. .
~
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
V ซ
""
~
* *
"
7211
~ "
7381
METH NO.
FINAL
UPDT. II
DATED
9/94
* -
* ~
**
V
~ ~
*
" ~
**
METHOD TITLE
Chromium, Hexavalent
(Colorimetric)
Chromium, Hexavalent
(Chelation/Extrac-
tion)
Chromium, Hexavalent
(Differential Pulse
Polarography)
Cobalt (Atomic
Absorption, Direct
Aspiration)
Cobalt (Atomic
Absorption, Furnace
Technique)
Copper (Atomic
Absorption, Direct
Aspiration)
Copper (Atomic
Absorption, Furnace
Technique)
Iron (Atomic
Absorption, Direct
Aspiration)
Iron (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
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
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH 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
** ~
*m ~
" .
~ * .
* ~
~
7470A
7471A
"
METHOD 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)
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
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
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
7481
7520
7550
7610
7740
7741
~
7760
"..
NETH NO.
FINAL
UPDATE I
DATED
7/92
"* *
* ~
~
"
~
"
7760A
7761
HETH 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 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
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
-------
SH-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
7770
~
7840
7841
7870
7910
7911
7950
METH NO.
FINAL
UPDATE I
DATED
7/92
w
7780
""
~
.
~ ~
~ ~
7951
METH 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
i
Rev 0
9/86
7911
Rev 0
9/86
7950
Rev 0
9/86
7951
Rev 0
7/92
11
-------
SH-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
8015A
_ *.
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-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
SH-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
801 5A
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
-------
SW-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
~
METH 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 (GC/ECD)
Nitrosamines 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
SH-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
METH NO.
FINAL
UPDATE I
DATED
7/92
V
8110
" -
8141
8150A
METH NO.
FINAL
UPDT. II
DATED
9/94
"
"
8120A
8121
~ "
8141A
8150B
8151
METHOD TITLE
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 Methyl ati on or
Pentafluorobenzyl-
ation Derivati-
zation: Capillary
Column Technique
SH-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
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
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
8240
8250
8270
8280
METH 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)
Semivolatile Organic
Compounds
by Gas
Chromatography/Mass
Spectrometry (GC/MS)
Volatile Organic
Compounds by Gas
Chromatography/Mass
Spectrometry
(GC/MS): Capillary
Column Technique
Semivolatile Organic
Compounds by Gas
Chromatography/Mass
Spectrometry
(GC/MS): Capillary
Column Technique
Thermal
Chromatography/Mass
Spectrometry (TC/MS)
for Screening
Semivolatile Organic
Compounds
The Analysis of
Polychlorinated
Dibenzo-p-Dioxins
and Polychlorinated
Dibenzofurans
SH-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
METH NO.
THIRD ED
DATED
9/86
8310
~
METH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
~
METH NO.
FINAL
UPDT. II
DATED
9/94
8290
* *
8315
8316
8318
METHOD TITLE
Polychlorinated
Dibenzodioxins
(PCDDs) and
Polychlorinated
Dibenzofurans
(PCDFs) by High-
Resolution Gas
Chromatography/High-
Resolutlon 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
Chromatography
(HPLC)
N-Methylcarbamates
by High Performance
Liquid Chroma-
tography (HPLC)
SW-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
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9010
9012
METH NO.
FINAL
UPDATE I
DATED
7/92
9010A
METH NO.
FINAL
UPDT. II
DATED
9/94
.8321
8330
8331
8410
"
"
METHOD TITLE
Solvent Extractable
Non-Volatile
Compounds by High
Performance Liquid
Chromatography/Ther-
mospray/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)
Gas Chroma-
tography/Fourier
Transform Infrared
(GC/FT-IR) Spec-
trometry for
Semivolatile
Organics: Capillary
Column
Total and Amenable
Cyanide
(Colorimetric,
Manual)
Total and Amenable
Cyanide
(Colorimetric,
Automated UV)
SW-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
~ ~
9020
"
9022
9030
9035
9036
9038
METH NO.
FINAL
UPDATE I
DATED
7/92
9013
9020A
9021
~ ~
9030A
9031
"
"* ~
METH NO.
FINAL
UPDT. II
DATED
9/94
~ ~
90206
"
, ~
~
~ ~
~ ~
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
Sulfides
Extractable Sulfides
Sulfate
(Colorimetric,
Automated,
Chloranilate)
Sulfate
(Colorimetric,
Automated,
Methyl thymol Blue,
AA II)
Sulfate
(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
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
HETH NO.
THIRD ED
DATED
9/86
9040
9041
9045
9050
"
9060
9065
9066
9067
HETH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
9041A
9045A
* ~
* ~
~ ~
*"
ซ.
."
METH NO.
FINAL
UPDT. II
DATED
9/94
9040A
~
9045B
*
9056
~ ~
"
METHOD TITLE
pH Electrometric
Measurement
pH Paper Method
Soil and Waste pH
Specific Conductance
Determination of
Inorganic Anions by
Ion Chromatography
Total Organic Carbon
Phenol ics
(Spectrophotometri c ,
Manual 4-AAP with
Distillation)
Phenol ics
(Colorimetric,
Automated 4-AAP with
Distillation)
Phenol ics
(Spectrophotometri c ,
MBTH with
Distillation)
SW-846
VOLUME/
CHAPTER/
SECTION
LOCATION
Vol 1C
Chap 6
VolIC
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
9040A
Rev 1
9/94
9041A
Rev 1
7/92
9045B
Rev 2
9/94
9050
Rev 0
9/86
9056
Rev 0
9/94
9060
Rev 0
9/86
9065
Rev 0
9/86
9066
Rev 0
9/86
9067
Rev 0
9/86
19
-------
SW-846 METHOD STATUS TABLE (9/94), CONTINUED
METH NO.
THIRD ED
DATED
9/86
9070
9071
9080
9081
METH NO.
FINAL
UPDATE I
DATED
7/92
~ ~
_
METH NO.
FINAL
UPDT. II
DATED
9/94
9071A
9075
9076
9077
~ ~
"
METHOD TITLE
Total Recoverable
Oil & Grease
(Gravimetric,
Separatory Funnel
Extraction)
Oil and Grease
Extraction Method
for Sludge and
Sediment
Samples
Test Method for
Total Chlorine in
New and Used
Petroleum Products
by X-Ray
Fluorescence
Spectrometry (XRF)
Test Method for
Total Chlorine in
New and Used
Petroleum Products
by Oxi dative
Combustion and
Microcoulometry
Test Methods for
Total Chlorine in
New and Used
Petroleum Products
(Field Test Kit
Methods)
Cation-Exchange
Capacity of Soils
(Ammonium Acetate)
Cation-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
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
~ *~
"
~ ~
" ~*
* ~
~
"
HETH NO.
FINAL
UPDT. II
DATED
9/94
."
~ ~
9096
~ ~
ซ. _
"" ~
~ ~
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
Ferricyanide AAI)
Chloride
(Colorimetric,
Automated
Ferricyanide AAII)
SW-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
METH NO.
FINAL
UPDATE I
DATED
7/92
_ _
"
-"
~ ~
**
HCN Test
Method
H2S Test
Method
METH NO.
FINAL
UPDT. II
DATED
9/94
9252A
9253
* ~
~
~ ~
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- 228
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
9253
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
-------
DISCLAIMER
Mention of trade names or commercial products does not constitute
endorsement or recommendation for use by the U.S. Environmental Protection
Agency.
SU-846 methods are designed to be used with equipment from any manufacturer
that results in suitable method performance (as assessed by accuracy, precision,
detection limits and matrix compatibility). In several SW-846 methods, equipment
specifications and settings are given for the specific instrument used during
method development, or subsequently approved for use in the method. These
references are made to provide the best possible guidance to laboratories using
this manual. Equipment not specified in the method may be used as long as the
laboratory achieves equivalent or superior method performance. If alternate
equipment is used, the laboratory must follow the manufacturer's instructions for
their particular instrument.
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.
DISCLAIMER - 1 Revision 0
July 1992
-------
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.
U.S. Environmental Protection Agency
5 Library (PL-12J)
ABSTRACT - 1 Revision 2
September 1994
-------
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.
Method Number,
Current Revision
Third Edition
Ten
Ten
Ten
Eight
Eight
Eight
Eight
Six
Six
Three
Three
Three
Three
Three
(8.1)
(8.1)
8.2)
8.4)
Four (4.2.1)
Four (4.2.1
Four (4.2.1
Four
Four
4.2.1
4.2.1
Four (4.2.1
Four
Four
Four
Four
Four
Four
Four
Four
Four
Four
Four
Four
Three
Three
Three
4.2.2
4.2.2)
4.2.2]
4.2.2;
4.2.2)
[4.2.2]
4.2.2;
4.2.2'
4.4)
4.4)
(4.2.1
(4.2.1
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, Chapter Number, Method Number, Current Revision
Third Edition Third Edition Second Edition Number
7040 Three 7040 0
7041 Three 7041 0
7060 Three 7060 0
7061 Three 7061 0
7080 Three 7080 0
7090 Three 7090 0
7091 Three 7091 0
7130 Three 7130 0
7131 Three 7131 0
7140 Three 7140 0
7190 Tnree 7190 0
7191 Three 7191 0
7195 Three 7195 0
7196 Three 7196 0
7197 Three 7197 0
7198 Three 7198 0
7200 Three 7200 0
7201 Three 7201 0
7210 Three 7210 0
7380 Three 7380 0
7420 Three 7420 0
7421 Three 7421 0
7450 Three 7450 0
7460 Three 7460 0
7470 Three 7470 0
7471 Three 7471 0
7480 Three 7480 0
7481 Three 7481 0
7520 Three 7520 0
7550 Three 7550 0
7610 Three 7610 0
7740 Three 7740 0
7741 Three 7741 0
7760 Three 7760 0
7770 Three 7770 0
METHOD INDEX - 2
Revision
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
Chapter Number,
Third Edition
Three
Three
Three
Three
Three
Three
Four (4.3.1)
Four (
Four 1
4.3.1)
4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four |
Four i
,4.3.1)
,4.3.1)
Four (4.3.1)
Four (4.3.1)
Four <
Four
Four
Four
Four
Four
Four
[4.3.1)
[4.3.1)
[4.3.1)
14.3.2)
4.3.2)
4.3.2)
4.3.2)
Four (4.3.3)
Five
Five
Five
Five
Five
Five
Five
Six
Six
Six
Six
Method Number,
Second Edition
Current Revision
Number
7840 0
7841 0
7870 0
7910 0
7911 0
7950 0
None (new method) 0
8010 0
8015 0
8020 0
8030 0
8040 0
8060 0
8080 0
8090 0
8100 0
8120 0
8140 0
8150 0
8240 0
8250 0
-8270 0
None (new method) 0
8310 0
9010 0
9020 0
9022 0
9030 0
9035 0
9036 0
9038 0
9040 0
9041 0
9045 0
9050 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
Number
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
-------
PREFACE AND OVERVIEW
PURPOSE OF THE MANUAL
Test Methods for Evaluating Solid Waste (SW-846) is 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
in 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 in 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 in this manual are meant to be comprehensive and
detailed, coupled with the realization that the problems encountered in
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 is possible to use
this manual in rote fashion. In other situations, it 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, it is unavoidable because of the variety of sampling and
analytical conditions found with hazardous wastes.
ORGANIZATION AND FORMAT
This manual is divided into two volumes. Volume I focuses on laboratory
activities and is 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 in 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 0
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
in 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 in 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 is hazardous because 1t
exhibits a particular characteristic.
Volume II gives background Information on statistical and nonstatistlcal
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 in 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 is 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
-------
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 . .
Page
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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
4.3.5 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. More 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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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 b^e
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 Evaluation
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 of Field 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
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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 of Anomalous 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.
Validation of 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
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exceed regulatory limits, action levels, or target concentrations
specified in the QAPjP.
Evaluation of Data with Respect 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 in the RCRA Ground-Water Monitoring 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 in 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/Standard Preparation
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 Decontamination
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 Calibration 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.
Pro.iect-specific records 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.
Field operations 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^cTeaHy 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 Corrective Action
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 in 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 in
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 1 aboratory 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 Preparation
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 Technigues
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 concentration(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 QC
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 Proficiency
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 MDL and the reporting limit should be
well-defined and well-documented. Documented precision, bias, and MDL
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 in place for
determining the MDL 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 Handling
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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QC Data -- 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
(*. ~ xu) 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)/ K
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 rigorous, or cursory,
depending on project DQOs. The available data reviewed
will include analytical results, field QC data and lab QC
data, and may also include field records.
see Matrix Duplicate, Field Duplicate, Matrix Spike
Duplicate.
see Equipment Rinsate.
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 thet
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 in
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:
i-l
where xs = 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
fol1ows:
2\1/2
s = (S2)
Determine the MDL for each analyte as follows:
MDL = t
(n-1, a = .99)
(S)
where t(n., wx 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 ป the arithmetic mean of the xf measurements, and S -
variance; and the relative percent difference (RPD) when
only two samples are available.
RPD = 100
- x2)/{(Xl
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.
ONE - 29 Revision 1
July 1992
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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.
ONE - 30 Revision 1
July 1992
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CHAPTER FIVE
MISCELLANEOUS TEST METHODS
The following methods are found in Chapter Five:
Method 5050:
Method 9010A:
Method 9012:
Method 9013:
Method 9020B:
Method 9021:
Method 9022:
Method 9030A:
Method 9031:
Method 9035:
Method 9036:
Method 9038:
Method 9056:
Method 9060:
Method 9065:
Method 9066:
Method 9067:
Method 9070:
Method 9071A:
Method 9075:
Method 9076:
Method 9077:
Method 9131:
Method
Method
Method
Method
Method
Method
Method
9132:
9200:
9250:
9251:
9252A:
9253:
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, Methyl thymol
Blue, AA II)
Sulfate (Turbidimetric)
Determination of Inorganic
Chromatography Method
Total Organic Carbon
Phenolics (Spectrophotometric,
Distillation)
Phenolics (Colorimetric, Automated
Distillation)
Phenolics (Spectrophotometric, MBTH with
Distillation)
Total Recoverable Oil & Grease (Gravimetric,
Separatory Funnel Extraction)
Oil and Grease Extraction Method for Sludge and
Sediment Samples
Chlorine in New and Used
by X-Ray
Anions by Ion
Manual 4-AAP with
4-AAP with
Fluorescence
Chlorine in New and Used
Oxidative Combustion and
Test Method for Total
Petroleum Products
Spectrometry (XRF)
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
Chloride (Colorimetric, Automated Ferricyanide AAI)
Chloride (Colorimetric, Automated FerricyanideAAII)
Mercuric Nitrate)
Silver Nitrate)
Chloride (Titrimetric,
Chloride (Titrimetric,
Radium-228
FIVE - 1
Revision 1
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 /ug/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.
5050 - 2 Revision 0
September 1994
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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 atm.
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 NaHC03/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
September 1994
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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.
Ornery 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., Phillipsburg, NJ.
5050 - 4 Revision 0
September 1994
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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 100-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:
Vcom x DF
(1)
where:
Vcom
DF
W
concentration of element in the sample,
concentration of element in the combustate, jug/mL
total volume of combustate, ml
dilution factor
weight of sample combusted, g.
Report the concentration of each element detected in the sample in
micrograms per gram.
5050 - 5
Revision 0
September 1994
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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 /ug/mL. The concentration of chlorine in the original
sample is then calculated as shown below:
5 UQ x (10 ml) x (10)
C0 - ' ml (2)
0.5 g
C0 = 1,000 M (3)
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 resuHs.
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
f ol 1 owed .
9.0 PERFORMANCE
See analytical methods referenced in Step 2.2.
10.0 REFERENCES
1. ASTM 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.
68-01-7075, WA 80. July 1988.
5050 - 6 Revision 0
September 1994
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300 to 350
350 to 400
400 to 450
450 to 500
TABLE 1.
GAGE PRESSURES
Capacity of bomb, ml
Minimum
gage
pressure8, atm
Maximum
gage
pressure8,
atm
38
35
30
27
40
37
32
29
aThe 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.
5050 - 7
Revision 0
September 1994
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APPENDIX
Al. PRECAUTIONARY STATEMENTS
Al.1 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.
5050 - 8 Revision 0
September 1994
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METHOD 5050
BOMB PREPARATION METHOD FOR SOLID WASTE
START
7.1.1 Prepare bomb
and sample
1
7.1.2 Slowly add
o ity gen to sample
cup
7.1.3 Immerse bomb
in cold wa ter ;
igni te sample ;
remove bomb from
water ; release
pressure; open bomb
I
7,1.4 Rinse bomb,
sample cup,
terminals . and bomb
. cover with water
.
*
7 . 1 . 5 Rinse bomb ,
sample cup,
terminals , and bomb
cover with hot
water
1
7 . 2 Analyze
combus ta te
1
7.3 Calculate
concentration of
each element
detected
/" ^\
| STOP |
V J
5050 - 9
Revision 0
September 1994
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METHOD 9010A
TOTAL AND AMENABLE CYANIDE
1.0 SCOPE AND APPLICATION
1.1 Method 9010 is used to determine the concentration of inorganic
cyanide (CAS Registry Number 57-12-5) in wastes or leachate. The method detects
inorganic cyanides that are present as either soluble salts or complexes. It is
used to determine values for both total cyanide and cyanide amenable to
chlorination. The "reactive" cyanide content of a waste, that is, the cyanide
content that could generate toxic fumes when exposed to mild acidic conditions,
is not distilled by Method 9010 (refer to Chapter Seven). However, Method 9010
is used to quantify the concentration of cyanide from the reactivity test.
1.2 The titration procedure using silver nitrate with p-dimethylamino-
benzal-rhodanine indicator is used for measuring concentrations of cyanide
exceeding 0.1 mg/L (0.025 mg/250 mL of absorbing liquid).
1.3 The colorimetric procedure is used for concentrations below 1 mg/L
of cyanide and is sensitive to about 0.02 mg/L.
1.4 This method was designed to address the problem of "trace" analyses
(<1000 ppm). The method may also be used for "minor" (1000 ppm - 10,000 ppm) and
"major" (>10,000 ppm) analyses by adapting the sample preparation techniques or
cell path length. However, the amount of sodium hydroxide in the standards and
the sample analyzed must be the same.
2.0 SUMMARY OF METHOD
2.1 The cyanide, as hydrocyanic acid (HCN), is released from samples
containing cyanide by means of a reflux-distillation operation under acidic
conditions and absorbed in a scrubber containing sodium hydroxide solution. The
cyanide in the absorbing solution is then determined colorimetrically or
titrametrically.
2.2 In the colorimetric measurement, the cyanide is converted to
cyanogen chloride (CNC1) by reaction of cyanide with chloramine-T at a pH less
than 8. After the reaction is complete, color is formed on the addition of
pyridine-barbituric acid reagent. The absorbance is read at 578 nm for the
complex formed with pyridine-barbituric acid reagent and CNC1. To obtain colors
of comparable intensity, it is essential to have the same salt content in both
the sample and the standards.
2.3 The titration measurement uses a standard solution of silver
nitrate to titrate cyanide in the presence of a silver sensitive indicator.
3.0 INTERFERENCES
3.1 Interferences are eliminated or reduced by using the distillation
procedure. Chlorine and sulfide are interferences in Method 9010.
9010A - 1 Revision 1
July 1992
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3.2 Oxidizing agents such as chlorine decompose most cyanides.
Chlorine interferences can be removed by adding an excess of sodium arsenite to
the waste prior to preservation and storage of the sample to reduce the chlorine
to chloride which does not interfere.
3.3 Sulfide interference can be removed by adding an excess of bismuth
nitrate to the waste (to precipitate the sulfide) before distillation. Samples
that contain hydrogen sulfide, metal sulfides, or other compounds that may
produce hydrogen sulfide during the distillation should be treated by the
addition of bismuth nitrate.
3.4 High results may be obtained for samples that contain nitrate
and/or nitrite. During the distillation, nitrate and nitrite will form nitrous
acid, which will react with some organic compounds to form oximes. These
compounds once formed will decompose under test conditions to generate HCN. The
possibility of interference of nitrate and nitrite is eliminated by pretreatment
with sulfamic acid just before distillation. Nitrate and nitrite are
interferences when present at levels higher than 10 mg/L and in conjunction with
certain organic compounds.
3.5 Thiocyanate is reported to be an interference when present at very
high levels. Levels of 10 mg/L were not found to interfere.
3.6 Fatty acids, detergents, surfactants, and other compounds may cause
foaming during the distillation when they are present in large concentrations and
will make the endpoint of the titration difficult to detect. They may be
extracted at pH 6-7.
4.0 APPARATUS AND MATERIALS
4.1 Reflux distillation apparatus such as shown in Figure 1 or Figure
2. The boiling flask should be of one liter size with inlet tube and provision
for condenser. The gas scrubber may be a 270-mL Fisher-Milligan scrubber
(Fisher, Part No. 07-513) or equivalent. The reflux apparatus may be a Wheaton
377160 distillation unit or equivalent.
4.2 Spectrophotometer - Suitable for measurements at 578 nm with a
1.0 cm cell or larger.
4.3 Hot plate stirrer/heating mantle.
4.4 pH meter.
4.5 Amber light.
4.6 Vacuum source.
4.7 Refrigerator.
4.8 5 mL microburette
4.9 7 Class A volumetric flasks - 100 and 250 mL
4.10 Erlenmeyer flask - 500 mL
9010A - 2 Revision 1
July 1992
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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 Reagent water. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Reagents for sample collection, preservation, and handling
5.3.1 Sodium arsenite (0.1N), NaAs02. Dissolve 3.2 g NaAs02 in
250 ml water.
5.3.2 Ascorbic acid, C6H806.
5.3.3 Sodium hydroxide solution (50%), NaOH. Commercially
available.
5.3.4 Acetic acid (1.6M) CH3COOH. Dilute one part of
concentrated acetic acid with 9 parts of water.
5.3.5 2,2,4-Trimethylpentane, C8H18.
5.3.6 Hexane, C6H14.
5.3.7 Chloroform, CHC13.
5.4 Reagents for cyanides amenable to chlorination
5.4.1 Calcium hypochlorite solution (0.35M), Ca(OCl)2. Combine
5 g of calcium hypochlorite and 100 ml of water. Shake before using.
5.4.2 Sodium hydroxide solution (1.25N), NaOH. Dissolve 50 g of
NaOH in 1 liter of water.
5.4.3 Sodium arsenite (0.1N). See Step 5.3.1.
5.4.4 Potassium iodide starch paper.
5.5 Reagents for distillation
5.5.1 Sodium hydroxide (1.25N). See Step 5.4.2.
5.5.2 Bismuth nitrate (0.062M), Bi(NO)3 5H,0. Dissolve 30 g
Bi(NO)3 5H20 in 100 ml of water. While stirring, adcf 250 ml of glacial
acetic acid, CH3COOH. Stir until dissolved and dilute to 1 liter with
water.
5.5.3 Sulfamic acid (0.4N), H2NS03H. Dissolve 40 g H2NS03H in
1 liter of water.
9010A - 3 Revision 1
July 1992
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5.5.4 Sulfuric acid (18N), H2S04. Slowly and carefully add 500
ml of concentrated H2S04 to 500 ml of water.
5.5.5 Magnesium chloride solution (2.5M), MgCl2ซ 6H20. Dissolve
510 g of MgCl2 6H20 in 1 liter of water.
5.5.6 Lead acetate paper.
5.6 Reagents for spectrophotometric determination
5.6.1 Sodium hydroxide solution (0.25N), NaOH. Dissolve 10 g
NaOH in 1 liter of water.
5.6.2 Sodium phosphate monobasic (1M), NaH2P04 H20. Dissolve
138 g of NaH2P04 H20 in 1 liter of water. Refrigerate this solution.
5.6.3 Chloramine-T solution (0.44%), C^ClNNa02S. Dissolve
1.0 g of white, water soluble chloramine-T in 100 ml of water and
refrigerate until ready to use.
5.6.4 Pyridine-Barbituric acid reagent, C5H5N C4H4N203. Place
15 g of barbituric acid in a 250-mL volumetric flask and add just enough
water to wash the sides of the flask and wet the barbituric acid. Add 75
ml of pyridine and mix. Add 15 ml of concentrated hydrochloric acid
(HC1), mix, and cool to room temperature. Dilute to 250 ml with water.
This reagent is stable for approximately six months if stored in a cool,
dark place.
5.6.5 Stock potassium cyanide solution (1 ml = 1000 M9 CN"), KCN.
Dissolve 2.51 g of KCN and 2 g KOH in 900 ml of water. Standardize with
0.0192N silver nitrate, AgN03. Dilute to appropriate concentration to
achieve 1 ml = 1000 p,g of CN".
NOTE: Detailed procedure for AgN03 standardization is described in
"Standard Methods for the Examination of Water and Wastewater",
16th Edition, (1985), Methods 412C and 407A.
5.6.6 Intermediate standard potassium cyanide solution, (1 ml =
100 /itg CN"), KCN. Dilute 100 ml of stock potassium cyanide solution (1 ml
= 1000 /ig CN") to 1000 ml with water.
5.6.7 Working standard potassium cyanide solution (1 mL = 10 M9
CN"), KCN. Prepare fresh daily by diluting 100 ml of intermediate standard
potassium cyanide solution and 10 mL of IN NaOH to 1 liter with water.
5.7 Reagents for titration procedure
5.7.1 Rhodanine indicator - Dissolve 20 mg of p-dimethylamino-
benzal-rhodanine, C12H12N2OS2, in 100 mL of acetone.
5.7.2 Standard silver nitrate solution (0.0192N), AgN03. Prepare
by crushing approximately 5 g AgN03 and drying to constant weight at 40ฐC.
Weigh out 3.2647 g of dried AgN03. Dissolve in 1 liter of water.
9010A - 4 Revision 1
July 1992
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NOTE: Detailed procedure for AgN03 standardization is described in
"Standard Methods for the Examination of Water and Wastewater",
16th Edition, (1985), Methods 412C and 407A.
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 Samples should be collected in plastic or glass containers. All
containers must be thoroughly cleaned and rinsed.
6.3 Oxidizing agents such as chlorine decompose most cyanides. To
determine whether oxidizing agents are present, test a drop of the sample with
potassium iodide-starch test paper. A blue color indicates the need for
treatment. Add 0.1N sodium arsenite solution a few mL at a time until a drop of
sample produces no color on the indicator paper. Add an additional 5 mL of
sodium arsenite solution for each liter of sample. Ascorbic acid can be used as
an alternative although it is not as effective as arsenite. Add a few crystals
of ascorbic acid at a time until a drop of sample produces no color on the
indicator paper. Then add an additional 0.6 g of ascorbic acid for each liter
of sample volume.
6.4 Aqueous samples must be preserved by adding 50% sodium hydroxide
until the pH is greater than or equal to 12 at the time of collection.
6.5 Samples should be chilled to 4ฐC.
6.6 When properly preserved, cyanide samples can be stored for up to
14 days prior to sample preparation steps.
6.7 Solid and oily wastes may be extracted prior to analysis by method
9013. It uses a dilute NaOH solution (pH = 12) as the extractant. This yields
extractable cyanide.
6.8 If fatty acids, detergents, and surfactants are a problem, they may
be extracted using the following procedure. Acidify the sample with acetic acid
(1.6M) to pH 6.0 to 7.0.
CAUTION: This procedure can produce lethal HCN gas.
Extract with isooctane, hexane, or chloroform (preference in order named) with
solvent volume equal to 20% of the sample volume. One extraction is usually
adequate to reduce the compounds below the interference level. Avoid multiple
extractions or a long contact time at low pH in order to keep the loss of HCN at
a minimum. When the extraction is completed, immediately raise the pH of the
sample to above 12 with 50% NaOH solution.
9010A - 5 Revision 1
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7.0 PROCEDURE
7.1 Pretreatment for cyanides amenable to chlorination
7.1.1 This test must be performed under amber light. K3[Fe-
(CN)J may decompose under UV light and hence will test positive for
cyamde amenable to chlorination if exposed to fluorescent lighting or
sunlight. Two identical sample aliquots are required to determine cyanides
amenable to chlorination.
7.1.2 To one 500 mL sample or to a sample diluted to 500 ml, add
calcium hypochlorite solution dropwise while agitating and maintaining the
pH between 11 and 12 with 1.25N sodium hydroxide until an excess of
chlorine is present as indicated by Kl-starch paper turning blue. The
sample will be subjected to alkaline chlorination by this step.
CAUTION: The initial reaction product of alkaline chlorination is the very
toxic gas cyanogen chloride; therefore, it is necessary that this
reaction be performed in a hood.
7.1.3 Test for excess chlorine with Kl-starch paper and maintain
this excess for one hour with continuous agitation. A distinct blue color
on the test paper indicates a sufficient chlorine level. If necessary,
add additional calcium hypochlorite solution.
7.1.4 After one hour, add 1 ml portions of 0.1N sodium arsenite
until Kl-starch paper shows no residual chlorine. Add 5 ml of excess
sodium arsenite to ensure the presence of excess reducing agent.
7.1.5 Test for total cyanide as described below in both the
chlorinated and the unchlorinated samples. The difference of total
cyanide in the chlorinated and unchlorinated samples is the cyanide
amenable to chlorination.
7.2 Distillation Procedure
7.2.1 Place 500 ml of sample, or sample diluted to 500 ml in the
one liter boiling flask. Pipet 50 ml of 1.25N sodium hydroxide into the
gas scrubber. If the apparatus in Figure 1 is used, add water until the
spiral is covered. Connect the boiling flask, condenser, gas scrubber and
vacuum trap.
7.2.2 Start a slow stream of air entering the boiling flask by
adjusting the vacuum source. Adjust the vacuum so that approximately two
bubbles of air per second enter the boiling flask through the air inlet
tube.
7.2.3 If samples are known or suspected to contain sulfide, add
50 ml of 0.062M bismuth nitrate solution through the air inlet tube. Mix
for three minutes. Use lead acetate paper to check the sample for the
presence of sulfide. A positive test is indicated by a black color on the
paper.
9010A - 6 Revision 1
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7.2.4 If samples are known or suspected to contain nitrate or
nitrite, or if bismuth nitrate was added to the sample, add 50 ml of 0.4N
sulfamic acid solution through the air inlet tube. Mix for three minutes.
Note: Excessive use of sulfamic acid could create method bias.
7.2.5 Slowly add 50 ml of 18N sulfuric acid through the air inlet
tube. Rinse the tube with water and allow the airflow to mix the flask
contents for three minutes. Add 20 ml of 2.5M magnesium chloride through
the air inlet and wash the inlet tube with a stream of water.
7.2.6 Heat the solution to boiling. Reflux for one hour. Turn
off heat and continue the airflow for at least 15 minutes. After cooling
the boiling flask, and closing the vacuum source, disconnect the gas
scrubber.
7.2.7 Transfer the solution from the scrubber into a 250-mL
volumetric flask. Rinse the scrubber into the volumetric flask. Dilute
to volume with water.
7.2.8 If the manual spectrophotometric determination will be
performed, proceed to Step 7.3.1. If the titration procedure will be-
performed, proceed to Step 7.7.
7.3 Manual spectrophotometric determination
7.3.1 Pipet 50 ml of the scrubber solution into a 100-mL
volumetric flask. If the sample is later found to be beyond the linear
range of the colorimetric determination and redistillation of a smaller
sample is not feasible, a smaller aliquot may be taken. If less than
50 ml is taken, dilute to 50 ml with 0.25N sodium hydroxide solution.
NOTE: Temperature of reagents and spiking solution can affect the
response factor of the colorimetric determination. The reagents
stored in the refrigerator should be warmed to ambient temperature
before use. Samples should not be left in a warm instrument to
develop color, but instead they should be aliquoted to a cuvette
immediately prior to reading the absorbance.
7.3.2 Add 15 ml of 1M sodium phosphate solution and mix. Add 2
ml of chloramine-T and mix. Some distillates may contain compounds that
have chlorine demand. One minute after the addition of chloramine-T, test
for excess chlorine with Kl-starch paper. If the test is negative, add
0.5 ml chloramine-T. After one minute recheck with Kl-starch paper.
Continue to add chloramine-T in 0.5 ml increments until an excess is
maintained. After 1 to 2 minutes, add 5 ml of pyridine-barbituric acid
solution and mix.
7.3.3 Dilute to 100 ml with water and mix again. Allow 8 minutes
for color development and then read the absorbance at 578 nm in a 1-cm
cell within 15 minutes. The sodium hydroxide concentration will be
0.125N.
9010A - 7 Revision 1
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7.4 Standard curve for samples without sulfide
7.4.1 Prepare a series of standards by pipetting suitable volumes
of working standard potassium cyanide solution into 250-mL volumetric
flasks. To each flask, add 50 ml of 1.25N sodium hydroxide and dilute to
250 ml with water. Prepare using the following table. The sodium
hydroxide concentration will be 0.25N.
ml of Working Standard Solution Concentration
_ (1 mL = 10 uo. CN') (uq CNVL)
0 Blank
1.0 40
2.0 80
5.0 v 200
10.0 400
15.0 600
20.0 800
7.4.2 After the standard solutions have been prepared according
to the table above, pipet 50 ml of each standard solution into a 100-mL
volumetric flask and proceed to Steps 7.3.2 and 7.3.3 to obtain absorbance
values for the standard curve. The final concentrations for the standard
curve will be one half of the amounts in the above table (final
concentrations ranging from 20 to 400 M9/L)-
7.4.3 It is recommended that at least two standards (a high and
a low) be distilled and compared to similar values on the curve to ensure
that the distillation technique is reliable. If distilled standards do
not agree within ฑ 10% of the undistilled standards, the analyst should
find the cause of the apparent error before proceeding.
7.4.4 Prepare a standard curve ranging from 20 to 400 jugA by
plotting absorbance of standard versus the cyanide concentration
7.5 Standard curve for samples with sulfide
7.5.1 It is imperative that all standards be distilled in the
same manner as the samples using the method of standard additions.
Standards distilled by this method will give a linear curve, at low
concentrations, but as the concentration increases, the recovery
decreases. It is recommended that at least five standards be distilled.
7.5.2 Prepare a series of standards similar in concentration to
those mentioned in Step 7.4.1 and analyze as in Step 7.3. Prepare a
standard curve by plotting absorbance of standard versus the cyanide
concentration.
7.6 Calculation - If the spectrophotometric procedure is used,
calculate the cyanide, in p.g/1, in the original sample as follows.
CN" (Mg/L) = A x B x C
D x E
9010A - 8 Revision 1
July 1992
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where:
A = M9/L CN" read from standard curve.
B = ml of sample after preparation of colorimetric analysis
(100 mL recommended).
C = ml of sample after distillation (250 mL recommended).
D = ml of original sample for distillation (500 mL
recommended) .
E = mL used for colorimetric analysis (50 mL recommended).
7.7 Titration Procedure
7.7.1 Transfer the gas scrubber solution or a suitable aliquot
from the 250-mL volumetric flask to a 500-mL Erlenmeyer flask. Add 10-12
drops of the rhodanine indicator.
7.7.2 Titrate with standard 0.0192N silver nitrate to the first
change in color from yellow to brownish-pink. The titration must be
performed slowly with constant stirring. Titrate a water blank using the
same amount of sodium hydroxide and indicator as in the sample. The
analyst should be familiar with the endpoint of the titration and the
amount of indicator to be used before actually titrating the samples. A
5-mL buret may be conveniently used to obtain a precise titration.
NOTE: The titration is based on the following reaction:
Ag+ + 2CN -ป [Ag(CN)2r
When all of the cyanide has complexed and more silver nitrate is
added, the excess silver combines with the rhodanine indicator to turn the
solution yellow and then brownish-pink.
7.7.3 Calculation - If the titrimetric procedure is used,
calculate concentration of CN" in p.q/1 in the original sample as follows:
- (A ~B) xDx*x 2 mole CN~ x 26. 02 gOT x 1 x 10'nflr
C F 1 eg. AgN03 i mole CAT 1 9
where:
A = mL of AgN03 for titration of sample.
B = mL of AgNO, for titration of blank.
C = mL of sample titrated (250 recommended).
D = actual normality of AgNO, (0.0192N recommended).
E = mL of sample after distillation (250 recommended).
F = mL of original sample before distillation (500
recommended).
9010A - 9 Revision 1
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8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Employ a minimum of one reagent blank per analytical batch or one
in every 20 samples to determine if contamination or any memory effects are
occurring.
8.3 Analyze check standards with every analytical batch of samples.
If the standards are not within 15% of the expected value, then the samples must
be reanalyzed.
8.4 Run one replicate sample for every 20 samples. A replicate sample
is a sample brought through the entire sample preparation and analytical process.
The CV of the replicates should be 20% or less. If this criterion is not met,
the samples should be reanalyzed.
8.5 Run one matrix spiked sample every 20 samples to check the
efficiency of sample distillation by adding cyanide from the working standard or
intermediate standard to 500 mL of sample to ensure a concentration of
approximately 40 jug/L. The matrix spiked sample is brought through the entire
sample preparation and analytical process.
8.6 The method of standard additions shall be used for the analysis of
all samples that suffer from matrix interferences such as samples which contain
sulfides.
9.0 METHOD PERFORMANCE
9.1 The titration procedure using silver nitrate is used for measuring
concentrations of cyanide exceeding 0.1 mg/L. The colorimetric procedure is used
for concentrations below 1 mg/L of cyanide and is sensitive to about 0.02 mg/L.
9.2 EPA Method 335.2 (sample distillation with titration) reports that
in a single laboratory using mixed industrial and domestic waste samples at
concentrations of 0.06 to 0.62 mg/L CN', the standard deviations for precision
were + 0.005 to + 0.094, respectively. In a single laboratory using mixed
industrial and domestic waste samples at concentrations of 0.28 and 0.62 mg/L
CN", recoveries (accuracy) were 85% and 102%, respectively.
9.3 In two additional studies using surface water, ground water, and
landfill leachate samples, the titration procedure was further evaluated. The
concentration range used in these studies was 0.5 to 10 mg/L cyanide. The
detection limit was found to be 0.2 mg/L for both total and amenable cyanide
determinations. The precision (CV) was 6.9 and 2.6 for total cyanide
determinations and 18.6 and 9.1 for amenable cyanide determinations. The mean
recoveries were 94% and 98.9% for total cyanide, and 86.7% and 97.4% for amenable
cyanide.
9010A - 10 Revision 1
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10.0 REFERENCES
1. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification for
Reagent Water"; ATSM: Philadelphia, PA, 1985,; D1193-77.
2. 1982 Annual Book ASTM Standards. Part 19; "Standard Test Methods for
Cyanide in Water"; ASTM: Philadelphia, PA, 1982; 2036-82.
3. Bark, L.S.; Higson, H.G. Talanta 1964, 2, 471-479.
4. Britton, P.; Winter, J.; Kroner, R.C. "EPA Method Study 12, Cyanide in
Water"; final report to the U.S. Environmental Protection Agency. National
Technical Information Service: Springfield, VA, 1984; PB80-196674.
5. Casey, J.P.; Bright, J.W.; Helms, B.D. "Nitrosation Interference in
Distillation Tests for Cyanide"; Gulf Coast Waste Disposal Authority: Houston,
Texas.
6. Egekeze, J.O.; Oehne, F.W. J. Anal. Toxicology 1979, 3, 119.
7. Elly, C.T. iL Water Pollution Control Federation 1968, 40, 848-856.
8. Fuller, W. Cyanide in the Environment; Van Zyl, D., Ed.; Proceedings of
Symposium; December, 1984.
9. Gottfried, G.J. "Precision, Accuracy, and MDL Statements for EPA Methods
9010, 9030, 9060, 7520, 7521,7550, 7551, 7910, and 7911"; final report to the
U.S. Environmental Protection Agency. Environmental Monitoring and Support
Laboratory. Biospheric: Cincinnati, OH, 1984.
10. Methods for Chemical Analysis of Water and Wastes; 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, 1983; EPA-600/4-79-020.
11. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; American Chemical Society: Washington, DC, 1986.
12. Standard Methods for the Examination of Water and Wastewater, 16th ed.;
Greenberg, A.E.; Trussell, R.R.; Clesceri, L.S., Eds.; American Water Works
Association, Water Pollution Control Federation, American Public Health
Association: Washington, DC, 1985.
13. Umafia, M.; Beach, J.; Sheldon, L. "Revisions to Method 9010"; final report
to the U.S. Environmental Protection Agency. Office of Solid Waste. Research
Triangle Institute: Research Triangle Park, NC, 1986.
14. Umafia, M.; Sheldon, L. "Interim Report: Literature Review"; interim report
to the U.S. Environmental Protection Agency. Office of Solid Waste. Research
Triangle Institute: Research Triangle Park, NC, 1986.
9010A - 11 Revision 1
July 1992
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FIGURE 1.
APPARATUS FOR CYANIDE DISTILLATION
Cooling Water
Inlet Tube *
Screw Clamp
I
To Low Vacuum Source
Gas Scrubber
Distilling Flask
Heater
O
9010A - 12
Revision 1
July 1992
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FIGURE 2.
APPARATUS FOR CYANIDE DISTILLATION
Connecting Tubing
Allihn Condenser
Air Inlet Tube
One-Liter
Boiling Flask
Suction
9010A - 13
Revision 1
July 1992
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METHOD 9010A
TOTAL AND AMENABLE CYANIDE
START
7.1 Pretreat sample
to determine
cyanides amenable
to chlorination
7.2.1 Place sample
in round bottom
flask; transfer *
NaOH solution into
scrubber; construct
distillation
assembly
7.2.2 Turn vaccum
on and adjust
bubble rate
7.2.3 Add bismuth
nitrate solution to
boil ing flask
Yes
7.2.4 Add sulfamic
acid solution to
boiling flask
72.5 Add sulfuric
acid; rinse inlet
tube with water;
add magnesium
chloride; rinse
inlet tube with
wa ter
7 2.6 Boil
solution; reflux;
cool; close vacuum
source
7.2.7 Drain
scrubber solution
into Erlenmeyer
flask
73 Perform
colorimetric
analysis of sample
9010A - 14
Revision 1
July 1992
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METHOD 9010A
(Continued)
7.41 Prepare a
series of cyanide
standards through
dilution
7.4 Does
sample contain
sulfides?
7.5.1 Distill
standards in same
manner as samples
742 Perform
co1 orimetric
analysis of
standards
7.7 Transfer sample
to flask; add
rhodanine indicator
75.2 Prepare
standard curve of
absorbances
7.4.3 Distill at
least two standards
to check
distillation
recovery
7.4 4 Prepare
standard curve of
abs orbances
7.45 Check
efficiency of
sample distillation
7.6 Compute
concentrations
7 7.2 Titrate
sample and water
blank with silver
nitrate
7.7.3 Calculate
concentration of
cyanide in sample
STOP
STOP
9010A - 15
Revision 1
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METHOD 9012
TOTAL AND AMENABLE CYANIDE (COLORIMETRIC. AUTOMATED UV)
1.0 SCOPE AND APPLICATION
1.1 Method 9012 1s used to determine the concentration of Inorganic
cyanide 1n an aqueous waste or leachate. The method detects Inorganic
cyanides that are present as either simple soluble salts or complex radicals.
It is used to determine values for both total cyanide and cyanide amenable to
chlorlnation. Method 9012 1s not intended to determine if a waste is
hazardous by the characteristic of reactivity.
2.0 SUMMARY OF METHOD
2.1 The cyanide, as hydrocyanic add (HCN), is released by refluxlng the
sample with strong acid and distillation of the HCN Into an absorber-scrubber
containing sodium hydroxide solution. The cyanide 1on 1n the absorbing
solution Is then determined by automated UV colorimetry.
2.2 In the color1metric measurement, the cyanide 1s converted to
cyanogen chloride (CNC1) by reaction with Chloramine-T at a pH less than 8
without hydrolyzing to the cyanate. After the reaction Is complete, color 1s
formed on the addition of pyrldine-barblturic add reagent. The concentration
of NaOH must be the same in the standards, the scrubber solutions, and any
dilution of the original scrubber solution to obtain colors of comparable
Intensity.
3.0 INTERFERENCES
3.1 Interferences are eliminated or reduced by procedures described In
Paragraphs 7.2.3, 7.2.4, and 7.2.5.
3.2 Sulfides adversely affect the colorlmetric procedures. Samples that
contain hydrogen sulfide, metal sulfides, or other compounds that may produce
hydrogen sulfide during the distillation should be treated by addition of
bismuth nitrate prior to distillation as described in Paragraph 7.2.3.
3.3 High results may be obtained for samples that contain nitrate and/or
nitrite. During the distillation, nitrate and nitrite will form nitrous add,
which will react with some organic compounds to form oxlmes. These compounds
will decompose under test conditions to generate HCN. The possible
Interference of nitrate and nitrite 1s eliminated by pretreatment with
sulfamic add.
9012 - 1
Revision 0
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Reflux distillation apparatus; Such as shown in Figure 1 or 2. The
boiling flask should be of1-litersize with inlet tube and provision for
condenser. The gas absorber 1s a Fisher-Milligan scrubber (Fisher Catalog
#07-513) or equivalent.
4.2 Potassium iodide-starch test paper.
4.3 Automated continuous-flow analytical instrument with;
4.3.1 Sampler.
4.3.2 Manifold with UV digester.
4.3.3 Proportioning pump.
4.3.4 Heating bath with distillation coll.
4.3.5 Distillation head.
4.3.6 Colorimeter equipped with a 15-mm flowcell and 570 nm filter.
v 4.3.7 Recorder.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193); Water should be monitored for
Impurities.
5.2 Sodium hydroxide solution, 1.25 N; Dissolve 50 g of NaOH in Type II
water and dilute to 1 liter with Type II water.
5.3 Bismuth nitrate solution: Dissolve 30.0 g of B1(N03)3 in 100 ml of
Type II water.While stirring, add 250 ml of glacial acetic acid. Stir until
dissolved. Dilute to 1 liter with Type II water.
5.4 Sulfuric acid. 1:1: Slowly add 500 ml of concentrated ^$04 to
500 ml of Type II water.
CAUTION: this Is an exothermic reaction.
5.5 Sodium dihydrogenphosphate, 1 M: Dissolve 138 g of NaH2P04ปH20 in
1 liter of Type II water.
5.6 Stock cyanide solution: Dissolve 2.51 g of KCN and 2 g KOH in
900 ml of Type II water. Standardize with 0.0192 N AgNOs. Dilute to
appropriate concentration so that 1 ml = 1 mg CN.
5.7 Intermediate standard cyanide solution; Dilute 100.0 ml of stock
(1 mL = 1 mg CN) to 1,000 ml with Type II water (1 ml = 100 ug CN).
5.8 Working standard cyanide solution; Prepare fresh daily by diluting
100.0 ml of intermediatecyanide solution to 1,000 ml with Type II water
(1 ml = 10.0 ug CN). Store in a glass-stoppered bottle.
9012 - 2
Revision
Date September 1986
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Connecting Tubing
Allihn Condenser
Air Inlet Tube
One-Liter
Boiling Flask
Suction
Figure 1. Apparatus for cyanide distillation.
9012 - 3
Revision 0
Date September 1986
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COOLING WATER
INLET TUBE*
SCREW CLAMP
HEATER~
TO LOW VACUUM
SOURCE
- ABSORBER
~ DISTILLING FLASK
O
Figure 2. Cyanide distillation apparatus.
9012 - 4
Revision 0
Date September 1986
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5.9 Magnesium chloride solution; Weigh 510 g of MgCl2'6H20 Into a
1,000-mL flask, dissolve, and dilute to 1 liter with Type II water.
5.10 Sulfamlc add solution: Dissolve 40 g of sulfamlc add 1n Type II
water. Dilute to 1 liter.
5.11 Calcium hypochlorlte solution; Dissolve 5 g of calcium hypo-
chlorite [Ca(OCl)2] In 100 mL of Type II water.
5.12 Reagents for automated colorlmetrlc determination;
5.12.1 Pyr1d1ne-barb1tur1c acid reagent: Place 15 g of barbituric
add 1n a 250-mL volumetric flask, add just enough Type II water to wash
the sides of the flask, and wet the barbituric acid. Add 75 ml of
pyrldlne and mix. Add 15 mL of concentrated HC1, mix, and cool to room
temperature. Dilute to 250 ml with Type II water and mix. This reagent
1s stable for approximately six months 1f stored 1n a cool, dark place.
5.12.2 Chloramlne-T solution: Dissolve 2.0 g of white, water
soluble chloram1ne-T 1n 500 ml of Type II water and refrigerate until
ready to use.
5.12.3 Sodium hydroxide, 1 N: Dissolve 40 g of NaOH In Type II
water, and dilute to 1 liter.
5.12.4 All working standards should contain 2 ml of 1 N NaOH
(Paragraph 5.12.3) per 100 ml.
5.12.5 Dilution water and receptacle wash water (NaOH, 0.25 N):
Dissolve 10.0 g NaOH 1n 500 ml of Type II water. Dilute to 1 liter.
5.13 Ascorbic add; Crystals.
5.14 Phosphate buffer. pH 5.2: Dissolve 13.6 g of potassium dlhydrogen
phosphate and 0.28 g of disodium phosphate 1n 900 ml of Type II water and
dilute to 1 liter.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.
6.2 Samples should be collected 1n plastic or glass bottles of 1-Hter
size or larger. All bottles must be thoroughly cleaned and thoroughly rinsed
to remove soluble materials from containers.
6.3 Oxidizing agents such as chlorine decompose most cyanides. To
determine whether oxidizing agents are present, test a drop of the sample with
acidified potassium Iodide (Kl)-starch test paper at the time the sample 1s
collected; a blue color Indicates the need for treatment. Add ascorbic add a
9012 - 5
Revision
Date September 1986
-------
few crystals at a time until a drop of sample produces no color on the
Indicator. Then add an additional 0.6 g of ascorbic add for each liter of
water.
6.4 Samples must be preserved by addition of 10 N sodium hydroxide until
sample pH 1s greater than or equal to 12 at the time of collection.
6.5 Samples should be refrigerated at 4*C, when possible, and analyzed
as soon as possible.
7.0 PROCEDURE
7.1 Pretreatment for cyanides amenable to chlorlnation;
7.1.1 Two sample allquots are required to determine cyanides
amenable to chlorlnation. To one 500-mL aliquot, or to a volume diluted
to 500 ml, add calcium hypochlorlte solution (Paragraph 5.11) dropwlse
while agitating and maintaining the pH between 11 and 12 with sodium
hydroxide (Paragraph 5.2).
CAUTION; The Initial reaction product of alkaline chlorlnatlon 1s
th~e very toxic gas cyanogen chloride; therefore, It Is
recommended that this reaction be performed 1n a hood. For
convenience, the sample may be agitated 1n a 1-Hter beaker by
means of a magnetic stirring device.
7.1.2 Test for residual chlorine with Kl-starch paper (Paragraph
4.4) and maintain this excess for 1 hr, continuing agitation. A distinct
blue color on the test paper Indicates a sufficient chlorine level. If
necessary, add additional hypochlorlte solution.
7.1.3 After 1 hr, add 0.5 g portions of ascorbic add until KI-
starch paper shows no residual chlorine. Add an additional 0.5 g of
ascorbic add to ensure the presence of excess reducing agent.
7.1.4 Test for total cyanide .1n both the chlorinated and
unchlorlnated allquots. (The difference of total cyanide 1n the
chlorinated and unchlorlnated allquots 1s the cyanide amenable to
chlorlnatlon.) .
7.2 Distillation Procedure;
7.2.1 Place 500 ml of sample, or an aliquot diluted to 500 ml, In
the 1-Hter boiling flask. P1pet 50 ml of sodium hydroxide (Paragraph
5.2) Into the absorbing tube. If the apparatus 1n Figure 1 1s used, add
Type II water until the spiral 1s covered. Connect the boiling flask,
condenser, absorber, and trap 1n the train (Figure 1 or 2).
7.2.2 By adjusting the vacuum source, start a slow stream of air
entering the boiling flask so that approximately two bubbles of air per
second enter the flask through the air Inlet tube.
9012 - 6
Revision 0
Date September 1986
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7.2.3 Use lead acetate paper to check the sample for the presence
of sulfide. A positive test 1s indicated by a black color on the paper.
If positive, treat the sample by adding 50 ml of bismuth nitrate solution
(Paragraph 5.3) through the air inlet tube after the air rate is set.
Mix for 3 min prior to addition of H2S04.
7.2.4 If samples are suspected to contain N03 and/or N02, add 50 ml
of sulfamic acid solution (Paragraph 5.10) after the air rate is set
through the air inlet tube. Mix for 3 min prior to addition of ^$04.
7.2.5 Slowly add 50 ml 1:1 ^$04 (Paragraph 5.4) through the air
inlet tube. Rinse the tube with Type II water and allow the airflow to
mix the flask contents for 3 min. Pour 20 ml of magnesium chloride
(Paragraph 5.9) into the air inlet and wash down with a stream of water.
7.2.6 Heat the solution to boiling. Reflux for 1 hr. Turn off
heat and continue the airflow for at least 15 min. After cooling the
boiling flask, disconnect absorber and close off the vacuum source.
7.2.7 Drain the solution from the absorber into a 250-mL volumetric
flask. Wash the absorber with Type II water and add the washings to the
flask. Dilute to the mark with Type II water.
7.3 Automated colorimetric determination;
7.3.1 Set up the manifold in a hood or a well-ventilated area as
shown in Figure 3.
7.3.2 Allow colorimeter and recorder to warm up for 30 min. Run a
)ase!1ne with all reagents, feeding Type II water through the sample
line.
7.3.3 Place appropriate standards in the sampler in order of
decreasing concentration. Complete loading of the sampler tray with
unknown samples.
7.3.4 When the baseline becomes steady, begin the analysis.
7.4 Standard curve for samples without sulfide;
7.4.1 Prepare a series of standards by pipetting suitable volumes
of standard solution (Paragraph 5.8) Into 250-mL volumetric flasks. To
each standard add 50 ml of 1.25 N sodium hydroxide and dilute to 250 ml
with Type II water. Prepare as follows:
9012 - 7
Revision 0
Date September 1986
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ft! SAMPLE
10
o
ป-*
ro
I
oo
O 70
01 n
rt- <
n -*
o
rv a
o
VAST!
1^ 15
\8 tO
COIORIMETIB
57U MM
IS mm I/C
199 BO23 0
70751 157
TURNS
/r/c
PUMP IUBE
1 0 MM ID
6
WASTE
8089
20 TURNS
TO SAMPLER WASH
^ RECEPTACLE
j ff? TO TOP OF PROBE
A 10
1
i/o oin.1 r~ '
5 TURNS \
PUR ORN
BLK BLK
RED RIO
RED RtO
WHT WMT
BLK BLK
GRY GRV
ORN ORN
ORN ORN
CRY GRY
CRY CRY
M1/MIM
340 SAMPLE WASH
0.3? AIR
O 70 SAMPLE
0 70 DILUTION WATER
O 6O R| SAMPIE WASTE
O.3? AIR 1
I.OO RE SAMPLE C 3
0.4? BUMtR
0.10 r.HLOROMINE T
1.00 PVRIOIN* BARBITURIC
i.oo FROM r/c
PROPORTIONING
PUMP
o>
Figure 3. Cyanide manifold AA11.
-------
ml of Working Standard Solution Concentration.
(1 ml = 10 ug CN) (ug CN/250 ml)
0 BUNK
1.0 10
2.0 20
5.0 50
10.0 100
15.0 150
20.0 200
7.4.2 It 1s not Imperative that all standards be distilled 1n the
same manner as the samples. It 1s recommended that at least two
standards (a high and a low) be distilled and compared with similar
values on the curve to ensure that the distillation technique 1s
reliable. If distilled standards do not agree within + 10% of the
undlstilled standards, the analyst should find the cause of the apparent
error before proceeding.
7.4.3 Prepare a standard curve by plotting absorbances of standards
vs. cyanide concentrations.
7.4.4 To check the efficiency of the sample distillation, add an
Increment of cyanide from either the Intermediate standard (Paragraph
5.7) or the working standard (Paragraph 5.8) to 500 ml of sample to
ensure a level of 20 ug/L. Proceed with the analysis as 1n Paragraph
7.2.1.
7.5 Standard curve for samples with sulflde;
7.5.1 All standards must be distilled 1n the same manner as the
samples. A minimum of 3 standards shall be distilled.
7.5.2 Prepare a standard curve by plotting absorbances of standards
vs. cyanide concentration.
7.6 Calculation; Prepare a standard curve by plotting peak heights of
standards against th~e1r concentration values. Compute concentrations of
samples by comparing sample peak heights with the standard curve.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Employ a minimum of one blank per sample batch to determine If
contamination or any memory effects are occurring.
8.3 Verify calibration with an Independently prepared check standard
every 15 samples.
9012 - 9
Revision
Date September 1986
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8.4 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the whole sample preparation process.
8.5 The method of standard additions shall be used for the analysis of
all samples that suffer from matrix Interferences.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
10.0 REFERENCES
1. Annual Book of ASTM Standards, Part 31, "Water," Standard D2036-75,
Method B, p. 505 (1976).
2. Goulden, P.O., B.K. Afghan, and P. Brooksbank, Determination of Nanogram
Quantities of Simple and Complex Cyanides 1n Water, Anal. Chem., 44(11), pp.
1845-49 (1972).
3. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
pp. 376 and 370, Method 413F and D (1975).
4. Technlcon AutoAnalyzer II Methodology, Industrial Method No. 315-74 WCUV
Digestion and Distillation, Technlcon Industrial Systems, Tarrytown, New York,
10591 (1974).
9012 - 10
Revision
Date September 1986
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METHOD 9018
TOTAL AND AMENABLE CYANIDE (COLORIMETRIC. AUTOMATED UV)
7.1
I Pretreat
to determine
cyanides
amenable to
chlorination
7.2.1 Place
sample
in flack:
pipet sodium
hydroxide into
absorbing tube
Are samples
suspected to
contain NO
and/or
NO 7
I Add
sul?amlc
acid solution
through air
inlet tube
rinse tube with
Type II water;
add magnesuim
chloride
7.2.2
Introduce air
stream into
boiling flask
7.2.3
7.2.6
I Boll
solution:
reflux: cool:
close off
vacuum source
Treat
sample by
adding bismuth
nitrate
solution
7.2.7
Drain solution
from absorber
into flask
7.3
Perform
baseline
colorimetric
analysis
o
9012 - 11
Revision 0
Date September 1986
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METHOD 9012
TOTAL AND AMENABLE CYANIDE (COLOPIMETfllC. AUTOMATED UV)
(Continued)
7.5.1
Distill
standards In
same manner
as sample
7.5.Z
Prepare
standard curve
of absorbances
7.4.2 Distill
at least
two standards
to check
distillation
techniques
7.4.3
Prepare
standard curve
of absorbances
7.6
Compute
concentrations
7.4.41
Check
efficiency
of sample
distillation
( Stop J
9012 - 12
Revision 0
Date September 1986
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METHOD 9013
(APPENDIX TO METHOD 9010)
CYANIDE EXTRACTION PROCEDURE FOR SOLIDS AND OILS
1.0 SCOPE AND APPLICATION
1.1 The extraction procedure described in this method is designed for
the extraction of soluble cyanides from solid and oil wastes. The method is
applicable to oil, solid, and multiphasic samples. This method is not applicable
to samples containing insoluble cyanide compounds.
2.0 SUMMARY OF METHOD
2.1 If the waste sample contains so much solid, or solids of such a
size as to interfere with agitation and homogenization of the sample mixture in
the distillation flask, or so much oil or grease as to interfere with the
formation of a homogeneous emulsion, the sample may be extracted with water at
pH 10 or greater, and the extract distilled and analyzed by Method 9010. Samples
that contain free water are filtered and separated into an aqueous component and
a combined oil and solid component. The nonaqueous component may then be
extracted, and an aliquot of the extract combined with an aliquot of the filtrate
in proportion to the composition of the sample. Alternatively, the components
may be analyzed separately, and cyanide levels reported for each component.
However, if the sample solids are known to contain sufficient levels of cyanide
(about 50 Mg/g) as to be well above the limit of detection, the extraction step
may be deleted and the solids analyzed directly by Method 9010. This can be
accomplished by diluting a small aliquot of the waste solid (1-10 g) in 500 mL
water in the distillation flask and suspending the slurry during distillation
with a magnetic stir-bar.
3.0 INTERFERENCES
3.1 Potential interferences that may be encountered during analysis are
discussed in Method 9010.
4.0 APPARATUS AND MATERIALS
4.1 Extractor - Any suitable device that sufficiently agitates a sealed
container of one liter volume or greater. For the purpose of this analysis,
agitation is sufficient when:
1. All sample surfaces are continuously brought into contact
with extraction fluid, and
2. The agitation prevents stratification of the sample and
fluid.
4.2 Buchner funnel apparatus
4.2.1 Buchner funnel - 500-mL capacity, with 1-liter vacuum
filtration flask.
9013 - 1 Revision 0
July 1992
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4.2.2 Glass wool - Suitable for filtering, 0:8 m diameter such
as Corning Pyrex 3950.
4.2.3 Vacuum source - Preferably a water driven aspirator. A
valve or stopcock to release vacuum is required.
4.3 Top-loading balance - capable of weighing 0.1 g.
4.4 Separatory funnels - 500 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.
5.2 Reagent water. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Sodium hydroxide (50% w/v), NaOH. Commercially available.
5.4 n-Hexane, C6HU.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must be collected using a plan that addresses the
considerations discussed in Chapter 4 of this manual. See Section 6.0 of Method
9010 for additional guidance.
7.0 PROCEDURE
7.1 If the waste does not contain any free aqueous phase, go to Step
7.5. If the sample is a homogeneous fluid or slurry that does not separate or
settle in the distillation flask when using a Teflon coated magnetic stirring bar
but mixes so that the solids are entirely suspended, then the sample may be
analyzed by Method 9010 without an extraction step.
7.2 Assemble Buchner funnel apparatus. Unroll glass filtering fiber
and fold the fiber over itself several times to make a pad about 1 cm thick when
lightly compressed. Cut the pad to fit the Buchner funnel. Weigh the pad, then
place it in the funnel. Turn the aspirator on and wet the pad with a known
amount of water.
7.3 Transfer the sample to the Buchner funnel in small aliquots, first
decanting the fluid. Rinse the sample container with known amounts of water and
add the rinses to the Buchner funnel. When no free water remains in the funnel,
slowly open the stopcock to allow air to enter the vacuum flask. A small amount
of sediment may have passed through the glass fiber pad. This will not interfere
with the analysis.
9013 - 2 Revision 0
July 1992
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7.4 Transfer the solid and the glass fiber pad to a tared weighing
dish. Since most greases and oils will not pass through the fiber pad, solids,
oils, and greases will be extracted together. If the filtrate includes an oil
phase, transfer the filtrate to a separatory funnel. Collect and measure the
volume of the aqueous phase. Transfer the oil phase to the weighing dish with
the solid.
7.5 Weigh the dish containing solid, oil (if any), and filter pad.
Subtract the weight of the dry filter pad. Calculate the net volume of water
present in the original sample by subtracting the total volume of rinses used
from the measured volume of the filtrate.
7.6 Place the following in a 1-liter wide-mouthed bottle:
500 ml water
5 ml 50% w/v NaOH
50 ml n-Hexane (if a heavy grease is present)
If the weight of the solids (Step 7.5) is greater than 25 g, weigh
out a representative aliquot of 25 g and add it to the bottle; otherwise
add all of the solids. Cap the bottle.
7.7 The pH of the extract must be maintained above 10 throughout the
extraction step and subsequent filtration. Since some samples may release acid,
the pH must be monitored as follows. Shake the extraction bottle and after one
minute, check the pH. If the pH is below 12, add 50% NaOH in 5 ml increments
until it is at least 12. Recap the bottle, and repeat the procedure until the
pH does not drop.
7.8 Place the bottle or bottles in the tumbler, making sure
there is enough foam insulation to cushion the bottle. Turn the tumbler on and
allow the extraction to run for about 16 hours.
7.9 Prepare a Buchner funnel apparatus as in Step 7.2 with a glass fiber
pad filter.
7.10 Decant the extract to the Buchner funnel. Full recovery of the
extract is not necessary.
7.11 If the extract contains an oil phase, separate the aqueous phase
using a separatory funnel. Neither the separation nor the filtration are
critical, but are necessary to be able to measure the volume of the aliquot of
the aqueous extract analyzed. Small amounts of suspended solids and oil
emulsions will not interfere.
7.12 At this point, an aliquot of the filtrate of the original sample may
be combined with an aliquot of the extract in a proportion representative of the
sample. Alternatively, they may be distilled and analyzed separately and
concentrations given for each phase. This is described by the following
equation:
Liquid Sample AliauotfmU _ Solid Extracted(g)a x Total Sample Fi1trate(mL)c
Extract Aliquot(mL) Total Solid(g)D Total Extraction Fluid(mL)0
9013 - 3 Revision 0
July 1992
-------
"From Step 7.6. Weight of solid sample used for extraction.
bFrom Step 7.5. Weight of solids and oil phase with the dry weight of
filter and tared dish subtracted.
Includes volume of all rinses added to the filtrate (Steps 7.2 and 7.3).
d500 ml water plus total volume of NaOH solution. Does not include hexane,
which is subsequently removed (Step 7.11).
Alternatively, the aliquots may be distilled and analyzed separately,
concentrations for each phase reported separately, and the amounts of each phase
present in the sample reported separately.
8.0 QUALITY CONTROL
8.1 Refer to Method 9010.
9.0 METHOD PERFORMANCE
9.1 In a single laboratory study, recoveries of 60 to 90% are reported
for solids and 88 to 92% for oils. The reported CVs are less than 13.
10.0 REFERENCES
10.1 Refer to Method 9010.
9013 - 4 Revision 0
July 1992
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METHOD 9013
(APPENDIX TO METHOD 9010)
CYANIDE EXTRACTION PROCEDURE FOR SOLIDS AND OILS
7 .1 Analyze by
7.1 Does
sample
contain any
free fluid?
7.1 Is sample
a homogeneous
slurry?
7 . 2 Assemble filter
apparatus; weigh
filter pad; place
in funnel; wet pad
with known amount
of water
7.3 Filter sample;
rinse sample
container wi th
known amount of
water
7.4 Separate phases
in separatory
funnel; transfer
oil phase to
weighing dish
Yes
7.5 Heigh solid &
oil phases in tared
weighing dish;
calculate amount of
water in sample
9013 - 5
Revision 0
July 1992
-------
METHOD 9013
(APPENDIX TO METHOD 9010)
CYANIDE EXTRACTION PROCEDURE FOR SOLIDS AND OILS (CONTINUED)
9013 - 6
Revision 0
July 1992
-------
METHOD 9020B
TOTAL ORGANIC HALIDES (TOX)
1.0 SCOPE AND APPLICATION
1.1 Method 9020 determines Total Organic Hal ides (TOX) as chloride in
drinking water and ground waters. The method uses carbon adsorption with a
microcoulometric-titration detector.
1.2 Method 9020 detects all organic halides containing chlorine,
bromine, and iodine that are adsorbed by granular activated carbon under the
conditions of the method. Fluorine-containing species are not determined by this
method.
1.3 Method 9020 is applicable to samples whose inorganic-halide concen-
tration does not exceed the organic-halide concentration by more than 20,000
times.
1.4 Method 9020 does not measure TOX of compounds adsorbed to
undissolved solids.
1.5 Method 9020 is restricted to use by, or under the supervision of,
analysts experienced in the operation of a pyrolysis/microcoulometer and in the
interpretation of the results.
1.6 This method is provided as a recommended procedure. It may be used
as a reference for comparing the suitability of other methods thought to be
appropriate for measurement of TOX (i .e., by comparison of sensitivity, accuracy,
and precision of data).
2.0 SUMMARY OF METHOD
2.1 A sample of water that has been protected against the loss of
volatiles by the elimination of headspace in the sampling container, and that is
free of undissolved solids, is passed through a column containing 40 mg of
activated carbon. The column is washed to remove any trapped inorganic halides
and is then combusted to convert the adsorbed organohalides to HX, which is
trapped and titrated electrolytically using a microcoulometric detector.
3.0 INTERFERENCES
3.1 Method interferences may be caused by contaminants, reagents,
glassware, and other sample-processing hardware. All these materials must be
routinely demonstrated to be free from interferences under the conditions of the
analysis by running method blanks.
3.1.1 Glassware must be scrupulously cleaned. Clean all
glassware as soon as possible after use by treating with chromate cleaning
solution. This should be followed by detergent washing in hot water.
Rinse with tap water and distilled water and drain dry; glassware which is
not volumetric should, in addition, be heated in a muffle furnace at 400ฐC
for 15 to 30 min. (Volumetric ware should not be heated in a muffle
9020B - 1 Revision 2
September 1994
-------
furnace.) Glassware should be sealed and stored in a clean environment
after drying and cooling to prevent any accumulation of dust or other
contaminants.
3.1.2 The use of high-purity reagents and gases helps to minimize
interference problems.
3.2 Purity of the activated carbon must be verified before use. Only
carbon samples that register less than 1,000 ng CV/40 mg should be used. The
stock of activated carbon should be stored in its granular form in a glass
container with a Teflon seal. Exposure to the air must be minimized, especially
during and after milling and sieving the activated carbon. No more than a 2-wk
supply should be prepared in advance. Protect carbon at all times from all
sources of halogenated organic vapors. Store prepared carbon and packed columns
in glass containers with Teflon seals.
3.3 Particulate matter will prevent the passage of the sample through
the adsorption column. Particulates must, therefore, be eliminated from the
sample. This must be done as gently as possible, with the least possible sample
manipulation, in order to minimize the loss of volatiles. It should also be
noted that the measured TOX will be biased by the exclusion of TOX from compounds
adsorbed onto the particulates. The following techniques may be used to remove
particulates; however, data users must be informed of the techniques used and
their possible effects on the data. These techniques are listed in order of
preference:
3.3.1 Allow the particulates to settle in the sample container
and decant the supernatant liquid into the adsorption system.
3.3.2 Centrifuge sample and decant the supernatant liquid into
the adsorption system.
3.3.3 Measure Purgeable Organic Hal ides (POX) of sample (see SW-
846 Method 9021) and Non-Purgeable Organic Hal ides (NPOX, that is, TOX of
sample that has been purged of volatiles) separately, where the NPOX
sample is centrifuged or filtered.
4.0 APPARATUS AND MATERIALS
4.1 Adsorption system (a schematic diagram of the adsorption system is
shown in Figure 1):
4.1.1 Adsorption module: Pressurized sample and nitrate-wash
reservoirs.
4.1.2 Adsorption columns: Pyrex, 5-cm-long x 6-mm-O.D. x
2-mm-I.D.
4.1.3 Granular activated carbon (GAC): Filtrasorb-400, Calgon-
APC or equivalent, ground or milled, and screened to a 100/200 mesh range.
Upon combustion of 40 mg of GAC, the apparent halide background should be
1,000 ng Cl" equivalent or less.
9020B - 2 Revision 2
September 1994
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4.1.4 Cerafelt (available from Johns-Manville) or equivalent:
Form this material into plugs to fit the adsorption module and to hold
40 mg of GAC in the adsorption columns.
CAUTION: Do not touch this material with your fingers. Oily residue
will contaminate carbon.
4.1.5 Column holders.
4.1.6 Class A volumetric flasks: 100-mL and 50-mL.
4.2 Analytical system:
4.2.1 Microcoulometric-titration system: Containing the
following components (a flowchart of the analytical system is shown in
Figure 2):
4.2.1.1 Boat sampler: Muffled at 800ฐC for at least 2-
4 min and cleaned of any residue by vacuuming after each run.
4.2.1.2 Pyrolysis furnace.
4.2.1.3 Microcoulometer with integrator.
4.2.1.4 Titration cell.
4.2.2 Recording device.
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 Sodium sulfite (0.1 M), Na2S03: Dissolve 12.6 g ACS reagent grade
Na2S03 in reagent water and dilute to 1 L.
5.4 Concentrated nitric acid (HN03).
5.5 Nitrate-wash solution (5,000 mg N03"/L), KN03: Prepare a nitrate-
wash solution by transferring approximately 8.2 g of potassium nitrate (KN03)
into a 1-liter Class A volumetric flask and diluting to volume with reagent
water.
5.6 Carbon dioxide (C02): Gas, 99.9% purity.
5.7 Oxygen (02): 99.9% purity.
9020B - 3 Revision 2
September 1994
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5.8 Nitrogen (N2): Prepurified.
5.9 Acetic acid in water (70%), C2H402: Dilute 7 volumes of glacial
acetic acid with 3 volumes of reagent water.
5.10 Trichlorophenol solution, stock (1 /xL = 10 fj,g CV): Prepare a stock
solution by accurately weighing accurately 1.856 g of trichlorophenol into a 100-
mL Class A volumetric flask. Dilute to volume with methanol.
5.11 Trichlorophenol solution, calibration (1 juL = 500 ng Cl"), C6H3C130:
Dilute 5 ml of the trichlorophenol stock solution to 100 ml with methanol.
5.12 Trichlorophenol standard, instrument calibration: First, nitrate-
wash a single column packed with 40 mg of activated carbon, as instructed for
sample analysis, and then inject the column with 10 /zL of the calibration
solution.
5.13 Trichlorophenol standard, adsorption efficiency (100 M9 Cl'/liter):
Prepare an adsorption-efficiency standard by injecting 10 juL of stock solution
into 1 liter of reagent water.
5.14 Blank standard: The methanol used to prepare the calibration
standard should be used as the blank standard.
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 All samples should be collected in bottles with Teflon septa (e.g..
Pierce #12722 or equivalent) and be protected from light. If this is not
possible, use amber glass 250-mL bottles fitted with Teflon-lined caps. Foil may
be substituted for Teflon if the sample is not corrosive. Samples must be
preserved by acidification to pH <2 with sulfuric acid, stored at 4ฐC, and
protected against loss of volatiles by eliminating headspace in the container.
Samples should be analyzed within 28 days. The container must be washed and
muffled at 400"C before use, to minimize contamination.
6.3 All glassware must be dried prior to use according to the method
discussed in Sec. 3.1.1.
7.0 PROCEDURE
7.1 Sample preparation:
7.1.1 Special care should be taken in handling the sample in
order to minimize the loss of volatile organohalides. The adsorption
procedure should be performed simultaneously on duplicates.
7.1.2 Reduce residual chlorine by adding sulfite (5 mg sodium
sulfite crystals per liter of sample). Sulfite should be added at the
time of sampling if the analysis is meant to determine the TOX
concentration at the time of sampling. It should be recognized that TOX
9020B - 4 Revision 2
September 1994
-------
may increase on storage of the sample. Samples should be stored at 4ฐC
without headspace.
7.2 Calibration:
7.2.1 Check the adsorption efficiency of each newly prepared
batch of carbon by analyzing 100 ml of the adsorption efficiency standard,
in duplicate, along with duplicates of the blank standard. The net
recovery should be within 10% of the standard value.
7.2.2 Nitrate-wash blanks (method blanks): Establish the
repeatability of the method background each day by first analyzing several
nitrate-wash blanks. Monitor this background by spacing nitrate-wash
blanks between each group of ten pyrolysis determinations. The nitrate-
wash blank values are obtained on single columns packed with40mgof
activated carbon. Wash with the nitrate solution, as instructed for
sample analysis, and then pyrolyze the carbon.
7.2.3 Pyrolyze duplicate instrument-calibration standards and the
blank standard each day before beginning sample analysis. The net
response to the calibration standard should be within 10% of the
calibration-standard value. Repeat analysis of the instrument-calibration
standard after each group of ten pyrolysis determinations and before
resuming sample analysis, and after cleaning or reconditioning the
titration cell or pyrolysis system.
7.3 Adsorption procedure:
7.3.1 Connect two columns in series, each containing 40 mg of
100/200-mesh activated carbon.
7.3.2 Fill the sample reservoir and pass a metered amount of
sample through the activated-carbon columns at a rate of approximately
3 mL/min.
NOTE: 100 ml of sample is the preferred volume for concentrations
of TOX between 5 and 500 jug/L, 50 ml for 501 to 1000 /ug/L, and 25
ml for 1001 to 2000 M9/L- If the anticipated TOX is greater than
2000 M9/U dilute the sample so that 100 ml will contain between
1 and 50 p.g TOX.
7.3.3 Wash the columns-in-series with 2 mL of the 5,000-mg/L
nitrate solution at a rate of approximately 2 mL/min to displace inorganic
chloride ions.
7.4 Pyrolysis procedure:
7.4.1 The contents of each column are pyrolyzed separately.
After being rinsed with the nitrate solution, the columns should be
protected from the atmosphere and other sources of contamination until
ready for further analysis.
9020B - 5 Revision 2
September 1994
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7.4.2 Pyrolysis of the sample is accomplished in two stages. The
volatile components are pyrolyzed in a C02-rich atmosphere at a low
temperature to ensure the conversion of brominated trihalomethanes to a
titratable species. The less volatile components are then pyrolyzed at a
high temperature in an 02-rich atmosphere.
7.4.3 Transfer the contents of each column to the quartz boat for
individual analysis.
7.4.4 Adjust gas flow according to manufacturer's directions.
7.4.5 Position the sample for 2 min in the 200ฐC zone of the
pyrolysis tube.
7.4.6 After 2 min, advance the boat into the 800ฐC zone (center)
of the pyrolysis furnace. This second and final stage of pyrolysis may
require from 6 to 10 min to complete.
7.5 Detection: The effluent gases are directly analyzed in the micro-
coulometric-titration cell. Carefully follow manual instructions for optimizing
cell performance.
7.6 ' Breakthrough: The unpredictable nature of the background bias
makes it especially difficult to recognize the extent of breakthrough of
organohalides from one column to another. All second-column measurements for a
properly operating system should not exceed 10% of the two-column total
measurement. If the 10% figure is exceeded, one of three events could have
happened: (1) the first column was overloaded and a legitimate measure of
breakthrough was obtained, in which case taking a smaller sample may be
necessary; (2) channeling or some other failure occurred, in which case the
sample may need to be rerun; or (3) a high random bias occurred, and the result
should be rejected and the sample rerun. Because it may not be possible to
determine which event occurred, a sample analysis should be repeated often enough
to gain confidence in results. As a general rule, any analysis that is rejected
should be repeated whenever a sample is available. In the event that repeated
analyses show that the second column consistently exceeds the 10% figure and the
total is too low for the first column to be saturated and the inorganic Cl is
less than 20,000 times the organic chlorine value, then the result should be
reported, but the data user should be informed of the problem. If the second-
column measurement is equal to or less than the nitrate-wash blank value, the
second-column value should be disregarded.
9020B - 6 Revision 2
September 1994
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7.7 Calculations: TOX as CV is calculated using the following formula:
(C, - C3) + (C2 - C3)
= M9A Total Organic Halide
V
where:
C, = jx9 CT on the first column in series;
C2 = jug Cl" on the second column in series;
C3 = predetermined, daily, average, method-blank value
(nitrate-wash blank for a 40-mg carbon column); and
V = the sample volume in liters.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control guidelines.
8.2 This method requires that all samples be run in duplicate.
8.3 Employ a minimum of two blanks to establish the repeatability of
the method background, and monitor the background by spacing method blanks
between each group of eight analytical determinations.
8.4 After calibration, verify it with an independently prepared check
standard.
8.5 Run matrix spike between every 10 samples and bring it through the
entire sample preparation and analytical process.
9.0 METHOD PERFORMANCE
9.1 Under conditions of duplicate analysis, the method detection limit
is 10 M9/L.
9.2 Analyses of distilled water, uncontaminated ground water, and
ground water from RCRA waste management facilities spiked with volatile
chlorinated organics generally gave recoveries between 75-100% over the
concentration range 10-500 ng/L. Relative standard deviations were generally
20% at concentrations greater than 25 M9/L- These data are shown in Tables 1
and 2.
10.0 REFERENCES
1. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
9020B - 7 Revision 2
September 1994
-------
2. Stevens, A.A., R.C. Dressman, R.K. Sorrell, and H.J. Brass, Organic Halogen
Measurements: Current Uses and Future Prospects, Journal of the American Water
Works Association, pp. 146-154, April 1985.
3. Tate, C., B. Chow, et al., EPA Method Study 32, Method 450.1, Total Organic
Hal ides (TOX), EPA/600/S4-85/080, NTIS: PB 86 136538/AS.
9020B - 8 Revision 2
September 1994
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TABLE 1. METHOD PERFORMANCE DATA8
Spiked
Compound
Bromobenzene
Bromodi chl oromethane
Bromoform
Bromoform
Bromoform
Bromoform
Bromoform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
D1 bromodi chl oromethane
D1 bromodi chl oromethane
Tetrachl oroethyl ene
Tetrachl oroethyl ene
Tetrachl oroethyl ene
trans -Di chl oroethyl ene
trans-Di chl oroethyl ene
trans-Dichl oroethyl ene
Matrixb
D.W.
D.W
D.W.
D.W.
G.W.
G.W.
G.W.
D.W.
D.W.
G.W.
G.W.
G.W.
D.W.
D.W.
G.W.
G.W.
G.W.
G.W.
G.W.
G.W.
TOX
Concentration
(M9/L)
443
160
160
238
10
31
100
98
112
10
30
100
155
374
10
30
101
10
30
98
Percent
Recovery
95
98
110
100
140
93
120
89
94
79
76
81
86
73
79
75
78
84
63
60
"Results from Reference 2.
bG.W. = Ground Water.
D.W. = Distilled Water.
9020B - 9
Revision 2
September 1994
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TABLE 2. METHOD PERFORMANCE DATA3
Sample
Matrix
Unspiked
TOX Levels
(M9/L)
Spike
Level
Percent
Recoveries
Ground Water 68, 69 100 98, 99
Ground Water 5, 12 100 110, 110
Ground Water 5, 10 100 95, 105
Ground Water 54, 37 100 111, 106
Ground Water 17, 15 100 98, 89
Ground Water 11, 21 100 97, 89
aResults from Reference 3.
9020B - 10 Revision 2
September 1994
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Fig. 1. Schematic Diagram of Adsorption System
Sample
Reservoir
(1 of 4)
Nitrate Wash
Reservoir
GAC Column 1
GAC Column 2
9020B - 11
Revision 2
September 1994
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Fig. 2. Flowchart of Analytical System
Sparging
Device
Titration
Cell
Pyrolysis
Furnace
Boat
Inlet
Hlcrocoulometer
with Integrator
Strip Chart
Recorder
Adsorption
Module
9020B - 12
Revision 2
September 1994
-------
r
START
METHOD 9020B
TOTAL ORGANIC HALIDES (TOX)
1
7.1.1 Take special
care in handl ing
ample to minimize
volati le loss
1
7.1.2 Add sulfite
to reduce residual
chlorine; store at
4 C without
headspace
1
7.2.1 Check
absorption
efficiency for each
batch of carbon
1
7.2.2 Analyze
nitrate- wash blanks
to es tabl ish
background
1
7.2.3 Pyrolyze
dupl ica te
ins t rument
calibration and
blank standards
each day
7.3.1 Connect in
series two columns
containing
activated carbon
+
7.3.2 Till sample
sample through
activated carbon
co lumns
1
7.3.3 Hash columns
with ni t ra te
solution
7.4.1 Protect
columns from
contamina tion
,,
7.4.2 Pyrolyze
volatile components
in C02-rich
atmosphere at low
tempera ture
1
7.4.2 Pyrolyze less
at high temperature
in 02-rich
atmosphere
7.4.3 Transfer
contents of each
co lumn to quar tz
boat for analysis
7.4.4 Adjust gas
flow
7.4.5 Position
sample for 2
minutes in 200 C
zone of pyrolysis
tube
7.4.6 Advance boat
into 800 C zone
7 . 5 Analyze
effluent gases in
microcoulometric-
titration cell
76 Is
2nd column
measurement = \. No
or < nitrate wash
blank?
7.6 Is 2nd
column
measurement >10%
of 2 column
total?
7,7 Calculate TOX
as Cl-
7.6 Disregard
d-column valu
7.6 Reject and
repeat
9020B - 13
Revision 2
September 1994
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METHOD 9021
PURGEABLE ORGANIC HALIDES (POX)
1.0 SCOPE AND APPLICATION
1.1 Method 9021 determines organically bound halides (chloride,
bromide, and iodide) purged from a sample of drinking water or ground water.
They are reported as chloride. This method is a quick screening procedure
requiring about 10 minutes. The method uses a sparging device, a pyrolysis
furnace, and a microcoulometric-titration detector.
1.2 Method 9021 detects purgeable organically bound chlorine, bromine,
and iodine. Fluorine containing species are not determined by this method.
Method 9021 measures POX concentrations ranging from 5 to 1,000 M9/L.
1.3 Method 9021 is restricted to use by, or under the supervision of,
analysts experienced in the operation of a pyrolysis/microcoulometer and in the
interpretation of the results.
2.0 SUMMARY OF METHOD
2.1 A sample of water, protected against the loss of volatiles by the
elimination of headspace in the sampling container, is transferred to a purging
vessel. The volatile organic halides are purged into a pyrolysis furnace using
a stream of C02 and the hydrogen halide (HX) pyrolysis product is trapped and
titrated electrolytically using a microcoulometric detector.
3.0 INTERFERENCES
3.1 Contaminants, reagents, glassware, and other sample processing
hardware may cause interferences. Method blanks must be routinely run to
demonstrate freedom from interferences under the conditions of the analysis.
3.1.1 Glassware must be scrupulously clean. Clean all glassware
as soon as possible after use by treating with chromate cleaning solution.
This should be followed by detergent washing in hot water. Rinse with tap
water and reagent water and dry at 105ฐC for 1 hour or until dry.
Glassware which is not volumetric should, in addition, be heated in a
muffle furnace at 300ฐC for 15 to 30 minutes (Class A volumetric ware
should not be heated in a muffle furnace). Glassware should be sealed and
stored in a clean environment after drying and cooling to prevent any
accumulation of dust or other contaminants.
3.1.2 Use high purity reagents and gases to minimize interference
problems.
3.1.3 Avoid using non-PTFE (polytetrafluoroethylene) plastic
tubing, non-TFE thread sealants, or flow controllers with rubber
components in the purge gas stream.
9021 - 1 Revision 0
July 1992
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3.2 Samples can be contaminated by diffusion of volatile organics
(methylene chloride) through the septum seal into the sample during shipment and
especially during storage. A trip blank prepared from water and carried through
the sampling and handling protocol serves as a check on such contamination. A
trip blank should be run with each analytical batch.
3.3 Contamination by carry-over occurs whenever high level and low
level samples are sequentially analyzed. To reduce carryover, the purging device
and sample syringe must be rinsed with water between sample analyses. Whenever
an unusually concentrated sample is encountered, it should be followed by an
analysis of water to check for cross contamination. For samples containing large
amounts of water-soluble materials, suspended solids, high boiling compounds or
high organohalide levels, wash out the purging device with a detergent solution,
rinse it with water, and then dry it in a 105ฐC oven between analyses.
3.4 All operations should be carried out in an area where halogenated
solvents, such as methylene chloride, are not being used.
3.5 Residual free chlorine interferes in the method. Free chlorine
must be destroyed by adding sodium sulfite when the sample is collected.
4.0 APPARATUS AND MATERIALS
4.1 Sampling equipment (for discrete sampling)
4.1.1 Vial - 25-mL capacity or larger, equipped with a screw-cap
with hole in center (Pierce #13075 or equivalent).
4.1.2 Septum - Teflon lined silicone (Pierce #12722 or
equivalent). Detergent wash, rinse with tap and reagent water, and dry at
105ฐC for 1 hour before use.
4.2 Analytical system
4.2.1 Microcoulometric-titration system containing the following
components (a schematic diagram of the microcoulometric-titration system
is shown in Figure 1).
4.2.1.1 Purging device.
4.2.1.2 Pyrolysis furnace.
4.2.1.3 Titration cell.
4.2.2 Strip chart recorder (optional) - The recorder is
recommended to make sure the peak is down to baselines before stopping
integration.
4.2.3 Microsyringes - 10-juL and 25-^L with 0.006 in i.d. needle
(Hamilton 702N or equivalent).
4.2.4 Syringe valve - 2 way, with Luer ends.
9021 - 2 Revision 0
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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 Reagent water. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Sodium sulfide, Na2S. Granular, anhydrous.
5.4 Acetic acid in water (70%), CH3COOH. Dilute 7 volumes of glacial
acetic acid with 3 volumes of water.
5.5 Sodium chloride calibration standard (1 /itg Cl'/ML). Dissolve
1.648 g NaCl in water and dilute to 1 liter.
5.6 Carbon dioxide.
5.7 Methanol, CH3OH. Store away from other solvents.
5.8 Chloroform, CHC13.
5.9 Chloroform (stock) solution (1 /xL = 11.2 Mg of CHC1, or 10 M9 Cl").
Prepare a stock solution by delivering accurately 760 ML (1120 mg) of chloroform
into a 100-mL Class A volumetric flask containing approximately 90 mL of
methanol . Dilute to volume with methanol (10,000 mg of chlorine/L).
5.10 Chloroform (calibration) solution (1 pi = 0.1 jug Cl"). Dilute 1 ml
of the chloroform stock solution to 100 ml with methanol (100 mg of chlorine/L).
5.11 Chloroform Quality Control (QC) reference sample (100
Prepare an aqueous standard by injecting 100 nl of the chloroform calibration
standard (100 mg of C1"/L) into a Class A volumetric flask containing 100 ml of
water. Mix and store in a bottle with zero headspace. Analyze within two hours
after preparation.
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 of this manual.
6.2 All samples should be collected in bottles with Teflon lined
silicone septa (e.g.. Pierce #12722 or equivalent) and be protected from light.
If this is not possible, use amber glass 250-mL bottles fitted with Teflon lined
caps.
6.3 All glassware must be cleaned prior to use according to the process
described in Step 3.1.1.
9021 - 3 Revision 0
July 1992
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6.4 Special care should be taken in handling the sample in order to
minimize the loss of volatile organohalides. This is accomplished through
elimination of headspace and by minimizing the number of transfers.
6.5 Reduce residual chlorine, if present, by adding sodium sulfite
(5 mg of sodium sulfite crystals per liter of sample). Sodium sulfite should be
added to empty sample bottles at the time of sampling. Shake vigorously for 1
minute after bottle has been filled with sample and properly sealed. Samples
should be stored at 4ฐC without headspace. POX may increase during storage of
the sample.
6.6 All samples must be analyzed within 14 days of collection.
7.0 PROCEDURE
7.1 Calibration.
7.1.1 Assembl e the spargi rig/pyrolysi s/mi crocoul ometri c-ti trati on
apparatus shown in Figure 1 in accordance with the manufacturer's
specifications. Typically a C02 flow of 150 mi/min and a sparger
temperature of 45 ฑ 5ฐC are employed. The pyrolysis furnace should be set
at 800 + 10ฐC. Attach the titration cell to the pyrolysis tube outlet and
fill with electrolyte (70% acetic acid). Flow rate and temperature
changes will affect the compounds that are purged and change the percent
recovery of marginal compounds. Therefore, these parameters should not be
varied. Adjust gas flow rate according to manufacturer's directions.
7.1.2 Turn on the instrument and allow the gas flow and
temperatures to stabilize. When the background current of the titration
cell has stabilized the instrument is ready for use.
7.1.3 Calibrate the microcoulometric-titration system for CT
equivalents by injecting various amounts (1 to 80 pi) of the sodium
chloride calibration standard directly into the titration cell and
integrating the response using the POX integration mode. If desired, the
analog output of the titration cell can be displayed on a strip chart
recorder. The range of sodium chloride amounts should cover the range of
expected sample concentrations and should always be less than 80 /ug of
CT. The integrated response should read within 2% or 0.05 jug of the
quantity injected (whichever is larger) over the range 1-80 ng CT. If
this calibration requirement is not met, then the instrument sensitivity
parameters should be adjusted according to the manufacturer's
specifications to achieve an accurate response.
7.1.4 Check the performance of the analytical system daily by
analyzing three 5-mL aliquots of a freshly prepared 100 jug/L chloroform
check standard. The mean of these three analyses should be between 0.4-
0.55 /xg of CT and the percent relative standard deviation should be 5% or
less. If these criteria are not met, the system should be checked as
described in the instrument maintenance manual in order to isolate the
problem.
9021 - 4 Revision 0
July 1992
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NOTE: Low chloroform recovery can often be traced to a vitrified inlet
tube. The tube should be checked regularly and the analyst should
be able to determine, based on chloroform recoveries, when the tube
should be replaced.
7.1.5 Determine an instrument blank daily by running an analysis
with the purge vessel empty. The instrument blank should be 0.00 ฑ 0.05
Mg of Cl". Analyze a calibration blank sample daily. The calibration
blank should be within 0.02 jug of Cl" of the reagent blank.
7.2 Sample analysis
7.2.1 Select a chloroform spike concentration representative of
the expected levels in the samples. Using the chloroform stock solution,
prepare a spiking solution in methanol which is 500 times more
concentrated than the selected spike concentration. Add 10 /nL of the
spiking solution to 5-mL aliquots of the samples chosen for spiking (refer
to Section 8.0, Quality Control, for guidance in selecting the appropriate
number of samples to be spiked).
7.2.2 Allow sample to come to ambient temperature prior to
drawing it into the syringe. Remove the plunger from a 5-mL or 10-mL
syringe and attach a closed syringe valve. If maximum sensitivity is
desired and the sample does not foam excessively, a 10-mL sample aliquot
may be analyzed. Otherwise 5-mL aliquots should be used. Open the sample
bottle (or standard) and carefully pour the sample into the syringe barrel
to just short of overflowing. Replace the syringe plunger and compress
the sample. Open the syringe valve and vent any residual air while
adjusting the sample volume to 5 mL. Since this process of taking an
aliquot destroys the validity of the sample for future analysis, the
analyst should fill a second syringe at this time to protect against
possible loss of data (e.g., accidental spill), or for duplicate analysis.
7.2.3 Attach the syringe valve assembly to the syringe valve on
the purging device. Place the pyrolysis/microcoulometer system in the POX
integration mode to activate the integration system. Immediately open the
syringe valves and inject the sample into the purging chamber.
7.2.4 Close both valves and purge the sample for 10 minutes.
7.2.5 After integration is complete, open the syringe valves and
withdraw the purged sample. Flush the syringe and purging device with
water prior to analyzing other samples.
7.2.6 If the integrated response exceeds the working range of the
instrument, prepare a dilution of the sample from the aliquot in the
second syringe with water and reanalyze. The water must meet the criteria
of Step 7.1.5. It may be necessary to heat and purge dilution waters.
7.3 Pyrolysis procedure
7.3.1 Pyrolysis of the purged organic component of the sample is
accomplished by pyrolyzing in a C02-rich atmosphere at a low temperature
9021 - 5 Revision 0
July 1992
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to ensure the conversion of brominated trihalomethanes to a titratable
species.
7.4 Directly analyze the effluent gases in the microcoulometric-
titration cell. Carefully follow instrument manual instructions for optimizing
cell performance.
7.5 Calculations - POX as Cl" is calculated using the following formula:
JL_ x 1000 = ng/l Purgeable Organic Halide
V
where:
Qs = Quantity of POX as ^9 of Cl" in the sample aliquot.
V = Volume of sample aliquot in mL.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for
easy reference or inspection for 3 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 guidelines.
8.2 Analyze a minimum of one reagent blank every 20 samples or per
analytical batch, whichever is more frequent, to determine if contamination or
any memory effects are occurring.
8.3 In addition to the performance check mentioned in Step 7.1.4,
verify calibration with an independently prepared chloroform QC reference sample
every 15 samples.
8.4 Analyze matrix spiked samples for every 10 samples or analytical
batch, whichever is more frequent. The spiked sample is carried through the
whole sample preparation process and analytical process.
8.5 Analyze all samples in replicate.
9.0 METHOD PERFORMANCE
9.1 Under conditions of duplicate analysis, the reliable limit of
detection is 5 jug/L.
9.2 Analyses of distilled water, uncontaminated ground water, and
ground water from RCRA waste management facilities spiked with volatile
chlorinated organics generally give recoveries of 44-128% over the concentration
range of 29-4500 p.g/1. Relative standard deviations are generally less than 20%
at concentrations greater than 25 ng/l. These data are shown in Tables 1 and
2.
9021 - 6 Revision 0
July 1992
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10.0 REFERENCES
1. Takahashi, Y.; Moore, R.T.; Joyce, R.J. "Measurement of Total Organic
Hal ides (TOX) and Purgeable Organic Hal ides (POX) in Water Using Carbon
Adsorption and Microcoulometric Determination"; Proceedings from Division
of Environmental Chemistry, American Chemical Society Meeting, March 23-
28, 1980.
2. Methods for Chemical Analysis of Water and Wastes; 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, 1983; EPA-600/4-79-
020.
3. Fed. Regist. 1979, 45, 69468-69473; December 3.
4. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; American Chemical Society: Washington, DC, 1986.
5. "Development and Evaluation of Methods for Total Organic Halide and
Purgeable Organic Halide in Wastewater"; U.S. Environmental Protection
Agency. Environmental Monitoring and Support Laboratory. Cincinnati, OH,
1984; EPA-600/4-84-008; NTIS-PB-84-134-337.
6. 1985 Annual Book of ASTM Standards, Vol. 11.01; "Standard Specification
for Reagent Water"; ATSM: Philadelphia, PA, 1985; D1193-77.
7. Dohrmann. Rosemount Analytical Division. Santa Clara, CA 95052-8007.
8. Cosa Instruments. Norwood, NJ 21942.
9021 - 7 Revision 0
July 1992
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TABLE 1.
PRECISION AND ACCURACY DATA FOR SELECTED PURGEABLE ORGANIC HALIDES
(Reference 5)
Compound
Chloroform
Trichloroethene
Tetrachloroethene
Chlorobenzene
Dose1
(M9/L
as CT)
11
10
10
8
Average
Recovery
(M9/L
as CT)
11
6
5
3
Average
Percent
Recovery
100
60
50
38
Standard
Deviation
1.4
0.7
0.8
0.6
MDL2
(M9A)
4.5
2.2
3.2
2.03
Number of
Replicates
7
7
7
7
1Ten milliliter aliquot of spiked reagent water analyzed.
2The method detection limit (MDL) is defined as the minimum concentration of a
substance that can be measured and reported with 99% confidence that the value
is above zero.
Practical MDL probably greater (approximately 5 to 6 jug/L) due to low recovery.
9021 - 8
Revision 0
July 1992
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TABLE 2.
PRECISION AND ACCURACY DATA FOR VARIOUS WATER SAMPLES
(Reference 5)
Sample1
Tap Water
POTW Sewage
Chlorinated
Hydrocarbon
Plant
Wastewater
Chlorinated
Hydrocarbon
Plant
Wastewater
Chlorinated
Hydrocarbon
Plant
Wastewater
Solid Waste2
Leachate
Industrial
Wastewater
Aniline3
Wastewater
Aniline3
Wastewater
Background
Spike
Component
Chloroform
Chloroform
Chloroform
Chloroform
1,1-Dichloro-
ethane
Methyl ene
chloride
Chloroform
Chloroform
Level
(M9/L
as CT)
68
114
32
32
171
510
15,700
15,700
Spike Level
(M9/L
as CV)
0
29
460
1,500
4,500
800
800
15,000
45,000
Average
Percent
Recovery
128
77
50
87
41
65
150
91
Standard
Deviation
2
5
36
32
470
17
120
58
400
Number
of
Replicates
3
3
3
3
3
3
3
3
3
1Five milliliter sample aliquots analyzed.
2Diluted 200:1 prior to analysis. Values for this sample are in mg/L for original
sample.
3Diluted 10:1 prior to analysis. Values are for undiluted sample.
9021 - 9
Revision 0
July 1992
-------
FIGURE 1. '
MICROCOULOMETRIC - TITRATION SYSTEM
j-
0)
o>
*-
O ซO
U t-
O O)
L. 01
O 4->
^- C
O
o
O
in
CM
t
o
O
o
GO
i
1
O)
XI
3
C
O
I/)
3
.O
C
O
o t. 'ฃ
i- 4> ซ- r
^- ^- +J r
O T- -r- O>
9021 - 10
Revision 0
July 1992
-------
METHOD 9021
PURGEABLE ORGANIC HALIDES (POX)
START
7.1.3 Adjust
ins t rument
sens i vi ty
parameters;
reca1ibra te
7.1.1 Assemble
appara tus; set
carbon dioxide flow
rate; set sparger
and pyrolysis
furnace temperature
7.1.2 Turn on
instrument; allow
gas flow and
temperatures to
stabilize; allow
background cur rent
of titration cell
to stabilize
7.1.2 Calibrate the
microcoulometric -
titration system
for Cl- equivalents
7.1.4 Analyze 3
aliquots of
chloroform check
standard
7.1.4 Is
XRSD <=* 5%
nd the mean
0 4-0.55 ug
C1-?
71.4 Check system;
reanalyze check
s tandard
7.1.5 Analyze
calibration blank;
determine
instrument blank
7.2.1 Select
spiking
concentration; add
spiking solution to
appropriate samples
7.2.2 Transfer
sample to syringe;
fill second syringe
9021 - 11
Revision 0
July 1992
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METHOD 9021
(Continued)
7.2.3 Attach syringe
valve assembly to
purging device; place
pyrolysis/
microcoulometer
system in POX
integration mode;
inject sample into
purging chamber
7 2 4 Purge for 10
minutes
I
7 2 5 Withdraw
purged sample;
flush syringe and
purging nevice with
ma t a r
water
7.2.6 Dilute sample
from second syringe
with water
731 Pyrolyze
sample in a, carbon
dioxide rich
atmosphere at a low
tempera ture
7 4 Analyze the
effluent gasses in
the
microcoulomet r ic-
titration eel 1
7.5 Calculate POX
as Cl-
STOP
9021 - 12
Revision 0
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METHOD 9022
TOTAL ORGANIC HALIDES (TOX) BY NEUTRON ACTIVATION ANALYSIS
1.0 SCOPE AND APPLICATION
1.1 Method 9022 determines Total Organic Halldes (TOX) 1n aqueous
samples. The method uses a carbon adsorption procedure Identical to that of
Method 9020 (TOX analysis using a m1crocoulometr1c-t1tration detector),
Irradiation by neutron bombardment, and then detection using a gamma-ray
detector.
1.2 Method 9022 detects all organic halldes containing chlorine,
bromine, and Iodine that are adsorbed by granular activated carbon under the
conditions of the method. Each halogen can be quantltated Independently.
1.3 Method 9022 1s restricted to use by, or under the supervision of,
analysts experienced 1n the operation of neutron activation analysis and
familiar with spectral Interferences.
1.4 This method, which may be used In place of Method 9020, has the
advantage of determining the Individual concentrations of the halogens
chlorine, bromine, and Iodine 1n addition to TOX.
2.0 SUMMARY OF METHOD
2.1 A sample of water that has been protected against the loss of
volatlles by the elimination of headspace 1n the sampling container, and that
1s free of undlssolved sol Ids, 1s passed through a column containing 40 mg of
granular activated carbon (GAC). The column Is washed to remove any trapped
Inorganic halldes. The GAC sample 1s exposed to thermal neutron bombardment,
creating a radioactive Isotope. Gamma-ray emission, which 1s unique to each
halogen, 1s counted. The areas of the resulting peaks are directly
proportional to the concentrations of the halogens.
3.0 INTERFERENCES
3.1 Method Interferences may be caused by contaminants, reagents,
glassware, and other sample processing hardware. All these materials must be
routinely demonstrated to be free from Interferences under the conditions of
the analysis by running method blanks.
3.1.1 Glassware must be scrupulously cleaned. Clean all glassware
as soon as possible after use by treating with chromatic cleaning
solution. This should be followed by detergent washing 1n hot water.
Rinse with tap water and distilled water and drain dry; glassware which
1s not volumetric should, In addition, be heated in a muffle furnace at
9022 - 1
Revision 0
Date September 1986
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400*C for 15 to 30 m1n. Volumetric ware should not be heated 1n a muffle
furnace. Glassware should be sealed and stored 1n a clean environment
after drying and cooling to prevent any accumulation of dust or other
contaminants.
3.1.2 The use of h1gh-pur1ty reagents and gases helps to minimize
Interference problems.
3.2 Purity of the activated carbon must be verified before use. Only
carbon samples that register less than 2,000 ng Cl"/40 mg GAC should be used.
The stock of activated carbon should be stored in Its granular form in a glass
container with a Teflon seal. Exposure to the air must be minimized,
especially during and after milling and sieving the activated carbon. No more
than a 2-wk supply should be prepared 1n advance. Protect carbon at all times
from all sources of halogenated organic vapors. Store prepared carbon and
packed columns in glass containers with Teflon seals.
4.0 APPARATUS AND MATERIALS
4.1 Adsorption system (a general schematic of the adsorption system is
shown 1n Figure 1):
4.1.1 Adsorption module with pressurized sample and nitrate-wash
reservoirs.
4.1.2 Adsorption columns: Pyrex, 5-cm long x 6-mm O.D. x 2-mm I.D.
4.1.3 Granular activated carbon (GAC): Filtrasorb-400, Calgon-APC
or equivalent, ground or milled, and screened to a 100/200 mesh range.
Upon combustion of 40 mg of GAC, the apparent halide background should be
1000 ng Cl~ equivalent or less.
4.1.4 Cerafelt (available from Johns-Manville) or equivalent: Form
this material Into plugs using a 2-mm-I.D. stainless steel borer with
ejection rod to hold 40 mg of GAC in the adsorption columns.
CAUTION: Do not touch this material with your fingers. 01ly
residue will contaminate carbon.
4.1.5 Column holders.
4.1.6 Volumetric flasks: 100-mL, 50-mL.
4.2 Containers suitable for containment of samples and standards during
Irradiation (e.g., 1/5-dram polyethylene snap-cap vial).
4.3 Sample introduction system and a reactor generating a thermal
neutron flux capableo?achieving enough halogen activity for counting
purposes (e.g., a reactor having a neutron flux of 5 x 10*2 neutrons/cm^/sec).
4.4 A gamma-ray detector and data-handling system capable of resolving
the halogen peaks from potential interferences and background.
9022 - 2
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Date September 1986
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N2
ซo
o
ro
ro
Sample
Reservoir
(1of4)
Nitrato Wash
Reservoir
u>
GAC Column 1
050
Bf (V
c* <
(/) O
ro a
a
r*
A
CT
GAG Column 2
OO
Figure 1. Schematic diagram of adsorption system.
-------
5.0 REAGENTS
5.1 Prepur1f1ed nitrogen.
5.2 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.3 Nitrate-wash solution (5,000 mg N03~/L): Prepare a nitrate-wash
solution by transferring approximately 8.2 g of potassium nitrate (KN03) Into
a 1-1 Her volumetric flask and diluting to volume with Type II water.
5.4 Acetone and nanograde hexane (50% v/v mixture).
5.5 Sodium sulflte. 0.1 M (ACS reagent grade, 12.6 g/L).
5.6 Concentrated nitric acid (HN03): Reagent grade.
5.7 Standards; 25-ug Cl, 2.5-ug Br, and 2.5-ug I.
5.8 Radioactive standards to be used for calibrating gamma-ray detection
systems.
5.9 Trlchlorophenol solution, stock (1 uL = 10 ug Cl'): Prepare a stock
solution by accurately weighing accurately 1.856 g of trlchlorophenol Into a
100-mL volumetric flask. Dilute to volume with methanol.
5.10 Trlchlorophenol standard, adsorption efficiency (100 ug Cl~/11ter):
Prepare an adsorption-efficiency standard by Injecting 10 uL of stock solution
Into 1 liter of Type II 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 1n Chapter Nine of this manual.
6.2 All samples should be collected 1n bottles with Teflon septa (e.g.,
Pierce #12722 or equivalent) and be protected from light. If this Is not
possible, use amber glass, 250-mL, fitted with Teflon-Hned caps. Foil may be
substituted for Teflon If the sample 1s not corrosive. Samples must be
protected against loss of volatlles by eliminating headspace 1n the container.
Containers must be washed and muffled at 400*C before use, to minimize
contamination.
6.3 All glassware must be dried prior to use according to the method
discussed In Paragraph 3.1.1.
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Date September 1986
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7.0 PROCEDURE
7.1 Sample preparation:
7.1.1 Special care should be taken 1n handling the sample 1n order
to minimize the loss of volatile organohalldes. The adsorption procedure
should be performed simultaneously on the front and back columns.
7.1.2 Reduce residual chlorine by adding sulfHe (1 ml of 0.1 M
sulflte per liter of sample). Sulflte should be added at the time of
sampling 1f the analysis 1s meant to determine the TOX concentration at
the time of sampling. It should be recognized that TOX may Increase on
storage of the sample. Samples should be stored at 4*C without
headspace.
7.1.3 Samples containing undlssolved solids should be centrlfuged
and decanted.
7.1.4 Adjust the pH of the sample to approximately 2 with
concentrated HN03 just prior to adding the sample to the reservoir.
7.2 Calibration;
7.2.1 Check the adsorption efficiency of each newly prepared batch
of carbon by analyzing 100 ml of the adsorption efficiency standard, 1n
duplicate, along with duplicates of the blank standard. The net recovery
should be within 5% of the standard value.
7.2.2 Nitrate-wash blanks (method blanks): Establish the
repeatability of the method background each day by first analyzing
several nitrate-wash blanks. Monitor this background by spacing nitrate-
wash blanks between each group of eight analysis determinations. The
nitrate-wash blank values are obtained on single columns packed with 40
mg of activated carbon. Wash with the nitrate solution, as Instructed
for sample analysis, and then analyze the carbon.
7.2.3 Prior to each day's operation, calibrate the Instrument using
radioactive standards (e.g., cobalt-60 and rad1um-226 sources). The
Instrument 1s calibrated such that gamma rays from the standards fall
within one channel of their true energies. A 100-sec blank 1s then
counted to verify that no stray radioactive sources are within sensing
distance of the detector. As data are obtained throughout the day, peak
locations 1n the standards are monitored to ensure there 1s no electronic
drift of the Instrument. If drift 1s noted, the system must be recali-
brated.
7.3 Adsorption procedure;
7.3.1 Connect 1n series two columns, each containing 40 mg of
100/200-mesh activated carbon.
9022 - 5
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Date September 1986
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7.3.2 Fill the sample reservoir and pass a metered amount of sample
through the activated-carbon columns at a rate of approximately 3 mL/m1n.
NOTE: 100 ml of sample 1s the preferred volume for concentrations
of TOX between 5 and 500 ug/L, 50 ml for 501 to 1000 ug/L,
and 25 ml for 1,001 to 2,000 ug/L.
7.3.3 Wash the columns-1n-series with at least 2 ml of the 5,000-
mg/L nitrate solution at a rate of approximately 2 mL/mln to displace
Inorganic chloride ions.
7.4 Activation;
7.4.1 After the quartz collection tube with the GAC 1s removed from
the extraction unit, the GAC and cerafelt pads are extruded, using the
packing rod, into a prewashed plastic container (e.g., 1/5-dram
polyethylene snap-cap vial). The vial has been prewashed to remove
inorganic and organic chlorine by a soak 1n distilled water, followed by
storage 1n a glass jar containing 50% v/v acetone and hexane. After
extrusion, the vial is removed by forceps and a1r-dr1ed to remove
residual water, acetone, and hexane. After extrusion, the vial 1s
snapped shut, the hinge removed with a scalpel blade, the cap heat-sealed
to the vial with an electric soldering gun reserved for that purpose, and
a single-digit number placed on the vial with a marker pen.
7.4.2 Samples plus a similar vial containing 25 ug Cl, 2.5 ug Br,
and 2.5 ug I standards are then Introduced into the reactor, generally by
placing them together 1n a 5-dram polyethylene vial and Inserting them
into a pneumatic-tube transfer "rabbit" for neutron Irradiation.
Irradiation 1s typically for a 15-min period at a thermal neutron
irradiation flux of 5 x 1012 neutrons/cm2/sec. After returning from the
reactor, the rabbit is allowed to "cool" for 20 min to allow short-lived
radioisotopes (primarily Al) present 1n the GAC to decay.
7.5 Detection;
7.5.1 Analysis is performed using a lithium-drifted germanium
[Ge(L1)] gamma-ray detector with an amplifier and a 4096-channel memory
unit for data storage. The analyses can be performed either manually,
with the operator changing samples and transferring the data to magnetic
tape, or automatically, with both functions performed by an automatic
sample changer.
7.5.2 Analysis begins by counting the standard and samples for a
suitable time period (e.g., 200-sec "live" time for the standards and
samples). The operator records the time Intervals between samples and
the "dead" time of each sample 1n a logbook for later use in calculating
halogen concentrations in each sample.
7.5.3 Breakthrough; The unpredictable nature of the background
bias makes 1t especially difficult to recognize the extent of
breakthrough of organohalides from one column to another. All second-
9022 - 6
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Date September 1986
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column measurements for a properly operating system should not exceed 10%
of the two-column total measurement. If the 10% figure is exceeded, one
of three events could have happened: (1) the first column was overloaded
and a legitimate measure of breakthrough was obtained, 1n which case
taking a smaller sample may be necessary; (2) channeling or some other
failure occurred, 1n which case the sample may need to be rerun; or (3) a
high random bias occurred, and the result should be rejected and the
sample rerun. Because 1t may not be possible to determine which event
occurred, a sample analysis should be repeated often enough to gain
confidence 1n results. As a general rule, any analysis that 1s rejected
should be repeated whenever a sample 1s available. In the event that
repeated analyses show that the second column consistently exceeds the
10% figure and the total 1s too low for the first column to be saturated
and the Inorganic Cl 1s less than 20,000 times the organic chlorine
value, then the result should be reported, but the data user should be
Informed of the problem. If the second-column measurement 1s equal to or
less than the nitrate-wash blank value, the second-column value should be
disregarded.
7.6 Calculations;
7.6.1 Chlorine, bromine, and Iodine can be analyzed within a 200-
sec counting period taking place 20 to 40 m1n after Irradiation.
7.6.2 Chlorine 1s analyzed using the 1642-KeV gamma ray produced by
37.l-m1n 38C1. Bromine 1s analyzed using the 616-KeV gamma ray from
!7.7-m1n 80Br, and Iodine 1s analyzed using the 442-KeV gamma ray
produced by 25-m1n W&l.
7.6.3 The calculation used for quantltatlon 1s:
counting time std. uq 1n std.
ppm halogen
where:
cts unk.
cts std.
counting time unk. sample vol.
x e
Xt
cts unk. = the Integrated area of the appropriate gamma-ray peak 1n
the unknown with background subtracted and the total
multiplied by 1 + [(% dead time unknown - % dead time
std.)/200]. The latter correction 1s usually less than
4% and corrects for pile-up errors.
cts std. = the Integrated area of the appropriate gamma-ray peak 1n
the standard with background subtracted.
counting time std. = the "live1
standard.
counting time 1n seconds of the
counting time unk. = the "live" counting time 1n seconds of the
unknown.
9022 - 7
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Date September 1986
-------
ug 1n std. = the number of mlcrograms of the stable element 1n
question in the standard (25 for Cl, 2.5 for Br and I).
sample vol. = the volume of sample passed through the GAC column, In
ml.
eXt = the decay correction to bring all statistics back to
t = 0; X = 0.693/ti/2, where tj/2 = the half-life 1n
minutes.
t = the time Interval 1n minutes from the end of the count of the
standard until the end of the count of the sample.
7.6.4 No further calculations are necessary as long as the final
sample Is counted within 40 min after the end of irradiation.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Before performing any analyses, the analyst must demonstrate the
ability to generate acceptable accuracy and precision with this procedure by
analyzing appropriate quality-control check samples.
8.3 The laboratory must develop and maintain a statement of method
accuracy for their laboratory. The laboratory should update the accuracy
statement regularly as new recovery measurements are made.
8.4 Employ a minimum of one blank per sample batch to determine If
contamination 1s occurring.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample is a sample brought through the whole sample preparation and analytical
process.
8.7 It is recommended that the laboratory adopt additional quality-
assurance practices for use with this method. The specific practices that
would be most productive will depend upon the needs of the laboratory and the
precision of the sampling technique. Whenever possible, the laboratory should
perform analysis of standard reference materials and participate in relevant
performance-evaluation studies.
8.8 Quality control for the analysis phase is very straightforward in as
much as the instrument is a noncontact analyzer. That 1s, only the radiation
emitted from the sample not the sample Itself should touch the analyzer.
9022 - 8
Revision
Date September 1986
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Because contamination of the system 1s not usually a problem (unless a sample
spills on 1t), the most serious quality-control Issues deal with uniform
neutron flux, counting geometry, and spectral Interpretation. The amount of
radioactivity Induced 1n a sample 1s directly proportional to the neutron flux
1t 1s exposed to. Because this flux can vary depending on how the sample 1s
positioned 1n relation to the reactor core during Irradiation, 1t 1s essential
that a known standard be Irradiated with every sample batch to act as a flux
monitor. Care must also be taken to ensure that the standard and all samples
associated with the standard are counted at the same distance from the
detector.
9.0 METHOD PERFORMANCE
9.1 The following statistics are based on seven replicate analyses:
Combined Pooled
Chlorine Bromlne Iodine average
River water 7
Well water * (ppb)
WWTP effluent
38.2
0.16
50.7
0.30
242
0.56
17
0.076
4.7
0.038
35.2
0.033
-------
METHOD 9022
TOTAL ORGANIC HALIOES (TOX) BY
NEUTRON ACTIVATION ANALYSIS
7.1.1
Take
special
care handling
cample to
minimize loss
of volat1les
7.1.2
7.2,2
Analyze nitratewash
blanks to establish
repeatability of
method background
each day
Add culfite to
reduce residual
chlorine
7.1.3
7.2.3
Remove GAC
quartz
collection tube
Calibrate
instrument
each day using
radioactive
standards
Centrifuge and
decant camples
with undls-
solved solids
7.3.1
7.4. 1
Extrude
GAC and
cerafelt
pads into a
preMashed
plastic vial
Connect
in aeries
two columns
containing
activated
carbon
7.4.2 Introduce
samples
and standards
into reactor
for neutron
irradiation
7.
1.3
' Adjust
pH of sample
prior to adding
ample to
reservoir
7.3.21
Fill
ample
reservlor: pass
ample through
activated
carbon columns
7.5.1
Anaylze using
Ge (Li) gamma
ray detector
7.2.1
c
ef f Ic
each
c
Check
Isorpt ion
lency for
batch of
rbon
i
7.3.3
Displace
Inorganic
chloride ions
by washing
columns with
nitrate aolut.
7.5.2
To
analyze.
count standard
and aamples
for a suitable
tine period
o
9022 - 10
Revision 0
Date September 1986
-------
METHOD 9OZZ
TOTAL ORGANIC HALIDES (TOX) BY NEUTRON ACTIVATION ANALYSIS
(Continued)
Is 2nd column
naacurement > 1OX
of S column
total?
OKregard
second-column
value
9022 - 11
Revision 0
Date September 1986
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METHOD 9030A
ACID-SOLUBLE AND ACID-INSOLUBLE SULFIDES
1.0 SCOPE AND APPLICATION
1.1 The distillation procedure described in this method is designed for
the determination of sulfides in aqueous, solid waste materials, or effluents.
1.2 This method provides only a semi-quantitative determination of
sulfide compounds considered "acid-insoluble" (e.g., CuS and SnS2) in solid
samples. Recovery has been shown to be 20 to 40% for CuS, one of the most stable
and insoluble compounds, and 40 to 60% for SnS2 which is slightly more soluble.
1.3 This method is not applicable to oil or multiphasic samples or
samples not amenable to the distillation procedure which can be analyzed by
Method 9031.
1.4 Method 9030 is suitable for measuring sulfide concentrations in
samples which contain between 0.2 and 50 mg/kg of sulfide.
1.5 This method is not applicable for distilling reactive sulfide,
however, Method 9030 is used to quantify the concentration of sulfide from the
reactivity test. Refer to Chapter Seven, Step 7.3.4.1 for the determination of
reactive sulfide.
1.6 This method measures total sulfide which is usually defined as the
acid-soluble fraction of a waste. If, however, one has previous knowledge of the
waste and is concerned about both soluble sulfides such as H.S, and metal
sulfides, such as CuS and SnS_, then total sulfide is defined as the combination
of both acid-soluble and acicf-insoluble fractions. For wastes where only metal
sulfides are suspected to be present, only the acid-insoluble fraction needs to
be performed.
2.0 SUMMARY OF METHOD
2.1 For acid-soluble sulfide samples, separation of sulfide from the
sample matrix is accomplished by the addition of sulfuric acid to the sample.
The sample is heated to 70ฐC and the hydrogen sulfide (H2S) which is formed is
distilled under acidic conditions and carried by a nitrogen stream into zinc
acetate gas scrubbing bottles where it is precipitated as zinc sulfide.
2.2 For acid-insoluble sulfide samples, separation of sulfide from the
sample matrix is accomplished by suspending the sample in concentrated
hydrochloric acid by vigorous agitation. Tin(II) chloride is present to prevent
oxidation of sulfide to sulfur by the metal ion (as in copper(II)), by the
matrix, or by dissolved oxygen in the reagents. The prepared sample is distilled
under acidic conditions at 100ฐC under a stream of nitrogen. Hydrogen sulfide
gas is released from the sample and collected in gas scrubbing bottles containing
zinc(II) and a strong acetate buffer. Zinc sulfide precipitates.
9030A - 1 Revision 1
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2.3 The sulfide in the zinc sulfide precipitate is oxidized to sulfur
with a known excess amount of iodine. Then the excess iodine is determined by
titration with a standard solution of phenyl arsine oxide (PAO) or sodium
thiosulfate until the blue iodine starch complex disappears. As the use of
standard sulfide solutions is not possible because of oxidative degradation,
quantitation is based on the PAO or sodium thiosulfate.
3.0 INTERFERENCES
3.1 Aqueous samples must be taken with a minimum of aeration to avoid
volatilization of sulfide or reaction with oxygen, which oxidizes sulfide to
sulfur compounds that are not detected.
3.2 Reduced sulfur compounds, such as sulfite and hydrosulfite,
decompose in acid, and may form sulfur dioxide. This gas may be carried over to
the zinc acetate gas scrubbing bottles and subsequently react with the iodine
solution yielding false high values. The addition of formaldehyde into the zinc
acetate gas scrubbing bottles removes this interference. Any sulfur dioxide
entering the scrubber will form an addition compound with the formaldehyde which
is unreactive towards the iodine in the acidified mixture. This method shows no
sensitivity to sulfite or hydrosulfite at concentrations up to 10 mg/kg of the
interferant.
3.3 Interferences for acid-insoluble sulfides have not been fully
investigated. However, sodium sulfite and sodium thiosulfate are known to
interfere in the procedure for soluble sulfides. Sulfur also interferes because
it may be reduced to sulfide by tin(II) chloride in this procedure.
3.4 The iodometric method suffers interference from reducing^substances
that react with iodine, including thiosulfate, sulfite, and various organic
compounds.
3.5 The insoluble method should not be used for the determination of
soluble sulfides because it can reduce sulfur to sulfide, thus creating a
positive interference.
4.0 APPARATUS AND MATERIALS
4.1 Gas evolution apparatus as shown in Figure 1
4.1.1 Three neck flask - 500-mL, 24/40 standard taper joints.
4.1.2 Dropping funnel - 100-mL, 24/40 outlet joint.
4.1.3 Purge gas inlet tube - 24/40 joint, with coarse frit.
4.1.4 Purge gas outlet - 24/40 joint reduced to 1/4 in. tube.
4.1.5 Gas scrubbing bottles - 125-mL, with 1/4 in. o.d. inlet
and outlet tubes. Impinger tube must be fritted.
4.1.6 Tubing - 1/4 in. o.d. Teflon or polypropylene. Do not use
rubber.
9030A - 2 Revision 1
July 1992
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NOTE: When analyzing for acid-insoluble sulfides, the distillation
apparatus is identical to that used in the distillation procedure
for acid-soluble sulfides except that the tubing and unions
downstream of the distillation flask must be all Teflon,
polypropylene or other material resistant to gaseous HC1. The
ground glass joints should be fitted with Teflon sleeves to prevent
seizing and to prevent gas leaks. Pinch clamps should also be used
on the joints to prevent leaks.
4.2 Hot plate stirrer.
4.3 pH meter.
4.4 Nitrogen regulator.
4.5 Flowmeter.
4.6 Top-loading balance - capable of weighing 0.1 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 Zinc acetate solution for sample preservation (2N), Zn(CH,COO)2
2H20. Dissolve 220 g of zinc acetate dihydrate in 500 mL of reagent water.
5.4 Sodium hydroxide (IN), NaOH. Dissolve 40 g of NaOH in reagent
water and dilute to 1 liter.
5.5 Formaldehyde (37% solution), CH20. This solution is commercially
available.
5.6 Zinc acetate for the scrubber
5.6.1 For acid-soluble sulfides: Zinc acetate solution
(approximately 0.5M). Dissolve about 110 g zinc acetate dihydrate in
200 ml of reagent water. Add 1 mL hydrochloric acid (concentrated), HC1,
to prevent precipitation of zinc hydroxide. Dilute to 1 liter.
5.6.2 For acid-insoluble sulfides: Zinc acetate/sodium acetate
buffer. Dissolve 100 g sodium acetate, NaC2H302, and 11 g zinc acetate
dihydrate in 800 mL of reagent water. Add 1 mL concentrated hydrochloric
acid and dilute to 1 liter. The resulting pH should be 6.8.
5.7 Acid to acidify the sample
9030A - 3 Revision 1
July 1992
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H2S04.
5.7.1 For acid-soluble sulfides: Sulfuric acid (concentrated),
5.7.2 For acid-insoluble sulfides: Hydrochloric acid (9.8N),
HC1. Place 200 ml of reagent water in a 1-liter beaker. Slowly add
concentrated HC1 to bring the total volume to 1 liter.
5.8 Starch solution - Use either an aqueous solution or soluble starch
powder mixtures. Prepare an aqueous solution as follows. Dissolve 2 g soluble
starch and 2 g salicylic acid, C?H603, as a preservative, in 100 ml hot reagent
water.
5.9 Nitrogen.
5.10 Iodine solution (approximately 0.025N)
5.10.1 Dissolve 25 g potassium iodide, KI, in 700 ml of reagent
water in a 1-liter volumetric flask. Add 3.2 g iodine, I2. Allow to
dissolve. Add the type and amount of acid specified in Step 7.3.2.
Dilute to 1 liter and standardize as follows.
5.10.2 Dissolve approximately 2 g KI in 150 ml of reagent water.
Add exactly 20 ml of the iodine solution (Step 5.10.1) to be titrated and
dilute to 300 ml with reagent water.
5.10.3 Titrate with 0.025N standardized phenylarsine oxide or
0.025N sodium thiosulfate until the amber color fades to yellow. Add
starch indicator solution. Continue titration drop by drop until the blue
color disappears.
5.10.4 Run in replicate.
5.10.5 Calculate the normality as follows.
Normality (I2) = ml of titrant x normality of titrant
sample size in ml
5.11 Sodium sulfide nonanhydrate, Na2S 9H20. For the preparation of
standard solutions to be used for calibration curves. Standards must be prepared
at pH > 9 and < 11. Protect standard from exposure to oxygen by preparing it
without headspace. These standards are unstable and should be prepared daily.
5.12 Tin(II) chloride, SnCl2, granular.
5.13 Titrant.
5.13.1 Standard phenylarsine oxide solution (PAO) (0.025N),
C6H5AsO. This solution is commercially available.
CAUTION: PAO is toxic.
9030A - 4 Revision 1
July 1992
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5.13.2 Standard sodium thiosulfate solution (0.025N), Na2S20,
5H,0. Dissolve 6.205 ฑ 0.005 g Na2S,0, 5H20 in 500 ml reagent water. Add
9 ml IN NaOH and dilute to 1 liter.
5.14 Sodium hydroxide (6N), NaOH. Dissolve 240 g of sodium hydroxide
in 1 liter of reagent water.
5.15 Hydrochloric acid (6N), HC1. Place 51 mL of reagent water in a 100
mL Class A volumetric flask. Slowly add concentrated HC1 to bring the total
volume to 100 ml.
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 aqueous samples and effluents must be preserved with zinc
acetate and sodium hydroxide. Use four drops of 2N zinc acetate solution per 100
mL of sample. Adjust the pH to greater than 9 with 6N sodium hydroxide solution.
Fill the sample bottle completely and stopper with a minimum of aeration. The
treated sample is relatively stable and can be held for up to seven days. If
high concentrations of sulfide are expected to be in the sample, continue.adding
zinc acetate until all the sulfide has precipitated. For solid samples, fill the
surface of the solid with 2N zinc acetate until moistened. Samples must be
cooled to 4ฐC and stored headspace free.
6.3 Sample Preparation
6.3.1 For an efficient distillation, the mixture in the
distillation flask must be of such a consistency that the motion of the
stirring bar is sufficient to keep the solids from settling. The mixture
must be free of solid objects that could disrupt the stirring bar.
Prepare the sample using one of the procedures in this section then
proceed with the distillation step (Section 7.0).
6.3.2 If the sample is aqueous, shake the sample container to
suspend any solids, then quickly decant the appropriate volume (up to
250 mL) of the sample to a graduated cylinder, weigh the cylinder,
transfer to the distillation flask and reweigh the cylinder to the nearest
milligram. Be sure that a representative aliquot is used, or use the
entire sample.
6.3.3 If the sample is aqueous but contains soft clumps of
solid, it may be possible to break the clumps and homogenize the sample by
placing the sample container on a jar mill and tumble or roll the sample
for a few hours. The slurry may then be aliquotted and weighed as above
to the nearest milligram then diluted with reagent water up to a total
volume of 250 mL to produce a mixture that is completely suspended by the
stirring bar.
6.3.4 If the sample is primarily aqueous, but contains a large
proportion of solid, the sample may be roughly separated by phase and the
amount of each phase measured and weighed to the nearest milligram into
9030A - 5 Revision 1
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the distillation flask in proportion to their abundance in the sample.
Reagent water may be added up to a total volume of 250 ml_. As a
guideline, no more than 25 g dry weight or 50 g of sludge can be
adequately suspended in the apparatus.
6.3.5 If the sample contains solids which absorb water and
swell, limit the sample size to 25 g dry weight. Otherwise, the solids
will restrict the fluid motion and lower the recovery.
6.3.6 If the sample contains solid objects that cannot be
reduced in size by tumbling, the solids must be broken manually. Clay-
like solids should be cut with a spatula or scalpel in a crystallizing
dish. If the solids can be reduced to a size that they can be suspended
by the stirring bar, the solid and liquid can be proportionately weighed.
6.3.7 Non-porous harder objects, for example stones or pieces
of metal, may be weighed and discarded. The percent weight of non-porous
objects should be reported and should be used in the calculation of
sulfide concentration if it has a significant effect on the reported
result.
7.0 PROCEDURE
For acid-soluble sulfide samples, go to 7.1
For acid-insoluble sulfide samples, go to 7.2
7.1 Acid-Soluble Sulfide
7.1.1 In a preliminary experiment, determine the approximate
amount of sulfuric acid required to adjust a measured amount of the sample to pH
less than or equal to 1. The sample size should be chosen so that it contains
between 0.2 and 50 mg of sulfide. Place a known amount of sample or sample
slurry in a beaker. Add reagent water until the total volume is 200 ml. Stir
the mixture and determine the pH. Slowly add sulfuric acid until the pH is less
than or equal to 1. Discard this preliminary sample.
CAUTION: Toxic hydrogen sulfide may be generated from the acidified sample.
This operation must be performed in the hood and the sample left
in the hood until the sample has been made alkaline or the sulfide
has been destroyed. From the amount of sulfuric acid required to
acidify the sample and the mass or volume of the sample acidified,
calculate the amount of acid required to acidify the sample to be
placed in the distillation flask.
7.1.2 Prepare the gas evolution apparatus as shown in Figure 1
in a fume hood.
7.1.2.1 Prepare a hot water bath at 70ฐC by filling a
crystallizing dish or other suitable container with water and place
it on a hot plate stirrer. Place a thermometer in the bath and
monitor the temperature to maintain the bath at 70ฐC.
9030A - 6 Revision 1
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7.1.2.2 Assemble the three neck 500-mL flask, fritted
gas inlet tube, and exhaust tube. Use Teflon sleeves to seal the
ground glass joints. Place a Teflon coated stirring bar into the
flask.
i
7.1.2.3 Place into each gas scrubbing bottle 10 ฑ 0.5
mi of the 0.5M zinc acetate solution, 5.0 ฑ 0.1 ml of 37%
formaldehyde and 100 + 5.0 ml reagent water.
7.1.2.4 Connect the gas evolution flask and gas
scrubbing bottles as shown in Figure 1. Secure all fittings and
joints.
7.1.3 Carefully place an accurately weighed sample which
contains 0.2 to 50 mg of sulfide into the flask. If necessary, dilute to
approximately 200 ml with reagent water.
7.1.4 Place the dropping funnel onto the flask making sure its
stopcock is closed. Add the volume of sulfuric acid calculated in Step
7.1.1 plus an additional 50 ml into the dropping funnel. The bottom
stopcock must be closed.
7.1.5 Attach the nitrogen inlet to the top of the dropping
funnel gas shut-off valve. Turn on the nitrogen purge gas and adjust the
flow through the sample flask to 25 mL/min. The nitrogen in the gas
scrubbing bottles should bubble at about five bubbles per second.
Nitrogen pressure should be limited to approximately 10 psi to prevent
excess stress on the glass system and fittings. Verify that there are no
leaks in the system. Open the nitrogen shut-off valve leading to the
dropping funnel. Observe that the gas flow into the sample vessel will
stop for a short period while the pressure throughout the system
equalizes. If the gas flow through the sample flask does not return
within a minute, check for leaks around the dropping funnel. Once flow
has stabilized, turn on magnetic stirrer. Purge system for 15 minutes
with nitrogen to remove oxygen.
7.1.6 Heat sample to 70ฐC. Open dropping funnel to a position
that will allow a flow of sulfuric acid of approximately 5 mL/min.
Monitor the system until most of the sulfuric acid within the dropping
funnel has entered the sample flask. Solids which absorb water and swell
will restrict fluid motion and, therefore, lower recovery will be
obtained. Such samples should be limited to 25 g dry weight.
7.1.7 Purge, stir, and maintain a temperature of 70ฐC for a
total of 90 minutes from start to finish. Shut off nitrogen supply. Turn
off heat.
7.1.8 Proceed to Step 7.3 for the analysis of the zinc sulfide
by titration.
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7.2 Acid-Insoluble Sulfide
7.2.1 As the concentration of HC1 during distillation must be
within a narrow range for successful distillation of H2S, the water content
must be controlled. It is imperative that the fina-1 concentration of HC1
in the distillation flask be about 6.5N and that the sample is mostly
suspended in the fluid by the action of the stirring bar. This is
achieved by adding 50 ml of reagent water, including water in the sample,
100 ml of 9.8N HC1, and the sample to the distillation flask. Solids
which absorb water and swell will restrict fluid motion and, therefore,
lower recovery will be obtained. Such samples should be limited to 25 g
dry weight. Other samples can range from 25 to 50 g.
7.2.2 If the matrix is a dry solid, weigh a portion of the
sample such that it contains 0.2 to 50 mg of sulfide. The solid should be
crushed to reduce particle size to 1 mm or less. Add 50 ml of reagent
water.
7.2.3 If the matrix is aqueous, then a maximum of 50 g of the
sample may be used. No additional water may be added. As none of the
target compounds are volatile, drying the sample may be preferable to
enhance the sensitivity by concentrating the sample. If less than 50 g of
the sample is required to achieve the 0.2 to 50 mg of sulfide range for
the test, then add reagent water to a total volume of 50 ml.
7.2.4 If the matrix is a moist solid, the water content of the
sample must be determined (Karl Fischer titration, loss on drying, or
other suitable means) and the water in the sample included in the total
50 ml of water needed for the correct HC1 concentration. For example, if
a 20 g sample weight is needed to achieve the desired sulfide level of
0.2 to 50 mg and the sample is 50% water then 40 ml rather than 50 ml of
reagent water is added along with the sample and 100 ml of 9.8N HC1 to the
distillation flask.
7.2.5 Weigh the sample and 5 g SnCU into the distillation
flask. Use up to 50 ml of reagent water, as calculated above, to rinse
any glassware.
7.2.6 Assemble the distillation apparatus as in Figure 1. Place
100 ฑ 2.0 ml of zinc acetate/sodium acetate buffer solution and 5.0 ฑ 0.1
ml of 37% formaldehyde in each gas scrubbing bottle. Tighten the pinch
clamps on the distillation flask joints.
7.2.7 Make sure the stopcock is closed and then add 100 ฑ1.0
ml of 9.8N HC1 to the dropping funnel. Connect the nitrogen line to the
top of the funnel and turn the nitrogen on to pressurize the dropping
funnel headspace.
7.2.8 Set the nitrogen flow at 25 mL/min. The nitrogen in the
gas scrubbing bottles should bubble at about five bubbles per second.
Purge the oxygen from the system for about 15 minutes.
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7.2.9 Turn on the magnetic stirrer. Set the stirring bar to
spin as fast as possible. The fluid should form a vortex. If not, the
distillation will exhibit poor recovery. Add all of the HCL from the
dropping funnel to the flask.
7.2.10 Heat the water bath to the boiling point (100ฐC). The
sample may or may not be boiling. Allow the purged distillation to
proceed for 90 minutes at 100ฐC. Shut off nitrogen supply. Turn off
heat.
7.2.11 Proceed to Step 7.3 for the analysis of the zinc sulfide
by titration.
7.3 Titration of Distillate
7.3.1 Pipet a known amount of standardized 0.025N iodine
solution (See Step 5.10.5) in a 500-mL flask, adding an amount in excess
of that needed to oxidize the sulfide. Add enough reagent water to bring
the volume to 100 ml. The volume of standardized iodine solution should
be about 65 mL for samples with 50 mg of sulfide.
7.3.2 If the distillation for acid-soluble sulfide is being
used, add 2 ml of 6N HC1. If the distillation for acid-insoluble sulfides
is performed, 10 ml of 6N HC1 should be added to the iodine.
7.3.3 Pipet both of the gas scrubbing bottle solutions to the
flask, keeping the end of the pipet below the surface of the iodine
solution. If at any point in transferring the zinc acetate solution or
rinsing the bottles, the amber color of the iodine disappears or fades to
yellow, more 0.025N iodine must be added. This additional amount must be
added to the amount from Step 7.3.1 for calculations. Record the total
volume of standardized 0.025N iodine solution used.
7.3.4 Prepare a rinse solution of a known amount of standardized
0.025N iodine solution, 1 ml of 6N HC1, and reagent water to rinse the
remaining white precipitate (zinc sulfide) from the gas scrubbing bottles
into the flask. There should be no visible traces of precipitate after
rinsing.
7.3.5 Rinse any remaining traces of iodine from the gas
scrubbing bottles with reagent water, and transfer the rinsate to the
flask.
7.3.6 Titrate the solution in the flask with standard 0.025N
phenylarsine oxide or 0.025N sodium thiosulfate solution until the amber
color fades to yellow. Add enough starch indicator for the solution to
turn dark blue and titrate until the blue disappears. Record the volume
of titrant used.
9030A - 9 Revision 1
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7.3.7 Calculate the concentration of sulfide using the following
equation:
(ml I2 x N I2) - (ml titrant x N titrant) x 1 2 eq.
32.06 g
sulfide(mg/kg)or
sample weight (kg) or sample volume (L) (rog/L)
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 guidelines.
8.2 A reagent blank should be run once in twenty analyses or per
analytical batch, whichever is more frequent.
8.3 Check standards are prepared from water and a known amount of
sodium sulfide. A check standard should be run with each analytical batch of
samples, or once in twenty samples. Acceptable recovery will depend on the level
and matrix.
8.4 A matrix spiked sample should be run for each analytical batch or
twenty samples, whichever is more frequent, to determine matrix effects. If
recovery is low, acid-insoluble sulfides are indicated. A matrix spiked sample
is a sample brought through the whole sample preparation and analytical process.
9.0 METHOD PERFORMANCE
9.1 Accuracy - Accuracy for this method was determined by three
independent laboratories by measuring percent recoveries of spikes for both clean
matrices (water) and actual waste samples. The results are summarized below.
For Acid-Soluble Sulfide
Accuracy of titration step only
Lab A 84-100% recovery
Lab B 110-122% recovery
Accuracy for entire method for clean matrices (H20)
Lab C 94-106% recovery
Accuracy of entire method for actual waste samples
Lab C 77-92% recovery
Spiking levels ranged from 0.4 to 8 mg/L
For Acid-Insoluble Sulfide
The percent recovery was not as thoroughly studied for acid-insoluble
sulfide as it was for acid-soluble sulfide.
9030A - 10 Revision 1
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Accuracy of entire method for synthetic waste samples
Lab C 21-81% recovery
Spiking levels ranged from 2.2 to 22 mg/kg
9.2 Precision
For Acid-Soluble Sulfide
Precision of titration step only
Lab A CV% 2.0 to 37
Lab B CV% 1.1 to 3.8
Precision of entire method for clean matrices (H20)
Lab C CV% 3.0 to 12
Precision of entire method for actual waste samples
Lab C CV% 0.86 to 45
For Acid-Insoluble Sulfide
Precision of entire method with synthetic wastes
Lab C CV 1.2 to 42
9.3 Detection Limit - The detection limit was determined by analyzing
seven replicates at 0.45 and 4.5 mg/L. The detection limit was calculated as the
standard deviation times the student's t-value for a one-tailed test with n-1
degrees of freedom at 99% confidence level. The detection limit for a clean
matrix (H20) was found to be between 0.2 and 0.4 mg/L. <
10.0 REFERENCES
1. Test Methods for Evaluating Solid Waste, Physical/Chemical Methods, 2nd
ed.; U.S. Environmental Protection Agency. Office of Solid Waste and Emergency
Response. U.S. Government Printing Office: Washington, DC, 1982, revised 1984;
SW-846.
2. Methods for Chemical Analysis of Water and Wastes; 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, 1979; EPA-600/4-79-020.
3. CRC Handbook of Chemistry and Physics. 66th ed.; Weast, R., Ed.; CRC: Boca
Raton, FL, 1985.
4. Standard Methods for the Examination of Water and Wastewater, 16th ed.;
Greenberg, A.E.; Trussell, R.R.; Clesceri, L.S., Eds.; American Water Works
Association, Water Pollution Control Federation, American Public Health
Association: Washington, DC, 1985; Methods 427, 427A, 427B, and 427D.
5. . Andreae, M.O.; Banard, W.R. Anal. Chem. 1983, 55, 608-612.
6. Barclay, H. Adv. Instrum. 1980, 35(2). 59-61.
9030A - 11 Revision 1
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7. Bateson, S.W.; Moody, G.J.; Thomas, J.P.R. Analyst 1986, 111. 3-9.
8. Berthage, P.O. Anal. Chim. Acta 1954, 10 310-311.
9. Craig, P.O.; Moreton, P.A. Environ. Techno!. Lett. 1982, 3, 511-520.
10. Franklin, G.O.; Fitchett, A.M. Pulp & Paper Canada 1982, 83(10), 40-44.
11. Fuller, W. In Cyanide in the Environment; Van Zyl, D., Ed.; Proceedings of
Symposium; December, 1984.
12. Gottfried, G.J. "Precision, Accuracy, and MDL Statements for EPA Methods
9010, 9030, 9060, 7520, 7521, 7550, 7551, 7910, and 7911"; final report to the
U.S. Environmental Protection Agency (EMSL-CI); Biopheric.
13. Kilroy, W.P. Talanta 1983, 30(6). 419-422.
14. Kurtenacher, V.A.; Wallak, R. L, Anorq. \L Allg. Chem. 1927, 161 202-209.
15. Landers, D.H.; David, M.B.; Mitchell, M.J. Int. J. Anal. Chem 1983, 14,
245-256.
16. Opekar, F.; Brukenstein, S. Anal. Chem. 1984, 56ป 1206-1209.
17. Ricklin, R.D.; Johnson, E.L. Anal. Chem. 1983, 55, 4.
18. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; American Chemical Society: Washington, DC, 1986.
19. Snedecor, G.W.; Ghran, W.G. Statistical Methods; Iowa State University:
Ames, IA, 1980.
20. Umana, M.; Beach, J.; Sheldon, L. "Revisions to Method 9010"; final report
to the U.S. Environmental Protection Agency on Contract No. 68-01-7266; Research
Triangle Institute: Research Triangle Park, NC, 1986; Work Assignment No. 1.
21. Umana, M.; Sheldon, L. "Interim Report: Literature Review"; interim report
to the U.S. Environmental Protection Agency in Contract No. 68-01-7266; Research
Triangle Institute: Research Triangle Park, NC, 1986; Work Assignment No. 3.
22. Wang, W.; Barcelona, M.J. Environ. Inter. 1983, 9, 129-133.
23. Wronski, M. Talanta 1981, 28, 173-176.
24. Application Note 156; Princeton Applied Research Corp.: Princeton, NJ.
25. Guidelines for Assessing and Reporting Data Quality for Environmental
Measurements; U.S. Environmental Protection Agency. Office of Research and
Development. U.S. Government Printing Office: Washington, DC, 1983.
26. Fed. Regist. 1980, 45(98). 33122.
9030A - 12 Revision 1
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27. The Analytical Chemistry of Sulfur and Its Compounds. Part I; Karchmer,
J.H., Ed.; Wiley-Interscience: New York, 1970.
28. Methods for the Examination of Water and Associated Materials; Department
of the Environment: England, 1983.
29. "Development and Evaluation of a Test Procedure for Reactivity Criteria for
Hazardous Waste"; final report to the U.S. Environmental Protection Agency on
Contract 68-03-2961; EAL: Richmond, CA.
30. Test Method to Determine Hydrogen Sulfide Released from Wastes; U.S.
Environmental Protection Agency. Office of Solid Waste. Preliminary unpublished
protocol, 1985.
31. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
9030A - 13 Revision 1
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FIGURE 1.
GAS EVOLUTION APPARATUS
H2SO4 (HCI for Acid Insoluble Sulfides)
Hot Water Bath
with Magnetic Stirrer
N2 Out
Zinc Acetate
and
Formaldehyde
Scrubbing
Bottles
Stirring Bar
9030A - 14
Revision 1
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METHOD 9030A
ACID-SOLUBLE AND ACID-INSOLUBLE SULFIDES
START
7.1.1 Choose sample
size; place sample
in beaker: add
water; measure pK;
add cone, sulfuric
acid to pH 1;
discard sample
Acid-Soluble
Acid - Ins oluble
7.1.1 Calculate
amt. of sulfuric
acid needed to
acidify fresh
sample for purge;
fresh sample is to
be used for Step
7.1.4
7.1.2 Prepare gas
evolution apparatus
71.3 Place weighed
sample in flask;
dilute with water
if necessary
7.1.4 Place
dropping funnel
onto flask; add
sulfuric acid (from
Step 7 1.1) to
dropping funnel
7.1.5 Adjust
nitrogen flow;
check for leaks;
turn on 3tirrer;
purge system of
oxygen for 15 mins.
7.1.6 Heat to 70 C;
add sulfuric acid
to flask; close
dropping funnel
when acid nears
depletion
7.1.7 Purge, stir,
and heat for 90
mins.; shut off
nitrogen; turn off
heat
7.1.8 Analyze by
titration
9030A - 15
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METHOD 9030A
(Continued)
7.2.1 Hater content
of distillation
must be controlled;
cone, of HC1 should
be 6.5N
7.2.1 Limit sample
size to 25 g dry
eight
7.2.1 Sample size
may be 25 - SO g
7.2.2 Weigh sample;
crush if necessary;
add SO mL Hater
7.2.2-7.2.4
Type of matrix?
7.2.3 Is <
50g sample
needed?
7.2.4 Determine
ater content of
sample; include
total oater needed
for correct HC1
cone .
7.2.3 Add .ater to
sample for a total
volume of SO mL
9030A - 16
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METHOD 9030A
(Continued)
7.2.5 Place sample
in flask; add
stannous chloride
7.2.6 Assembl e
dis ti 1 la t ion
apparatus; place
zinc aceta te/ sodium
acetate buffer and
f o rmaldehyde in
scrubbing bottles
7.2.7 Add 100 ml
9.8N HC1 to
dropping funnel
7.2.8 Set nitrogen
flow; purge ays tern
of oxygen for 15
mins .
7.2.9 Turn on
stirrer ; add HC1 to
distillation flask
7 2.10 Heat water
bath to boil;
distill for 90
mins. at 100 C;
shut off nitrogen;
turn off heat
7.2.11 Analyze by
titration
7.3.1 Pipet known
amount of 0.025N
iodine solution in
flask; bring to
volume with water
7.3.2 Add 10 ml 6N
HC1
7.3.2 Add 2 ml 6N
HC1
9030A - 17
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METHOD 9030A
(Continued)
7.3.3 Pipet
scrubbing bottle
solution into
Erlenmeyer flask
7.3.4 Prepare rinse
solution of 0.02SN
iodine solution, 6N
HC1. and water
733
Does the
amber color
of iodine
disappear?
No
7.3.3 Add more
iodine; record
total volume of
iodine used
7.3.5 Rinse traces
of iodine from
scrubbing bottles;
transfer rinses to
flask
7.3.6 Titrate
solution until
amber color fades;
add starch
indicator; titrate
until blue color
disappears; record
volume of titrant
used
7.3.7 Calculate the
cone, of sulfide in
the sample
STOP
9030A - 18
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METHOD 9031
EXTRACTABLE SULFIDES
1.0 SCOPE AND APPLICATION
1.1 The extraction procedure described in this method is designed for
the extraction of sulfides from matrices that are not directly amenable to the
distillation procedure Method 9030. Specifically, this method is designed for
the extraction of soluble sulfides. This method is applicable to oil, solid,
multiphasic, and all other matrices not amenable to analysis by Method 9030.
This method is not applicable for reactive sulfide. Refer to Chapter Seven for
the determination of reactive sulfide.
1.2 Method 9031 is suitable for measuring sulfide in solid samples at
concentrations above 1 mg/kg.
2.0 SUMMARY OF METHOD
2.1 If the sample contains solids that will interfere with agitation
and homogenization of the sample mixture, or so much oil or grease as to
interfere with the formation of a homogeneous emulsion in the distillation
procedure, the sample may be filtered and the solids extracted with water at pH
> 9 and < 11. The extract is then combined with the filtrate and analyzed by the
distillation procedure. Separation of sulfide from the sample matrix is
accomplished by the addition of sulfuric acid to the sample. The sample is
heated to 70ฐC and the hydrogen sulfide (H2S) which is formed is distilled under
acidic conditions and carried by a nitrogen stream into zinc acetate gas
scrubbing bottles where it is precipitated as zinc sulfide.
2.2 The sulfide in the zinc sulfide precipitate is oxidized to sulfur
with a known amount of excess iodine. Then the excess iodine is determined by
titration with a standard solution of phenylarsine oxide (PAO) or sodium
thiosulfate until the blue iodine starch complex disappears. The use of standard
sulfide solutions is not possible because of their instability to oxidative
degradation. Therefore quantitation is based on the PAO or sodium thiosulfate.
3.0 INTERFERENCES
3.1 Samples with aqueous layers must be taken with a minimum of
aeration to avoid volatilization of sulfide or reaction with oxygen which
oxidizes sulfide to sulfur compounds that are not detected.
3.2 Sulfur compounds such as sulfite and hydrosulfite decompose in acid
and may form sulfur dioxide. This gas may be carried over to the zinc acetate
gas scrubbing bottles and subsequently react with the iodine solution yielding
false high values. The addition of formaldehyde into the zinc acetate gas
scrubbing bottles removes this interference. Any sulfur dioxide entering the
scrubber will form an addition compound with the formaldehyde which is unreactive
towards the iodine in the acidified mixture. This method shows no sensitivity
to sulfite or hydrosulfite at concentrations up to 10 mg/kg of the interferant.
9031 - 1 Revision 0
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3.3 The iodometric method suffers interference from reducing substances
that react with iodine including thiosulfate, sulfite, and various organic
compounds.
3.4 Interferences have been observed when analyzing samples with high
metal content such as electroplating waste and chromium containing tannery waste.
4.0 APPARATUS AND MATERIALS
4.1 Extractor - Any suitable device that sufficiently agitates a sealed
container of one liter volume or greater. For the purpose of this analysis,
agitation is sufficient when:
1. All sample surfaces are continuously brought into contact
with extraction fluid, and
2. The agitation prevents stratification of the sample and
fluid.
Examples of suitable extractors are shown in Figures 2 and 3. The tumble-
extractors turn the extraction bottles end-over-end at a rate of about 30 rpm.
The apparatus in Figure 2 may be easily fabricated from plywood. The jar
compartments must be padded with polyurethane foam to absorb shock. The drive
apparatus is a Norton jar mill.
4.2 Buchner funnel apparatus
4.2.1 Buchner funnel - 500-mL capacity, with 1-liter vacuum
filtration flask.
4.2.2 Glass wool - Suitable for filtering, 0.8 m diameter such
as Corning Pyrex 3950.
4.2.3 Vacuum source - Preferably a water driven aspirator. A
valve or stopcock to release vacuum is required.
4.3 Gas Evolution apparatus as shown in Figure 1
4.3.1 Three neck flask - 500-mL, 24/40 standard tapered joints.
4.3.2 Dropping funnel - 100-mL, 24/40 outlet joint.
4.3.3 Purge gas inlet tube - 24/40 joint with course frit.
4.3.4 Purge gas outlet - 24/40 joint reduced to 1/4 inch tube.
4.3.5 Gas scrubbing bottles - 125-mL, with 1/4 in. o.d. inlet and
outlet tubes. Impinger tube must not be fritted.
4.3.6 Tubing - 1/4 in. o.d. Teflon or polypropylene. Do not use
rubber.
4.4 Hot plate stirrer.
9031 - 2 Revision 0
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4.5 pH meter.
4.6 Nitrogen regulator.
4.7 Flowmeter.
4.8 Separatory funnels - 500-mL.
4.9 Tumbler - See Figures 2 and 3.
4.10 Top-loading balance - capable of weighing 0.1 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 Zinc acetate (for sample preservation) (2N), Zn(CH3COO)2 2H20.
Dissolve 220 g of zinc acetate dihydrate in 500 mL of water.
5.4 Sodium hydroxide (50% w/v in water), NaOH. Commercially available.
5.5 Tin (II) chloride, SnCl2 2H20, granular.
5.6 n-Hexane, C6H,..
5.7 Nitrogen, N2.
5.8 Sulfuric acid (concentrated), H2S04.
5.9 Zinc acetate for the scrubber (approximately 0.5M). Dissolve 110
g zinc acetate dihydrate in 200 mL of water. Add 1 mL concentrated hydrochloric
acid, HC1, to prevent precipitation of zinc hydroxide. Dilute to 1 liter.
5.10 Formaldehyde (37% solution), CH20. Commercially available.
5.11 Starch solution. Use either an aqueous solution or soluble starch
powder mixtures. Prepare an aqueous solution as follows. Dissolve 2 g soluble
starch and 2 g salicylic acid, C7H603, as a preservative, in 100 mL hot water.
5.12 Iodine solution (approximately 0.025N). Dissolve 25 g of potassium
iodide, KI, in 700 mL of water in a 1-liter volumetric flask. Add 3.2 g of
iodine, I2. Allow to dissolve. Dilute to 1 liter and standardize as follows.
Dissolve approximately 2 g KI in 150 mL of water. Pipet exactly 20 mL of the
iodine solution to be titrated and dilute to 300 mL with water. Titrate with
0.025N standard phenylarsine oxide, or 0.025N sodium thiosulfate, Na2S203, until
the amber color fades. Add starch indicator solution until the solution turns
9031 - 3 Revision 0
July 1992
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deep blue. Continue titration drop by drop until the blue color disappears.
Run in replicate. Calculate the normality as follows:
Normality (I2) = ml of titrant x normality of titrant
Volume of sample (ml)
5.13 Sodium sulfide nonanhydrate Na2S 9H20, for the preparation of
standard solutions to be used for calibration curves. Standards must be prepared
at pH > 9 and < 11.
5,14 Titrant.
5.14.1 Standard phenylarsine oxide (PAO) solution (0.025N),
C^HjAsO. This solution is commercially available.
CAUTION: PAO is toxic.
5.14.2 Standard sodium thiosulfate solution (0.025N), Na2S20,
5H20. Dissolve 6.205 ฑ 0.005 g Na2S,03 5H,0 in 500 ml of water. Add
9 ml IN NaOH and dilute to 1 liter.
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 samples must be preserved with zinc acetate and sodium
hydroxide. Use four drops of 2N zinc acetate solution per 100 mL of aqueous or
multiphasic sample. Adjust the pH to greater than 9.0 with 50% NaOH. Fill the
sample bottle completely and stopper with a minimum of aeration. For solid
samples, fill the surface of solid with 2N zinc acetate until moistened. Samples
must be cooled to 4ฐC during storage.
7.0 PROCEDURE
7.1 Assemble the Buchner funnel apparatus. Unroll the glass wool and
fold the fiber over itself several times to make a pad about 1 cm thick when
lightly compressed. Cut the pad to fit the Buchner funnel. Dry and weigh the
pad, then place it in the funnel. Turn on the aspirator and wet the pad with a
known amount of water.
7.2 Transfer a sample that contains between 1 and 50 mg of sulfide to
the Buchner funnel. Rinse the sample container with known amounts of water and
add the rinses to the Buchner funnel. When no free water remains in the funnel,
slowly open the stopcock to allow air to enter the vacuum flask. A small amount
of sediment may have passed through the glass fiber pad. This will not interfere
with the analysis.
7.3 Transfer the solid and the glass fiber pad to a dried tared
weighing dish. Since most greases and oils will not pass through the fiber pad,
solids, oils, and greases will be extracted together. If the filtrate includes
an oil phase, transfer the filtrate to a separatory funnel. Collect and measure
the volume of the aqueous phase. Transfer the oil phase to the weighing dish
with the solid and glass fiber pad.
9031 - 4 Revision 0
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7.4 Weigh the dish containing solid, oil (if any), and glass fiber pad.
Subtract the weight of the dry glass fiber pad. Calculate the volume of water
present in the original sample by subtracting the total volume of rinses from the
measured volume of the filtrate.
7.5 Place the following in a 1-liter wide-mouth bottle:
500 ml water
5 ml 50% w/v NaOH
1 g SnCl, . 2H20
50 ml n-hexane (if an oil or grease is present).
Cap the bottle with a Teflon or polyethylene lined cap and shake vigorously to
saturate the solution with stannous chloride. Direct a stream of nitrogen gas
at about 10 mL/min into the bottle for about 1 minute to purge the headspace of
oxygen. If the weight of the solids (Step 7.4) is greater than 25 g, weigh out
a representative aliquot of 25 g and add it to the bottle while still purging
with nitrogen. Otherwise, add all of the solids. Cap the bottle; avoid the
influx of air.
7.6 The pH of the extract must be maintained at > 9 or < 11 throughout
the extraction step and subsequent filtration. Since some samples may release
acid, the pH must be monitored as follows. Shake the extraction bottle and wait
1 minute. Open the bottle under a stream of nitrogen and check the pH. If the
pH is below 9, add 50% NaOH in 5 ml increments until it is at least 9. Recap the
bottle, and repeat the procedure until the pH does not drop. The bottle must be
thoroughly purged of oxygen before each recapping. Oxygen will oxidize sulfide
to elemental sulfur or other sulfur containing compounds that will not be
detected.
7.7 Place the bottle in the tumbler, making sure there is enough foam
insulation to cushion the bottle. Turn the tumbler on and allow the extraction
to run for about 18 hours.
7.8 Prepare a Buchner funnel apparatus as in Step 7.1 with a glass
fiber pad filter.
7.9 Decant the extract to the Buchner funnel.
7.10 If the extract contains an oil phase, separate the aqueous phase
using a separatory funnel. Neither the separation nor the filtration are
critical, but are necessary to be able to measure the volume of the aqueous
extract analyzed. Small amounts of suspended solids and oil emulsions will not
interfere with the extraction.
7.11 At this point, an aliquot of the filtrate of the original sample
may be combined with an aliquot of the extract in a proportion representative cf
the sample. Calculate the proportions as follows:
Aliquot of the Filtrate(mL) Solid Extracted(q)a x Total Sample Filtrate(mL)0
Aliquot of the Extract(mL) " Total Solid(g)6 Total Extraction Fluid(mL)d
9031 - 5 Revision 0
July 1992
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aFrom Step 7.5. Weight of solid sample used for extraction.
bFrom Step 7.4. Weight of solids and oil phase with the dry weight of filter and
tared dish subtracted.
Includes volume of all rinses added to the filtrate (Steps 7.1 and 7.2).
d500 mL water plus total volume of NaOH solution. Does not include hexane, which
is subsequently removed (Step 7.10).
Alternatively, the samples may be distilled and analyzed separately,
concentrations for each phase reported separately, and the amounts of each phase
present in the sample reported separately.
7.12 Distillation of Sulfide
7.12.1 In a preliminary experiment, determine the approximate
amount of sulfuric acid required to adjust a measured amount of the sample
to pH less than or equal to 1. The sample size should be chosen so that
it contains between 1.0 and 50 mg of sulfide. Place a known amount of
sample or sample slurry in a beaker. Add water until the total volume is
200 ml. Stir the mixture and determine the pH. Slowly add sulfuric acid
until the pH is less than or equal to 1.
CAUTION; Toxic hydrogen sulfide may be generated from the acidified sample.
This operation must be performed in the hood and the sample left
in the hood until the sample has been made alkaline or the sulfide
has been destroyed.
From the amount of sulfuric acid required to acidify the sample and the
mass or volume of the sample acidified, calculate the amount of acid
required to acidify the sample to be placed in the distillation flask.
7.12.2 Prepare the gas evolution apparatus as shown in Figure 1
in a fume hood.
7.12.2.1 Prepare a hot water bath at 70'C by filling a
crystallizing dish or other suitable container with water and place
it on a hotplate stirrer. Place a thermometer in the bath and
monitor the temperature to maintain the bath at 70ฐC.
7.12.2.2 Assemble the three neck 500-mL flask, fritted
gas inlet tube, and exhaust tube. Use Teflon sleeves to seal the
ground glass joints. Place a Teflon coated stirring bar into the
flask.
7.12.2.3 Place into each gas scrubbing bottle 10 ฑ 0.5
mL of the 0.5M zinc acetate solution, 5.0 ฑ 0.1 ml of 37%
formaldehyde and 100 + 5.0 ml water.
7.12.2.4 Connect the gas evolution flask and gas
scrubbing bottles as shown in Figure 1. Secure all fittings and
joints.
9031 - 6 Revision 0
July 1992
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7.12.3 Carefully place an accurately weighed sample which contains
1.0 to 50 mg of sulfide into the flask. If necessary, dilute to
approximately 200 mL with water.
7.12.4 Place the dropping funnel onto the flask making sure its
stopcock is closed. Add the volume of sulfuric acid calculated in Step
7.1.1 plus an additional 50 ml into the dropping funnel. The bottom
stopcock must be closed.
7.12.5 Attach the nitrogen inlet to the top of the dropping funnel
gas shut-off valve. Turn on the nitrogen purge gas and adjust the flow
through the sample flask to 25 mL/min. The nitrogen in the gas scrubbing
bottles should bubble at a rate of about five bubbles per second.
Nitrogen pressure should be limited to approximately 10 psi to prevent
excess stress on the glass system and fittings. Verify that there are no
leaks in the system. Open the nitrogen shut-off valve leading to the
dropping funnel. Observe that the gas flow into the sample vessel will
stop for a short period while the pressure throughout the system
equalizes. If the gas flow through the sample flask does not return
within a minute, check for leaks around the dropping funnel. Once flow
has stabilized, turn on the magnetic stirrer. Purge the system for 15
minutes with nitrogen to remove oxygen.
7.12.6 Heat sample to 70ฐC. Open dropping funnel to a position
that will allow a flow of sulfuric acid of approximately 5 mL/min. Monitor
the system until most of the sulfuric acid contained within the dropping
funnel has entered the sample flask. Close the dropping funnel while a
small amount of acid remains. Immediately close the gas shut-off valve to
the dropping funnel.
7.12.7 Purge, stir, and maintain a temperature of 70ฐC for a total
of 90 minutes from start to finish. Shut off nitrogen supply. Turn off
heat.
7.13 Titration of Distillate
7.13.1 Pipet a known amount of standardized 0.025N iodine solution
(see Step 5.12). in a 500-ml flask, adding an amount in excess of that
needed to oxidize the sulfide. Add enough water to bring the volume to
100 ml. The volume of standardized iodine solution should be about 65 ml
for samples with 50 mg of sulfide.
7.13.2 Add 2 ml of 6N HC1 to the iodine.
7.13.3 Pipet both of the gas scrubbing bottle solutions into the
flask, keeping the end of the pipet below the surface of the iodine
solution. If at any point in transferring the zinc acetate solution or
rinsing the bottles, the amber color of the iodine disappears or fades to
yellow, more 0.025N iodine must be added. This additional amount must be
added to the amount from Step 7.13.1 for calculations. Record the total
volume of standardized 0.025N iodine solution used.
7.13.4 Prepare a rinse solution of a known amount of standardized
0.025N iodine solution, 1 ml of 6N HC1, and water to rinse the remaining
9031 - 7 Revision 0
July 1992
-------
white precipitate (zinc sulfide) from the gas scrubbing bottles into the
flask. There should be no visible traces of precipitate after rinsing.
7.13.5 Rinse any remaining traces of iodine from the gas scrubbing
bottles with water, and transfer the rinses to the flask.
7.13.6 Titrate the solution in the flask with standard 0.025N
phenylarsine oxide or 0.025N sodium thiosulfate solution until the amber
color fades to yellow. Add enough starch indicator for the solution to
turn dark blue and titrate until the blue disappears. Record the volume
of titrant used.
7.13.7 Calculate the concentration of sulfide in the sample as
follows:
[(ml of I2 x N of I2) - (ml of titrant x N of titrant)](16.03)
= sulfide(mg/kg)
sample weight (kg)
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 requirements.
8.2 A reagent blank should be run every twenty analyses or per
analytical batch, whichever is more frequent.
8.3 Check standards are prepared from water and a known amount of
sodium sulfide. A check standard should be run with each analytical batch of
samples or once every twenty samples. Acceptable recovery will depend on the
level and matrix.
8.4 A matrix spiked sample should be run for each analytical batch or
twenty samples, whichever is more frequent, to determine matrix effects. If
recovery is low, acid-insoluble sulfides are indicated. A matrix spiked sample
is a sample brought through the whole sample preparation and analytical process.
8.5 Verify the calibration with an independently prepared QC reference
sample every twenty samples or once per analytical batch, whichever is more
frequent.
9.0 METHOD PERFORMANCE
9.1 Accuracy - Accuracy for this method was determined by three
independent laboratories by measuring percent recoveries of spikes for waste
samples. The results are summarized below.
Accuracy for the entire method for four synthetic waste samples 70-104%
recovery
9031 - 8 Revision 0
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9.2 Precision
Precision of entire method for four synthetic waste samples
Percent coefficient of variation 1.0-34
10.0 REFERENCES
1. Test Methods 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,1987; SW-846; 955-001-
00000-1.
2. Methods for Chemical Analysis of Water and Wastes; U.S. Environmental
Protection Agency. Office of Research and Development. Environmental Monitoring
and Support Laboratory. ORD Publications Office. Center for Environmental
Research Information: Cincinnati, OH, 1979; EPA-600/4-79-020, Method 376.1.
3. CRC Handbook of Chemistry and Physics. 66th ed.; Weast, R., Ed.; CRC: Boca
Raton, FL, 1985.
4. Standard Methods for the Examination of Water and Wastewater. 16th ed.;
Greenberg, A.E.; Trussell, R.R.; Clesceri, L.S., Eds.; American Water Works
Association, Water Pollution Control Federation, American Public Health
Association: Washington, DC, 1985; Methods 427, 427A, 427B, and 427D.
5. Andreae, M.O.; Bernard, W.R. Anal. Chem. 1983, 55, 608-612.
6. Barclay, H. Adv. Instrum. 1980, 35(2K 59-61.
7. Bateson, S.W.; Moody, G.J.; Thomas, J.P.R. Analyst 1986, 111. 3-9.
8. Berthage, P.O. Anal. Chim. Acta 1954, 10, 310-311.
9. Craig, P.O.; Moreton, P.A. Environ. Techno!. Lett. 1982, 3, 511-520.
10. Franklin, G.O.; Fitchett, A.W. Pulp & Paper Canada 1982, 83(10K 40-44.
11. Fuller, W. Cyanide in the Environment; Van Zyl, D., Ed.; Proceedings of
Symposium; December 1984.
12. Gottfried, G.J. "Precision, Accuracy, and MDL Statements for EPA Methods
9010, 9030, 9060, 7520, 7521, 7550, 7551, 7910, and 7911"; final report to the
U.S. Environmental Protection Agency (EMSL-CI); Biopheric.
13. Kilroy, W.P. Talanta 1983, 30(6). 419-422.
14. Kurtenacher, V.A.; Wallak, R. Z. Anorq. U. Chem. 1927, 161. 202-209.
15. Landers, D.H.; David, M.B.; Mitchell, M.J. Int. J. Anal. Chem. 1983, 14,
245-256.
16. Opekar, F.; Brukenstein, S. Anal. Chem. 1984, 56, 1206-1209.
17. Ricklin, R.D.; Johnson, E.L. Anal. Chem. 1983, 55, 4.
9031 - 9 Revision 0
July 1992
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18. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; American Chemical Society: Washington, DC, 1986.
19. Snedecor, G.W.; Ghran, W.G. Statistical Methods; Iowa State University
Press: Ames, IA, 1980.
20. Umana, M.; Beach, J.; Sheldon, L. "Revisions to Method 9010"; final report
to the Environmental Protection Agency on Contract No. 68-01-7266; Research
Triangle Institute: Research Triangle Park, NC, 1986; Work Assignment No. 1.
21. Umana, M.; Sheldon, L. "Interim Report: Literature Review"; interim report
to the U.S. Environmental Protection Agency in Contract No. 68-01-7266; Research
Triangle Institute: Research Triangle Park, NC, 1986; Work Assignment No. 3.
22. Wang, W.; Barcelona, M.J. Environ. Inter. 1983, 9, 129-133.
23. Wronksi, M. Talanta 1981, 28, 173-176.
24. Application Note 156; Princeton Applied Research Corp.: Princeton, NJ.
25. Guidelines for Assessing and Reporting Data Quality for Environmental
Measurements: U.S. Environmental Protection Agency Office of Research and
Development: Washington, DC, 1983.
26. Fed. Regist. 1980, 45(98), 33122.
27. The Analytical Chemistry of Sulfur and Its Compounds. Part I; Karchmer,
J.H., Ed.; Wiley-Interscience: New York, 1970.
28. Methods for the Examination of Water and Associated Materials; Department
of the Environment: England, 1983.
29. "Development and Evaluation of a Test Procedure for Reactivity Criteria for
Hazardous Waste"; final report to the U.S. Environmental Protection Agency on
Contract 68-03-2961; EAL: Richmond, CA.
30. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification for
Reagent Water"; ATSM: Philadelphia, PA, 1985; D1193-77.
9031 - 10 Revision 0
July 1992
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FIGURE 1.
GAS EVOLUTION APPARATUS
H2S04 (HCI for Acid Insoluble Sulfides)
Hot Water Bath
with Magnetic Stirrer
Zinc Acetate
and
Formaldehyde
Scrubbing
Bottles
Stirring Bar
N20ut
9031 - 11
Revision 0
July 1992
-------
FIGURE 2.
TUMBLER-EXTRACTOR
Foam-Inner Liner
1-L Bottle
with Cap
Jar Mill Drive
Box Wheels Plywood Construction
9031 - 12
Revision 0
July 1992
-------
FIGURE 3.
EXTRACTOR
l-Gallon PlasUc
or Glass Bottle
Foam Bonded lo Cover
Box Assembly
Plywood Construction
Totally Enclosed
Fan Cooled Motor
30 rpm, 1/8 HP
9031 - 13
Revision 0
July 1992
-------
METHOD 9031
SULFIDES
START
7 . 1 Assemble
Buchner funnel
apparatus
1
7.2 Transfer s mple
to funnel ; rise
sample contain r w/
known amt . f
wa ter ; add r i ses
to funnel; filter
until no free water
remains in funnel
7 . 3 Transfer solid
and fiber pad to
dried tared
weighing dish
73 Transfer S \v
filtrate to / N.
separator/ funnel; ^r 7.3 Does x_^
collect aqueous Yes S fil trate x^
phase and measure ' C include an oil )
volume ; transfer x^ phase? /
oil phase to ^v /
weighing dish X. >^
t)o
7.4 Heigh dish and
contents; subtract
glass fiber pad (if
total volume of
rinses from volume
of filtrate
7 5 Place nater ,
NaOH, stannous
chloride, and
* n-hexane (if oil or
grease is present)
in 1 L bottle
1
7.5 Cap bottle with
Teflon lined cap
and shake; direct
ni trogen into
bottle for 1 minute
to purge oxygen
1
//.B Is weight \No 7.5 Add all solids;
f of the solids > J f cap bottle
V 25 9? S
Yes
7.5 Welgh out 25 g;
add to bottle nhile
purging
o
9031 - 14
Revision 0
July 1992
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METHOD 9031
(Continued)
7.6 PH of
extraction must be
> 9 and < 11; shake
bottle 1 min.; open
under nitrogen;
check pH
7.6 Add 5 mL
aliquot of NaOH
No
7.7 Place bottle in
tumbler; turn on
and extract for 18
hours
7.8 Prepare Buchner
funnel apparatus as
in Step 7.1
7.9 Decant extract
into funnel
7.10 Place extract
in separatory
funnel; collect and
measure volume of
aqueous phase
7 .11 Combine
aqueous en tract and
original sample
filtrate in
aliquots
propertional to the
sample; calculate
proportions
7.12.1 Choose
ize; place
amt. of
in beaker;
sample
knoii
sample
add -at
dd cone.
sulfuri acid to
pH = 1
7 12.2 Calculate
amount of sulfuric
acid needed to
acidify sample
9031 - 15
Revision 0
July 1992
-------
METHOD 9031
(Continued)
7.12.2 Prepare gas
evolution apparatus
7.12.3 Place
weighed sample in
flask; dilute with
water if necessary
7.12.4 Place
dropping funnel
onto flask; add
sulfuric acid from
Step 7.12.1 to
dropping funnel
7.12.5 Adjust
ni t r ogen flow;
check for leaks;
turn on stirrer;
purge system of
OMygen for 15
minutes
1
7.12.6 Heat to 70C;
add sulfuric acid
to flaak ; close
funnel when acid
near a depletion
7 . 12. 7 Purge, stir .
and heat for 90
* min . ; shut off
nitrogen; turn off
heat
7.13 Analyze by
ti tra tion
I
7.13.1 Pipet known,
amount of 0.025N
an Erlenmeyer
flask; dilute with
water
i
7.13.2 Add 2 mL 6N
HC1 to flask
1
7.13.3 Pipet
scrubber solution
into flask
1
/ 7.13.3 >v 7.13.3 Add more
S Does amber >,Yes iodine solution;
( iodine color J > record total volume
>v disappear? / of iodine solution
N. / used
No
7.13.4 Prepare
iodine solution, 6N
HC1 , and water
1
7.135 Rinse traces
of iodine from
scrubbing bottle;
transfer rinses to
flask with pipet
1
7.13 6 Titrate
flask solution
until amber color
fades; add starch
indicator; titrate
until blue color
disappears; record
volume of titrant
used
1
7.13.7 Calculate
the concentration
of sulfide in the
sample
STOP
9031 - 16
Revision 0
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METHOD 9035
SULFATE (COLORIMETRIC. AUTOMATED, CHLORANILATE)
1.0 SCOPE AND APPLICATION
1.1 This automated method 1s applicable to ground water, drinking and
surface waters, and domestic and Industrial wastes containing 10 to 400 mg
$04-2/11ter.
2.0 SUMMARY OF METHOD
2.1 When solid barium chloranllate 1s added to a solution containing
sulfate, barium sulfate 1s precipitated, releasing the highly colored add
chloranllate 1on. The color Intensity 1n the resulting chloranlUc add
solution 1s proportional to the amount of sulfate present.
3.0 INTERFERENCES
3.1 Cations such as calcium, aluminum, and Iron Interfere by precipi-
tating the chloranllate. These Ions are removed by passage through an Ion-
exchange column.
3.2 Samples should be centrlfuged or filtered before analysis.
4.0 APPARATUS AND MATERIALS
4.1 Automated continuous-flow analytical Instrument, with;
4.1.1 Sampler I.
4.1.2 Continuous filter.
4.1.3 Manifold.
4.1.4 Proportioning pump.
4.1.5 Colorimeter: Equipped with 15 mm tubular flowcell and 520 nm
filters.
4.1.6 Recorder.
4.1.7 Heating bath, 45*C.
4.2 Magnetic stlrrer.
9035 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Barium chloranllate; Add 9 g of barium chloranllate (BaC^C^O^ to
333 ml of spectrophotometrlc grade ethyl alcohol and dilute to 1 liter with
Type II water.
5.3 Acetate buffer, pH 4.63: Dissolve 13.6 g of sodium acetate 1n Type
II water. Add 6.4 ml of acetic add and dilute to 1 liter with Type II water.
Make fresh weekly.
5.4 NaOH-EDTA solution; Dissolve 65 g of NaOH and 6 g EDTA 1n Type II
water and dilute to 1 liter. This solution 1s also used to clean out the
manifold system at end of sampling run.
5.5 Ion exchange resin; Dowex-50 W-X8, 1on1c form-H+. The column 1s
prepared by sucking a slurry of the resin Into 12 1n. of 3/l6-1n O.D. tubing.
This may be conveniently done by using a plpet and a loose-fitting glass wool
plug 1n the tube. The column, upon exhaustion, turns red. Ensure that air
does not enter the column.
5.6 Stock solution; Dissolve 1.4790 g of oven-dried (105*C) Na2S04 1n
Type II water and dilute to 1 liter 1n a volumetric flask (1.0 ml = 1.0 mg).
5.7 Standards ; Prepare a series of standards by diluting suitable
volumes of stock solution to 100.0 ml with Type II water. The following
dilutions are suggested.
Stock Solution (ml) Concentration (mg/L)
1.0 10
2.0 20
4.0 40
6.0 60
8.0 80
10.0 100
15.0 150
20.0 200
30.0 300
40.0 400
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.
6.2 Refrigerate at 4'C.
9035 - 2
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Set up manifold as shown 1n Figure 1. (Note that any precipitated
BaS04 and the unused barium chloranllate are removed by filtration. If any
BaS04 should come through the filter, 1t 1s complexed by the NaOH-EDTA
reagent.)
7.2 Allow both colorimeter and recorder to warm up for 30 min. Run a
baseline with all reagents, feeding Type II water through the sample line.
Adjust dark current and operative opening on colorimeter to obtain suitable
baseline.
7.3 Place Type II water wash tubes 1n alternate openings in sampler and
set sample timing at 2.0 min.
7.4 Place working standards in sampler 1n order of decreasing concen-
tration. Complete filling of sampler tray with unknown samples.
7.5 Switch sample line from Type II water to sampler and begin analysis.
7.6 Calculation;
7.6.1 Prepare a standard curve by plotting peak heights of
processed standards against known concentrations. Compute concentration
of samples by comparing sample peak heights with standard curve.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A linear calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples 1f they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of cne blank per sample batch to determine 1f
contamination has occurred.
8.5 Verify calibration with an independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A spike
duplicate sample is a sample brought through the whole sample preparation and
analytical process.
9035 - 3
Revision
Date September 1986
-------
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S ONE
FIGURE 1 - SUIFATE MANIFOLD AA I
-------
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 375.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Bertolacinl, R.J., and J.E. Barney, II, Colorlmetric Determination of
Sulfate with Barium Chloranilate, Anal. Chem., 29(2), pp. 281-283 (1957).
2. Gales, M.E., Jr., W.H. Kaylor, and J.E. Longbottom, Determination of
Sulphate by Automatic Colorlmetric Analysis, Analyst, 93, 97 (1968).
9035 - 5
Revision
Date September 1986
-------
METHOD 9035
SULFATE (COLORIMETRIC. AUTOMATED. CHLORANILATE)
0
7.1
Set up manifold
7.3
7 '
1 Place
work ing
standards in
sampler: fill
sampler tray
Warm up
colorimeter.
recorder;
obtain suitable
baseline
7.5
Switch sample
line to sampler
and analyze
7.3
Place water
wash tubes in
ampler
7.6.1
Compute
concentration
of samples
o
[ Stop J
9035 - 6
Revision 0
Date September 1986
-------
METHOD 9036
SULFATE (COLORIMETRIC. AUTOMATED, METHYLTHYMOL BLUE. AA II)
1.0 SCOPE AND APPLICATION
1.1 This automated method 1s applicable to ground water, drinking and
surface waters, and domestic and Industrial wastes.
1.2 Samples 1n the range of 0.5 to 300 mg S04~2/I1ter can be analyzed.
2.0 SUMMARY OF METHOD
2.1 The sample 1s first passed through a sodium-form cation-exchange
column to remove multlvalent metal Ions. The sample containing sulfate 1s
then reacted with an alcohol solution of barium chloride and methyl thymol blue
(MTB) at a pH of 2.5-3.0 to form barium sulfate. The combined solution 1s
raised to a pH of 12.5-13.0 so that excess barium reacts with MTB. The
uncomplexed MTB color 1s gray; 1f 1t 1s all chelated with barium, the color 1s
blue. Initially, the barium and MTB are equlmolar and equivalent to 30 mg
S04~2/I1ter; thus the amount of uncomplexed MTB 1s equal to the sulfate
present.
3.0 INTERFERENCES
3.1 The Ion-exchange column eliminates Interferences from multlvalent
cations. A mid-scale sulfate standard containing Ca++ should be analyzed
periodically to ensure that the column 1s functioning properly.
3.2 Samples with pH below 2 should be neutralized because high add
concentrations elute cations from the Ion-exchange resin.
3.3 Turbid samples should be filtered or centrlfuged.
4.0 APPARATUS AND MATERIALS
4.1 Automated continuous-flow analytical Instrument:
4.1.1 Sampler.
4.1.2 Manifold: High- or low-level (Figure 1).
4.1.3 Proportioning pump.
4.1.4 Heating bath: Operable at the temperature specified.
4.1.5 Colorimeter: Equipped with 15 mm flowcell and 460 nm
Interference filters.
9036 - 1
Revision
Date September 1986
-------
TO WASTE O>
n- <
ION EXC
COLUMN
WASTES
.w
fir"
:HANGE
116 GOO6 01
o no ST/
SLEEVING
157-B095
J20
TURNS
TO SAMPLER
WASH RECEPTACLE
170 0103 01
A 7
5 UinNS |
tNDARD
157 0370
[ . J
7? I 116-04B9
7UMNS
1
116 O4R9 01
01
COLORIMETER *
TO F/C PUMP wAซ:Tr
TUBE
460 NM
5 mm F/C "2.0 mm 10
GRN. GRN.
BLK. BLK.
GRN. GRN.
ORN. GRN.
GRY, GRY.
BLK. BLK.
RED RED
ORN. ORN.
GRN. GRN.
PROPORTIONl
PIIMD
MVMIN
2.0
0.32 AIR
2.OO DILUTION WATER
O.1O SAMPLE
7.OO WASTE
O.32 AIR
0.70 METHYLTHYMOL BLUE
O.42*"SOniUM HYDROXIDE
2.00 FROM F/C
MG
RANGE 0 30 mci/l CHANGE THE WATER
AND SAMPLE TUBES TO GRY/GRY (1.00)
SAMPLING RATE 30/hr. 8.1
0.034 POLYETHYLENE
SILICONF RURRER
(/> o
n> 3
o
FIGURE 1 SULFATE MANIFOLD AA11
n
-j
vo
00
O)
-------
4.1.6 Filters: Of specified transmittance.
4.1.7 Recorder.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Barium chloride; Dissolve 1.526 g of barium chloride dlhydrate
(BaCl2'2H20) in 500 mL of Type II water and dilute to 1 liter.
5.3 Methyl thymol blue; Dissolve 0.1182 g of methylthymol blue
(3'3"-bi s-N,N-b1s carboxymethyl-ami no methyl thymolsulfone-phthale1n
pentasodium salt) 1n 25 ml of barium chloride solution (Paragraph 5.2). Add
4 ml of 1.0 N hydrochloric add, which changes the color to bright orange.
Add 71 ml of water and dilute to 500 mL with ethanol. The pH of this solution
1s 2.6. This reagent should be prepared the day before and stored 1n a brown
plastic bottle 1n the freezer.
5.4 Buffer, pH 10.5 + 0.5: Dissolve 6.75 g of ammonium chloride 1n
500 mL of Type II water. Add 57 mL of concentrated ammonium hydroxide and
dilute to 1 liter with Type II water.
5.5 Buffered EDTA; Dissolve 40 g of tetrasodlum EDTA 1n pH 10.5 buffer
(Paragraph 5.4) and dilute to 1 liter with buffer.
5.6 Sodium hydroxide solution (50%): Dissolve 500 g NaOH In 600 mL of
Type II water, cool, and dilute to 1 liter.
5.7 Sodium hydroxide. 0.18 N: Dilute 14.4 mL of sodium hydroxide
solution (Paragraph 5.6) to 1 liter.
5.8 Ion-exchange resin: Bio-Rex 70, 20-50 mesh, sodium form, Bio-Rad
Laboratories, Richmond, California. Free from fines by stirring with several
portions of Type II water and decant the supernate before settling 1s
complete.
5.9 Dilution water: Add 0.75 mL of sulfate stock solution (Paragraph
5.10) and 3 drops of Brij-35 (available from Technicon) to 2 liters of Type II
water.
5.10 Sulfate stock solution, 1 mL = 1 mg S04~2: Dissolve 1.479 g of
dried Na2S04 (105*C) In Type II water and dilute to 1 liter.
5.11 Dilute sulfate solution, 1 mL = 0.1 mg S04~2: Dilute 100 mL of
sulfate stock solution (Paragraph 5.10) to 1 liter.
9036 - 3
Revision
Date September 1986
-------
5.12 High-level working standards, 10-300 mg/L: Prepare high-level
working standards by diluting the following volumes of stock standard
(Paragraph 5.10) to 100 ml:
Stock Solution (ml) Concentration (mg/L)
1 10
5 50
10 100
15 150
25 250
30 300
5.13 Low-level working standards. 0.5-30 mg/L: Prepare low-level
working standards by diluting the following volumes of dilute sulfate solution
(Paragraph 5.11) to 100 mL:
Stock Solution (mL) Concentration (mg/L)
0.5 0.5
1 1.0
5 5.0
10 10.0
15 15.0
25 25.0
30 30.0
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 Refrigerate at 4*C.
7.0 PROCEDURE
7.1 Set up manifold for high- (10-300 mg/L SO^2) or low- (0.5-30 mg/L
S04"2) level samples as described in Figure 1.
7.2 The ion-exchange column is prepared by pulling a slurry of the resin
into a piece of glass tubing 7.5-1n. long, 2.0-mrn I.D., and 3.6-mm O.D. This
is conveniently done by using a pi pet and a loose-fitting glass wool plug in
the tubing. Care should be taken to avoid allowing air bubbles to enter the
column. If air bubbles become trapped, the column should be prepared again.
The column can exchange the equivalent of 35 mg of calcium. For the high-
level manifold, this corresponds to about 900 samples with 200 mg/L Ca. The
column should be prepared as often as necessary to ensure that no more than
50% of its capacity 1s used.
9036 - 4
Revision
Date September 1986
-------
7.3 Allow the colorimeter, recorder, and printer to warm up for 30 min.
Pump all reagents until a stable baseline 1s achieved.
7.4 Analyze all working standards 1n duplicate at the beginning of a run
to develop a standard curve. The A and B control standards must be analyzed
every hour to ensure that the system remains properly calibrated. Because the
chemistry 1s nonlinear, the 180-mg/L standard 1s set at 50% on the recorder
using the standard calibration control on the colorimeter.
7.5 At the end of each day, the system should be washed with the
buffered EDTA solution (Paragraph 5.5). This 1s done by placing the
methyl thymol blue line and the sodium hydroxide line 1n water for a few
minutes and then 1n the buffered EDTA solution for 10 m1n. Wash the system
with water for 15 m1n before shutting down.
7.6 Prepare a standard curve by plotting peak heights of five processed
standards against known concentrations. Compute concentration of samples by
comparing sample peak heights with the standard curve. Note that this is not
a linear curve but a third order curve.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum, of one blank per sample batch to determine if
contamination has occurred.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample is a sample brought through the whole sample preparation and analytical
process.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 375.2 of Methods
for Chemical Analysis of Water and Wastes.
9036 - 5
Revision 0
Date September 1986
-------
10.0 REFERENCES
1. Coloros, E., M.R. Panesar, and P.P. Parry, "Linearizing the Calibration
Curve in Determination of Sulfate by the Methyl thymol Blue Method," Anal.
Chem. 48, 1693 (1976).
2. Lazrus, A.L., K.C. Hill, and J.P. Lodge, "Automation in Analytical
Chemistry," Technicon Symposia, 1965.
9036 - 6
Revision
Date September 1986
-------
METHOD 9036
SUUFATE (COLORXMETRIC. AUTOMATED. METMYLTHVMOL BLUE. A* II)
O
Set up manifold
7.4
Oevelop
standard
curve: check
calibration
every hour
7.2
Prepare Ion
change column
7.5
Mash syntem
down at end of
day
7.3
I Kara up
colorimeter.
recorder end
printer. Get
table baseline
7.6
Compute
concentration
Of samples
Q
f Stop J
9036 - 7
Revision 0
Date September 1986
-------
METHOD 9038
SULFATE (TURBIDIMETRIC)
1.0 SCOPE AND APPLICATION
1.1 This method 1s applicable to ground water, drinking and surface
waters, and domestic and Industrial wastes.
1.2 This method 1s suitable for all concentration ranges of sulfate
(S04~2); however, 1n order to obtain reliable readings, use a sample aliquot
containing not more than 40 mg/L of S04~2.
1.3 The minimum detectable limit 1s approximately 1 mg/L of S04~2.
2.0 SUMMARY OF METHOD
2.1 Sulfate 1on 1s converted to a barium sulfate suspension under
controlled conditions. The resulting turbidity Is determined by a nephelo-
meter, filter photometer, or spectrophotometer and compared with a curve
prepared from standard sulfate solution.
3.0 INTERFERENCES
3.1 Color and turbidity due to the sample matrix can cause positive
Interferences which must be accounted for by use of blanks.
3.2 Silica 1n concentrations over 500 mg/L will Interfere.
4.0 APPARATUS AND MATERIALS
4.1 Magnetic stlrrer; Variable speed so that 1t can be held constant
just below splashing.Use Identical shapes and sizes of magnetic stirring
bars.
4.2 Photometer (one of the following, given 1n order of preference):
4.2.1 Nephelometer.
4.2.2 Spectrophotometer: For use at 420 nm with light path of
4 to 5 cm.
4.2.3 Filter photometer: With a violet filter having a maximum
near 420 nm and a light path of 4 to 5 cm.
4.3 Stopwatch; If the magnetic stlrrer Is not equipped with an accurate
timer.
9038 - 1
Revision
Date September 1986
-------
4.4 Measuring spoon; Capacity 0.2 to 0.3 ml.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Conditioning reagent; Slowly add 30 ml concentrated HC1 to 300 ml
Type II water, 100 ml 95% ethanol or Isopropanol, and 75 g NaCl In solution in
a container. Add 50 ml glycerol and mlx.b
5.3 Barium chloride (BaCl2): Crystals, 20 to 30 mesh.
5.4 Sodium carbonate solution; (approximately 0.05 N): Dry 3 to 5 g
primary standard N32C03 at 250*Cfor 4 hr and cool in a desiccator. Weigh
2.5 + 0.2 g (to the nearest mg), transfer to a 1-1 Her volumetric flask, and
fill to the mark with Type II water.
5.5 Proprietary reagents; Such as Hach Sulfaver or equivalent, are
acceptable.
5.6 Standard sulfate solution (1.00 ml = 100 ug S04"2): Prepare by
Paragraph 5.6.1 or 5.6.2.
5.6.1 Standard sulfate solution from
5.6.1.1 Standard sulfuric add, 0.1 N: Dilute 3.0 ml
concentrated ^04 to 1 liter with Type II water. Standardize
against 40.0 ml of 0.05 N Na2C03 solution (Paragraph 5.4) with about
60 ml Type II water by titrating potentlometrically to a pH of about
5. Lift electrodes and rinse Into beaker. Boll gently for 3 to 5
m1n under a watch glass cover. Cool to room temperature. Rinse
cover glass Into beaker. Continue tltratlon to the pH Inflection
point. Calculate the normality of ^04 using:
N = A x B
53.00 x C
where:
A = g Na2C03 weighed into 1 liter flask (Paragraph 5.4);
B = ml N32C03 solution used in the standardization;
C = ml acid used in tltratlon;
5.6.1.2 Standard acid, 0.02 N: Dilute appropriate amount of
standard add, 0.1 N (Paragraph 5.6.1.1) to 1 liter (use 200.00 ml
standard acid 1f normality 1s 0.1000 N). Check by standardization
against 15 ml of 0.05 N Na2C03 solution (Paragraph 5.4).
9038 - 2
Revision 0
Date September 1986
-------
5.6.1.3 Place 10 ml standard sulfurlc add, 0.02 N (Paragraph
5.6.1.2) in a 100-mL volumetric flask and dilute to the mark.
5.6.2 Standard sulfate solution from NapSO^ Dissolve 147.9 mg
anhydrous Na2S04 in Type II water in a 1-liter volumetric flask and
dilute to the mark with Type II 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 Preserve by refrigerating at 4*C.
7.0 PROCEDURE
7.1 Formation of barium sulfate turbidity;
7.1.1 Place a 100-mL sample, or a suitable portion diluted to
100 mL, into a 250-mL Erlenmeyer flask.
7.1.2 Add exactly 5.0 mL conditioning reagent (Paragraph 5.2).
7.1.3 Mix in the stirring apparatus.
7.1.4 While the solution is being stirred, add a measured spoonful
of BaCl2 crystals (Paragraph 5.3) and begin timing immediately.
7.1.5 Stir exactly 1.0 min at constant speed.
7.2 Measurement of barium sulfate turbidity;
7.2.1 Immediately after the stirring period has ended, pour
solution into absorbance cell.
7.2.2 Measure turbidity at 30-sec intervals for 4 min.
7.2.3 Record the maximum reading obtained in the 4-min period.
7.3 Preparation of calibration curve;
7.3.1 Prepare calibration curve using standard sulfate solution
(Paragraph 5.6).
7.3.2 Space standards at 5-mg/L increments in the 0-40 mg/L sulfate
range.
7.3.3 Above 50 mg/L the accuracy decreases and the suspensions lose
stability.
9038 - 3
Revision 0
Date September 1986
-------
7.3.4 Check reliability of calibration curve by running a standard
with every three or four samples.
7.4 Correction for sample color and turbidity;
7.4.1 Run a sample blank using steps 7.1 and 7.2, without the
addition of barium chloride (Paragraph 7.1.4).
7.5 Calculation;
7.5.1 Read mg $04-2 from linear calibration curve:
_o
2 mg SO. x 1,000
m9 S0~ /L '
4 ml sample
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples if they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine if
contamination has occurred.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A spike
duplicate sample 1s a sample brought through the whole sample preparation and
analytical process.
9.0 METHOD PERFORMANCE
9.1 Thirty-four analysts 1n 16 laboratories analyzed six synthetic water
samples containing exact Increments of Inorganic sulfate with the following
results:
9038 - 4
Revision
Date September 1986
-------
Increment as
Sulfate
(mg/L)
8.6
9.2
110
122
188
199
Precision as
Standard Deviation
(mg/L)
2.30
1.78
7.86
7.50
9.58
11.8
Accuracy
Bias
(X)
-3.72
-8.26
-3.01
-3.37
+0.04
-1.70
as
Bias
(mg/L)
-0.3
-0.8
-3.3
-4.1
+0.1
-3.4
(Data from: FWPCA Method Study 1, Mineral and Physical Analyses.)
9.2 A synthetic unknown sample containing 259 mg/L sulfate, 108 mg/L Ca,
82 mg/L Mg, 3.1 mg/L K, 19.9 mg/L Na, 241 mg/L chloride, 0.250 mg/L nitrite N,
1.1 mg/L nitrate N, and 42.5 mg/L total alkalinity (contributed by NaHC03),
was analyzed 1n 19 laboratories by the turb1d1metr1c method, with a relative
standard deviation of 9.IX and a relative error of 1.2%.
10.0 REFERENCES
1. Annual Book of ASTM Standards, Part 31, "Water," Standard D516-68,
Method B, p. 430 (1976).
2. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
p. 496, Method 427C, (1975).
9038 - 5
Revision
Date September 1986
-------
METHOD 9036
SULFATE (TUR0IDZMETAIC)
C
7.1.1
Place
ample
In flask for
formation of
barium aulfate
turbidity
7.1.8
Add
conditioning
reagent and mix
7.1.4
Add BaClt
crystals: stir
for 1 minute
7.3.1
Pour solution
into absorbance
cell
o
o
Measure
turbidity;
record mm*.
reading
7.3
Prepare
calibration
curve
7.4
Correct for
ample color
and turbidity
7.5
-2
Calculate SO,
f Stop J
9038 - 6
Revision 0
Date September 1986
-------
METHOD 9056
DETERMINATION OF INORGANIC ANIONS BY ION CHROMATOGRAPHY
1.0 SCOPE AND APPLICATION
1.1 This method addresses the sequential determination of the anions
chloride, fluoride, bromide, nitrate, nitrite, phosphate, and sulfate in the
collection solutions from the bomb combustion of solid waste samples, as well as
all water samples.
1.2 The method detection limit (MDL), the minimum concentration of a
substance that can be measured and reported with 99% confidence that the value
is above zero, varies for anions as a function of sample size and the
conductivity scale used. Generally, minimum detectable concentrations are in the
range of 0.05 mg/L for P and 0.1 mg/L for Br", CT, N03", N02", P043', and S042' with
a 100-jiL sample loop and a 10-/Ltmho full-scale setting on the conductivity
detector. Similar values may be achieved by using a higher scale setting and an
electronic integrator. Idealized detection limits of an order of magnitude lower
have been determined in reagent water by using a l-jumho/cm full-scale setting
(Table 1). The upper limit of the method is dependent on total anion
concentration and may be determined experimentally. These limits may be extended
by appropriate dilution.
2.0 SUMMARY OF METHOD
2.1 A small volume of combustate collection solution or other water
sample, typically 2 to 3 ml, is injected into an ion chromatograph to flush and
fill a constant volume sample loop. The sample is then injected into a stream
of carbonate-bicarbonate eluent of the same strength as the collection solution
or water sample.
2.2 The sample is pumped through three different ion exchange columns and
into a conductivity detector. The first two columns, a precolumn or guard column
and a separator column, are packed with low-capacity, strongly basic anion
exchanger. Ions are separated into discrete bands based on their affinity for
the exchange sites of the resin. The last column is a suppressor column that
reduces the background conductivity of the eluent to a low or negligible level
and converts the anions in the sample to their corresponding acids. The
separated anions in their acid form are measured using an electrical-conductivity
cell. Anions are identified based on their retention times compared to known
standards. Quantitation is accomplished by measuring the peak height or area and
comparing it to a calibration curve generated from known standards.
3.0 INTERFERENCES
3.1 Any species with a retention time similar to that of the desired ion
will interfere. Large quantities of ions eluting close to the ion of interest
will also result in an interference. Separation can be improved by adjusting the
eluent concentration and/or flow rate. Sample dilution and/or the use of the
method of standard additions can also be used. For example, high levels of
organic acids may be present in industrial wastes, which may interfere with
9056 - 1 Revision 0
September 1994
-------
inorganic anion analysis. Two common species, formate and acetate, elute between
fluoride and chloride.
3.2 Because bromide and nitrate elute very close together, they are
potential interferences for each other. It is advisable not to have Br"/N03"
ratios higher than 1:10 or 10:1 if both anions are to be quantified. If nitrate
is observed to be an interference with bromide, use of an alternate detector
(e.g.. electrochemical detector) is recommended.
3.3 Method interferences may be caused by contaminants in the reagent
water, reagents, glassware, and other sample processing apparatus that lead to
discrete artifacts or elevated baseline in ion chromatograms.
3.4 Samples that contain particles larger than 0.45 /xm and reagent
solutions that contain particles larger than 0.20 jum require filtration to
prevent damage to instrument columns and flow systems.
3.5 If a packed bed suppressor column is used, it will be slowly consumed
during analysis and, therefore, will need to be regenerated. Use of either an
anion fiber suppressor or an anion micromembrane suppressor eliminates the time-
consuming regeneration step through the use of a continuous flow of regenerant.
4.0 APPARATUS AND MATERIALS
4.1 Ion chromatograph, capable of delivering 2 to 5 ml of eluent per
minute at a pressure of 200 to 700 psi (1.3 to 4.8 MPa). The chromatograph shall
be equipped with an injection valve, a 100-/uL sample loop, and set up with the
following components, as schematically illustrated in Figure 1.
4.1.1 Precolumn, a guard column placed before the separator column
to protect the separator column from being fouled by particulates or
certain organic constituents (4 x 50 mm, Dionex P/N 030825 [normal run],
or P/N 030830 [fast run], or equivalent).
4.1.2 Separator column, a column packed with low-capacity
pellicular anion exchange resin that is styrene divinylbenzene-based has
been found to be suitable for resolving F", Cl", N02", P04"3, Br', N03", and
S04"2 (see Figure 2) (4 x 250 mm, Dionex P/N 03827 [normal run], or P/N
030831 [fast run], or equivalent).
4.1.3 Suppressor column, a column that is capable of converting
the eluent and separated anions to their respective acid forms (fiber,
Dionex P/N 35350, micromembrane, Dionex P/N 38019 or equivalent).
4.1.4 Detector, a low-volume, flowthrough, temperature-
compensated, electrical conductivity cell (approximately 6 juL volume,
Dionex, or equivalent) equipped with a meter capable of reading from 0 to
1,000 /Ltseconds/cm on a linear scale.
4.1.5 Pump, capable of delivering a constant flow of approximately
2 to 5 mL/min throughout the test and tolerating a pressure of 200 to
700 psi (1.3 to 4.8 MPa).
9056 - 2 Revision 0
September 1994
-------
4.2 Recorder, compatible with the detector output with a full-scale
response time in 2 seconds or less.
4.3 Syringe, minimum capacity of 2 ml and equipped with a male pressure
fitting.
4.4 Eluent and regenerant reservoirs, suitable containers for storing
eluents and regenerant. For example, 4 L collapsible bags can be used.
4.5 Integrator, to integrate the area under the chromatogram. Different
integrators can perform this task when compatible with the electronics of the
detector meter or recorder. If an integrator is used, the maximum area
measurement must be within the linear range of the integrator.
4.6 Analytical balance, capable of weighing to the nearest 0.0001 g.
4.7 Pipets, Class A volumetric flasks, beakers: assorted sizes.
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. Column life may be extended by passing
reagent water through a 0.22-jum filter prior to use.
5.3 Eluent, 0.003M NaHC03/0.0024M Na2C03. Dissolve 1.0080 g of sodium
bicarbonate (0.003M NaHC03) and 1.0176 g of sodium carbonate (0.0024M Na2C03) in
reagent water and dilute to 4 L with reagent water.
5.4 Suppressor regenerant solution. Add 100 ml of IN H2S04 to 3 L of
reagent water in a collapsible bag and dilute to 4 L with reagent water.
5.5 Stock solutions (1,000 mg/L).
5.5.1 Bromide stock solution (1.00 ml = 1.00 mg Br'). Dry
approximately 2 g of sodium bromide (NaBr) for 6 hours at 150ฐC, and cool
in a desiccator. Dissolve 1.2877 g of the dried salt in reagent water,
and dilute to 1 L with reagent water.
5.5.2 Chloride stock solution (1.00 ml = 1.00 mg Cl"). Dry sodium
chloride (NaCl) for 1 hour at 600ฐC, and cool in a desiccator. Dissolve
1.6484 g of the dry salt in reagent water, and dilute to 1 L with reagent
water.
5.5.3 Fluoride stock solution (1.00 ml = 1.00 mg F"). Dissolve
2.2100 g of sodium fluoride (NaF) in reagent water, and dilute to 1 L with
reagent water. Store in chemical-resistant glass or polyethylene.
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5.5.4 Nitrate stock solution (l.OQ ml = 1.00 mg N03'). Dry
approximately 2 g of sodium nitrate (NaN03) at 105ฐC for 24 hours.
Dissolve exactly 1.3707 g of the dried salt in reagent water, and dilute
to 1 L with reagent water.
5.5.5 Nitrite stock solution (1.00 ml = 1.00 mg N02"). Place
approximately 2 g of sodium nitrate (NaN02) in a 125 mL beaker and dry to
constant weight (about 24 hours) in a desiccator containing concentrated
H2S04. Dissolve 1.4998 g of the dried salt in reagent water, and dilute
to 1 L with reagent water. Store in a sterilized glass bottle.
Refrigerate and prepare monthly.
NOTE: Nitrite is easily oxidized, especially in the presence of
moisture, and only fresh reagents are to be used.
NOTE: Prepare sterile bottles for storing nitrite solutions by
heating for 1 hour at 170ฐC in an air oven.
5.5.6 Phosphate stock solution (1.00 ml = 1.00 mg P043"). Dissolve
1.4330 g of potassium dihydrogen phosphate (KH2P04) in reagent water, and
dilute to 1 L with reagent water. Dry sodium sulfate (Na2S04) for 1 hour
at 105ฐC and cool in a desiccator.
5.5.7 Sulfate stock solution (1.00 mL = 1.00 mg S042"). Dissolve
1.4790 g of the dried salt in reagent water, and dilute to 1 L with
reagent water.
5.6 Anion working solutions. Prepare a blank and at least three
different working solutions containing the following combinations of anions. The
combination anion solutions must be prepared in Class A volumetric flasks. See
Table 2.
5.6.1 Prepare a high-range standard solution by diluting the
volumes of each anion specified in Table 2 together to 1 L with reagent
water.
5.6.2 Prepare the intermediate-range standard solution by diluting
10.0 ml of the high-range standard solution (see Table 2) to 100 ml with
reagent water.
5.6.3 Prepare the low-range standard solution by diluting 20.0 ml
of the intermediate-range standard solution (see Table 2) to 100 ml with
reagent water.
5.7 Stability of standards. Stock standards are stable for at least 1
month when stored at 4ฐC. Dilute working standards should be prepared weekly,
except those that contain nitrite and phosphate, which should be prepared fresh
daily.
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.
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6.2 Analyze the samples as soon as possible after collection. Preserve
by refrigeration at 4ฐC.
7.0 PROCEDURE
7.1 Calibration
7.1.1 Establish ion chromatographic operating parameters
equivalent to those indicated in Table 1.
7.1.2 For each analyte of interest, prepare calibration standards
at a minimum of three concentration levels and a blank by adding
accurately measured volumes of one or more stock standards to a Class A
volumetric flask and diluting to volume with reagent water. If the
working range exceeds the linear range of the system, a sufficient number
of standards must be analyzed to allow an accurate calibration curve to be
established. One of the standards should be representative of a concen-
tration near, but above, the method detection limit if the system is
operated on an applicable attenuator range. The other standards should
correspond to the range of concentrations expected in the sample or should
define the working range of the detector. Unless the attenuator range
settings are proven to be linear, each setting must be calibrated
individually.
7.1.3 Using injections of 0.1 to 1.0 ml (determined by injection
loop volume) of each calibration standard, tabulate peak height or area
responses against the concentration. The results are used to prepare a
calibration curve for each analyte. During this procedure, retention
times must be recorded.
7.1.4 The working calibration curve must be verified on each
working day, or whenever the anion eluent strength is changed, and for
every batch of samples. If the response or retention time for any analyte
varies from the expected values by more than ฑ 10%, the test must be
repeated, using fresh calibration standards. If the results are still
more than + 10%, an entirely new calibration curve must be prepared for
that analyte.
7.1.5 Nonlinear response can result when the separator column
capacity is exceeded (overloading). Maximum column loading (all anions)
should not exceed about 400 ppm.
7.2 Analyses
7.2.1 Sample preparation. When aqueous samples are injected, the
water passes rapidly through the columns, and a negative "water dip" is
observed that may interfere with the early-eluting fluoride and/or
chloride ions. The water dip should not be observed in the combustate
samples; the collecting solution is a concentrated eluent solution that
will "match" the eluent strength when diluted to 100-mL with reagent water
according to the bomb combustion procedure. Any dilutions required in
analyzing other water samples should be made with the eluent solution.
The water dip, if present, may be removed by adding concentrated eluent to
9056 - 5 Revision 0
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all samples and standards. When a manual system is used, it is necessary
to micropipet concentrated buffer into each sample. The recommended
procedures follow:
(1) Prepare a 100-mL stock of eluent 100 times normal concentration by
dissolving 2.5202 g NaHC03 and 2.5438 g Na2C03 in 100-mL reagent
water. Protect the volumetric flask from air.
(2) Pipet 5 ml of each sample into a clean polystyrene micro-beaker.
Micropipet 50 /xL of the concentrated buffer into the beaker and stir
well.
Dilute the samples with eluent, if necessary, to concentrations within the
linear range of the calibration.
7.2.2 Sample analysis.
7.2.2.1 Start the flow of regenerant through the
suppressor column.
7.2.2.2 Set up the recorder range for maximum sensitivity
and any additional ranges needed.
7.2.2.3 Begin to pump the eluent through the columns.
After a stable baseline is obtained, inject a midrange standard. If
the peak height deviates by more than 10% from that of the previous
run, prepare fresh standards.
7.2.2.4 Begin to inject standards starting with the
highest concentration standard and decreasing in concentration. The
first sample should be a quality control reference sample to check
the calibration.
7.2.2.5 Using the procedures described in Step 7.2.1,
calculate the regression parameters for the initial standard curve.
Compare these values with those obtained in the past. If they
exceed the control limits, stop the analysis and look for the
problem.
7.2.2.6 Inject a quality control reference sample. A
spiked sample or a sample of known content must be analyzed with
each batch of samples. Calculate the concentration from the
calibration curve and compare the known value. If the control
limits are exceeded, stop the analysis until the problem is found.
Recalibration is necessary.
7.2.2.7 When an acceptable value has been obtained for
the quality control sample, begin to inject the samples.
7.2.2.8 Load and inject a fixed amount of well-mixed
sample. Flush injection loop thoroughly, using each new sample.
Use the same size loop for standards and samples. Record the
9056 - 6 Revision 0
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resulting peak size in area or peak height units. An automated
constant volume injection system may also be used.
7.2.2.9 The width of the retention time window used to
make identifications should be based on measurements of actual
retention time variations of standards over the course of a day.
Three times the standard deviation of a retention time can be used
to calculate a suggested window size for a compound. However, the
experience of the analyst should weigh heavily in the interpretation
of chromatograms.
7.2.2.10 If the response for the peak exceeds the working
range of the system, dilute the sample with an appropriate amount of
reagent water and reanalyze.
7.2.2.11 If the resulting chromatogram fails to produce
adequate resolution, or if identification of specific anions is
questionable, spike the sample with an appropriate amount of
standard and reanalyze.
NOTE: Nitrate and sulfate exhibit the greatest amount of change,
although all anions are affected to some degree. In some cases,
this peak migration can produce poor resolution or
misidentification.
7.3 Calculation
7.3.1 Prepare separate calibration curves for each anion of
interest by plotting peak size in area, or peak height units of standards
against concentration values. Compute sample concentration by comparing
sample peak response with the standard curve.
7.3.2 Enter the calibration standard concentrations and peak
heights from the integrator or recorder into a calculator with linear
least squares capabilities.
7.3.3 Calculate the following parameters: slope (s), intercept
(I), and correlation coefficient (r). The slope and intercept define a
relationship between the concentration and instrument response of the
form:
(1)
where:
yi = predicted instrument response
$i = response slope
Xj = concentration of standard i
I = intercept
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Rearrangement of the above equation yields the concentration corresponding
to an instrumental measurement:
x, = (y, - I)/s, (2)
where:
Xj = calculated concentration for a sample
yj = actual instrument response for a sample
Sj and I are calculated slope and intercept from calibration above.
7.3.4 Enter the sample peak height into the calculator, and
calculate the sample concentration in milligrams per liter.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference and inspection. Refer to Chapter One for additional quality control
guidelines.
8.2 After every 10 injections, analyze a midrange calibration standard.
If the instrument response has changed by more than 5%, recalibrate.
8.3 Analyze one in every ten samples in duplicate. Take the duplicate
sample through the entire sample preparation and analytical process.
8.4 A matrix spiked sample should be run for each analytical batch or
twenty samples, whatever is more frequent, to determine matrix effects.
9.0 METHOD PERFORMANCE
9.1 Single-operator accuracy and precision for reagent, drinking and
surface water, and mixed domestic and industrial wastewater are listed in Table
3.
9.2 Combustate samples. These data are based on 41 data points obtained
by six laboratories who each analyzed four used crankcase oils and three fuel oil
blends with crankcase in duplicate. The oil samples were combusted using Method
5050. A data point represents one duplicate analysis of a sample. One data
point was judged to be an outlier and was not included in the results.
9.2.1 Precision. The precision of the method as determined by the
statistical examination of interlaboratory test results is as follows:
Repeatability - The difference between successive results obtained
by the sample operator with the same apparatus under constant operating
conditions on identical test material would exceed, in the long run, in
the normal and correct operation of the test method, the following values
only in 1 case in 20 (see Table 4):
*where x is the average of two results in /ng/g.
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Repeatability =20.9
Reproduclbilitv - The difference between two single and independent
results obtained by different operators working in different laboratories
on identical test material would exceed, in the long run, the following
values only in 1 case in 20:
Reproducibility =42.1
*where x is the average value of two results in M9/9-
9.2.2 Bias. The bias of this method varies with concentration,
as shown in Table 5:
Bias = Amount found - Amount expected
10.0 REFERENCES
1. Environmental Protection Agency. Test Method for the Determination of
Inorganic Anions in Water by Ion Chromatography. EPA Method 300.0. EPA-600/4-
84-017. 1984.
2. Annual Book of ASTM Standards, Volume 11.01 Water D4327, Standard Test
Method for Anions in Water by Ion Chromatography, pp. 696-703. 1988.
3. Standard Methods for the Examination of Water and Wastewater, Method 429,
"Determination of Anions by Ion Chromatography with Conductivity Measurement,"
16th Edition of Standard Methods.
4. Dionex, 1C 16 Operation and Maintenance Manual, PN 30579, Dionex Corp.,
Sunnyvale, CA 94086.
5. Method detection limit (MDL) as described in "Trace Analyses for
Wastewater," J. Glaser, D. Foerst, G. McKee, S. Quave, W. Budde, Environmental
Science and Technology, Vol. 15, Number 12, p. 1426, December 1981.
6. 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. 68-
01-7075, WA 80. July 1988.
9056 - 9 Revision 0
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TABLE 1.
CHROMATOGRAPHIC CONDITIONS AND METHOD DETECTION
LIMITS IN REAGENT WATER
Analyte
Fluoride
Chlorine
Nitrite-N
o-Phosphate-P
Nitrate-N
Sul fate
Retention8
time
min
1.2
3.4
4.5
9.0
11.3
21.4
Relative
retention
time
1.0
2.8
3.8
7.5
9.4
17.8
Method"
detection limit,
mg/L
0.005
0.015
0.004
0.061
0.013
0.206
Standard conditions:
Columns - As specified in 4.1.1-4.1.3
Detector - As specified in 4.1.4
Eluent - As specified in 5.3
Concentrations of mixed standard (mg/L)
Fluoride 3.0
Chloride 4.0
Nitrite-N 10.0
Sample loop - 100 juL
Pump volume - 2.30 mL/min
o-Phosphate-P 9.0
Nitrate-N 30.0
Sulfate 50.0
aThe retention time given for each anion is based on the equipment and analytical
conditions described in the method. Use of other analytical columns or different
elutant concentrations will effect retention times accordingly.
bMDL calculated from data obtained using an attentuator setting of l-/umho/cm full
scale. Other settings would produce an MDL proportional to their value.
9056 - 10
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TABLE 2.
PREPARATION OF STANDARD SOLUTIONS FOR INSTRUMENT CALIBRATION
High
Range
Standard1
Fluoride (F")
Chloride (CV)
Nitrite (N02")
Phosphate (P043')
Bromide (Br)
Nitrate (N(V)
Sulfate (S042-)
10
10
20
50
10
30
100
An ion
concentration
mg/L
10
10
20
50
10
30
100
Intermediate-
range standard,
mg/L
(see 5.6.2)
1.0
1.0
2.0
5.0
1.0
3.0
10.0
Low-range
standard,
mg/L (see
5.6.3)
0.2
0.2
0.4
1.0
0.2
0.6
2.0
1Milliliters of each stock solution (1.00 mL = 1.00 mg) diluted to 1 L (see sec.
5.6.1).
9056 - 11 Revision 0
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TABLE 3.
SINGLE-OPERATOR ACCURACY AND PRECISION
Samp] e
Analyte type
Chloride
Fluoride
Nitrate-N
Nitrite-N
o-Phosphate-P
Sulfate
RW
DW
SW
WW
RW
DW
SW
WW
RW
DW
SW
WW
RW
DW
SW
WW
RW
DE
SW
WW
RW
DW
SW
WW
Spike
mg/L
0.050
10.0
1.0
7.5
0.24
9.3
0.50
1.0
0.10
31.0
0.50
4.0
0.10
19.6
0.51
0.52
0.50
45.7
0.51
4.0
1.02
98.5
10.0
12.5
Number
of
replicates
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
7
Mean
recovery,
%
97.7
98.2
105.0
82.7
103.1
87.7
74.0
92.0
100.9
100.7
100.0
94.3
97.7
103.3
88.2
100.0
100.4
102.5
94.1
97.3
102.1
104.3
111.6
134.9
Standard
deviation,
mg/L
0.0047
0.289
0.139
0.445
0.0009
0.075
0.0038
0.011
0.0041
0.356
0.0058
0.058
0.0014
0.150
0.0053
0.018
0.019
0.386
0.020
0.04
0.066
1.475
0.709
0.466
RW = Reagent water.
DW = Drinking water.
SW = Surface water.
WW = Wastewater.
9056 - 12
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TABLE 4.
REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN
USED OILS BY BOMB OXIDATION AND ION CHROMATOGRAPHY
Average value, ' Repeatability, Reproducibility,
M9/9 M9/9 M9/9
500
1,000
1,500
2,000
2,500
3,000
467
661
809
935
1,045
1,145
941
1,331
1,631
1,883
2,105
2,306
TABLE 5.
RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY
BOMB OXIDATION AND ION CHROMATOGRAPHY
Amount
Expected
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found
M9/9
567
773
1,050
1,694
1,772
3,026
2,745
Bias,
M9/9
247
293
130
196
245
-3
-300
Percent,
bias
+77
+61
+14
+13
+16
0
-10
9056 - 13 Revision 0
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FIGURE 1
SCHEMATIC OF ION CHROMATOGRAPH
WASTE
(1) Eluent reservoir
(2) Pump
(3) Precolumn
(4) Separator column
(5) Suppressor column
(6) Detector
(7) Recorder or Integrator, or both
9056 - 14
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September 1994
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FIGURE 2
TYPICAL ANION PROFILE
so;1
MINUTES
9056 - 15
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September 1994
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( Start J
METHOD 9056
DETERMINATION OF INORGANIC ANIONS BY ION CHROMATOGRAPHY
1
7.1.1 Establish ion
chromatographic
operating
parameters.
1
7.1 .2 Prepare
calibration
standards at a
minimum of three
concentration
levels and a blank.
\r
7.1 .3 Prepare
calibration curve.
V
7.1.4 Verify the
calibration curves
each working day or
whenever the anion
eluent is changed,
and for every batch
of samples.
/ ^\^ 7.2.1 If a dilution
/ 7.2.1 Are\ Aqueous is necessary the
/samples aqueousSj w, dilution should
\ <" extracts?/ w bซ madซ witn
N. / eluent solution.
[Extracts
7.2.2 Analyze
standards beginning
with the highest
concentration and
decreasing in
concentration.
1
7.2.1 Add
concentrated
4 ซli|ซnt tn qll
samples and
standards to
remove water dip.
w
W
7.2.2.5 Compare
results to
calibration curve;
if results exceed
control limits,
identify problem
before proceeding.
\1
7.2.2.6 Inject a
spiked sample of
known cone.;
calculate the cone.
from the calibration
curve; if result
exceeds control
limits, find problem
before proceeding.
> f
7.2.2.7 Begin
sample analysis.
\r
7.2.2.8 Analyze all
samples in same
manner.
^r
./7.2.2.10\
./Does responseV
f for peak exceed
>^ working /
\^ range? /
TNO
Y
7.3.1 Prepare
sample calibration
curves for each
anion of interest
and compute sample
concentration.
^
7.2.2.10 Dilute
! ^ sample with
reagent water.
7.3.3 Calculate
w concentrations
f from instrumental
response.
4
( Stop J
9056 - 16
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METHOD 9060
TOTAL ORGANIC CARBON
1.0 SCOPE AND APPLICATION
1.1 Method 9060 1s used to determine the concentration of organic carbon
1n ground water, surface and saline waters, and domestic and Industrial
wastes. Some restrictions are noted 1n Sections 2.0 and 3.0.
1.2 Method 9060 1s most applicable to measurement of organic carbon
above 1 mg/L.
2.0 SUMMARY OF METHOD
2.1 Organic carbon 1s measured using a carbonaceous analyzer. This
Instrument converts the organic carbon 1n a sample to carbon dioxide (C02) by
either catalytic combustion or wet chemical oxidation. The C02 formed 1s then
either measured directly by an Infrared detector or converted to methane (CH4)
and measured by a flame 1on1zat1on detector. The amount of C02 or CH4 In a
sample 1s directly proportional to the concentration of carbonaceous material
1n the sample.
2.2 Carbonaceous analyzers are capable of measuring all forms of carbon
1n a sample. However, because of various properties of carbon-containing
compounds 1n liquid samples, the manner of preliminary sample treatment as
well as the Instrument settings will determine which forms of carbon are
actually measured. The forms of carbon that can be measured by Method 9060
are:
1. Soluble, nonvolatile organic carbon: e.g., natural sugars.
2. Soluble, volatile organic carbon: e.g., mercaptans, alkanes, low
molecular weight alcohols.
3. Insoluble, partially volatile carbon: e.g., low molecular weight
oils.
4. Insoluble, particulate carbonaceous materials: e.g., cellulose
fibers.
5. Soluble or Insoluble carbonaceous materials adsorbed or entrapped
on Insoluble Inorganic suspended matter: e.g., oily matter adsorbed
on silt particles.
2.3 Carbonate and bicarbonate are Inorganic forms of carbon and must be
separated from the total organic carbon value. Depending on the Instrument
manufacturer's Instructions, this separation can be accomplished by either a
simple mathematical subtraction, or by removing the carbonate and bicarbonate
by converting them to C02 with degassing prior to analysis.
9060 - 1
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3.0 INTERFERENCES
3.1 Carbonate and bicarbonate carbon represent an Interference under the
terms of this test and must be removed or accounted for 1n the final calcula-
tion.
3.2 This procedure 1s applicable only to homogeneous samples which can
be Injected Into the apparatus reprodudbly by means of a m1crol1ter-type
syringe or plpet. The openings of the syringe or plpet limit the maximum size
of particle which may be Included 1n the sample.
3.3 Removal of carbonate and bicarbonate by acidification and purging
with nitrogen, or other Inert gas, can result 1n the loss of volatile organic
substances.
4.0 APPARATUS AND MATERIALS
4.1 Apparatus for blending or homogenizing samples; Generally, a
War1 ng-type blender Is satisfactory.
4.2 Apparatus for total and dissolved organic carbon;
4.2.1 Several companies manufacture analyzers for measuring
carbonaceous material In liquid samples. The most appropriate system
should be selected based on consideration of the types of samples to be
analyzed, the expected concentration range, and the forms of carbon to be
measured.
4.2.2 No specific analyzer 1s recommended as superior. If the
technique of chemical oxidation 1s used, the laboratory must be certain
that the Instrument Is capable of achieving good carbon recoveries In
samples containing parti culates.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193); Water should be monitored for
Impurities, and should be boiled and cooled to remove
5.2 Potassium hydrogen phthalate, stock solution, 1,000 mg/L carbon:
Dissolve 0.2128 g of potassium hydrogen phthalate (primary standard grade) 1n
Type II water and dilute to 100.0 ml.
NOTE; Sodium oxalate and acetic add are not recommended as stock
solutions.
5.3 Potassium hydrogen phthalate, standard solutions; Prepare standard
solutions from the stock solution by dilution with Type II water.
9060 - 2
Revision
Date September 1986
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5.4 Carbonate-bicarbonate, stock solution, 1,000 mg/L carbon: Weigh
0.3500 g of sodium bicarbonate and0.4418g of sodium carbonate and transfer
both to the same 100-mL volumetric flask. Dissolve with Type II water.
5.5 Carbonate-bicarbonate, standard solution; Prepare a series of
standards similar to Step 5.3.
NOTE; This standard 1s not required by some Instruments.
5.6 Blank solution; Use the same Type II water as was used to prepare
the standard solutions.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must be collected using a sampling plan that addresses
the considerations discussed 1n Chapter Nine of this manual.
6.2 Sampling and storage of samples 1n glass bottles 1s preferable.
Sampling and storage 1n plastic bottles such as conventional polyethylene and
cubital ners 1s permissible 1f 1t 1s established that the containers do not
contribute contaminating organlcs to the samples.
NOTE; A brief study performed 1n the EPA Laboratory Indicated that Type
II water stored 1n new, 1-qt cubital ners did not show any Increase
1n organic carbon after 2 weeks' exposure.
6.3 Because of the possibility of oxidation or bacterial decomposition
of some components of aqueous samples, the time between sample collection and
the start of analysis should be minimized. Also, samples should be kept cool
(4*C) and protected from sunlight and atmospheric oxygen.
6.4 In Instances where analysis cannot be performed within 2 hr from
time of sampling, the sample 1s acidified (pH ฃ 2) with HC1 or
7.0 PROCEDURE
7.1 Homogenize the sample 1n a blender.
NOTE; To avoid erroneously high results, Inorganic carbon must be
accounted for. The preferred method 1s to measure total carbon and
Inorganic carbon and to obtain the organic carbon by subtraction.
If this 1s not possible, follow Steps 7.2 and 7.3 prior to analysis;
however, volatile organic carbon may be lost.
7.2 Lower the pH of the sample to 2.
7.3 Purge the sample with nitrogen for 10 m1n.
7.4 Follow Instrument manufacturer's Instructions for calibration,
procedure, and calculations.
7.5 For calibration of the Instrument, a series of standards should be
used that encompasses the expected concentration range of the samples.
9060 - 3
Revision 0
Date September 1986
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7.6 Quadruplicate analysis 1s required. Report both the average and the
range.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Employ a minimum of one blank per sample batch to determine 1f
contamination or any memory effects are occurring.
8.3 Verify calibration with an Independently prepared check standard
every 15 samples.
8.4 Run one spike duplicate sample for every 10 samples. A duplicate
sample Is a sample brought through the whole sample preparation and analytical
process.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 415.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Annual Book of ASTM Standards, Part 31, "Water," Standard D 2574-79,
p. 469 (L976).
2. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
p. 532, Method 505 (1975).
9060 - 4
Revision
Date September 1986
-------
METHOD 9060
TOTAL ORGANIC CARBON
(
5"rt
o
7.1
Homogenize
the ample in
e blender
7.2
Follow manufacturer's
Instructions for
cal Ibretlon.
procedure, ana
calculatlonc using
carbonaceous analyzer
Lower the
ample PH
7.3
7.5
Use series of
standards for
calibration
Purge the
ample with
nitrogen
7.6
Ouadruplicate
analysis
O
f Stop j
9060 - 5
Revision 0
Date September 1986
-------
METHOD 9065
PHENOLICS (SPECTROPHOTOMETRIC. MANUAL 4-AAP WITH DISTILLATION)
1.0 SCOPE AND APPLICATION
1.1 This method 1s applicable to the analysis of ground water, drinking,
surface, and saline waters, and domestic and Industrial wastes.
1.2 The method 1s capable of measuring phenolic materials at the 5 ug/L
level when the colored end product 1s extracted and concentrated 1n a solvent
phase using phenol as a standard.
1.3 The method 1s capable of measuring phenolic materials that contain
more than 50 ug/L 1n the aqueous phase (without solvent extraction) using
phenol as a standard.
1.4 It 1s not possible to use this method to differentiate between
different kinds of phenols.
2.0 SUMMARY OF METHOD
2.1 Phenolic materials react with 4-am1noant1pyr1ne 1n the presence of
potassium ferrlcyanide at a pH of 10 to form a stable reddish-brown antlpyrlne
dye. The amount of color produced 1s a function of the concentration of
phenolic material.
3.0 INTERFERENCES
3.1 For most samples a preliminary distillation 1s required to remove
Interfering materials.
3.2 Color response of phenolic materials with 4-am1noant1pyr1ne Is not
the same for all compounds. Because phenolic-type wastes usually contain a
variety of phenols, 1t 1s not possible to duplicate a mixture of phenols to be
used as a standard. For this reason phenol has been selected as a standard
and any color produced by the reaction of other phenolic compounds 1s reported
as phenol. This value will represent the minimum concentration of phenolic
compounds present 1n the sample.
3.3 Interferences from sulfur compounds are eliminated by acidifying the
sample to a pH of <4 with H2S04 and aerating briefly by stirring.
3.4 Oxidizing agents such as chlorine, detected by the liberation of
Iodine upon acidification 1n the presence of potassium Iodide, are removed
Immediately after sampling by the addition of an excess of ferrous ammonium
sulfate. If chlorine 1s not removed, the phenolic compounds may be partially
oxidized and the results may be low.
9065 - 1
Revision
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Distillation apparatus; All glass, consisting of a 1-liter Pyrex
distilling apparatus with Graham condenser.
4.2 pH meter.
4.3 Spectrophotometer; For use at 460 or 510 nm.
4.4 Funnels.
4.5 Filter paper.
4.6 Membrane filters.
4.7 Separatory funnels; 500- or 1,000-mL.
4.8 Nessler tubes; Short or long form.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Sulfurlc add solution. ^504; Concentrated.
5.3 Buffer solution; Dissolve 16.9 g NfyCl 1n 143 ml concentrated NfyOH
and dilute to 250 ml with Type II water. Two ml of buffer should adjust
100 ml of distillate to pH 10.
5.4 Am1noant1pyr1ne solution; Dissolve 2 g of 4-am1noant1pyr1ne (4-AAP)
In Type II water and dilute to 100 ml.
5.5 Potassium ferrlcyanlde solution; Dissolve 8 g of K3Fe(CN)s 1n Type
II water and dilute to 100 ml.
5.6 Stock phenol .solution; Dissolve 1.0 g phenol 1n freshly boiled and
cooled Type II water and dilute to 1 liter (1 ml 1 ng phenol).
NOTE; This solution Is hydroscoplc and toxic.
5.7 Working solution A; Dilute 10 ml stock phenol solution to 1 liter
with Type II water (1 ml = 10 ug phenol).
5.8 Working solution B; Dilute 100 ml of working solution A to 1,000 ml
with Type II water (1 ml = 1 ug phenol).
5.9 Chloroform.
9065 - 2
Revision
Date September 1986
-------
5.10 Ferrous ammonium sulfate; Dissolve 1.1 g 1n 500 ml Type II water
containing 1 mL concentrated H2S04 and dilute to 1 liter with freshly boiled
and cooled Type II 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 1n Chapter Nine of this manual.
6.2 Biological degradation 1s Inhibited by the addition of 1^04 to
pH <4. Store at 4*C. The sample should be stable for 28 days.
7.0 PROCEDURE
7.1 Distillation;
7.1.1 Measure 500 ml of sample Into a beaker. Lower the pH to
approximately 4 with concentrated ^$04 (1 mL/L), and transfer to the
distillation apparatus.
7.1.2 Distill 450 mL of sample, stop the distillation, and when
boiling ceases, add 50 mL of warm Type II water to the flask and resume
distillation until 500 mL have been collected.
7.1.3 If the distillate 1s turbid, filter through a prewashed
membrane filter.
7.2 Direct photometric method;
7.2.1 Using working solution A (5.6), prepare the following
standards 1n 100-mL volumetric flasks:
Working Solution A (mL) Concentration (ug/L)
0.0 0.0
0.5 50.0
1.0 100.0
2.0 200.0
5.0 500.0
8.0 800.0
10.0 1000.0
7.2.2 To 100 mL of distillate or to an aliquot diluted to 100 mL
and/or standards, add 2 mL of buffer solution (5.2) and mix. The pH of
the sample and standards should be 10 + 0.2.
7.2.3 Add 2.0 mL am1noant1pyr1ne solution (5.3) and mix.
7.2.4 Add 2.0 mL potassium ferr1 cyanide solution (5.4) and mix.
7.2.5 After 15 m1n read absorbance at 510 nm.
9065 - 3
Revision 0
Date September 1986
-------
7.3 Chloroform extraction method:
CAUTION:This method should be performed 1n a hood; chloroform
1s toxic.
7.3.1 Using working solution B (5.7), prepare the following
standards. Standards may be prepared by pipetting the required volumes
Into the separatory funnels and diluting to 500 ml with Type II water:
Working Solution B (ml) Concentration (uq/L)
0.0 0.0
3.0 6.0
5.0 10.0
10.0 20.0
20.0 40.0
25.0 50.0
7.3.2 Place 500 ml of distillate or an aliquot diluted to 500 ml In
a separatory funnel. The sample should not contain more than 50 ug/L
phenol.
7.3.3 To sample and standards add 10 ml of buffer solution (5.2)
and mix. The pH should be 10 + 0.2.
7.3.4 Add 3.0 ml am1noant1pyr1ne solution (5.3) and mix.
7.3.5 Add 3.0 ml potassium ferr1cyanide solution (5.4) and mix.
7.3.6 After 3 mln, extract with 25 ml of chloroform (5.9). Shake
the separatory funnel at least 10 times, let CHC13 settle, shake again 10
times, and let chloroform settle again.
7.3.7 Filter chloroform extract through filter paper. Do not add
more chloroform.
7.3.8 Read the absorbance of the samples and standards against the
blank at 460 nm.
7.4 Calculation;
7.4.1 Prepare a standard curve by plotting the absorbance values of
standards versus the corresponding phenol concentrations.
7.4.2 Obtain concentration value of sample directly from standard
curve.
9065 - 4
Revision
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples 1f they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine 1f
contamination has occurred.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
9.0 METHOD PERFORMANCE
9.1 In a single laboratory using sewage samples at concentrations of
3.8, 15, 43, and and 89 ug/L, the standard deviations were +0.5, +0.6, +0.6,
and +1.0 ug/L, respectively. At concentrations of 73, 146, 299, anH 447 ug/L,
the standard deviations were +1.0, +1.8, +4.2, and +5.3 ug/L, respectively.
9.2 In a single laboratory using sewage samples at concentrations of 5.3
and 82 ug/L, the recoveries were 78% and 98%,respectively. At concentrations
of 168 and 489 ug/L, the recoveries were 97% and 98%, respectively.
10.0 REFERENCES
1. Annual Book of ASTM Standards, Part 31, "Water," Standard D1783-70,
p. 553 (1976).
2. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
pp. 574-581, Method 510 through 510C (1975).
9065 - 5
Revision
Date September 1986
-------
METHOD 9065
PHENOLICS (SPECTROPHOTOMETRIC. MANUAL 4-AAP KITH DISTILLATION)
C
o
7.1.1
Measure
' sample
Into beaker;
lower pH wltn
concentrated
7.1.2|
Olซtlll cample
! distillate
turbid?
Add buffer
solution; Din
7.3.3
Add
amlnoantpyrlna
solution
7.2.4
Add potassium
ferrlcyanlda
solution:
7.a.g[
Read abaorbanca
7.3.1
Prepare
standards
using working
solution 8
0
9065 - 6
Revision 0
Date September 1986
-------
METHOD 906S
PHENOLICS (SPECTROPHOTOMETRIC. MANUAL 4-AAP WITH DISTILLATION)
(Continued)
o
7.3.8
1 Place
distillate or
dilutea aliquot
In separatory
funnel
7.3.3)
Add
buffer solution
to cample and
standards: mix
7.3.4
Add
aminoantipyrlne
solution; mix
7.3.5
Add potassium
ferricyanide
solution: mix
0
O
7.3.6
Extract with
chloroform
7.3.7
Filter
chloroform
xtracts
7.3.8|
Read absorbance
7.4
Calculate
concentration
value of sample
f Stop J
9065 - 7
Revision 0
Date September 1986
-------
METHOD 9066
PHENOLICS (COLORIMETRIC. AUTOMATED 4-AAP WITH DISTILLATION)
f.
1.0 SCOPE AND ALLIGATION
1.1 This method 1s applicable to the analysis of ground water and of
drinking, surface, and saline waters.
1.2 The method 1s capable of measuring phenolic materials from 2 to
500 ug/L 1n the aqueous phase using phenol as a standard.
2.0 SUMMARY OF METHOD
2.1 This automated method 1s based on the distillation of phenol and
subsequent reaction of the distillate with alkaline ferrlcyanide (K3Fe(CN)6)
and 4-am1no-ant1pyr1ne (4-AAP) to form a red complex which 1s measured at 505
or 520 nm.
3.0 INTERFERENCES
3.1 Interferences from sulfur compounds are eliminated by acidifying the
sample to a pH of <4.0 with H2S04 and aerating briefly by stirring.
3.2 Oxidizing agents such as chlorine, detected by the liberation of
Iodine upon acidification 1n the presence of potassium Iodide, are removed
Immediately after sampling by the addition of an excess of ferrous ammonium
sulfate (5.5). If chlorine 1s not removed, the phenolic compounds may be
partially oxidized and the results may be low.
3.3 Background contamination from plastic tubing and sample containers
1s eliminated by filling the wash receptacle by siphon (using Kel-F tubing)
and using glass tubes for the samples and standards.
4.0 APPARATUS AND MATERIALS
4.1 Automated continuous-flow analytical Instrument;
4.1.1 Sampler: Equipped with continuous mixer.
4.1.2 Manifold.
4.1.3 Proportioning pump II or III.
4.1.4 Heating bath with distillation coll.
4.1.5 Distillation head.
9066 - 1
Revision
Date September 1986
-------
4.1.6 Colorimeter: Equipped with a 50 mm flowcell and 505 or
520 nm filter.
4.1.7 Recorder.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Distillation reagent; Add 100 ml of concentrated phosphoric add
(85% H3P04) to 800 ml of Type II water, cool and dilute to 1 liter.
5.3 Buffered potassium ferrlcyanlde; Dissolve 2.0 g potassium
ferrlcyanide, 3.1 g boric add, and 3.75 g potassium chloride 1n 800 ml of
Type II water. Adjust to pH of 10.3 with IN sodium hydroxide (5.3) and
dilute to 1 liter. Add 0.5 ml of Brlj-35 (available from Technlcon).
(Br1j-35 1s a wetting agent and 1s a proprietary Technlcon product.) Prepare
fresh weekly.
5.4 Sodium hydroxide (1 N): Dissolve 40 g NaOH 1n 500 ml of Type II
water, cool and dilute to 1 liter.
5.5 4-Am1noant1pyr1ne; Dissolve 0.65 g of 4-am1noant1pyr1ne 1n 800 mL
of Type II water and dilute to 1 liter. Prepare fresh each day.
5.6 Ferrous ammonium sulfate; Dissolve 1.1 g ferrous ammonium sulfate
In 500 ml Type IIwatercontaining 1 ml ^$04 and dilute to 1 liter with
freshly boiled and cooled Type II water.
5.7 Stock phenol; Dissolve 1.00 g phenol 1n 500 mL of Type II water and
dilute to 1,000 ml. Add 0.5 mL concentrated ^$04 as preservative (1.0 mL =
1.0 mg phenol).
CAUTION: This solution Is toxic.
5.8 Standard phenol solution A; Dilute 10.0 mL of stock phenol solution
(5.6) to 1,000 mL (1.0 mL - 0.01 mg phenol).
5.9 Standard phenol solution B; Dilute 100.0 mL of standard phenol
solution A (5.8) to 1,000 mL with Type II water (1.0 mL = 0.001 mg phenol).
5.10 Standard phenol solution C; Dilute 100.0 mL of standard phenol
solution B (5.9) to 1,000 mL with Type II water (1.0 mL = 0.0001 mg phenol).
5.11 Using standard solution A, B, or C, prepare the following standards
1n 100-mL volumetric flasks. Each standard should be preserved by adding 2
drops of concentrated HgSCty to 100.0 mL:
9066 - 2
Revision
Date September 1986
-------
Standard Solution (ml) Concentration (ug/L)
Solution C
1.0 1.0
2.0 2.0
3.0 3.0
5.0 5.0
Solution B
1.0 10.0
2.0 20.0
5.0 50.0
10.0 100.0
Solution A
2.0 200.0
3.0 300.0
5.0 500.0
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.
6.2 Biological degradation 1s Inhibited by the acidification to a pH <4
with H2$04. The sample should be kept at 4*C and analyzed within 28 days of
collection.
7.0 PROCEDURE
7.1 Set up the manifold as shown In Figure 1.
7.2 Fill the wash receptacle by siphon. Use Kel-F tubing with a fast
flow (1 I1ter/hr).
7.3 Allow colorimeter and recorder to warm up for 30 m1n. Run a
baseline with all reagents, feeding Type II water through the sample line.
Use polyethylene tubing for sample line. When new tubing Is used, about 2 hr
may be required to obtain a stable baseline. This 2-hr time period may be
necessary to remove the residual phenol from the tubing.
7.4 Place appropriate phenol standards 1n sampler 1n order of decreasing
concentration. Complete loading of sampler tray with unknown samples, using
glass tubes. If samples have not been preserved as Instructed 1n Paragraph
6.2, add concentrated ^04 to 100 ml of sample. Run with sensitivity setting
at full scale or 500.
9066 - 3
Revision
Date September 1986
-------
To Waste
* N ป
I
e*
n
<
oo o
fO 3
ft)
00
Ml/min
SAMPLER
x^
RESAMPLE
| QQfflL -
f S.M.
BATH WITH
riON COIL
N
1
\
157-8089
nnnn
i
1
(
t
ป-
r
5O5uซn filters
50 mm Tubular f/c
b
pi
Jf
4T
^
IO H
BLACK ^ RACK
G ^ G
0 ^ O
O _ O
GRAY ^ GRAY
BLACK ^ BLACK
Y < r
0 ^ W
0 _ W
GRAY ^ GRAY
0.32 AIR
2.00 SAMPLE
0.42 DISTILLING SOL.
O.42 WASTE FROM
STILL
1.0 RESAMPLE WASTE
O.32 AIR
1.2 RESAMPLE
O.23 4 AAP
r
A-2
O 23 BUFFERED POTASSIUM
FERRI CYANIDE
J.O WASTE FROM F/C
PROPORTIONING
PUMP
SAMPLE RATE 2O/hr. 1:2
* Kซi-r
ซ 100 ACIOFLEX
ป POLYETHYLENE
COLORIMETER RECORDER
Figure 1. Phenol Autoanalyzer II
-------
7.5 Switch sample from Type II water to sampler and begin analysis.
7.6 Calculation;
7.6.1 Prepare a linear standard curve by plotting peak heights of
standards against concentration values. Compute concentration of samples
by comparing sample peak heights with standards.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for
easy reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples 1f they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine If
contamination has occurred.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
9.0 METHOD PERFORMANCE
9.1 In a single laboratory using sewage samples at concentrations of
3.8, 15, 43, and 89 ug/L, the standard deviations were +0.5, +0.6, +0.6, and
+1.0 ug/L, respectively. At concentrations of 73, 146, 2997 and 447 ug/L,
the standard deviations were +1.0, +1.8, +4.2, and +5.3 ug/L, respectively.
9.2 In a single laboratory using sewage samples at concentrations of 5.3
and 82 ug/L, the recoveries were 78% and 98%, respectively. At concentrations
of 168 and 489 ug/L, the recoveries were 97% and 98%, respectively.
9066 - 5
Revision
Date September 1986
-------
10.0 REFERENCES
1. Gales, M.E. and R.L. Booth, "Automated 4AAP Phenolic Method," AWWA 68,
540 (1976).
2. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
p. 574, Method 510, (1975).
3. Technlcon AutoAnalyzer II Methodology, Industrial Method No.l27-71W,
AA II.
9066 - 6
Revision
Date September 1986
-------
METHOD 9066
PHENOLICS (COLORIMETRXC. AUTOMATED 4-AAP WITH DISTILLATION)
C
7.1 I
Set up manifold
7.2
Fill wash
receptacla
7.3
warm up
colorimeter end
recorder
7.3 J
Run e beeellne
Q
O
7.4
Lead phenol
tenderdc end
unknown aamp1e
7.5
Switch eenple
to ampler:
analyze
7.6
Compute
eoncentratIon
of sample*
f stop j
7.4
Add cone.
9066 - 7
Revision 0
Date September 1986
-------
METHOD 9067
PHENOLICS (SPECTROPHOTOMETRIC. MBTH WITH DISTILLATION)
1.0 SCOPE AND APPLICATION
1.1 This method 1s applicable to the analysis of ground water, drinking,
surface, and saline waters, and .domestic and Industrial wastes.
1.2 The method 1s capable of measuring phenolic materials at the 2 ug/L
level when the colored end product 1s extracted and concentrated 1n a solvent
phase using phenol as a standard.
1.3 The method 1s capable of measuring phenolic materials that contain
from 50 to 1,000 ug/L 1n the aqueous phase (without solvent extraction) using
different kinds of phenols.
1.4 It Is not possible to use this method to differentiate between
different kinds of phenols.
2.0 SUMMARY OF METHOD
2.1 This method 1s based on the coupling of phenol with MBTH 1n an add
medium using eerie ammonium sulfate as an oxldant. The coupling takes place
1n the p-pos1t1on; 1f this position 1s occupied, the MBTH reagent will react
at a free opposition. The colors obtained have maximum absorbance from 460 to
595 nm. For phenol and most phenolic mixtures, the absorbance 1s 520 and
490 nm.
3.0 INTERFERENCES
3.1 For most samples a preliminary distillation 1s required to remove
Interfering materials.
3.2 Color response of phenolic materials with MBTH 1s not the same for
all compounds. Because phenol1c-type wastes usually contain a variety of
phenols, 1t 1s not possible to duplicate a mixture of phenols to be used as a
standard. For this reason, phenol has been selected as a standard and any
color produced by the reaction of other phenolic compounds 1s reported as
phenol. This value will represent the minimum concentration of phenolic
compounds present 1n the sample.
3.3 Interferences from sulfur compounds are eliminated by acidifying the
sample to a pH of less than 4.0 with H2S04 and aerating briefly by stirring.
3.4 Oxidizing agents such as chlorine, detected by the liberation of
Iodine upon acidification 1n the presence of potassium Iodide, are removed
Immediately after sampling by the addition of an excess of ferrous ammonium
9067 - 1
Revision 0
Date September 1986
-------
sulfate (see Paragraph 5.11). If chlorine 1s not removed, the phenolic
compounds may be partially oxidized and the results may be low.
3.5 Phosphate causes a precipitate to form; therefore, phosphoric add
should not be used for preservation. All glassware should be phosphate free.
3.5 High concentrations of aldehydes may cause Interferences.
4.0 APPARATUS AND MATERIALS
4.1 Distillation apparatus; All glass, consisting of a 1-Hter Pyrex
distilling apparatus with Graham condenser.
4.2 pH Meter.
4.3 Spectrophotometer.
4.4 Funnels.
4.5 Filter paper.
4.6 Membrane filters.
4.7 Separatory funnels.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Sulfurlc add. IN: Add 28 ml of concentrated H2S(>4 to 900 mL of
Type II water, mix, and dilute to 1 liter.
5.3 MBTH solution. 0.05%: Dissolve 0.1 g of 3-methyl-2-benzo-
thlazoHnone hydrazone hydrochlorlde 1n 200 ml of Type II water.
5.4 Cerlc ammonium sulfate solution; Add 2.0 g of
and 2.0 ml of concentrated ^$04 to 150 ml of Type
solid has dissolved, dilute to 200 ml with Type II water.
2H?0 and 2.0 ml of concentrated ^$04 to 150 ml of Type II water. After the
5.5 Buffer solution; Dissolve, 1n the following order: 8 g of sodium
hydroxide, 2 g EDTA (dlsodium salt), and 8 g boric add 1n 200 ml of Type II
water. Dilute to 250 ml with Type II water.
5.6 Working buffer solution; Make a working solution by mixing an
appropriate volume of buffer solution (5.5) with an equal volume of ethanol.
5.7 Chloroform.
9067 - 2
Revision
Date September 1986
-------
5.8 Stock phenol; Dissolve 1.00 g phenol 1n 500 ml of Type II water and
dilute to 1,000 ml. Add 1 g CuS04 and 0.5 ml concentrated H2S04 as
preservative (1.0 ml = 1.0 mg phenol).
5.9 Standard phenol solution A; Dilute 10.0 ml of stock phenol solution
(5.8) to 1,000 ml (1.0 ml = 0.01 mg phenol).
5.10 Standard phenol solution B: Dilute 100.0 ml of standard phenol
solution A (5.9) to 1,000 ml with Type II water (1.0 ml ซ= 0.001 mg phenol).
5.11 Ferrous ammonium sulfate; Dissolve 1.1 g ferrous ammonium sulfate
1n 500 ml Type II watercontaining 1 ml concentrated H2S04 and dilute to 1
liter with freshly sorted and cooled Type II 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 1n Chapter Nine of this manual.
6.2 Biological degradation 1s Inhibited by acidification to a pH of <4
with H2$04. The sample should be kept at 4*C and analyzed within 28 days of
collection.
7.0 PROCEDURE
7.1 Distillation;
7.1.1 To 500 ml of sample, adjust the pH to approximately 4 with
1 N sulfurlc add solution (5.2).
7.1.2 Distill over 450 mL of sample, add 50 mL of warm Type II
water to flask, and resume distillation until 500 mL has been collected.
7.1.3 If the distillate 1s turbid, f11ter through a prewashed
membrane filter.
7.2 Concentration above 50 ug/Li
7.2.1 To 100 mL of distillate or an aliquot diluted to 100 mL, add
4 mL of MBTH solution (5.3).
7.2.2 After 5 m1n, add 2.5 mL of eerie ammonium sulfate solution
(5.4).
7.2.3 Walt another 5 m1n and add 7 mL of working buffer solution
(5.6).
7.2.4 After 15 m1n, read the absorbance at 520 nm against a reagent
blank. The color 1s stable for 4 hr.
9067 - 3
Revision
Date September 1986
-------
7.3 Concentration below 50 ug/L;
7.3.1 To 500 ml of distillate 1n a separatory funnel, add 4 ml of
MBTH solution (5.3).
7.3.2 After 5 m1n, add 2.5 ml of eerie ammonium sulfate solution
(5.4).
7.3.3 After an additional 5 m1n, add 7 ml of working buffer
solution (5.6).
7.3.4 After 15 m1n, add 25 ml of chloroform. Shake the separatory
funnel at least 20 times. Allow the layer to separate and pass the
chloroform layer through filter paper.
7.3.5 Read the absorbance at 490 nm against a reagent blank.
7.4 Calculation;
7.4.1 Prepare a standard curve by plotting absorbances against
concentration values.
7.4.2 Obtain concentration value of sample directly from prepared
standard curve.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples 1f they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine 1f
contamination has occurred.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
9067 - 4
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
10.0 REFERENCES
1. FHestad, H.O., E.E. Ott, and F.A. Gunther, "Automated Colorometrlc Micro
Determination of Phenol by 0x1dative Coupling with 3-Methyl-benzoth1azol1none
Hydrazone," Technlcon International Congress, 1969. i
2. Gales, M.E., "An Evaluation of the 3-Methyl-benzoth1azol1none Hydrazone
Method for the Determination of Phenols 1n Water and Wastewater," Analyst,
100, No. 1197, 841 (1975).
9067 - 5
Revision
Date September 1986
-------
METHOD 9067
PHENOLICS (SPECTHOPHOTOMETRIC. MBTM WITH DISTILLATION]
7.1.1
1 Add
copper sulfate
solution
to sample to
adjust pH
7. 1.2
Distill sample
Ic distillate
turbid?
9067 - 6
Revision 0
Date September 1986
-------
METHOD 9067
PHENOLICS (SPECTflOPHOTOMETRIC. MBTH WITH DISTILLATION)
(Continued)
7.2. 1
Add MBTH
solution
to distillate
or Olluted
allauot
Above
Amount of >>^Be low
concentration
7.3.1
Add MBTH
SOlution
to distil late
in separatory
funne 1
7 .2.2
Add
eerie ammonium
culfate
solution
7.2.3
7.3.2
Add cerlc
ammonia sulfate
solution
Add working
buffer solution
7.3.3
Add working
buffer solution
7.2.4
Read absorbance
7.3.4
Add
enJoroform;
shake: f 1 Iter
chloroform
layer
7.4
Calculate
concentration
value of cample
7.3.5
Read cbsorbanca
( Stop J
9067 - 7
Revision 0
Date September 1986
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METHOD 9070
TOTAL RECOVERABLE OIL AND GREASE (GRAVIMETRIC. SEPARATORY FUNNEL EXTRACTION)
1.0 SCOPE AND APPLICATION
1.1 This method measures the fluorocarbon-113 extractable matter from
surface and saline waters and Industrial, domestic, and aqueous wastes. It 1s
applicable to the determination of relatively nonvolatile hydrocarbons,
vegetable oils, animal fats, waxes, soaps, greases, and related matter.
1.2 The method 1s not applicable to measurement of light hydrocarbons
that volatilize at temperatures below 70*C. Petroleum fuels, from gasoline
through No. 2 fuel oils, are completely or partially lost 1n the solvent
removal operation.
1.3 Some crude oils and heavy fuel oils contain a significant percentage
of residue-type materials that are not soluble 1n fluorocarbon-113.
Accordingly, recoveries of these materials will be low.
1.4 The method covers the range from 5 to 1,000 mg/L of extractable
material.
1.5 When determining the level of oil and grease In sludge samples,
Method 9071 1s to be employed.
2.0 SUMMARY OF METHOD
2.1 The 1-liter sample 1s acidified to a low pH (2) and serially
extracted with fluorocarbon-113 1n a separatory funnel. The solvent 1s
evaporated from the extract and the residue 1s weighed.
3.0 INTERFERENCES
3.1 Matrix Interferences will likely be coextracted from the sample.
The extent of these Interferences will vary from waste to waste, depending on
the nature and diversity of the waste being analyzed.
4.0 APPARATUS AND MATERIALS
4.1 Separatory funnel; 2,000-mL, with Teflon stopcock.
4.2 Vacuum pump, or other source of vacuum.
4.3 Flask; Boiling, 125-mL (Corning No. 4100 or equivalent).
4.4 Distilling head; Clalsen or equivalent.
9070 - 1
Revision
Date September 1986
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4.5 Filter paper; Whatman No. 40, 11 cm.
5.0 REAGENTS
5.1 Hydrochloric add, 1:1: Mix equal volumes of concentrated HC1 and
Type II water.
5.2 Fluorocarbon-113 (l,l,2-trichloro-l,2,2-trifluoroethane): Boiling
point, 48ฐC.
5.3 Sodium sulfate; Anhydrous crystal.
5.4 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 A representative sample should be collected 1n a 1-Hter glass
bottle. If analysis 1s to be delayed for more than a few hours, the sample 1s
preserved by the addition of 5 mL HC1 (5.1) at the time of collection and
refrigerated at 4*C.
6.2 Collect a representative sample 1n a wide-mouth glass bottle that
has been rinsed with the solvent to remove any detergent film and acidify 1n
the sample bottle.
6.3 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.4 Because losses of grease will occur on sampling equipment, the
collection of a composite sample is impractical. Individual portions
collected at prescribed time Intervals must be analyzed separately to obtain
the average concentration over an extended period.
7.0 PROCEDURE
7.1 Mark the sample bottle at the water meniscus for later determination
of sample volume. If the sample was not acidified at time of collection, add
5 mL HC1 (5.1) to the sample bottle. After mixing the sample, check the pH by
touching pH-sensitive paper to the cap to ensure that the pH 1s 2 or lower.
Add more add if necessary.
7.2 Pour the sample Into a separatory funnel.
7.3 Tare a boiling flask (pre-dried 1n an oven at 103ฐ and stored in a
desiccator). Use gloves when handling flask to avoid adding fingerprints.
9070 - 2
Revision
Date September 1986
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7.4 Add 30 ml fluorocarbon-113 (5.2) to the sample bottle and rotate the
bottle to rinse the sides. Transfer the solvent Into the separatory funnel.
Extract by shaking vigorously for 2 min. Allow the layers to separate and
filter the solvent layer through a funnel containing solvent-moistened filter
paper.
NOTE: An emulsion that fails to dissipate can be broken by pouring about
1 g sodium sulfate (5.3) into the filter paper cone and slowly
draining the emulsion through the salt. Additional 1-g portions can
be added to the cone as required.
7.5 Repeat Step 7.4 twice more, with additional portions of fresh
solvent, combining all solvent in the boiling flask.
7.6 Rinse the tip of the separatory funnel, the filter paper, and then
the funnel with a total of 10-20 ml solvent and collect the rinsings in the
flask.
7.7 Connect the boiling flask to the distilling head and evaporate the
solvent by Immersing the lower half of the flask 1n water at 70*C. Collect
the solvent for reuse. A solvent blank should accompany each set of samples.
7.8 When the temperature 1n the distilling head reaches 50*C or the
flask appears dry, remove the distilling head. To remove solvent vapor, sweep
out the flask for 15 sec with air by inserting a glass tube that Is connected
to a vacuum source. Immediately remove the flask from heat source and wipe
the outside to remove excess moisture and fingerprints.
7.9 Cool the boiling flask 1n a desiccator for 30 min and weigh.
7.10 Calculation;
mg/L total oil and grease =
where:
R = residue, gross weight of extraction flask minus the tare
weight;
B = blank determination, residue of equivalent volume of
extraction solvent, mg; and
V = volume of sample in liters, determined by refilling sample
bottle to calibration line and correcting for acid
addition, if necessary.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
9070 - 3
Revision
Date September 1986
-------
8.2 Employ a minimum of one blank per sample batch to determine 1f
contamination has occurred.
8.3 Verify calibration with an Independently prepared check standard
every 15 samples.
8.4 Run one spike duplicate sample for every 10 samples 1f possible. A
duplicate sample 1s a sample brought through the whole sample preparation and
analytical process.
9.0 METHOD PERFORMANCE
9.1 The two oil and grease methods (Methods 9070 and 9071) 1n this
manual were tested on sewage by a single laboratory. This method determined
the oil and grease level 1n the sewage to be 12.6 mg/L. When 1-Hter portions
of the sewage were dosed with 14.0 mg of a mixture of No. 2 fuel oil and
Wesson oil, the recovery was 93%, with a standard deviation of +0.9 mg/L.
10.0 REFERENCES
1. Blum, K.A., and M.J. Taras, "Determination of Emulsifying 011 1n
Industrial Wastewater," JWPCF Research Suppl., 40, R404 (1968).
2. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
p. 515.
9070 - 4
Revision
Date September 1986
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METHOD 9070
TOTAL RECOVERABLE OIL AND GREASE
(Gravimetric. Separatory Funnel Extraction)
Has
cample acidified?
Pour cample
Into ceparatory
funnel
O
0
7.3
Tare boiling
flask
7.4
1
flourc
113: E
filter
la>
Vdd
jcarbon-
ixtract:
solvent
rer
7.5
Repeat twice
adding fresh
solvent
7.5
Combine solvent
In boiling
flask
o
7.7 1
Evaporate
solvent:
collect for
reuse
7.8
Remove solvent
vapor
7.9
Cool
flask ana
weigh
O C
9.0
Calculate total
amount of
grease and oil
9070 - 5
Revision o
Date September 1986
-------
METHOD 9071A
OIL AND GREASE EXTRACTION METHOD FOR SLUDGE AND SEDIMENT SAMPLES
1.0 SCOPE AND APPLICATION
1.1 Method 9071 is used to quantify low concentrations of oil and
grease (10 mg/L) by chemically drying a wet sludge sample and then extracting via
the Soxhlet apparatus. It is also used to recover oil and grease levels in
sediment and soil samples.
1.2 Method 9071 is used when relatively polar, heavy petroleum
fractions are present, or when the levels of nonvolatile greases challenge the
solubility limit of the solvent.
1.3 Specifically, Method 9071 is suitable for biological lipids,
mineral hydrocarbons, and some industrial wastewaters.
1.4 Method 9071 is not recommended for measurement of low-boiling
fractions that volatilize at temperatures below 70ฐC.
2.0 SUMMARY OF METHOD
2.1 A 20-g sample of wet sludge with a known dry-sol ids content is
acidified to pH 2.0 with 0.3 mL concentrated HC1.
2.2 Magnesium sulfate monohydrate will combine with 75% of its own
weight in water in forming MgS04 7H20 and is used to dry the acidified sludge
sample.
2.3 Anhydrous sodium sulfate is used to dry samples of soil and
sediment.
2.4 After drying, the oil and grease are extracted with
trichlorotrifluoroethane (Fluorocarbon-113)1 using the Soxhlet apparatus.
3.0 INTERFERENCES
3.1 The method is entirely empirical, and duplicate results can be
obtained only by strict adherence to all details of the processes.
3.2 The rate and time of extraction in the Soxhlet apparatus must be
exactly as directed because of varying solubilities of the different greases.
3.3 The length of time required for drying and cooling extracted
material must be constant.
3.4 A gradual increase in weight may result due to the absorption of
oxygen; a gradual loss of weight may result due to volatilization.
Replacement solvent will be specified in a forthcoming regulation.
9071A - 1 Revision 1
September 1994
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4.0 APPARATUS AND MATERIALS
4.1 Soxhlet extraction apparatus.
4.2 Analytical balance.
4.3 Vacuum pump or some other vacuum source.
4.4 Extraction thimble: Filter paper.
4.5 Glass wool or small glass beads to fill thimble.
4.6 Grease-free cotton: Extract nonabsorbent cotton with solvent.
4.7 Beaker: 150-mL.
4.8 pH Indicator to determine acidity.
4.9 Porcelain mortar.
4.10 Extraction flask: 150-mL.
4.11 Distilling apparatus: Waterbath at 70ฐC.
4.12 Desiccator.
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 Concentrated hydrochloric acid (HC1).
5.4 Magnesium sulfate monohydrate: Prepare MgS04 H20 by spreading a
thin layer in a dish and drying in an oven at 150ฐC overnight.
5.5 Sodium sulfate, granular, anhydrous (Na2S04): Purify by heating at
400ฐC 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.
9071A - 2 Revision 1
September 1994
-------
5.6 Trichlorotrif1uoroethane (1,1,2-trichloro-1,2,2-trif1uoroethane):
Boiling point, 47ฐC. The solvent should leave no measurable residue on
evaporation; distill if necessary.2
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Transfers of the solvent trichlorotrifluoroethane should not
involve any plastic tubing in the assembly.
6.2 Sample transfer implements: Implements are required to transfer
portions of solid, semisolid, and liquid wastes from sample containers to
laboratory glassware. Liquids may be transferred using a glass hypodermic
syringe. Solids may be transferred using a spatula, spoon, or coring device.
6.3 Any turbidity or suspended solids in the extraction flask should
be removed by filtering through grease-free cotton or glass wool.
7.0 PROCEDURE
7.1 Determination of Sample Dry Weight Fraction
Weigh 5-10 g of the sample into a tared crucible. Determine the dry weight
fraction of the sample by drying overnight at 105ฐC.
NOTE: The drying oven should be contained in a hood or vented.
Significant laboratory contamination may result from a heavily
contaminated hazardous waste sample.
Allow to cool in a desiccator before weighing:
dry weight fraction = q of dry sample
g of sample
7.2 Sample Handling
7.2.1 Sludge Samples
7.2.1.1 Weigh out 20 + 0.5 g of wet sludge with a known
dry-weight fraction (Section 7.1). Place in a 150-mL beaker.
7.2.1.2 Acidify to a pH of 2 with approximately 0.3 mL
concentrated HC1.
7.2.1.3 Add 25 g prepared Mg2S04 H20 and stir to a
smooth paste.
7.2.1.4 Spread paste on sides of beaker to facilitate
evaporation. Let stand about 15-30 min or until substance is
solidified.
Replacement solvent will be specified in a forthcoming regulation.
9071A - 3 Revision 1
September 1994
-------
7.2.1.5 Remove solids and grind to fine powder in a
mortar.
7.2.1.6 Add the powder to the paper extraction thimble.
7.2.1.7 Wipe beaker and mortar with pieces of filter
paper moistened with solvent and add to thimble.
7.2.1.8 Fill thimble with glass wool (or glass beads).
7.2.2 Sediment/Soil Samples
7.2.2.1 Decant and discard any water layer on a sediment
sample. Mix sample thoroughly, especially composited samples.
Discard any foreign objects such as sticks, leaves, and rocks.
7.2.2.2 Blend 10 g of the solid sample of known dry
weight fraction 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.
7.3 Extraction
7.3.1 Extract in Soxhlet apparatus using trichlorotrifluorocarbon
at a rate of 20 cycles/hr for 4 hr.
7.3.2 Using grease-free cotton, filter the extract into a pre-
weighed 250-mL boiling flask. Use gloves to avoid adding fingerprints to
the flask.
7.3.3 Rinse flask and cotton with solvent.
7.3.4 Connect the boiling flask to the distilling head and
evaporate the solvent by immersing the lower half of the flask in water at
70ฐC. Collect the solvent for reuse. A solvent blank should accompany
each analytical batch of samples.
7.3.5 When the temperature in the distilling head reaches 50ฐC
or the flask appears dry, remove the distilling head. To remove solvent
vapor, sweep out the flask for 15 sec with air by inserting a glass tube
that is connected to a vacuum source. Immediately remove the flask from
the heat source and wipe the outside to remove excess moisture and
fingerprints.
7.3.6 Cool the boiling flask in a desiccator for 30 min and
weigh.
7.3.7 Calculate oil and grease as a percentage of the total dry
solids. Generally:
% of oil and grease = gain in weight of flask (q) x 100
wt. of wet solids (g) x dry weight fraction
9071A - 4 Revision 1
September 1994
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8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for
easy reference and inspection. Refer to Chapter One for additional quality
control guidelines.
8.2 Employ a minimum of one blank per analytical batch or twenty
samples, whichever is more frequent, to determine if contamination has occurred.
8.3 Run one matrix duplicate and matrix spike sample every twenty
samples or analytical batch, whichever is more frequent. Matrix duplicates and
spikes are brought through the whole sample preparation and analytical process.
8.4 The use of corn oil is recommended as a reference sample solution.
9.0 METHOD PERFORMANCE
9.1 Two oil and grease methods (Methods 9070 and 9071) were tested on
sewage by a single laboratory. When 1-liter portions of the sewage were dosed
with 14.0 mg of a mixture of No. 2 fuel oil and Wesson oil, the recovery was 93%,
with a standard deviation of + 0.9 mg/L.
10.0 REFERENCES
1. Blum, K.A. and M.J. Taras, "Determination of Emulsifying Oil in Industrial
Wastewater," JWPCF Research Suppl., 40, R404 (1968).
2. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
p. 515, Method 502A (1975).
9071A - 5 Revision 1
September 1994
-------
METHOD 9071A
OIL AND GREASE EXTRACTION METHOD FOR SLUDGE AND SEDIMENT SAMPLES
( Start J
7.1 Determine
dry weight fraction
of sample.
7.2.1.1 Weigh
a sample of
wet sludge
and place in
beaker.
Sludge
7.2 Is
sample
sludge or
sediment/
soil?
Soil/Sediment
7.2.2.1 Decant
water; mix
sample; discard
foreign objects.
7.2.1.2
Acidify to
pH 2.
7.2.2.2 Blend
with sodium
sulfate; add
to extraction
thimble.
7.2.1.3 Add
and stir
magnesium sulfate
monohydrate.
1
7.2.1.5
Remove and
grind solids
to a fine
powder.
o
9071A - 6
Revision 1
Septenter 1994
-------
METHOD 9071A
OIL AND GREASE EXTRACTION METHOD FOR SLUDGE AND SEDIMENT SAMPLES
(Continued)
7.2.1.6 Add
powder to
paper
extraction
thimble.
7.2.1.7 Wipe
beaker and
mortar; add
to thimble.
7.2.1.8 Fill
thimble with
glass wool.
7.3.1 Extract
in Soxhlet
apparatus for
4 hours.
7.3.2 Filter
extract into
boiling flask.
7.3.3 Rinse
flask with
solvent.
7.3.4
Evaporate and
collect
solvent for reuse.
7.3.5 Remove
solvent vapor.
7.3.6 Cool
and weigh
boiling flask.
7.3.7
Calculate %
oil and
grease.
( StฐP )
9071A - 7
Revision 1
September 1994
-------
METHOD 9075
TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED
PETROLEUM PRODUCTS BY X-RAY FLUORESCENCE SPECTROMETRY (XRF)
1.0 SCOPE AND APPLICATION
1.1 This test method covers the determination of total chlorine in new
and used oils, fuels, and related materials, including crankcase, hydraulic,
diesel, lubricating and fuel oils, and kerosene. The chlorine content of
petroleum products is often required prior to their use as a fuel.
1.2 The applicable range of this method is from 200 /ug/g to percent
levels.
1.3 Method 9075 is restricted to use by, or under the supervision of,
analysts experienced in the operation of an X-ray fluorescence spectrometer and
in the interpretation of the results.
2.0 SUMMARY OF METHOD
2.1 A well-mixed sample, contained in a disposable plastic sample cup,
is loaded into an X-ray fluorescence (XRF) spectrometer. The intensities of the
chlorine Ka and sulfur Ka lines are measured, as are the intensities of
appropriate background lines. After background correction, the net intensities
are used with a calibration equation to determine the chlorine content. The
sulfur intensity is used to correct for absorption by sulfur.
3.0 INTERFERENCES
3.1 Possible interferences include metals, water, and sediment in the
oil. Results of spike recovery measurements and measurements on diluted samples
can be used to check for interferences.
Each sample, or one sample from a group of closely related samples, should
be spiked to confirm that matrix effects are not significant. Dilution of
samples that may contain water or sediment can produce incorrect results, so
dilution should be undertaken w'ith caution and checked by spiking. Sulfur
interferes with the chlorine determination, but a correction is made.
Spike recovery measurements of used crankcase oil showed that diluting
samples five to one allowed accurate measurements on approximately 80% of the
samples. The other 20% of the samples were not accurately analyzed by XRF.
3.2 Water in samples absorbs X-rays emmitted by chlorine. For this
inter-ference, use of as short an X-ray counting time as possible is beneficial.
This appears to be related to stratification of samples into aqueous and
nonaqueous layers while in the analyzer.
Although a correction for water may be possible, none is currently
available. In general, the presence of any free water as a separate phase or a
9075 - 1 Revision 0
September 1994
-------
water content greater than 25% will reduce the chlorine signal by 50 to 90%. See
Sec. 6.4.
4.0 APPARATUS AND MATERIALS
4.1 XRF spectrometer, either energy dispersive or wavelength dispersive.
The instrument must be able to accurately resolve and measure the intensity of
the chlorine and sulfur lines with acceptable precision.
4.2 Disposable sample cups with suitable plastic film such as Mylar9.
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 Mineral oil, mineral spirits or paraffin oil (sulfur- and chlorine-
free), for preparing standards and dilutions.
5.3 1-Chlorodecane (Aldrich Chemical Co.), 20.1% chlorine, or similar
chlorine compound.
5.4 .Di-n-butyl sulfide (Aldrich Chemical Co.), 21.9% sulfur by weight.
5.5 Quality control standards such as the standard reference materials
NBS 1620, 1621, 1622, 1623, and 1624 for sulfur in oil standards; and NBS 1818
for chlorine in oil standards.
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 The collected sample should be kept headspace free prior to prepara-
tion and analysis to minimize volatilization losses of organic halogens. Because
waste oils may contain toxic and/or carcinogenic substances, appropriate field
and laboratory safety procedures should be followed.
6.3 Laboratory sampling of the sample should be performed on a well-mixed
sample of oil. The mixing should be kept to a minimum and carried out as nearly
headspace free as possible to minimize volatilization losses of organic halogens.
6.4 Free water, as a separate phase, should be removed and cannot be
analyzed by this method.
9075 - 2 Revision 0
September 1994
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7.0 PROCEDURE
7.1 Calibration and standardization.
7.1.1 Prepare primary calibration standards by diluting the
chlorodecane and n-butyl sulfide with mineral spirits or similar material.
7.1.2 Prepare working calibration standards that contain sulfur,
chlorine, or both according to the following table:
Cl:
S:
1.
2.
3.
4.
500, 1,000, 2,000, 4,000, and 6,000 /ig/g
0.5, 1.0, and 1.5% sulfur
0.5% S, 1,000 jig/g Cl
0.5% S, 4,000 Mg/g Cl
1.0% S, 500 Mg/g Cl
1.0% s, 2,000 Mg/g ci
5.
6.
7.
s.
1.0% S, 6,000 Mg/g Cl
1.5% s, 1,000 Mg/g ci
1.5% s, 4,000 Mg/g ci
1.5% s, 6,000 Mg/g ci
Once the correction factor for sulfur interference with chlorine is
determined, fewer standards may be required.
7.1.3 Measure the intensity of the chlorine Ka line and the
sulfur Ka line as well as the intensity of a suitably chosen background.
Based on counting statistics, the relative standard deviation of each peak
measurement should be 1% or less.
7.1.4 Determine the net chlorine and sulfur intensities by
correcting each peak for background. Do this for all of the calibration
standards as well as for a paraffin blank.
7.1.5 Obtain a linear calibration curve for sulfur by performing
a least squares fit of the net sulfur intensity to the standard concentra-
tions, including the blank. The chlorine content of a standard should
have little effect on the net sulfur intensity.
7.1.6 The calibration equation for chlorine must include a
correction term for the sulfur concentration. A suitable equation
follows:
where:
I
m,
S
b, k*
Cl = (ml + b) (1 + k*S)
= net chlorine intensity
= adjustable parameters
= sulfer concentration
(1)
Using a least squares procedure, the above equation or a suitable
substitute should be fitted to the data. Many XRF instruments are
equipped with suitable computer programs to perform this fit. In any
case, the resulting equation should be shown to be accurate by analysis of
suitable standard materials.
9075 - 3
Revision 0
September 1994
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7.2 Analysis.
7.2.1 Prepare a calibration curve as described in Sec. 7.1. By
periodically measuring a very stable sample containing both sulfur and
chlorine, it may be possible to use the calibration equations for more
than 1 day. During each day, the suitability of the calibration curve
should be checked by analyzing standards.
7.2.2 Determine the net chlorine and sulfur intensities for a
sample in the same manner as done for the standards.
7.2.3 Determine the chlorine and sulfur concentrations of the
samples from the calibration equations. If the sample concentration for
either element is beyond the range of the standards, the sample should be
diluted with mineral oil and reanalyzed.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
8.2 One sample in ten should be analyzed in triplicate and the relative
standard deviation reported. For each triplicate, a separate preparation should
be made, starting from the original sample.
8.3 Each sample, or one sample in ten from a group of similar samples,
should be spiked with the elements of interest by adding a known amount of
chlorine or sulfur to the sample. The spiked amount should be between 50% and
200% of the sample concentration, but the minimum addition should be at least
five times the limit of detection. The percent recovery should be reported and
should be between 80% and 120%. Any sample suspected of containing >25% water
should also be spiked with organic chlorine.
8.4 Quality control standard check samples should be analyzed every day
and should agree within 10% of the expected value of the standard.
9.0 METHOD PERFORMANCE
9.1 These data are based on 47 data points obtained by seven laboratories
who each analyzed four used crankcase oils and three fuel oil blends with
crankcase in duplicate. A data point represents one duplicate analysis of a
sample. Two data points were determined to be outliers and are not included in
these results.
9.2 Precision. The precision of the method as determined by the
statistical examination of interlaboratory test results is as follows:
Repeatability - The difference between successive results obtained
by the same operator with the same apparatus under constant operating
conditions on identical test material would exceed, in the long run, in
the normal and correct operation of the test method, the following values
only in 1 case in 20 (see Table 1):
9075 - 4 Revision 0
September 1994
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Repeatability =5.72
*where x is the average of two results in /xg/g.
Reproducibility - The difference between two single and independent
results obtained by different operators working in different laboratories
on identical test material would exceed, in the long run, the following
values only in 1 case in 20:
Reproducibility = 9.83
*where x is the average value of two results in
9.3 Bias. The bias of this test method varies with concentration, as
shown in Table 2:
Bias = Amount found - Amount expected.
10.0 REFERENCE
1. Gaskill, A.; Estes, E.D.; Hardison, D.L.; and Myers, I.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. 68-01-7075, WA 80. July 1988.
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TABLE 1. REPEATABILITY AND REPRODUCIBILITY
FOR CHLORINE IN USED OILS BY
X-RAY FLUORESCENCE SPECTROMETRY
Average value, Repeatability, Reproducibility,
M9/9 M9/9 M9/9
500
1,000
1,500
2,000
2,500
3,000
128
181
222
256
286
313
220
311
381
440
492
538
TABLE 2. RECOVERY AND BIAS DATA FOR CHLORINE IN
USED OILS BY X-RAY FLUORESCENCE SPECTROMETRY
Amount
expected,
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found,
M9/9
278
461
879
1,414
1,299
2,806
2,811
Bias,
M9/9
-42
-19
-41
-84
-228
-223
-234
Percent
bias
-13
-4
-4
-6
-15
-7
-8
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METHOD 9075
TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED
PETROLEUM PRODUCTS BY X-RAY FLUORESCENCE SPECTROMETRY
(XRF)
START
7 1.1 7 1.2
Prepare calibration
s tandards
713 Measure
intensity of
standard! and
background
7 14 Determine net
intensity for
standards and a
paraffin blank
7.1 5 - 7 1.6
Construct
calibration curves
for sulfur and
chlorine
72.1 Check
calibration curves
periodically
throughout the day
722 Determine net
chlorine and sulfur
intensities for
sample
7.23 Determine
chlorine and sulfur
concentrations from
calibration curves
72.3
Is sample
concentration
beyond range of
standards?
723 Dilute sanpli
ith mineral oil
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METHOD 9076
TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED PETROLEUM
PRODUCTS BY OXIDATIVE COMBUSTION AND MICROCOULOMETRY
1.0 SCOPE AND APPLICATION
1.1 This test method covers the determination of total chlorine in new
and used oils, fuels and related materials, including crankcase, hydraulic,
.diesel, lubricating and fuel oils, and kerosene by oxidative combustion and
microcoulometry. The chlorine content of petroleum products is often required
prior to their use as a fuel.
1.2 The applicable range of this method is from 10 to 10,000 /zg/g
chlorine.
2.0 SUMMARY OF METHOD
2.1 The sample is placed in a quartz boat at the inlet of a high-
temperature quartz combustion tube. An inert carrier gas such as argon, carbon
dioxide, or nitrogen sweeps across the inlet while oxygen flows into the center
of the combustion tube. The boat and sample are advanced into a vaporization
zone of approximately 3008C to volatilize the light ends. Then the boat is
advanced to the center of the combustion tube, which is at 1,000'C. The oxygen
is diverted to pass directly over the sample to oxidize any remaining refractory
material. All during this complete combustion cycle, the chlorine is converted
to chloride and oxychlorides, which then flow into an attached titration cell
where they quantitatively react with silver ions. The silver ions thus consumed
are coulometrically replaced. The total current required to replace the silver
ions is a measure of the chlorine present in the injected samples.
2.2 The reaction occurring in the titration cell as chloride enters is:
CV + Ag+ - > AgCl (1)
The silver ion consumed in the above reaction is generated coulometrically
thus:
Agฐ > Ag+ + e (2)
2.3 These microequivalents of silver are equal to the number of micro-
equivalents of titratable sample ion entering the titration cell.
3.0 INTERFERENCES
3.1 Other titratable halides will also give a positive response. These
titratable halides include HBr and HI (HOBr + HOI do not precipitate silver).
Because these oxyhalides do not react in the titration cell, approximately 50%
microequivalent response is detected from bromine and iodine.
3.2 Fluorine as fluoride does not precipitate silver, so it is not an
interferant nor is it detected.
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3.3 This test method is applicable in the presence of total sulfur
concentrations of up to 10,000 times the chlorine level.
4.0 APPARATUS AND MATERIALS1
4.1 Combustion furnace. The sample should be oxidized in an electric
furnace capable of maintaining a temperature of 1,000ฐC to oxidize the organic
matrix.
4.2 Combustion tube, fabricated from quartz and constructed so that a
sample, which is vaporized completely in the inlet section, is swept into the
oxidation zone by an inert gas where it mixes with oxygen and is burned. The
inlet end of the tube connects to a boat insertion device where the sample can
be placed on a quartz boat by syringe, micropipet, or by being weighed
externally. Two gas ports are provided, one for an inert gas to flow across the
boat and one for oxygen to enter the combustion tube.
4.3 Microcoulometer, Stroehlein Coulomat 702 CL or equivalent, having
variable gain and bias control, and capable of measuring the potential of the
sensing-reference electrode pair, and comparing this potential with a bias
potential, and applying the amplified difference to the working-auxiliary
electrode pair so as to generate a titrant. The microcoulometer output signal
shall be proportional to the generating current. The microcoulometer may have
a digital meter and circuitry to convert this output signal directly to a mass
of chlorine (e.g., nanograms) or to a concentration of chlorine (e.g., micrograms
of chlorine or micrograms per gram).
4.4 Titration cell. Two different configurations have been applied to
coulometrically titrate chlorine for this method.
4.4.1 Type I uses a sensor-reference pair of electrodes to detect
changes in silver ion concentration and a generator anode-cathode pair of
electrodes to maintain constant silver ion concentration and an inlet for
a gaseous sample from the pyrolysis tube. The sensor, reference, and
anode electrodes are silver electrodes. The cathode electrode is a
platinum wire. The reference electrode resides in a saturated silver
acetate half-cell. The electrolyte contains 70% acetic acid in water.
4.4.2 Type II uses a sensor-reference pair of electrodes to
detect changes in silver ion concentration and a generator anode-cathode
pair of electrodes to maintain constant silver ion concentration, an inlet
for a gaseous sample that passes through a 95% sulfuric acid dehydrating
tube from the pyrolysis tube, and a sealed two-piece titration cell with
an exhaust tube to vent fumes to an external exhaust. All electrodes can
be removed and replaced independently without reconstructing the cell
assembly. The anode electrode is constructed of silver. The cathode
electrode is constructed of platinum. The anode is separated from the
1Any apparatus that meets the performance criteria of this section may be
used to conduct analyses by this methodology. Three commercial analyzers that
fulfill the requirements for apparatus Steps 4.1 through 4.4 are: Dohrmann
Models DX-20B and MCTS-20 and Mitsubishi Model TSX-10 available from Cosa
Instrument.
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cathode by a 10% KN03 agar bridge, and continuity is maintained through an
aqueous 10% KN03 salt bridge. The sensor electrode is constructed of
silver. The reference electrode is a silver/silver chloride ground glass
sleeve, double-junction electrode with aqueous 1M KN03 in the outer chamber
and aqueous 1M KC1 in the inner chamber.
4.5 Sampling syringe, a microliter syringe of 10 /zL capacity capable of
accurately delivering 2 to 5 p.1 of a viscous sample into the sample boat.
4.6 Micropipet, a positive displacement micropipet capable of accurately
delivering 2 to 5 /uL of a viscous sample into the sample boat.
4.7 Analytical balance. When used to weigh a sample of 2 to 5 mg onto
the boat, the balance shall be accurate to + 0.01 mg. When used to determine the
density of the sample, typically 8 g per 10 mL, the balance shall be accurate to
ฑ 0.1 g.
4.8 Class A volumetric flasks: 100 mL.
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 Acetic acid, CH3C02H. Glacial.
5.4 Isooctane, (CH3)2CHCH2C(CH3)3 (2,2,4-Trimethylpentane).
5.5 Chlorobenzene, C6H5C1.
5.6 Chlorine, standard stock solution - 10,000 ng Cl//iL, weigh
accurately 3.174 g of chlorobenzene into 100-mL Class A volumetric flask. Dilute
to the mark with isooctane.
5.7 Chlorine, standard solution. 1,000 ng Cl//iL, pipet 10.0 mL of
chlorine stock solution (Sec. 5.6) into a 100-mL volumetric flask and dilute to
volume with isooctane.
5.8 Argon, helium, nitrogen, or carbon dioxide, high-purity grade (HP)
used as the carrier gas. High-purity grade gas has a minimum purity of 99.995%.
5.9 Oxygen, high-purity grade (HP), used as the reactant gas.
5.10 Gas regulators. Two-stage regulator must be used on the reactant and
carrier gas.
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5.11 Cell Type 1.
5.11.1 Cell electrolyte solution. 70% acetic acid: combine 300
ml reagent water with 700 ml acetic acid (Sec. 5.3) and mix well.
5.11.2 Silver acetate, CH3C02Ag. Powder purified for saturated
reference electrode.
5.12 Cell Type 2.
5.12.1 Sodium acetate, CH3C02Na.
5.12.2 Potassium nitrate, KN03.
5.12.3 Potassium chloride, KC1.
5.12.4 Sulfuric acid (concentrated), H2S04.
5.12.5 Agar, (jelly strength 450 to 600 g/cm2).
5.12.6 Cell electrolyte solution - 85% acetic acid: combine 150
ml reagent water with 1.35 g sodium acetate (Sec. 5.12.1) and mix well;
add 850 ml acetic acid (Sec. 5.3) and mix well.
5.12.7 Dehydrating solution - Combine 95 ml sulfuric acid (Sec.
5.12.4) with 5 ml reagent water and mix well.
CAUTION: This is an exothermic reaction and may proceed with bumping
unless controlled by the addition of sulfuric acid. Slowly add
sulfuric acid to reagent water. Do not add water to sulfuric acid.
5.12.8 Potassium nitrate (10%), KN03. Add 10 g potassium nitrate
(Sec. 5.12.2) to 100 ml reagent water and mix well.
5.12.9 Potassium nitrate (1M), KN03. Add 10.11 g potassium
nitrate (Sec. 5.12.2) to 100 mL reagent water and mix well.
5.12.10 Potassium chloride (1M), KC1. Add 7.46 g potassium
chloride (Sec. 5.12.3) to 100 ml reagent water and mix well.
5.12.11 Agar bridge solution - Mix 0.7 g agar (Sec. 5.12.5), 2.5g
potassium nitrate (Sec. 5.12.2), and 25 ml reagent water and heat to
boiling.
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 Because the collected sample will be analyzed for total halogens, it
should be kept headspace free and refrigerated prior to preparation and analysis
to minimize volatilization losses of organic halogens. Because waste oils may
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contain toxic and/or carcinogenic substances, appropriate field and laboratory
safety procedures should be followed.
6.3 Laboratory subsampling of the sample should be performed on a well-
mixed sample of oil.
7.0 PROCEDURES
7.1 Preparation of apparatus.
7.1.1 Set up the analyzer as per the equipment manufacturer's
instructions.
7.1.2 Typical operating conditions: Type 1.
Furnace temperature 1,000'C
Carrier gas flow 43 cm3/min
Oxygen gas flow 160 cm3/min
Coulometer
Bias 250 mV
Gain 25%
7.1.3 Typical operating conditions: Type 2.
Furnace temperature H-1 850ฐC
H-2 1,000'C
Carrier gas flow 250 cm3/min
Oxygen gas flow 250 cm3/min
Coulometer
End point potential (bias) 300 mV
Gain G-l 1.5 coulombs/A mV
G-2 3.0 coulombs/A mV
G-3 3.0 coulombs/A mV
ES-1 (range 1) 25 mV
ES-2 (range 2) 30 mV
NOTE: Other conditions may be appropriate. Refer to the
instrumentation manual.
7.2 Sample introduction.
7.2.1 Carefully fill a 10-juL syringe with 2 to 5 /uL of sample
depending on the expected concentration of total chlorine. Inject the
sample through the septum onto the cool boat, being certain to touch the
boat with the needle tip to displace the last droplet.
7.2.2 For viscous samples that cannot be drawn into the syringe
barrel, a positive displacement micropipet may be used. Here, the 2-5 /iL
of sample is placed on the boat from the micropipet through the opened
hatch port. The same technique as with the syringe is used to displace
the last droplet into the boat. A tuft of quartz wool in the boat can aid
in completely transferring the sample from the micropipet into the boat.
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NOTE: Dilution of samples to reduce viscosity is not recommended due
to uncertainty about the solubility of the sample and its
chlorinated constituents. If a positive displacement micropipet is
not available, dilution may be attempted to enable injection of
viscous samples.
7.2.3 Alternatively, the sample boat may be removed from the
instrument and tared on an analytical balance. A sample of 2-5 mg is
accurately weighed directly into the boat and the boat and sample returned
to the inlet of the instrument.
2-5 juL = 2-5 mg
NOTE: Sample dilution may be required to ensure that the titration
system is not overloaded with chlorine. This will be somewhat
system dependent and should be determined before analysis is
attempted. For example, the MCTS-20 can titrate up to 10,000 ng
chlorine in a single injection or weighed sample, while the DX-20B
has an upper limit of 50,000 ng chlorine. For 2 to 5 juL sample
sizes, these correspond to nominal concentrations in the sample of
800 to 2,000 /xg/g and 4,000 to 10,000 jug/g, respectively. If the
system is overloaded, especially with inorganic chloride, residual
chloride may persist in the system and affect results of subsequent
samples. In general, the analyst should ensure that the baseline
returns to normal before running the next sample. To speed baseline
recovery, the electrolyte can be drained from the cell and replaced
with fresh electrolyte.
NOTE: To determine total chlorine, do not extract the sample either
with reagent water or with an organic solvent such as toluene or
isooctane. This may lower the inorganic chlorine content as well as
result in losses of volatile solvents.
7.2.4 Follow the manufacturer's recommended procedure for moving
the sample and boat into the combustion tube.
7.3 Calibration and standardization.
7.3.1 System recovery - The fraction of chlorine in a standard
that is titrated should be verified every 4 hours by analyzing the
standard solution (Sec. 5.7). System recovery is typically 85% or better.
The pyrolysis tube should be replaced whenever system recovery drops below
75%.
NOTE: The 1,000 ;ug/g system recovery sample is suitable for all
systems except the MCTS-20 for which a 100 /ig/g sample should be
used.
7.3.2 Repeat the measurement of this standard at least three
times.
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7.3.3 System blank - The blank should be checked daily with
isooctane. It is typically less than 1 /zg/g chlorine. The system blank
should be subtracted from both samples and standards.
7.4 Calculations.
7.4.1 For systems that read directly in mass units of chloride,
the following equations apply:
Chlorine, M9/9 (wt/wt) = (V ) (Ds) (RF) " B (3)
or
Chlorine, M9/9 (wt/wt) = (M)P(Rh) - B (4)
where:
Display = Integrated value in nanograms (when the integrated values are
displayed in micrograms, they must be multiplied by 103)
DisplayB = blank measurement Displays = sample measurement
V = Volume of sample injected in microliters
VB = blank volume Vs = sample volume
D = Density of sample, grams per cubic centimeters
DB = blank density Ds = sample density
RF = Recovery factor = ratio of chlorine = Found - Blank
determined in standard minus the system Known
blank, divided by known standard content
B = System blank, /zg/g chlorine = Disp1ayB
M = Mass of sample, mg
7.4.2 Other systems internally compensate for recovery factor,
volume, density, or mass and blank, and thus read out directly in parts
per million chlorine units. Refer to instrumentation manual.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
8.2 Each sample should be analyzed twice. If the results do not agree
to within 10%, expressed as the relative percent difference of the results,
repeat the analysis.
8.3 Analyze matrix spike and matrix spike duplicates - spike samples with
a chlorinated organic at a level of total chlorine commensurate with the levels
being determined. The spike recovery should be reported and should be between
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80 and 120% of the expected value. Any sample suspected of containing >25% water
should also be spiked with organic chlorine.
9.0 METHOD PERFORMANCE
9.1 These data are based on 66 data points obtained by 10 laboratories
who each analyzed four used crankcase oils and three fuel oil blends with
crankcase in duplicate. A data point represents one duplicate analysis of a
sample. One laboratory and four additional data points were determined to be
outliers and are not included in these results.
9.2 Precision. The precision of the method as determined by the
statistical examination of interlaboratory test results is as follows:
Repeatability - The difference between successive results obtained by the
same operator with the same apparatus under constant operating conditions on
identical test material would exceed, in the long run, in the normal and correct
operation of the test method the following values only in 1 case in 20 (see Table
1):
Repeatability = 0.137 x*
*where x is the average of two results in
Reproducibility - The difference between two single and independent
results obtained by different operators working in different laboratories
on identical test material would exceed, in the long run, the following
values only in 1 case in 20:
Reproducibility = 0.455 x*
*where x is the average value of two results in ng/g.
9.3 Bias. The bias of this test method varies with concentration, as
shown in Table 2:
Bias = Amount found - Amount expected
10.0 REFERENCE
1. Gaskill, A.; Estes, E.D.; Hardison, D.L.; and Myers, I.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. 68-01-7075, WA80. July 1988.
2. Rohrobough, W.G.; et al. Reagent Chemicals, American Chemical Society
Specifications, 7th ed.; American Chemical Society: Washington, DC, 1986.
3. Standard Instrumentation, 3322 Pennsylvania Avenue, Charleston, WV 25302.
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TABLE 1.
REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN
USED OILS BY MICROCOULOMETRIC TITRATION
Average value Repeatability, Reproducibility,
M9/9 M9/9 M9/9
500
1,000
1,500
2,000
2,500
3,000
69
137
206
274
343
411
228
455
683
910
1,138
1,365
TABLE 2.
RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS
BY MICROCOULOMETRIC TITRATION
Amount
expected,
M9/9
320
480
920
1,498
1,527
3,029
3,045
Amount
found
M9/9
312
443
841
1,483
1,446
3,016
2,916
j
Bias,
M9/9
-8
-37
-79
-15
-81
-13
-129
Percent
bias
-3
-8
-9
-1
-5
0
-4
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METHOD 9076
TEST METHOD FOR TOTAL CHLORINE IN NEW AND USED PETROLEUM
PRODUCTS BY OXIDATIVE COMBUSTION AND MICROCOULOMETRY
7.2.2 Inject
sample into
cool boat
ซith
micropipet
724 Hove
sample and
boat into
combus tion
tube
7.3.1 Verify
sys tern
recovery
every 4 hours
7 2.1 Inject
sample into
cool boat
Kith syringe
732 R.p.at
tandard
raซaiurซraซnt
at Uaซt
thrซซ tiซซป
733 Cheek
>yit*n blank
daily ปith
iaooetan*
7.4 Calculate
chlorine
concentration
{ STOP )
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METHOD 9077
TEST METHODS FOR TOTAL CHLORINE IN NEW AND USED PETROLEUM
PRODUCTS (FIELD TEST KIT METHODS)
1.0 SCOPE AND APPLICATION
1.1 The method may be used to determine if a new or used petroleum
product meets or exceeds requirements for total halogen measured as chloride.
An analysis of the chlorine content of petroleum products is often required prior
to their use as a fuel. The method is specifically designed for used oils
permitting onsite testing at remote locations by nontechnical personnel to avoid
the delays for laboratory testing.
1.2 In these field test methods, the entire analytical sequence,
including sampling, sample pretreatment, chemical reactions, extraction, and
quantification, are combined in a single kit using predispensed and encapsulated
reagents. The overall objective is to provide a simple, easy to use procedure,
permitting nontechnical personnel to perform a test with analytical accuracy
outside of a laboratory environment in under 10 minutes. One of the kits is
preset at 1,000 ng/g total chlorine to meet regulatory requirements for used
oils. The other kits provide quantitative results over a range of 750 to
7,000 /Ltg/g and 300 to 4,000 ng/g.
2.0 SUMMARY OF METHOD
2.1 The oil sample (around 0.4 g by volume) is dispersed in a solvent
and reacted with a mixture of metallic sodium catalyzed with naphthalene and
diglyme at ambient temperature. This process converts all organic halogens to
their respective sodium halides. All halides in the treated mixture, including
those present prior to the reaction, are then extracted into an aqueous buffer,
which is then titrated with mercuric nitrate using diphenyl carbazone as the
indicator. The end point of the titration is the formation of the blue-violet
mercury diphenylcarbazone complex. Bromide and iodide are titrated and reported
as chloride.
2.2 Reagent quantities are preset in the fixed end point kit (Method
A) so that the color of the solution at the end of the titration indicates
whether the sample is above 1,000 /jg/g chlorine (yellow) or below 1,000 M9/g
chlorine (blue).
2.3 The first quantitative kit (Method B) involves a reverse titration
of a fixed volume of mercuric nitrate with the extracted sample such that the end
point is denoted by a change from blue to yellow in the titration vessel over the
range of the kit (750 to 7,000 /ng/g). The final calculation is based on the
assumption that the oil has a specific gravity of 0.9 g/cm .
2.4 The second quantitative kit (Method C) involves a titration of the
extracted sample with mercuric nitrate by means of a 1-mL microburette such that
the end point is denoted by a change from pale yellow to red-violet over the
range of the kit (300 to 4,000 ng/g). The concentration of chlorine in the
original oil is then read from a scale on the microburette.
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NOTE: WarningAll reagents are encapsulated or contained within
ampoules. Strict adherence to the operational procedures included
with the kits as well as accepted safety procedures (safety glasses
and gloves) should be observed.
NOTE; WarningWhen crushing the glass ampoules, press firmly in
the center of the ampoule once. Never attempt to recrush broken
glass because the glass may come through the plastic and cut
fingers.
NOTE; WarningIn case of accidental breakage onto skin or
clothing, wash with large amounts of water. All the ampoules are
poisonous and should not be taken internally.
NOTE; WarningThe gray ampoules contain metallic sodium. Metallic
sodium is a flammable water-reactive solid.
NOTE; WarningDo not ship kits on passenger aircraft. Dispose of
used kits properly.
NOTE; CautionWhen the sodium ampoule in either kit is crushed,
oils that contain more than 25% water will cause the sample to turn
clear to light gray. Under these circumstances, the results may
be biased excessively low and should be disregarded.
3.0 INTERFERENCES
3.1 Free water, as a second phase, should be removed. However, this
second phase can be analyzed separately for chloride content if desired.
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METHOD A
FIXED END POINT TEST KIT METHOD
4.0A APPARATUS AND MATERIALS
4.1A The CLOR-D-TECT 10001 is a complete self-contained kit. It
includes: a sampling tube to withdraw a fixed sample volume for analysis; a
polyethylene test tube #1 into which the sample is introduced for dilution and
reaction with metallic sodium; and a polyethylene tube #2 containing a buffered
aqueous extractant, the mercuric nitrate titrant, and diphenyl carbazone
indicator. Included are instructions to conduct the test and a color chart to
aid in determining the end point.
5.0A REAGENTS
5.1A 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 determina-
tion.
5.2A All necessary reagents are contained within the kit.
5.3A The kit should be examined upon opening to see that all of the
components are present and that all the ampoules (4) are in place and not
leaking. The liquid in Tube #2 (yellow cap) should be approximately 1/2 in.
above the 5-mL line and the tube should not be leaking. The ampoules are not
supposed to be completely full.
6.0A SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1A All samples must be collected using a sampling plan that addresses
the considerations discussed in Chapter Nine.
6.2A Because the collected sample will be analyzed for total halogens,
it should be kept headspace free and refrigerated prior to preparation and
analysis to minimize volatilization losses of organic halogens. Because waste
oils may contain toxic and/or carcinogenic substances, appropriate field and
laboratory safety procedures should be followed.
7.0A PROCEDURE
7.1A Preparation. Open analysis carton, remove contents, mount plastic
test tubes in the provided holder. Remove syringe and glass sampling capillary
from foil pouch.
Available from Dexsil Corporation, One Hamden Park Drive, Hamden, CT 06517.
9077 - 3 Revision 0
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NOTE: Perform the test in a warm, dry area with adequate light.
In cold weather, a truck cab is sufficient. If a warm area is not
available, Step 7.3A should be performed while warming Tube #1 in
palm of hand.
7.2A Sample introduction. Remove white cap from Tube #1. Using the
plastic syringe, slowly draw the oil up the capillary tube until it reaches the
flexible adapter tube. Wipe excess oil from the tube with the provided tissue,
keeping capillary vertical. Position capillary tube into Tube #1, and detach
adapter tubing, allowing capillary to drop to the bottom of the tube. Replace
white cap on tube. Crush the capillary by squeezing the test tube several times,
being careful not to break the glass reagent ampoules.
7.3A Reaction. Break the lower (colorless) capsule containing the clear
diluent solvent by squeezing the sides of the test tube. Mix thoroughly by
shaking the tube vigorously for 30 seconds. Crush the upper grey ampoule
containing metallic sodium, again by squeezing the sides of the test tube. Shake
vigorously for 20 seconds. Allow reaction to proceed for 60 seconds, shaking
intermittently several times while timing with a watch.
NOTE: CautionAlways crush the clear ampoule in each tube first.
Otherwise, stop the test and start over using another complete kit.
False (low) results may occur and allow a contaminated sample to
pass without detection if clear ampoule is not crushed first.
7.4A Extraction. Remove caps from both tubes. Pour the clear buffered
extraction solution from Tube #2 into Tube #1. Replace the white cap on Tube #1,
and shake vigorously for 10 seconds. Vent tube by partially unscrewing the
dispenser cap. Close cap securely, and shake for an additional 10 seconds. Vent
again, tighten cap, and stand tube upside down on white cap. Allow phases to
separate for 2 minutes.
7.5A Analysis. Put filtration funnel into Tube #2. Position Tube #1
over funnel and open nozzle on dispenser cap. Squeeze the sides of Tube #1 to
dispense the clear aqueous lower phase through the filter into Tube #2 to the
5 ml line on Tube #2. Remove the filter funnel. Replace the yellow cap on Tube
#2 and close the nozzle on the dispenser cap. Break the colorless lower capsule
containing mercuric nitrate solution by squeezing the sides of the tube, and
shake for 10 seconds. Then break the upper colored ampoule containing the
diphenylcarbazone indicator, and shake for 10 seconds. Observe color
immediately.
7.6A Interpretation of results
7.6.1A Because all reagent levels are preset, calculations are not
required. A blue solution in Tube #2 indicates a chlorine content in the
original oil of less than 1,000 ng/g, and a yellow color indicates that
the chlorine concentration is greater than 1,000 ng/g. Refer to the color
chart enclosed with the kit in interpreting the titration end point.
7.6.2A Report the results as < or > 1,000 jug/g chlorine in the oil
sample.
9077 - 4 Revision 0
September 1994
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8.0A QUALITY CONTROL
8.1A Refer to Chapter One for specific quality control procedures.
8.2A Each sample should be tested two times. If the results do not
agree, then a third test must be performed. Report the results of the two that
agree.
9.0A METHOD PERFORMANCE
9.1A No formal statement is made about either the precision or bias of
the overall test kit method for determining chlorine in used oil because the
result merely states whether there is conformance to the criteria for success
specified in the procedure, (i.e., a blue or yellow color in the final solution).
In a collaborative study, eight laboratories analyzed four used crankcase oils
and three fuel oil blends with crankcase in duplicate using the test kit. Of the
resulting 56 data points, 3 resulted in incorrect classification of the oil's
chlorine content (Table 1). A data point represents one duplicate analysis of
a sample. There were no disagreements within a laboratory on any duplicate
determinations.
9077 - 5 Revision 0
September 1994
-------
TABLE 1.
PRECISION AND BIAS INFORMATION FOR METHOD A-
FIXED END POINT TEST KIT METHOD
Expected
concentration,
M9/9
Percent aareementb
Expected results, Percent
correct3 Within Between
320
480
920
1,498
1,527
3,029
3,045
< 1,000
< 1,000
< 1,000
> 1,000
> 1,000
> 1,000
> 1,000
100
100
100
87
75
100
100
100
100
100
100
100
100
100
100
100
100
87
75
100
100
aPercent correct--percent correctly identified as above or below
1,000 /ug/g.
bPercent agreement--percent agreement within or between laboratories.
9077 - 6
Revision 0
September 1994
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START
METHOD 9077, METHOD A
FIXED END POINT TEST KIT METHOD
7.1A Open test kit
7.2A Draw oil into
capillary tube:
remove excess oil;
drop capillary tube
into Tube t\ and
cap Tube ฃ1; crush
capillary tube
7.3A Break
colorless capsule;
mix; crush grey
capsule; nix; allow
reaction to proceed
for 60 sec.
7.4A Pour Tube t2
solution into Tube
fl: mix; vent;
allow phases to
separate
7.5A Filter aqueous
lower phase in Tube
tl into Tube t2.
remove filter
funnel; break
colorless capsule;
mix; break upper
colored capsule;
ix; observe color
7.6.1 Chlorine
content is > 1000
"9/9
7.6A What
color is
solution in
Tube
7.6.1 Chlorine
content is < 1000
"9/9
7.6.2 Report
results
STOP
9077 - 7
Revision 0
Septenter 1994
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METHOD B
REVERSE TITRATION QUANTITATIVE END POINT TEST KIT METHOD
4.OB APPARATUS AND MATERIALS
4.IB QuantiClor2 kit components (see Figure 1).
4.1.IB Plastic reaction bottle: 1 oz, with flip-top dropper cap
and a crushable glass ampoule containing sodium.
4.1.2B Plastic buffer bottle: contains 9.5 ml of aqueous buffer
solution.
4.1.3B Titration vial: contains buffer bottle and indicator-
impregnated paper.
4.1.4B Glass vial: contains 2.0 ml of solvents.
4.1.5B Micropipet and plunger, 0.25 ml.
4.1.6B Activated carbon filtering column.
4.1.7B Titret and valve assembly.
4.2B The reagents needed for the test are packaged in disposable
containers.
4.3B The procedure utilizes a Titret. Titrets are hand-held,
disposable cells for titrimetric analysis. A Titret is an evacuated glass
ampoule (13 mm diameter) that contains an exact amount of a standardized liquid
titranta A flexible valve assembly is attached to the tip of the ampoule.
Titrets employ the principle of reverse titration; that is, small doses of
sample are added to the titrant to the appearance of the end point color. The
color change indicates that the equivalency point has been reached. The flow of
the sample into the Titret may be controlled by using an accessory called a
Titrettor* .
5.OB REAGENTS
5.IB The crushable glass ampoule, which is inside the reaction bottle,
contains 85 mg of metallic sodium in a light oil dispersion.
5.2B The buffer bottle contains 0.44 g of NaH?PO, 2H?0 and 0.32 ml of
HN03 in distilled water.
5.3B The glass vial contains 770 mg Stoddard Solvent (CAS No. 8052-
41-3), 260 mg toluene, 260 mg butyl ether, 260 mg diglyme, 130 mg naphthalene,
and 70 mg demulsifier.
2Quanti-Chlor Kit, Titrets , and Titrettor* are manufactured by Chemetrics,
Inc., Calverton, VA 22016. U.S. Patent No. 4,332,769.
9077 - 8 Revision 0
September 1994
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5.4B The Titret contains 1.12 mg mercuric nitrate in distilled water.
5.SB The indicator-impregnated paper contains approximately 0.3 mg of
diphenylcarbazone and 0.2 mg of brilliant yellow.
6.OB SAMPLE COLLECTION, PRESERVATION, AND HANDLING
See Section 6.0A of Method A.
7.OB PROCEDURE
7.IB Shake the glass vial and pour its contents into the reaction
bottle.
7.2B Fill the micropipet with a well-shaken oil sample by pulling the
plunger until its top edge is even with the top edge of the micropipet. Wipe off
the excess oil and transfer the sample into the reaction bottle (see Figure 2.1).
7.3B Gently squeeze most of the air out of the reaction bottle (see
Figure 2.2). Cap the bottle securely, and shake vigorously for 30 seconds.
7.4B Crush the sodium ampoule by pressing against the outside wall of
the reaction bottle (see Figure 2.3).
CAUTION: Samples containing a high percentage of water will
generate heat and gas, causing the reaction bottle walls to
expand. To release the gas, briefly loosen the cap.
7.5B Shake the reaction bottle vigorously for 30 seconds.
7.6B Wait 1 minute. Shake the reaction bottle occasionally during this
time.
7.7B Remove the buffer bottle from the titration vial, and slowly pour
its contents into the reaction bottle (see Figure 2.4).
7.8B Cap the reaction bottle and shake gently for a few seconds. As
soon as the foam subsides, release the gas by loosening the cap. Tighten the
cap, and shake vigorously for 30 seconds. As before, release any gas that has
formed, then turn the reaction bottle upside down (see Figure 2.5).
7.9B Wait 1 minute.
7.10B While holding the filtering column in a vertical position, remove
the plug. Gently tap the column to settle the carbon particles.
7.11B Keeping the reaction bottle upside down, insert the flip top into
the end of the filtering column and position the column over the titration vial
(see Figure 2.6). Slowly squeeze the lower aqueous layer out of the reaction
bottle and into the filtering column. Keep squeezing until the first drop of oil
is squeezed out.
9077 - 9 Revision 0
September 1994
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NOTE; CautionThe aqueous layer should flow through the filtering
column into the titration vial in about 1 minute. In rare cases,
it may be necessary to gently tap the column to begin the flow.
The indicator paper should remain in the titration vial.
7.12B Cap the titration vial and shake it vigorously for 10 seconds.
7.13B Slide the flexible end of the valve assembly over the tapered tip
of the Titret so that it fits snugly (see Figure 3.1).
7.14B Lift (see Figure 3.2) the control bar and insert the assembled
Titret into the Titrettor" .
7.15B Hold the Titrettor* with the sample pipe in the sample, and press
the control bar to snap the pre-scored tip of the Titret (see Figure 3.3).
NOTE: CautionBecause the Titret is sealed under vacuum, the
fluid inside may be agitated when the tip snaps.
7.16B With the tip of the sample pipe in the sample, briefly press the
control bar to pull in a SMALL amount of sample (see Figure 3.3). The contents
of the Titret will turn purple.
CAUTION; During the titration, there will be some undissolved
powder inside the Titret. This does not interfere with the
accuracy of the test.
7.17B Wait 30 seconds.
7.18B Gently press the control bar again to allow another SMALL amount
of the sample to be drawn into the Titret.
CAUTION: Do not press the control bar unless the sample pipe is
immersed in the sample. This prevents air from being drawn into
the Titret.
7.19B After each addition, rock the entire assembly to mix the contents
of the Titret. Watch for a color change from purple to very pale yellow.
7.20B Repeat Steps 7.18B and 7.19B until the color change occurs.
CAUTION; The end point color change (from purple to pale yellow)
actually goes through an intermediate gray color. During this
intermediate stage, extra caution should be taken to bring in
SMALL amounts of sample and to mix the Titret contents well.
7.21B When the color of the liquid in the Titret changes to PALEv YELLOW,
remove the Titret from the Titrettor*1 . Hold the Titret in a vertical position
and carefully read the test result on the scale opposite the liquid level.
7.22B Calculation
7.22.IB To obtain results in micrograms per gram total chlorine,
multiply scale units on the Titret by 1.3 and then subtract 200.
9077 - 10 Revision 0
September 1994
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8.OB QUALITY CONTROL
8.IB Refer to Chapter One for specific quality control procedures.
8.2B Each sample should be tested two times. If the results do not
agree to within 10%, expressed as the relative percent difference of the results,
a third test must be performed. Report the results of the two that agree.
9.OB METHOD PERFORMANCE
9.IB These data are based on 49 data points obtained by seven
laboratories who each analyzed four used crankcase oils and three fuel oil blends
with crankcase in duplicate. A data point represents one duplicate analysis of
a sample. There were no outlier data points or laboratories.
9.2B Precision. The precision of the method as determined by the
statistical examination of inter!aboratory test results is as follows:
Repeatability - The difference between successive results obtained
by the same operator with the same apparatus under constant
operating conditions on identical test material would exceed, in
the long run, in the normal and correct operation of the test
method, the following values only in 1 case in 20 (see Table 2):
Repeatability = 0.31 x*
*where x is the average of two results in M9/g-
Reproducibility - The difference between two single and
independent results obtained by different operators working in
different laboratories on identical test material would exceed,
in the long run, the following values only in 1 case in 20:
Reproducibility = 0.60 x*
*where x is the average value of two results in M9/9-
9.3B Bias. The bias of this test method varies with concentration, as
shown in Table 3:
Bias = Amount found - Amount expected
9077 - 11 Revision 0
September 1994
-------
TABLE 2.
REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
OILS BY THE QUANTITATIVE END POINT TEST KIT METHOD
Average value, Repeatability, Reproducibility,
Mg/g Mg/g Mg/g
1,000
1,500
2,000
2,500
3,000
310
465
620
775
930
600
900
1,200
1,500
1,800
TABLE 3.
RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY THE
QUANTITATIVE END POINT TEST KIT METHOD
Amount
expected,
Mg/g
320 (< 750)a
480 (< 750 )a
920
1,498
1,527
3,029
3,045
Amount
found,
Mg/g
776
782
1,020
1,129
1,434
1,853
2,380
Bias,
Mg/g
+16
+32
+100
-369
-93
-1,176
-665
Percent
bias
+3
+4
+11
-25
-6
-39
-22
a The lower limit of the kit is 750
9077 - 12 Revision 0
September 1994
-------
Reaction bottle
Titration via
x
f Buffer
bottle
Filtering
Column
Valve assembly
Micro pipet
Figure 1. Components of CHEMetrics Total Chlorine in Waste Oil Test Kit
(Cat. No. K2610).
9077 - 13
Revision 0
September 1994
-------
Push plunger
down to
transfer
sample
Figure 2.1
Figure 2.2
* Crush
Figure 23
Buffer Bottle
Figure 2.4
Reaction bottle
upsidedown in
component tray
Figure 2.5
Aqueous
Layer
Filtering Column
Figure 2.6
Titration Vial
Figure 2. Reaction-Extraction Procedure.
9077 - 14
Revision 0
September 1994
-------
Attaching
Valve
Assembly
Assembly
Figure 3.1
/ \
Titret
Lift control bar
Snapping
the Tip
Figure 3.2
Performing the
Analysis
Figure 33
Watch for
color change
here
Press control bar
Sample pipe
Readihg
the Result
Figure 3.4
Read
scale units
when color
changes
permanently
Figure 3. Titration Procedure
9077 - 15
Revision 0
September 1994
-------
METHOD 9077, METHOD B
REVERSE TITRATION QUANTITATIVE END POINT TEST KIT METHOD
STURT
7. IB Shake glass
vial ; pour into
reaction bottle
7.2B Fill
micropipet with
oil; remove excess
oil; t ransf er oil
to reaction bottle
1
from reaction
bottle; cap ; mix
1
7 . 4B Crush sodium
ampoule
1
7. SB - 7 .68 Shake
reaction bottle for
30 ปecondป ; wait
one minute
7 . 7B Pour buffer
into reaction
bottle
ป
7. SB - 7.9B Shake
gently; release
gaซ; shake; release
gas ; turn bottle
upside down; wait
one minute
1
7 .108 Prepare
filtering column
1
7.11B Filter lower
aqueous layer
through f il ter ing
column into
ti tration vial
1
7.12B Shake vial
I
7 .13B Assemble
valve assembly over
Titret
7.14B Insert Titret
into Titrettor
-ป
7 15B Snap tip of
Titret
1
7.16B - 7.20B Pull
mal 1 amount of
ample into Titret;
win ; wait 30
seconds ; repeat
changes from purple
to pale yel 1 ow
I
7.21B When color
changes to pale
yel 1 ow , remove
Titret; record test
result from Titret
1
7.22B Calculate
concentration of
chlorine in ug/g
STOP J
9077 - 16
Revision 0
Septenter 1994
-------
METHOD C
DIRECT TITRATION QUANTITAVE END POINT TEST KIT METHOD
4.0C APPARATUS AND MATERIALS
4.1C The CHLOR-D-TECT Q40003 is a complete self-contained kit. It
includes: a sampling syringe to withdraw a fixed sample volume for analysis; a
polyethylene test tube #1 into which the sample is introduced for dilution and
reaction with metallic sodium; a polyethylene tube #2 containing a buffered
aqueous extractant and the diphenylcarbazone indicator; a microburette containing
the mercuric nitrate titrant; and a plastic filtration funnel. Also included are
instructions to conduct the test.
5.0C REAGENTS
5.1C All necessary reagents are contained within the kit. The diluent
solvent containing the catalyst, the metallic sodium, and the diphenylcarbazone
are separately glass-encapsulated in the precise quantity required for analysis.
A predispensed volume of buffer is contained in the second polyethylene tube.
Mercuric.nitrate titrant is also supplied in a sealed titration burette.
5.2C The kit should be examined upon opening to see that all of the
components are present and that all ampoules (3) are in place and not leaking.
The liquid in Tube #2 (clear cap) should be approximately 1/2 in. above the 5-mL
line and the tube should not be leaking. The ampoules are not supposed to be
completely full.
6.0C SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1C See Section 6.0A of Method A.
7.0C PROCEDURE
7.1C Preparation. Open analysis carton, remove contents, mount plastic
test tubes in the provided holder.
NOTE: Perform the test in a warm, dry area with adequate light.
In cold weather, a truck cab is sufficient. If a warm area is not
available, Step 7.3C should be performed while warming Tube #1 in
palm of hand.
7.2C Sample introduction. Unscrew the white dispenser cap from Tube #1.
Slide the plunger in the empty syringe a few times to make certain that it slides
easily. Place the top of the syringe in the oil sample to be tested, and pull
back on the plunger until it reaches the stop and cannot be pulled further.
Remove the syringe from the sample container, and wipe any excess oil from the
outside of the syringe with the enclosed tissue. Place the tip of the syringe
in Tube #1, and dispense the oil sample by depressing the plunger. Replace the
white cap on the tube.
Available from Dexsil Corporation, One Hamden Park Drive, Hamden, CT 06517.
9077 - 17 Revision 0
September 1994
-------
7.3C Reaction. Break the lower (colorless) capsule containing the clear
diluent solvent by squeezing the sides of the test tube. Mix thoroughly by
shaking the tube vigorously for 30 seconds. Crush the upper grey ampoule
containing metallic sodium, again by squeezing the sides of the test tube. Shake
vigorously for 20 seconds. Allow reaction to proceed for 60 seconds, shaking
intermittently several times while timing with a watch.
CAUTION: Always crush the clear ampoule in each tube first.
Otherwise, stop the test and start over using another complete kit.
False (low) results may occur and allow a contaminated sample to
pass without detection if clear ampoule is not crushed first.
7.4C Extraction. Remove caps from both tubes. Pour the clear buffered
extraction solution from Tube #2 into Tube #1. Replace the white cap on Tube #1,
and shake vigorously for 10 seconds. Vent tube by partially unscrewing the
dispenser cap. Close cap securely, and shake for an additional 10 seconds. Vent
again, tighten cap, and stand tube upside down on white cap. Allow phases to
separate for 2 minutes.
NOTE: Tip Tube #2 to an angle of only about 45ฐ. This will prevent
the holder from sliding out.
7.5C Analysis. Put filtration funnel into Tube #2. Position Tube #1
over funnel and open nozzle on dispenser cap. Squeeze the sides of Tube #1 to
dispense the clear aqueous lower phase through the filter into Tube #2 to the 5-
mL line on Tube #2. Remove the filter funnel, and close the nozzle on the
dispenser cap. Place the plunger rod in the titration burette and press until
it clicks into place. Break off (do not pull off) the tip on the titration
burette. Insert the burette into Tube #2, and tighten the cap. Break the
colored ampoule, and shake gently for 10 seconds. Dispense titrant dropwise by
pushing down on burette rod in small increments. Shake the tube gently to mix
titrant with solution in Tube #2 after each increment. Continue adding titrant
until solution turns from yellow to red-violet. An intermediate pink color may
develop in the solution, but should be disregarded. Continue titrating until a
true red-violet color is realized. The chlorine concentration of the original
oil sample is read directly off the titrating burette at the tip of the black
plunger. Record this result immediatley as the red-violet color will fade with
time.
8.0C QUALITY CONTROL
8.1C Refer to Chapter One for specific quality control procedures.
8.2C Each sample should be tested two times. If the results do not
agree to within 10%, expressed as the relative percent difference of the results,
a third test must be performed. Report the results of the two that agree.
9.0C METHOD PERFORMANCE
9.1C These data are based on 96 data points obtained by 12 laboratories
who each analyzed six used crankcase oils and two fuel oil blends with crankcase
in duplicate. A data point represents one duplicate analysis of a sample.
9077 - 18 Revision 0
September 1994
-------
9.2C Precision. The precision of the method as determined by the
statistical examination of interlaboratory test results is as follows:
Repeatability - The difference between successive results obtained
by the same operator with the same apparatus under constant
operating conditions on identical test material would exceed, in
the long run, in the normal and correct operation of the test
method, the following values only in 1 case in 20 (see Table 4):
Repeatability = 0.175 x*
*where x is the average of two results in
Reproducibility - The difference between two single and independent
results obtained by different operators working in different
laboratories on identical test material would exceed, in the long
run, the following values only in 1 case in 20:
Reproducibility = 0.331 x*
*where x is the average value of two results in /xg/g.
9.3C Bias. The bias of this test method varies with concentration, as
shown in Table 5:
Bias = Amount found - Amount expected
10.0 REFERENCE
1. Gaskill, A.; Estes, E.D.; Hardison, D.L.; and Myers, I.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. 68-01-7075, wA 80. July 1988.
9077 - 19 Revision 0
September 1994
-------
TABLE 4.
REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
OILS BY THE QUANTITATIVE END POINT TEST KIT METHOD
Average value, Repeatability, Reproducibility,
500
1,000
1,500
2,000
2,500
3,000
4,000
88
175
263
350
438
525
700
166
331
497
662
828
993
1,324
TABLE 5.
RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY THE
QUANTITATIVE END POINT TEST KIT METHOD
Amount
expected,
Aig/9
664
964
1,230
1,445
2,014
2,913
3,812
4,190
Amount
found,
Mg/g
695
906
1,116
1,255
1,618
2,119
2,776
3,211
Bias,
Mg/g
31
-58
-114
-190
-396
-794
-1,036
-979
Percent
bias
+5
-6
-9
-13
-20
-27
-27
-23
9077 - 20 Revision 0
September 1994
-------
METHOD 9077, METHOD C
DIRECT TITRATION QUANTITAVE END POINT TEST KIT METHOD
START
7.1C Open test kit
7 2C Draw oil into
yringe; remove
excess oil;
dispense oil into
Tube #1
7 3C Break
colorless capsule;
mix; crush grey
capsule; mix; allow
reaction to proceed
for 60 seconds
7.4C Pour Tube #2
solution into Tube
tl; mix; vent;
allow phases to
separate
7.SC Filter aqueous
lower phase in Tube
t\ into Tube 12;
remove filter
funnel
7.SC Place plunger
in titraton
burette; press;
break off.burette
tip;- insert burette
in Tube f2\ break
colored ampoule;
shake
7.SC Dispense
titrant; shake;
repeat process
until solution
turns from yellow
to red-violet
7.SC Record level
from titrating
burette
STOP
9077 - 21
Revision 0
September 1994
-------
METHOD 9131
TOTAL COLIFORM; MULTIPLE TUBE FERMENTATION TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 This method is used to determine the presence of a member of the
coliform group in ground water and surface water.
1.2 The coliform group, as analyzed for in this procedure, is defined as
all aerobic and facultative anaerobic, gram-negative, non-spore-forming, rod-
shaped bacteria that ferment lactose with gas formation within 48 hr at 35*C.
2.0 SUMMARY OF METHOD
2.1 The multiple-tube fermentation technique is a three-stage procedure
1n which the results are statistically expressed 1n terms of the Most Probable
Number (MPN). These stages the presumptive stage, confirmed stage, and
completed test are briefly summarized below. (For the analysis to be
accurate, a five-tube test is required.)
2.1.1 Presumptive Stage: A series of lauryl tryptose broth primary
fermentation tubes are Inoculated with graduated quantities of the sample
to be tested. The Inoculated tubes are Incubated at 35 + 0.5*C for
24 + 2 hr, at which time the tubes are examined for gas formation. For
the~tubes in which no gas is formed, continue Incubation and examine for
gas formation at the end of 48 + 3 hr. Formation of gas in any amount
within 48 + 3 hr is a positive presumptive test.
2.1.2 Confirmed Stage: The confirmed stage is used on all primary
fermentation tubes showing gas formation during the 24-hr and 48-hr
periods. Fermentation tubes containing brilliant green lactose bile
broth are Inoculated with medium from the tubes showing a positive result
1n the presumptive test. Inoculation should be performed as soon as
possible after gas formation occurs. The inoculated tubes are Incubated
for 48 + 3 hr at 35 + 0.5*C. Formation of gas at any time 1n the tube
Indicates a positive confirmed test.
2.1.3 Completed Test: The completed test 1s performed on all
samples showing a positive result in the confirmed test. It can also be
used as a quality control measure on 20% of all samples analyzed. One or
more plates of eosin methylene blue are streaked with sample to be
analyzed. The streaked plates are incubated for 24 + 2 hr at 35 + 0.5*C.
After Incubation, transfer one or more typical colonies (nucleated, with
or without metallic sheen) to a lauryl tryptose broth fermentation tube
and a nutrient agar slant. The fermentation tubes and agar slants are
Incubated at 35 + 0.5*C for 24+2 hr, or for 48 + 3 hr 1f gas is not
produced. From the agar slants corresponding to the fermentation tubes
1n which gas formation occurs, gram-stained samples are examined
9131 - 1
Revision
Date September 1986
-------
microscopically. The formation of gas 1n the fermentation tube and the
presence of gram-negative, non-spore-forming, rod-shaped bacteria 1n the
agar culture may be considered a satisfactorily completed test,
demonstrating the positive presence of coHform bacteria 1n the analyzed
sample.
2.2 More detailed treatment of this method 1s presented 1n Standard
Methods for the Examination of Water and Wastewater and 1n Microbiological
Methods for Monitoring the Environment (see References, Section 10.0).
3.0 INTERFERENCES
3.1 The distribution of bacteria 1n water 1s Irregular. Thus, a
five-tube test 1s required 1n this method for adequate statistical accuracy.
3.2 The presence of residual chlorine or other halogens can prevent the
continuation of bacterial action. To prevent this occurrence, sodium
thlosulfate should be added to the sterile sample container.
3.3 Water samples high 1n copper, zinc, or other heavy metals can be
toxic to bacteria. Chelatlng agents such as ethylenedlaminetetraacetlc add
(EDTA) should be added only when heavy metals are suspected of being present.
3.4 It 1s Important to keep 1n mind that MPN tables are probability
calculations and Inherently have poor precision. They Include a 23% positive
bias that generally results in high value. The precision of the MPN can be
Improved by increasing the number of sample portions examined and the number
of samples analyzed from the same sampling point.
4.0 APPARATUS AND MATERIALS
4.1 Incubators:
4.1.1 Incubators must maintain a uniform and constant temperature
at all times in all areas, that 1s, they must not vary more than +0.5'C
1n the areas used. Obtain such accuracy by using a water-jacketed or
anhydric-type Incubator with thermostatically controlled low-temperature
electric heating units properly insulated and located 1n or adjacent to
the walls or floor of the chamber and preferably equipped with mechanical
means of circulating air. If a hot-air type incubator is used, humidity
must be maintained at 75-80%.
4.1.2 Alternatively, use special Incubating rooms well Insulated
and equipped with properly distributed heating units and with forced air
circulation, provided that they conform to desired temperature limits and
relative humidity. When such rooms are used, record the dally
temperature range in areas where plates or tubes are Incubated. Provide
Incubators with open metal wire or sheet shelves so spaced as to assure
temperature uniformity throughout the chamber. Leave a 2.5-cm space
between walls and stacks of dishes or baskets of tubes.
9131 - 2
Revision 0
Date September 1986
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4.1.3 Maintain an accurate thermometer with the bulb Immersed 1n
liquid (glycerine, water, or mineral oil) on each shelf 1n use within the
Incubator and record dally temperature readings (preferably morning and
afternoon). It 1s desirable, 1n addition, to maintain a maximum and
minimum registering thermometer within the incubator on the middle shelf
to record the gross temperature range over a 24-hr period. At intervals,
determine temperature variations within the Incubator when filled to
maximum capacity. Install a recording thermometer, whenever possible, to
maintain a continuous and permanent record of temperature. Mercury
thermometers should be graduated in 0.5'C increments and calibrated
annually against an NBS certified thermometer. Dial thermometers should
be calibrated quarterly.
4.1.4 Keep water depth 1n the water bath sufficient to Immerse
tubes to upper level of media.
4.2 Hot-a1r sterilizing ovens: Use hot-air sterilizing ovens of
sufficient size to prevent Internalcrowding, constructed to give uniform and
adequate sterilizing temperatures of 170 + 10*C and equipped with suitable
thermometers. As an alternative, use a temperature-recording Instrument.
4.3 Autoclaves:
4.3.1 Use autoclaves of sufficient size to prevent internal
crowding, constructed to provide uniform temperatures within the chambers
(up to and Including the sterilization temperature of 121*C); equipped
with an accurate thermometer, the bulb of which 1s located properly on
the exhaust line so as to register minimum temperature within the
sterilizing chambers (temperature-recording Instrument 1s optional);
equipped with pressure gauge and properly adjusted safety valves
connected directly with saturated-steam power lines or directly to a
suitable special steam generator (do not use steam from a boiler treated
with amines for corrosion control); and capable of reaching the desired
temperature within 30 m1n.
4.3.2 Use of a vertical autoclave or pressure cooker 1s not
recommended because of difficulty 1n adjusting and maintaining
sterilization temperature and the potential hazard. If a pressure cooker
1s used 1n emergency or special circumstances, equip 1t with an efficient
pressure gauge and a thermometer, the bulb of which is 2.5 cm above the
water level.
4.4 Colony counters; Use Quebec-type colony counter, dark-field model
preferred, or one providing equivalent magnification (1.5 diameters) and
satisfactory visibility.
4.5 pH Equipment; Use electrometrlc pH meters, accurate to at. least 0.1
pH units, for determining pH values of media. See Method 9040 for standardi-
zation of a pH meter.
9131 - 3
Revision
Date September 1986
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4.6 Balances; Use balances providing a sensitivity of at least 0.1 g at
a load of 150 g, with appropriate weights. Use an analytical balance having a
sensitivity of 1 mg under a load of 10 g for weighing small quantities (less
than 2 g) of materials. Single-pan rapid-weigh balances are most convenient.
4.7 Media preparation utensils; Use boroslHcate glass or other
suitable noncorroslve equipment such as stainless steel. Use glassware that
1s clean and free of residues, dried agar, or other foreign materials that may
contaminate media.
4.8 Pipets and graduated cylinders;
4.8.1 Use plpets of any convenient size, provided that they deliver
the required volume accurately and quickly. The error of calibration for
a given manufacturer's lot must not exceed 2.5%. Use plpets having
graduations distinctly marked and with unbroken tips. Bacteriological-
transfer plpets or plpets conforming to the APHA standards given 1n the
latest edition of Standard Methods for the Examination of Dairy Products
may be used. Optimally, protect themouth end of all plpets by a cotton
plug to eliminate hazards to the worker or possible sample contamination
by saliva.
4.8.2 Use graduated cylinders meeting ASTM Standards (D-86 and D-
216) and with accuracy limits established by the National Bureau of
Standards, where appropriate.
4.9 P1pet containers; Use boxes of aluminum or stainless steel, end
measurement 5 to 7.5 cm, cylindrical or rectangular, and length about 40 cm.
When these are not available, paper wrappings may be substituted. To avoid
excessive charring during sterilization, use best-quality sulfate pulp (Kraft)
paper. Do not use copper or copper alloy cans or boxes as plpet containers.
4.10 Dilution bottles or tubes;
4.10.1 Use bottles or tubes of resistant glass, preferably
boroslHcate glass, closed with glass stoppers or screw caps equipped
with liners that do not produce toxic or bacteriostatlc compounds on
sterilization.
4.10.2 Do not use cotton plugs as closures. Mark gradation levels
Indelibly on side of dilution bottle or tube. Plastic bottles of
nontoxlc material and acceptable size may be substituted for glass,
provided that they can be sterilized properly.
4.11 Petri dishes; Use glass or plastic Petri dishes about 100 x 15 mm.
Use dishes the bottoms of which are free from bubbles and scratches and flat
so that the medium will be of uniform thickness throughout the plate. For the
membrane-filter technique, use loose-Hd glass or plastic dishes, 60 x 15 mm,
or tight-lid dishes, 50 x 12 mm. Sterilize Petri dishes and store 1n metal
cans (aluminum or stainless steel, but not copper), or wrap 1n paper
preferably best-quality sulfate pulp (Kraft) before sterilizing.
9131 - 4
Revision
Date September 1986
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4.12 Fermentation tubes and vials; Use only 10-iran x 75-mm fermentation
tubes. When tubes areusedforatest of gas production, enclose a shell
vial, Inverted. Use a vial of such size that 1t will be filled completely
with medium and at least partly submerged 1n the tube.
4.13 Inoculating equipment; Use wire loops made of 22- or 24-gauge
nickel alloy (chromel, n1chrome, or equivalent) or plat1num-1r1d1um for flame
sterilization. Single-service transfer loops of aluminum or stainless steel
are satisfactory. Use loops at least 3 mm 1n diameter. Sterilize by dry heat
or steam. Single-service hardwood applicators also may be used. Make these
0.2 to 0.3 cm 1n diameter and at least 2.5 cm longer than the fermentation
tube; sterilize by dry heat and store 1n glass or other nontoxlc containers.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Buffered water;
5.2.1 To prepare stock phosphate buffer solution, dissolve 34.0 g
potassium d1hydrogen phosphate (KHgPC^) 1n 500 ml Type II water, adjust
to pH 7.2 + 0.5 with 1 N sodium hydroxide (NaOH), and dilute to 1 liter
with Type II water.
5.2.2 Add 1.25 ml stock phosphate buffer solution and 5.0 ml
magnesium chloride solution (38 g MgCl2/Hter Type II water or
81.1 g MgCl2-6H20/l1ter Type II water) to 1 liter Type II water.
Dispense 1n amounts that will provide 99 + 2.0 ml or 9 + 0.2 ml after
autoclavlng for 15 m1n.
5.2.3 Peptone water: Prepare a 10% solution of peptone in Type II
water. Dilute a measured volume to provide a final 0.1% solution. Final
pH should be 6.8.
5.2.4 Dispense 1n amounts to provide 99 + 2.0 ml or 9 + 0.2 ml
after autoclavlng for 15 m1n.
5.2.5 Do not suspend bacteria 1n any dilution water for more than
30 m1n at room temperature because death or multiplication may occur,
depending on the species.
9131 - 5
Revision
Date September 1986
-------
5.3 Lauryl tryptose broth;
5.3.1 Components of the broth are:
Tryptose 20.0 g
Lactose 5.0 g
01phosphate hydrogen
phosphate, K2HP04 2.75 g
Potassium d1hydrogen
phosphate, KH2P04 2.75 g
Sodium chloride, NaCl 5.0 g
Sodium lauryl sulfate 0.1 g
Type II water 1 liter
Lauryl tryptose broth 1s also available 1n a prepackaged dry powder form.
5.3.2 Make lauryl tryptose broth of such strength that adding
100-mL or 10-mL portions of sample to medium will not reduce Ingredient
concentrations below those of the standard medium. Prepare 1n accordance
with Table 1.
TABLE 1. PREPARATION OF LAURYL TRYPTOSE BROTH
Inoculum
(ปL)
1
10
10
100
100
100
Amount of
Medium 1n Tube
(mL)
10 or more
10
20
50
35
20
Volume of
Medium +
Inocul urn
(mL)
11 or more
20
30
150
135
120
Dehydrated Lauryl
Tryptose Broth
Required
(g/Hter)
35.6
71.2
53.4
106.8
137.1
213.6
5.3.3 Dispense the broth Into fermentation tubes which contain
Inverted vials. Add an amount sufficient to cover the Inverted vial, at
least partially, after sterilization has taken place. Sterilize at 121*C
for 12 to 15 m1n. The pH should be 6.8 + 0.2 after sterilization.
5.4 Brilliant green lactose bile broth;
5.4.1 Components of the broth are:
Peptone 10.0 g
Lactose 10.0 g
Oxgall 20.0 g
Brilliant green 0.0133 g
Type II water 1 liter
9131 - 6
Revision
Date September 1986
-------
This broth 1s also available 1n a prepackaged dry powder form.
5.4.2 Dispense the broth Into fermentation tubes which contain
Inverted vials. Add an amount sufficient to cover the Inverted vial, at
least partially, after sterilization has taken place. Sterilize at 121'C
for 12 to 15 m1n. The pH should be 7.2 + 0.2 after sterilization.
5.5 Ammonium oxalate-crystal violet (Mucker's); Dissolve 2 g crystal
violet (90% 3ye content) Tn 20 nil 95% ethyl alcohol, dissolve 0.8 g
(NH4)2C204'H20 1n 80 ml Type II water, mix the two solutions, and age for
24 hr before use; filter through paper Into a staining bottle.
5.6 Lugol's solution, Gram's modification: Grind 1 g Iodine crystals
and 2 g KI in a mortar.Add"TypeII water, a few m1111liters at a time, and
grind thoroughly after each addition until solution 1s complete. Rinse
solution Into an amber glass bottle with the remaining water (using a total of
300 ml).
5.7 Counterstain: Dissolve 2.5 g safranln dye 1n 100 ml 95% ethyl
alcohol. Add 10 ml to 100 ml Type II water.
5.8 Acetone alcohol; Mix equal volumes of ethyl alcohol, 95%, with
acetone.
5.9 Gram staining kits; Commercially available kits may be substituted
for 5.5, 5.6, 5.7, and 5.8.
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 U.S. EPA, 1978.
6.2 Clean all glassware thoroughly with a suitable detergent and hot
water, rinse with hot water to remove all traces of residual washing compound,
and finally rinse with Type II water. If mechanical glassware washers are
used, equip them with Influent plumbing of stainless steel or other nontoxic
material. Do not use copper piping to distribute Type II water. Use
stainless steel or other nontoxic material for the rinse-water system.
6.2.1 Sterilize glassware, except when 1n metal containers, for not
less than 60 min at a temperature of 170*C, unless 1t is known from
recording thermometers that oven temperatures are uniform, under which
exceptional condition use 160*C. Heat glassware in metal containers to
170*C for not less than 2 hr.
6.2.2 Sterilize sample bottles not made of plastic as above, or 1n
an autoclave at 121*C for 15 m1n. Perform a sterility check on one
bottle per batch.
9131 - 7
Revision
Date September 1986
-------
6.2.3 If water containing residual chlorine and other halogens 1s
to be collected, add sufficient ^$203 to clean sample bottle before
sterilization to give a concentration of about 100 mg/L 1n the sample.
To a 120-mL bottle add 0.1 ml 10% solution of ^28203 (this will
neutralize a sample containing about 15 mg/L residual chlorine). Stopper
bottle, cap, and sterilize by either dry or moist heat, as directed
previously.
6.2.4 Collect water samples high 1n copper or zinc and wastewater
samples high 1n heavy metals 1n sample bottles containing a chelatlng
agent that will reduce metal toxlclty. This 1s particularly significant
when such samples are 1n transit for 4 hr or more. Use 372 mg/L of the
tetrasodlum salt of ethylenedlaminetetraacetlc add (EDTA). Adjust EDTA
solution to pH 6.5 before use. Add EDTA separately to sample bottle
before bottle sterilization (0.3 mL 15% solution 1n a 120-mL bottle) or
combine It with the ^28203 solution before addition.
6.3 When the sample 1s collected, leave ample air space 1n the bottle
(at least 2.5 cm) to facilitate mixing by shaking, preparatory to examination.
Be careful to take samples that will be representative of the water being
tested and avoid sample contamination at time of collection or In period
before examination.
6.4 Keep sampling bottle closed until the moment 1t 1s to be filled.
Remove stopper and hood or cap as a unit, taking care to avoid soiling.
During sampling, do not handle stopper or cap and neck of bottle and protect
them from contamination. Hold bottle near base, fill 1t without rinsing,
replace stopper or cap Immediately, and secure hood around neck of bottle.
7.0 PROCEDURE
7.1 Presumptive stage;
7.1.1 Inoculate a series of fermentation tubes ("primary"
fermentation tubes) with appropriate graduated quantities (multiples and
submultlples of 1 mL) of sample. Be sure that the concentration of
nutritive Ingredients 1n the mixture of medium and added sample conforms
to the requirements given 1n Paragraph 5.3. Use a sterile plpet for
Initial and subsequent transfers from each sample container. If the
plpet becomes contaminated before transfers are completed, replace with a
sterile plpet. Use a separate sterile plpet for transfers from each
different dilution. Do not prepare dilutions 1n direct sunlight. Use
caution when removing sterile plpets from the container; to avoid
contamination, do not drag plpet tip across exposed ends of plpets or
across Ups and necks of dilution bottles. When removing sample, do not
Insert plpets more than 2.5 cm below the surface of sample or dilution.
When discharging sample portions, hold plpet at an angle of about 45*,
with tip touching the Inside neck of the tube. The portions of sample
used for Inoculating lauryl-tryptose-broth fermentation tubes will vary
1n size and number with the character of the water under examination, but
9131 - B
Revision 0
Date September 1986
-------
1n general use decimal multiples and submultiples of 1 ml. Use Figure 1
as a guide to preparing dilutions. After adding sample, mix thoroughly
by shaking the test tube rack. Do not invert the tubes.
7.1.2 Incubate inoculated fermentation tubes at 35 + 0.5*C. After
24 + 2 hr shake each tube gently and examine it and, if no gas has formed
and been trapped in the inverted vial, reincubate and reexamine at the
end of 48 + 3 hr. Record presence or absence of gas formation,
regardless of amount, at each examination of the tubes.
7.1.3 Formation of gas in any amount in the inner fermentation
tubes or vials within 48 + 3 hr constitutes a positive presumptive test.
Do not confuse the appearance of an air bubble in a clear tube with
actual gas production. If gas is formed as a result of fermentation, the
broth medium will become cloudy. Active fermentation may be shown by the
continued appearance of small bubbles of gas throughout the medium
outside the inner vial when the fermentation tube is shaken gently.
7.1.4 The absence of gas formation at the end of 48+3 hr of
incubation constitutes a negative test. An arbitrary limit of 48 hr for
observation doubtless excludes from consideration occasional members of
the coliform group that form gas very slowly and generally are of limited
sanitary significance.
7.2 Confirmed stage;
7.2.1 Submit all primary fermentation tubes showing any amount of
gas within 24 hr of incubation to the Confirmed Test. If active
fermentation appears in the primary fermentation tube earlier than 24 hr,
transfer to the confirmatory medium without waiting for the full 24-hr
period to elapse. If additional primary fermentation tubes show gas
production at the end of 48-hr incubation, submit these to the Confirmed
Test.
7.2.2 Gently shake or rotate primary fermentation tube showing gas
and do one of two things: (a) with a sterile metal loop, 3 mm 1n
diameter, transfer one loopful of culture to a fermentation tube
containing brilliant green lactose bile broth, or (b) Insert a sterile
wooden applicator at least 2.5 cm long Into the culture, remove it
promptly, and plunge it to the bottom of fermentation tube containing
brilliant green lactose bile broth. Remove and discard applicator.
7.2.3 Incubate the inoculated brilliant green lactose bile broth
tube for 48 + 3 hr at 35 + 0.5*C. Formation of gas in any amount 1n the
inverted viaT of the brilliant green lactose bile broth fermentation tube
at any time within 48 + 3 hr constitutes a positive Confirmed Test.
7.3 Completed test;
7.3.1 Use the Completed Test on positive confirmed tubes to
establish definitely the presence of col 1 form bacteria and provide
quality control data for 20% of all samples analyzed.
9131 - 9
Revision 0
Date September 1986
-------
Water
sample
1 ml
Delivery
volume
Culture dishes
Actual volume
of sample in
dish
\
1 ml
0.1 ml
1 ml
0.1 ml
10'2 ml
10'3 ml
Figure 1. Preparation of dilutions.
9131 - 10
Revision p_
Date September
1986
-------
7.3.2 Streak one or more eosin methylene blue plates from each tube
of brilliant green lactose bile broth showing gas as soon as possible
after the appearance of gas. Streak plates to ensure presence of some
discrete colonies separated by at least 0.5 cm. Observe the following
precautions when streaking plates to obtain a high proportion of
successful Isolations if coll form organisms are present: (a) use an
Inoculating needle slightly curved at the tip; (b) tap and Incline the
fermentation tube to avoid picking up any membrane or scum on the needle;
(c) Insert end of needle into the liquid in the tube to a depth of
approximately 5.0 mm; and (d) streak plate with curved section of the
needle 1n contact with the agar to avoid a scratched or torn surface.
7.3.3 Incubate plates (Inverted) at 35 + 0.5*C for 24+2 hr.
7.3.4 The colonies developing on eosin methylene blue agar are
called: typical (nucleated, with or without metallic sheen); atypical
(opaque, unnucleated, mucoid, pink after 24-hr Incubation); or negative
(all others). From each of these plates, pick one or more typical well-
Isolated coliform colonies or, 1f no typical colonies are present, pick
two or more colonies considered most likely to consist of organisms of
the coliform group and transfer growth from each isolate to a lauryl-
tryptose-broth fermentation tube and to a nutrient agar slant.
NOTE: If possible, when transferring colonies, choose well-Isolated
colonies and barely touch the surface of the colony with a
flame-sterilized, air-cooled transfer needle to minimize the
danger of transferring a mixed culture.
7.3.5 Incubate secondary broth tubes at 35 + 0.5*C for 24+2 hr;
1f gas 1s not produced within 24+2 hr, reincubate and examine again at
48+3 hr. Microscopically examine gram-stained preparations (see
Paragraph 7.4) from those 24-hr agar slant cultures corresponding to the
secondary tubes that show gas.
7.3.6 Formation of gas in the secondary tube of lauryl tryptose
broth within 48 + 3 hr and demonstration of gram-negative, non-spore-
forming, rod-shaped bacteria 1n the agar culture constitute a
satisfactory Completed Test, demonstrating the presence of a member of
the coliform group.
7.4 Gram-stain procedure;
7.4.1 Prepare a light emulsion of the bacterial growth from an agar
slant in a drop of Type II water on a glass slide. A1r-dry or fix by
passing the slide through a flame and stain for 1 m1n with the ammonium
oxalate-crystal violet solution. Rinse the slide 1n tap water; apply
Lugol's solution for 1 m1n. (See Paragraphs 5.5-5.8 for reagent.)
7.4.2 Rinse the stained slide in tap water. Decolorize for
approximately 15 to 30 sec with acetone alcohol by holding slide between
the fingers and letting acetone alcohol flow across the stained smear
until no more stain is removed. Do not over-decolorize. Counterstaln
with safranln (Paragraph 5.7) for 15 sec, then rinse with tap water, blot
dry with bibulous paper, and examine microscopically.
9131 - 11
Revision 0
Date September 1986
-------
7.4.3 Cells that decolorize and accept the safranln stain are pink
and defined as gram-negative 1n reaction. Cells that do not decolorize
but retain the crystal violet stain are deep blue and are defined as
gram-positive.
7.5 Computing and recording of MPN;
7.5.1 The calculated density of col 1 form bacteria 1n a sample can
be obtained from the MPN table, based on the number of positive tubes In
each dilution of the confirmed or completed test. Table 2 shows MPN
Indices and 95% confidence limits for potable water testing, and Table 3
describes the MPN Indices and 95% confidence limits for general use.
TABLE 2. MPN INDEX AND 95% CONFIDENCE LIMITS FOR VARIOUS COMBINATIONS OF
POSITIVE AND NEGATIVE RESULTS WHEN FIVE 10-mL PORTIONS ARE USED
Number of Tubes
Giving Positive
Reaction out of
5 of 10 mL each
0
1
2
3
4
5
MPN
Index per
100 mL
<2.2
2.2
5.1
9.2
16
>16
95% Confidence Limits
Lower Upper
0 6.0
0.1 12.6
0.5 19.2
1.6 29.4
3.3 52.9
8.0 Infinite
7.5.2 Three dilutions are necessary for the determination of the
MPN Index. For example (see Table 3), 1f five 10-mL, five 1.0-mL, and
five 0.1-mL portions of the samples are used as Inocula and four of the
10-mL, two of the 1-mL, and none of the 0.1-mL portions of Inocula give
positive results, the coded result 1s 4-2-0 and the MPN Index 1s 22 per
100 mL.
7.5.3 In cases when the serial decimal dilution 1s other than 10,
1, and 0.1 mL, or when more than three sample volumes are used 1n the
series, refer to the sources cited 1n Section 10.0, References, for the
necessary density determination procedures.
7.5.4 All MPN values for water samples should be reported on the
basis of a 100-mL sample.
8.0 QUALITY CONTROL
8.1 Extensive quality control procedures are provided In Part IV of U.S.
EPA, 1978 (see Section 10.0, References). These procedures should be adhered
to at all times.
9131 - 12
Revision 0
Date September 1986
-------
TABLE 3. MPN INDEX FOR SERIAL DILUTIONS OF SAMPLE
Number of Tubes
Giving Positive
Reaction out of
5 of
10 mL
each
0
0
0
0
1
1
1
1
1
2
2
2
2
2
2
3
3
3
3
3
3
3
4
4
4
4
4
5 Of
1 mL
each
0
0
1
2
0
0
1
1
2
0
0
1
1
2
3
0
0
1
1
2
2
3
0
0
1
1
1
5 of
0.1 mL
each
0
1
0
0
0
1
0
1
0
0
1
0
1
0
0
0
1
0
1
0
1
0
0
1
0
1
2
MPN
Index
per
100 mL
<2
2
2
4
2
4
4
6
6
5
7
7
9
9
12
8
11
11
14
14
17
17
13
17
17
21
26
95%
Confidence
Lower
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
<0.5
1
1
2
2
3
1
2
2
4
4
5
5
3
5
5
7
9
Limits
Upper
7
7
11
7
11
11
15
15
13
17
17
21
21
28
19
25
25
34
34
46
46
31
46
46
63
78
Source: U.S. EPA, 1978.
(Continued on next page)
9131 - 13
Revision 0
Date September 1986
-------
TABLE 3. MPN INDEX FOR SERIAL DILUTIONS OF SAMPLE
(Continued)
Number of Tubes
Giving Positive
Reaction out of
5 of
10 mL
each
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5 of
1 mL
each
2
2
3
3
4
0
0
0
1
1
1
2
2
2
3
3
3
3
4
4
4
4
4
5
5
5
5
5
5
5 of
0.1 mL
each
0
1
0
1
0
0
1
2
0
1
2
0
1
2
0
1
2
3
0
1
2
3
4
0
1
2
3
4
5
MPN
Index
per
100 mL
22
26
27
33
34
23
31
43
33
46
63
49
70
94
79
110
140
180
130
170
220
280
350
240
350
540
920
1600
^2400
95%
Confidence
Limits
Lower
7
9
9
11
12
7
11
15
11
16
21
17
23
28
25
31
37
. 44
35
43
57
90
120
68
120
180
300
640
Upper
67
78
80
93
93
70
89
110
93
120
150
130
170
220
190
250
340
500
300
490
700
850
1000
750
1000
1400
3200
5800
Source: U.S. EPA, 1978,
9131 - 14
Revision 0
Date September 1986
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8.2 Samples must be maintained as closely as possible to original
condition by careful handling and storage. Sample sites and sampling
frequency should provide data representative of characteristics and
variability of the water quality at that site. Samples should be analyzed
immediately. They should be refrigerated at a temperature of 1-4*C and
analyzed within 6 hr.
8.3 Quality control of culture media 1s critical to the validity of
microbiological analysis. Some important factors to consider are summarized
below:
8.3.1 Order media to last for only 1 yr; always use oldest stock
first. Maintain an inventory of all media ordered, including a visual
inspection record.
8.3.2 Hold unopened media for no longer than 2 yr. Opened media
containers should be discarded after 6 mo.
8.3.3 When preparing media keep containers open as briefly as
possible. Prepare media in delonized or distilled (Type II) water of
proven quality. Check the pH of the media after solution and
sterilization; it should be within 0.2 units of the stated value.
Discard and remake if it is not.
8.3.4 Autoclave media for the minimal time specified by the
manufacturer because the potential for damage increases with Increased
exposure to heat. Remove sterile media from the autoclave as soon as
pressure Is zero. Effectiveness of the sterilization should be checked
weekly, using strips or ampuls of Bacillus stearothemophelus.
8.3.5 Agar plates should be kept slightly open for 15 min after
pouring or removal from refrigeration to evaporate free moisture. Plates
must be free of lumps, uneven surfaces, pock marks, or bubbles, which can
prevent good contact between the agar and medium.
8.3.6 Avoid shaking fermentation tubes, which can entrap air 1n the
Inner vial and produce a false positive result.
8.3.7 Store fermentation tube media in the dark at room temperature
or 4*C. If refrigerated, Incubate overnight at room temperature to
detect false positive gas bubbles.
8.3.8 Quality control checks of prepared media should include the
incubation of 5% of each batch of medium for 2 days at 35'C to inspect
for growth and positive/negative checks with pure culture.
8.4 Analytical quality control procedures should include;
8.4.1 Duplicate analytical runs on at least 10% of all known
* positive samples analyzed.
9131 - 15
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Date September 1986
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8.4.2 At least one positive control sample should be run each month
for each parameter tested.
8.4.3 At least one negative (sterile) control should be run with
each series of samples using buffered water and the medium batch used at
the beginning of the test series and following every tenth sample. When
sterile controls indicate contamination, new samples should be obtained
and analyzed.
8.4.4 The Type II water used should be periodically checked for
contamination.
8.4.5 For routine MPN tests, at least 5% of the positive confirmed
samples should be tested by the complete test.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
1. Standard Methods for the Examination of Water and Wastewater, 15th ed.
(1980).
2. U.S. Environmental Protection Agency, Microbiological Methods for
Monitoring the Environment, EPA 600/8-78-017, December 1978.
9131 - 16
Revision
Date September 1986
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METHOD 9i3>
TOT*L COLIFOซM: MULTIPLE TUBE FERMENTATION TECHNIOJE
Presumpt1ve
Stage
7.1.1
Inoculate series of
fermentation tubes
with graouateo
quantities of cample
7.1.8
Incubate
Inoculates
fermentation
tubes
.X 7.1.2 ^s.
Has
f ormea
. hour
gas >v
ifter Z* > ป
-c? jr
Xres
7.1.2
Relncubate ane
reexamine at
eno of 46 hours
Confirmeo
Stage
7.2.1
Submit tubes
for whIch gas
'has formea. to
Conflrmeo Test
7.S.2
Shake
tube:
place culture
In tube with
green lactose
bile brotn
7.2.3
Incubate bile
broth tube for
48 hours
7.1.3
9131 ~ 17
Revision o
Date September 1986
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TOTAL COLIFORM:
MetnoB 913.1
MULTIPLE TUBE FERMENTATION' TECHNIQUE
(Contlnueo)
Comoleteo
Test
7.3.1
of bacterial
growth from
agar slant for
gram-staIn
Submit
tuoes for
which gas has
formed to
Completed Test
7.3.2
7.4. i
Air-dry or fix
Streak aosin
netnylene blue elates
from each tube of
bile broth
snowing gas
7.4.2
7.3.5
Reincubate:
examine again
at 6 hours
stained prep-
arations froT.
slant cultures
(see 7.4)
Decolor lie.
counterstein
with safrenln;
examine
7.3.3[
Incubate
inverted plates
7.4.3
Gram
negative cells
are pink: gram
positive cells
are deeo blue
7.3.4
Pick typical
colonies: transfer
growth to
fermentation tube
no agar slant
7.3.5
7.5
'Calculate
density of
collform
bacteria from
MPN table
Incubate
secondary
broth tubes
for 24 hours
( Stop 1
9131 - 18
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Date September 1986
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METHOD 9132
TOTAL COLIFORM; MEMBRANE-FILTER TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 This method 1s used to determine the presence of a member of a
collform group 1n wastewater and ground water.
1.2 The conform group analyzed 1n this procedure Includes all of the
organisms that produce a colony with a golden-green metallic sheen within
24 hr of Inoculation.
2.0 SUMMARY OF METHOD
2.1 A predetermined amount of sample 1s filtered through a membrane
filter which retains the bacteria found 1n the sample.
2.2 In the two-step enrichment procedure, the filters containing
bacteria are placed on an absorbent pad saturated with lauryl tryptose broth
and Incubated at 35'C + 0.5*C for 2 hr. The filters are then transferred to
an absorbent pad saturated with M-Endo media or to a dish containing M-Endo
agar and incubated for another 21+1 hr at 35ฐC + 0.5ฐC. Sheen colonies are
then counted under magnification and reported per 100 ml of original sample.
2.3 A more detailed treatment of this method 1s presented in Standard
Methods for the Examination of Water and Wastewater and 1n Microbiological
Methods for Monitoring the Environment (see References, Section 10.0).
3.0 INTERFERENCES
3.1 The presence of residual chlorine or other halogen can prevent the
continuation of bacterial action. To prevent this occurrence, sodium
thiosulfate should be added.
3.2 Water samples high 1n copper, zinc, or other heavy metals can be
toxic to bacteria. Chelating agents such as ethylenediaminetetraacetic acid
(EDTA) should only be added when heavy metals are suspected of being present.
3.3 Turbidity caused by the presence of algae or other interfering
material may not permit testing of a sample volume sufficient to yield
significant results. Low coliform estimates may be caused by the presence of
high numbers of noncoliforms or of toxic substances.
3.4 Samples containing large amounts of suspended solids will interfere
with colony growth and with the subsequent counting of colonies on the filter
membrane. When this is the case, use Method 9131.
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4.0 APPARATUS AND MATERIALS
4.1 Dilution bottles or tubes;
4.1.1 Use bottles or tubes of resistant glass, preferably borosill-
cate glass, closed with glass stoppers or screw caps equipped with liners
that do not produce toxic or bacterlostatlc compounds on sterilization.
4.1.2 Do not use cotton plugs as closures. Mark graduation levels
Indelibly on side of dilution bottle or tube. Plastic bottles of
nontoxlc material and acceptable size may be substituted for glass,
provided that they can be sterilized properly.
4.2 Plpets and graduated cylinders;
4.2.1 Use pipets of any convenient size, provided that they deliver
the required volume accurately and quickly. The error of calibration for
a given manufacturer's lot must not exceed 2.5%. Use pipets having
graduations distinctly marked and with unbroken tips. Bacteriological-
transfer pipets or pipets conforming to the APHA standards given 1n the
latest edition of Standard Methods for the Examination of Dairy Products
may be used. Optimally, protect themouth end of all pipets by a cotton
plug to eliminate hazards to the worker or possible sample contamination
by saliva.
4.2.2 Use graduated cylinders meeting ASTM Standards (D-86 and
D216) and with accuracy limits established by the National Bureau of
Standards where appropriate.
4.3 Containers for culture medium;
4.3.1 Use clean borosilicate glass flasks presterillzed to reduce
bacterial contamination. Any size or shape of flask may be used, but
Erlenmeyer flasks with metal caps, metal foil covers, or screw caps
provide for adequate mixing of the medium and are convenient for storage.
4.4 Culture dishes;
4.4.1 Use Petri-type dishes, 60 by 15 mm, 50 x 12 mm, or other
appropriate size. The bottoms of the dishes should be flat and large
enough so that the absorbent pads for the culture nutrient will lie flat.
Wrap clean culture dishes before sterilization, singly or 1n convenient
numbers, in metal foil if sterilized by dry heat, or in suitable paper
substitute when autoclaved. If glass Petri dishes are used, use
borosilicate or equivalent glass. Because covers for such dishes are
loose fitting, take precautions to prevent possible loss of medium by
evaporation, with resultant change in medium concentration, and to
maintain a humid environment for optimal colony development.
4.4.2 Disposable plastic dishes that are tight fitting and meet the
specifications noted above also may be used. Suitable sterile plastic
dishes are available commercially.
9132 - 2
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4.5 Filtration units;
4.5.1 The filter-holding assembly (constructed of glass, auto-
clavable plastic, porcelain, or any noncorroslve bacteriologically Inert
metal) consists of a seamless funnel fastened by a locking device or held
1n place by magnetic force or gravity. The design should be such that
the membrane filter will be held securely on the porous plate of the
receptacle without mechanical damage and all fluid will pass through the
membrane during filtration.
4.5.2 Separately wrap the two parts of the assembly 1n heavy
wrapping paper for sterilization by autoclavlng and storage until use.
Alternatively, treat unwrapped parts by ultraviolet radiation before
using them. Field units may be sanitized by Igniting methyl alcohol or
Immersing 1n boiling water for 5 m1n. Do not Ignite plastic parts.
4.5.3 For filtration, mount receptacle of filter-holding assembly
1n a 1-Hter filtering flask with a side tube or other suitable device
such that a pressure differential can be exerted on the filter membrane.
Connect flask to an electric vacuum pump, a filter pump operating on
water pressure, a hand aspirator, or other means of securing pressure
differential. Connect an additional flask between filtering flask and
vacuum source to trap carry-over water.
4.6 Filter membranes;
4.6.1 Use membrane filters with a rated pore diameter such that
there 1s complete retention of conform bacteria (0.45 + 0.02 urn). Use
only those filter membranes that have been found, through adequate
quality control testing and certification by the manufacturer, to exhibit
full retention of the organisms to be cultivated, stability 1n use,
freedom from chemical extractables Inimical to the growth and development
of bacteria, a satisfactory speed of filtration, no significant Influence
on medium pH, and no Increase 1n number of confluent colonies or
spreaders. Preferably, use membranes grid-marked 1n such a manner that
bacterial growth 1s neither Inhibited nor stimulated along the grid
lines. Store membrane filters held 1n stock 1n an environment without
extremes of temperature and humidity. Obtain no more than a year's
supply at any one time.
4.6.2 If presterlllzed membrane filters are to be used, use those
for which the manufacturer has certified that the sterilization technique
has neither Induced toxldty nor altered the chemical or physical
properties of the membrane. If the membranes are sterilized In the
laboratory, remove the paper separators but not the absorbent paper
pads from the packaged filters. Divide filters Into groups of 10 to
12, or other convenient units, and place 1n 10-cm Petrl dishes or wrap 1n
heavy wrapping paper. Autoclave for 10 mln at 121*C. At the end of the
sterilization period, let the steam escape rapidly to minimize
accumulation of water condensation on filters.
9132 - 3
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Date September 1986
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4.7 Absorbent pads;
4.7.1 Absorbent pads consist of disks of filter paper or other
material known to be of high quality and free of sulfites or other
substances that could Inhibit bacterial growth. Use pads approximately
48 mm 1n diameter and of sufficient thickness to absorb 1.8 to 2.2 ml of
medium. PresterlUzed absorbent pads or pads subsequently sterilized 1n
the laboratory should release less than 1 mg total acidity (calculated as
CaCOs) when titrated to the phenolphthaleln end point, pH 8.3, using
0.02 N NaOH. Where there 1s evidence of absorbent pad toxlclty, presoak
pads 1n Type II water at 121*C (In an autoclave) for 15 mln, decant the
water, and repackage pads 1n a large Petrl dish for sterilization and
subsequent use. Sterilize pads simultaneously with membrane filters
available In resealable Kraft envelopes or separately In other suitable
containers. Dry pads so they are free of visible moisture before use.
See sterilization procedure described above for membrane filters.
4.7.2 As a substrate substitution for nutrient-saturated absorbent
pads, 1.5% agar may be added to the total col 1 form M-Endo broth medium.
4.8 Forceps;
4.8.1 Forceps should be round-tipped, without corrugations on the
Inner sides of the tips. Sterilize before use by dipping in 95% ethyl or
absolute methyl alcohol and flaming.
4.9 Incubators
4.9.1 Use Incubators to provide a temperature of 35 + 0.5*C and to
maintain a high level of humidity (approximately 90% relative humidity).
4.10 Microscope and light source;
4.10.1 Count membrane-filter colonies with a magnification of 10 to
15 diameters and a light source adjusted to give maximum sheen discern-
ment. Optimally, use a binocular wide-field dissecting microscope.
However, a small fluorescent lamp with magnifier is acceptable. Use
cool-white fluorescent lamps. Do not use a microscope illuminator with
optical system for light concentration from an incandescent light source
for coliform colony identification on Endo-type media.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
9132 - 4
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5.2 M-Endo medium:
5.2.1 Components of the medium are:
Tryptose or polypeptone 10.0 g
Thlopeptone or thiotone 5.0 g
Casltone or trypticase 5.0 g
Yeast extract 1.5 g
Lactose 12.5 g
Sodium chloride, NaCl 5.0 g
D1potassium hydrogen
phosphate, K?HP04 4.375 g
Potassium d1hydrogen
phosphate, KH2P04 1.375 g
Sodium lauryl sulfate 0.050 g
Sodium desoxycholate 0.10 g
Sodium sulflte, Na2S03 2.10 g
Basic fuchsln 1.05 g
Distilled (Type II) water 1 liter
5.2.2 Rehydrate 1n 1 liter Type II water containing 20 ml 95%
ethanol. Heat to boiling 1n a water bath to avoid degradation of
carbohydrates, promptly remove from heat, and cool to below 45*C. Do not
sterilize by autoclavlng. Final pH should be between 7.1 and 7.3.
5.2.3 Store finished medium 1n the dark at 2 to 10ฐC and discard
any unused medium after 96 hr. Medium 1s light sensitive.
NOTE: This medium may be solidified by adding 1.2% to 1.5% agar
before boiling.
5.3 Lauryl tryptose broth; See Method 9131, Paragraph 5.3.
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 Clean all glassware thoroughly with a suitable detergent and hot
water, rinse with hot water to remove all traces of residual washing compound,
and finally, rinse with distilled (Type II) water. If mechanical glassware
washers are used, equip them with Influent plumbing of stainless steel or
other nontoxlc material. Do not use copper piping to distribute Type II
water. Use stainless steel or other nontoxlc material for the rinse-water
system.
6.2.1 Sterilize glassware, except when 1n metal containers, for not
less than 60 m1n at a temperature of 170*C, unless 1t 1s known from
recording thermometers that oven temperatures are uniform, under which
exceptional condition use 160*C. Heat glassware 1n metal containers to
170'C for not less than 2 hr.
9132 - 5
Revision
Date September 1986
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6.2.2 Sterilize sample bottles not made of plastic, as above, or 1n
an autoclave at 121*C for 15 m1n.
6.2.3 For plastic bottles that distort on autoclavlng, use low-
temperature ethylene oxide gas sterilization. If water containing
residual chlorine and other halogens 1s to be collected, add sufficient
Na2$203 to clean sample bottle before sterilization to give a
concentration of about 100 mg/L 1n the sample. To a 120-mL bottle add
0.1 ml 10% solution of Na?S203 (this will neutralize a sample containing
about 15 mg/L residual chlorine). Stopper bottle, cap, and sterilize by
either dry or moist heat, as directed previously.
6.2.4 Collect water samples high 1n copper or zinc and wastewater
samples high 1n heavy metals 1n sample bottles containing a chelatlng
agent that will reduce metal toxldty. This 1s particularly significant
when such samples are 1n transit for 4 hr or more. Use 372 mg/L of the
tetrasodlum salt of ethylenediaminetetraacetic add (EDTA). Adjust EDTA
solution to pH 6.5 before use. Add EDTA separately to sample bottle
before bottle sterilization (0.3 mL 15% solution 1n a 120-mL bottle) or
combine 1t with the N32S203 solution before addition.
6.3 When the sample 1s collected, leave ample air space 1n the bottle
(at least 2.5 cm) to facilitate mixing by shaking, preparatory to examination.
Be careful to take samples that will be representative of the water being
tested and avoid sample contamination at time of collection or 1n period
before examination.
6.4 Keep sampling bottle closed until the moment It 1s to be filled.
Remove stopper and hood or cap as a unit, taking care to avoid soiling.
During sampling, do not handle stopper or cap and neck of bottle, and protect
them from contamination. Hold bottle near base, fill 1t without rinsing,
replace stopper or cap Immediately, and secure hood around neck of bottle.
6.5 Start bacteriological examination of a water sample promptly after
collection to avoid unpredictable changes. If samples cannot be processed
within 1 hr of collection, use an Iced cooler for storage during transport to
the laboratory.
6.6 Hold temperature of all stream pollution samples below 10*C during a
maximum transport time of 6 hr. Refrigerate these samples upon receipt 1n the
laboratory and process within 2 hr. When local conditions necessitate delays
1n delivery of samples longer than 6 hr, make field examinations using field
laboratory facilities located at the site of collection or use delayed-
1ncubat1on procedures.
9132 - 6
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Date September 1986
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7.0 PROCEDURES
7.1 Selection of sample size;
7.1.1 Size of sample will be governed by expected bacterial
density, which In finished-water samples will be limited only by the
degree of turbidity.
7.1.2 An Ideal sample volume will yield growth of about 50 col 1 form
colonies and not more then 200 colonies of all types. Examine finished
waters by filtering duplicate portions of the same volume, such as 100 to
500 ml or more, or by filtering two diluted volumes. Examine other
waters by filtering three different volumes, depending on the expected
bacterial density. When less than 20 ml of sample (diluted or undiluted)
is filtered, add a small amount of sterile dilution water to the funnel
before filtration. This increase in water volume aids in uniform
dispersion of the bacterial suspension over the entire effective
filtering surface.
7.2 Filtration of sample;
7.2.1 Using sterile forceps, place a sterile filter over porous
plate of receptacle, grid side up. Carefully place matched funnel unit
over receptacle and lock 1t in place. Filter sample under partial
vacuum. With filter still in place, rinse funnel by filtering three
20- to 30-mL portions of sterile dilution water. Unlock and remove
funnel, immediately remove filter with sterile forceps, and place 1t on
sterile pad or agar with a rolling motion to avoid entrapment of air.
7.2.2 Use sterile filtration units at the beginning of each
filtration series as a minimum precaution to avoid accidental
contamination. A filtration series 1s considered to be interrupted when
an Interval of 30 min or longer elapses between sample filtratlons.
After such Interruption, treat any further sample filtration as a new
filtration series and sterilize all membrane-filter holders 1n use.
7.2.3 Decontaminate this equipment between successive filtratlons
by use of flowing steam, boiling water, or, 1f available, an ultraviolet
sterilizer. When using the UV sterilization procedure, a 2-m1n exposure
to UV radiation 1s sufficient and should kill 99.9% of all bacteria. Eye
protection is recommended to protect against stray radiation from a
non-light-tight sterilization cabinet. This UV equipment 1s not
commercially available and is not required, although its use 1s
recommended.
7.3 Two-step enrichment technique;
7.3.1 Place a sterile absorbent pad in the upper half of a sterile
culture dish and pipet enough enrichment medium (1.8 to 2.0 mL lauryl
tryptose broth) to saturate pad. Carefully remove any surplus liquid.
9132 - 7
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Date September 1986
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Aseptlcally place filter through which the sample has been passed on pad.
Incubate filter, without Inverting dish, for 1.5 to 2 hr at 35 + 0.5*C 1n
an atmosphere of at least 90% relative humidity.
7.3.2 Remove enrichment culture from Incubator, 11ft filter from
enrichment pad, and roll It onto the agar surface. Incorrect filter
placement 1s at once obvious, because patches of unstained membrane
Indicate entrapment of air. Where such patches occur, carefully reseat
filter on agar surface. If the liquid medium 1s used, prepare final
culture by removing enrichment culture from Incubator and separating the
dish halves. Place a fresh sterile pad 1n bottom half of dish and
saturate It with 1.8 to 2.0 ml of final M-Endo medium. Transfer filter,
with same precautions as above, to new pad. Discard used pad. With
either the agar or the liquid medium, invert dish and Incubate for 20 to
22 hr at 35 + 0.5'C.
7.4 Counting;
7.4.1 The typical coliform colony has a pink to dark-red color with
a metallic surface sheen. The sheen area may vary 1n size from a small
pinhead to complete coverage of the colony surface. Count sheen colonies
with the aid of a low-power (10 to 15 magnifications) binocular wide-
field dissecting microscope or other optical device, with a cool-white
fluorescent light source directed above and as nearly perpendicular as
possible to the plane of the filter. The total count of colonies
(coliform and noncollform) on Endo-type medium has no relation to the
total number of bacteria present in the original sample and, so far as 1s
known, no significance can be inferred or correlation made with the
quality of the water sample.
7.5 Calculation of coliform density;
7.5.1 Report coliform density as (total) collforms/100 mL. Compute
the count, using membrane filters with 20 to 80 coliform colonies and not
more than 200 colonies of all types per membrane, by the following
equation:
(Total) _ coliform colonies counted x 100
coliform colonies/100 ml ~ ml sample filtered
7.5.2 Water of drinking-water quality:
7.5.2.1 With water of good quality, the number of coliform
colonies will be less than 20 per membrane. In this event, count
all coliform colonies and use the formula given above to obtain
coliform density.
7.5.2.2 If confluent growth occurs, that 1s, growth covering
either the entire filtration area of the membrane or a portion
thereof, and colonies are not discrete, report results as "confluent
growth with or without conforms." If the total number of bacterial
9132 - 8
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Date September 1986
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colonies, conforms plus noncoliforms, exceeds 200 per membrane, or
1f the colonies are too indistinct for accurate counting, report
results as "too numerous to count" (TNTC). In either case, request
a new sample and select more appropriate volumes to be filtered per
membrane, remembering that the standard drinking-water portion is
100 mL. Thus, instead of filtering 100 mL per membrane, 50-mL
portions may be filtered through each of two membranes, 25-mL
portions may be filtered through each of four membranes, etc. Total
the coliform counts observed on the membranes and report as number
per 100 mL.
7.5.3 Water of other than drinking-water quality:
7.5.3.1 As with potable water samples, if no filter has a
coliform count falling in the ideal range, total the conform counts
on all filters and report as number per 100 mL. For example, if
duplicate 50-mL portions were examined and the two membranes had
five and three coliform colonies, respectively, report the count as
eight conform colonies per 100 mL, I.e.,
(5 + 3) x 100
(50 + 50)
7.5.3.2 Similarly, if 50-, 25-, and 10-mL portions were
examined and the counts were 15, 6, and 1 coliform colonies,
respectively, report the count as 25/100 mL, I.e.,
15 + 6) x 100
50 + 25 + 10)
7.5.3.3 On the other hand, if 10-, 1.0-, and 0.1-mL portions
were examined with counts of 40, 9, and 1 coliform colonies
respectively, select only the 10-mL portion for calculating the
coliform density because this filter had a coliform count falling in
the ideal range. The result is 400/100 mL, i.e.,
(40 x 100)
10
In this last example, if the membrane with 40 coliform colonies also
had a total bacterial colony count greater than 200, report the
coliform count as 400/100 mL.
7.5.3.4 Report confluent growth or membranes with colonies
too numerous to count, as described in 7.5.2, above. Request a new
sample and select more appropriate volumes for filtration.
7.5.4 Statistical reliability of membrane filter results: Although
the statistical reliability of the membrane filter technique is greater
than that of the MPN procedure, membrane counts really are not absolute
numbers. Table 1 illustrates some 95% confidence limits.
913-2 - 9
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Date September 1986
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TABLE 1. 95% CONFIDENCE LIMITS FOR MEMBRANE-FILTER RESULTS
USING 100-mL SAMPLE
95% Confidence Limits
Number of Coliform
Colonies Counted Lower Upper
1 0.05
2 0.35
3 0.81
4 1.4
5 2.0
3.0
4.7
6.3
7.7
9.2
8.0 QUALITY CONTROL
8.1 Extensive quality control procedures are provided in Part IV of U.S.
EPA, 1978 (see Section 10.0, References). These procedures should be adhered
to at all times.
8.2 Samples must be maintained as closely as possible to original
condition by careful handling and storage. Sample sites and sampling
frequency should provide data representative of characteristics and
variability of the water quality at that site. Samples should be analyzed
immediately. If this is not practical, they should be refrigerated at a
temperature of 1-4*C and analyzed within 6 hr.
8.3 Quality control of culture media is critical to the validity of
microbiological analysis. Some important factors to consider are summarized
below:
8.3.1 Order media to last for only 1 yr; always use oldest stock
first. Maintain an inventory of all media ordered, including a visual
inspection record.
8.3.2 Hold unopened media for no longer than 2 yr. Opened media
containers should be discarded after 6 mo.
8.3.3 When preparing media, keep containers open as briefly as
possible. Prepare media in deionized or distilled (Type II) water of
proven quality. Check the pH of the media after solution and
sterilization; it should be within 0.2 units of the stated value.
Discard and remake if it is not.
8.3.4 Autoclave media for the minimal time specified by the
manufacturer, because the potential for damage increases with increased
exposure to heat. Remove sterile media from the autoclave as soon as
pressure is zero. Effectiveness of the sterilization should be checked
weekly, using strips or ampuls of Bacillus stearothemophelus.
9132 - 10 '
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' Date September 1986
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8.3.5 Agar plates should be kept slightly open for 15 m1n after
pouring or removal from refrigeration to evaporate free moisture. Plates
must be free of lumps, uneven surfaces, pock marks, or bubbles, which can
prevent good contact between the agar and medium.
8.3.6 Quality control checks of prepared media should Include the
Incubation of 5% of each batch of medium for 2 days at 35*C to Inspect
for growth and positive/negative checks with pure culture.
8.4 Analytical quality control procedures should Include;
8.4.1 Duplicate analytical runs on at least 10% of all known
positive samples analyzed.
8.4.2 At least one positive control sample should be run each month
for each parameter tested.
8.4.3 At least one negative (sterile) control should be run with
each series of samples using buffered water and the medium batch used at
the beginning of the test series and following every tenth sample. When
sterile controls Indicate contamination, new samples should be obtained
and analyzed.
8.4.4 The Type II water used should be periodically checked for
contamination.
8.5 Quality control specifications for membrane filters;
8.5.1 Membrane filters can be purchased sterile or packaged for
sterilization. They can be sterilized by autoclavlng, ethylene oxide, or
Irradiation. Membrane manufacturers should certify that their membranes
meet stated specifications on sterility, retention, recovery, pore size,
flow rate, pH, total acidity, phosphate, and other extractables.
8.5.2 Membrane performance should be tested to ensure proper
results. Each lot ordered should be inspected for proper shape, grid
lines, diffusability, and correct colony development. Membranes
containing sizable areas with no colony development are questionable.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
1. Standard Methods for the Examination of Water and Wastewater, 15th ed.
2. Bordner, R.H., et al., Microbiological Methods for Monitoring the
Environment, Environmental Monitoring and Support Laboratory, U.S. EPA,
Cincinnati, OH, EPA-600/8-78-017, 1978.
9132 - 11
Revision 0
Date September 1986
-------
METHOD 9132
TOTAL COLIFORM: MEMBRANE FILTER TECHNIQUE
Start
7. 1
Select
sample size on
basis expected
Bacterial
density
7.2
Filter sample with
sterile aparatus;
rinse funnel: remove
filate and place on
sterile pad or agar
9132 - 12
Revision 0
Date September 1986
-------
METHOD 9132
TOTAL COLIFORM: MEMBRANE FILTER TECHNIQUE
(Continued)
7.4.1
Roll
filter onto
gar surface:
Incubate
Which medium >v based
7.3.2.
Remove
from Incuoator
roll filter
onto egar
surface
culture fllsn:
saturate with
M-Endc medium
7.4.2
Place
filter on pad:
Invert dish:
Incubate
7
.3.2 f
Inc
saturat
pad: tr
filter
7
.3.2
Remove
r om
:ubator;
.e fresh
ansf er
to pea
Invert dish
and Incubate
7
.5.1
Count sheen
colonies
7.6
Calculate
coliform
density
f Stop J
9132 - 13
Revision Q
Date September 1986
-------
METHOD 9200
NITRATE
1.0 SCOPE AND APPLICATION
1.1 This method 1s applicable to the analysis of ground water, drinking,
surface, and saline waters, and domestic and Industrial wastes. Modification
can be made to remove or correct for turbidity, color, salinity, or dissolved
organic compounds in the sample.
1.2 The applicable range of concentration 1s 0.1 to 2 mg N03-N per liter
of sample.
2.0 SUMMARY OF METHOD
2.1 This method 1s based upon the reaction of the nitrate 1on with
brudne sulfate 1n a 13 N H2S04 solution at a temperature of 100*C. The color
of the resulting complex 1s measured at 410 nm. Temperature control of the
color reaction 1s extremely critical.
3.0 INTERFERENCES
3.1 Dissolved organic matter will cause an off color in 13 N H?S04 and
must be compensated for by additions of all reagents except the Erucine-
sulfanilic acid reagent. This also applies to natural color, not due to
dissolved organics, that is present.
3.2 If the sample is colored or if the conditions of the test cause
extraneous coloration, this interference should be corrected by running a
concurrent sample under the same conditions but in the absence of the bruclne-
sulfanilic acid reagent.
3.3 Strong oxidizing or reducing agents cause interference. The
presence of oxidizing agents may be determined by a residual chlorine test;
reducing agents may be detected with potassium permanganate.
3.3.1 Oxidizing agents' Interference 1s eliminated by the addition
of sodium arsenite.
3.3.2 Reducing agents may be oxidized by addition of H202-
3.4 Ferrous and ferric Iron and quadrivalent manganese give slight
positive interferences, but in concentrations less than 1 mg/L these are
negligible.
9200 - 1
Revision 0
Date September 1986
-------
3.5 Uneven heating of the samples and standards during the reaction time
will result in erratic values. The necessity for absolute control of
temperature during the critical color development periodcannotb~e~too
strongly emphasized.
4.0 APPARATUS AND MATERIALS
4.1 Spectrophotometer or filter photometer suitable for measuring
absorbance at 410 nm.
4.2 Sufficient number of 40- to 50-mL glass sample tubes for reagent
blanks, standards, and samples.
4.3 Neoprene-coated wire racks to hold sample tubes.
4.4 Water bath suitable for use at 100*C. This bath should contain a
stirring mechanism so that all tubes are at the same temperature and should be
of sufficient capacity to accept the required number of tubes without a
significant drop in temperature when the tubes are immersed.
4.5 Water bath suitable for use at 10-15ฐC.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Sodium chloride solution (30%): Dissolve 300 g NaCl in Type II
water and dilute to 1 liter.
5.3 Sulfuric acid solution; Carefully add 500 ml concentrated H2S04 to
125 mL Type II water.Cooland keep tightly stoppered to prevent absorption
of atmospheric moisture.
5.4 Brucine-sulfam'lic acid reagent; Dissolve 1 g brucine sulfate
(C23H26N2ฐ4)2>H2S04*7H2ฐ ~ and O-1 9 sulfanilic acid (NH2C6H4S03H-H20) in
70 ml hot Type II water. Add 3 ml concentrated HC1, cool, mix, and dilute to
100 ml with Type II water. Store in a dark bottle at 5*C. This solution is
stable for several months; the pink color that develops slowly does not affect
its usefulness. Mark bottle with warning, "CAUTION: Brucine Sulfate is
toxic; do not ingest."
5.5 Potassium nitrate stock solution (1.0 ml = 0.1 mg N03-N): Dissolve
0.7218 g anhydrous potassium nitrate (KNOs) in Type II water and dilute to
1 liter in a volumetric flask. Preserve with 2 ml chloroform per liter. This
solution is stable for at least 6 mon.
5.6 Potassium nitrate standard solution (1.0 ml = 0.001'mg NO^-N):
Dilute 10.0 ml of the stock solution(5.5)to 1 liter in a volumetric flask.
This standard solution should be prepared fresh weekly.
9200 - 2
Revision 0
Date September 1986
-------
5.7 Acetic acid (1+3); Dilute 1 volume glacial acetic acid (CHsCOOH)
with 3 volumes of Type II water.
5.8 Sodium hydroxide (1 N): Dissolve 40 g of NaOH in Type II water.
Cool and dilute to 1 liter.
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 Analysis should be done as soon as possible. If analysis can be
done within 24 hr, the sample should be preserved by refrigeration at 4*C.
When samples must be stored for more than 24 hr, they should be preserved with
sulfuric acid (2 mL/L concentrated ^$04) and refrigerated.
7.0 PROCEDURE
7.1 Adjust the pH of the samples to approximately 7 with acetic acid
(Paragraph 5.7) or sodium hydroxide (Paragraph 5.8). If necessary, filter to
remove turbidity. Sulfuric acid can be used in place of acetic acid, if
preferred.
7.2 Set up the required number of sample tubes in the rack to handle
reagent blank, standards, and samples. Space tubes evenly throughout the rack
to allow for even flow of bath water between the tubes. This should assist in
achieving uniform heating of all tubes.
7.3 If it is necessary to correct for color or dissolved organic matter
which will cause color on heating, run a set of duplicate samples to which all
reagents, except the brucine-sulfanilic acid, have been added.
7.3.1 Add 0.5 mL brucine-sulfanilic acid reagent (Paragraph 5.4) to
each tube (except the interference control tubes) and carefully mix by
swirling; then place the rack of tubes in the 100'C water bath for
exactly 25 min.
CAUTION: Immersion of the tube rack into the bath should not
decrease the temperature of the bath by more than 1~2*C. In
order to keep this temperature decrease to an absolute minimum,
flow of bath water between the tubes should not be restricted
by crowding too many tubes into the rack. If color development
in the standards reveals discrepancies in the procedure, the
operator should repeat the procedure after reviewing the
temperature control steps.
7.4 Pipet 10.0 mL of standards and samples or an aliquot of the samples
diluted to 10.0 mL into the sample tubes.
9200 - 3
Revision 0
Date September 1986
-------
7.5 If the samples are saline, add 2 mL of the 30% sodium chloride
solution (Paragraph 5.2) to the reagent blank, standards, and samples. For
freshwater samples, sodium chloride solution may be omitted. Mix contents of
tubes by swirling and place rack 1n cold-water bath (0-10*C).
7.6 Plpet 10.0 ml of sulfurlc add solution (Paragraph 5.3) Into each
tube and mix by swirling. Allow tubes to come to thermal equilibrium 1n the
cold bath. Be sure that temperatures have equilibrated 1n all tubes before
continuing.
7.7 Remove rack of tubes from the hot-water bath, Immerse 1n the cold-
water bath, and allow to reach thermal equilibrium (20-25*C).
7.8 Read absorbance against the reagent blank at 410 nm using a 1-cm or
longer cell.
7.9 Calculation;
7.9.1 Obtain a standard curve by plotting the absorbance of
standards run by the above procedure against mg/L N03-N. (The color
reaction does not always follow Beer's law.)
7.9.2 Subtract the absorbance of the sample without the brudne-
sulfanlUc reagent from the absorbance of the sample containing brudne-
sulfanlUc add and determine mg/L N03-N. Multiply by an appropriate
dilution factor 1f less than 10 ml of sample 1s taken.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Linear calibration curves must be composed of a minimum of a blank
and five standards. A set of standards must be Included with each batch of
samples.
8.3 Dilute samples 1f they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Verify calibration with an Independently prepared check standard
every 15 samples.
8.5 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
9200 - 4
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 Twenty-seven analysts In fifteen laboratories analyzed natural-water
samples containing exact Increments of Inorganic nitrate, with the following
results:
Increment as
Nitrogen, Nitrate
(mg/L N)
0.16
0.19
1.08
1.24
Precision as
Standard Deviation
(mg/L N)
0.092
0.083
0.245
0.214
Accuracy
Bias
(%)
-6.79
+8.30
+4.12
+2.82
as
Bias
(mg/L N)
-0.01
+0.02
+0.04
+0.04
10.0 REFERENCES
1. Annual Book of ASTM Standards, Part 31, "Water," Standard D992-71, p. 363
(1976).
2. Jenkins, D. and L. Medsken, "A Bruclne Method for the Determination of
Nitrate 1n Ocean, Estuarlne, and Fresh Water," Anal.Chem., 36, p. 610 (1964).
3. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
p. 427, Method 419D (1975).
9200 - 5
Revision
Date September 1986
-------
METHOD 9200
NITRATE
7.1
Adjust pH
of camples to
7; filter If
necessary
7.2
Set up cample
tubes In rack
Correct for
color, dissolves
organic
matter?
Hun
duplicate
sulfanlllc
acid reagent
to each tube
ample* with
bruclne
sulfanlllc acid
Bathe
rack of tubes
in 100 *C water
for 25 mln
9200 - 6
Revision 0
Date September 1986
-------
METHOD 9200
NITRATE
(Continued)
Pipette
standards and
camples into
ample tubes
Read absorbance
against reagent
blank 410 nm
Yes
7.6
Pipette
sulfurlc acid
solution Into
each tube: mix
7.5
7.9.1
Obtain a
J standard
absorbance
curve and
calculate
mg NOj-N/1
Add 30X sodium
chloride
solution; mix
f Stop J
7.7
I Immerse
tubes In cold
water: allow to
reach thermal
equilibrium
9200 - 7
Revision 0
Date September 1986
-------
METHOD 9250
CHLORIDE (COLORIMETRIC. AUTOMATED FERRICYANIDE AAI)
1.0 SCOPE AND APPLICATION
1.1 This automated method 1s applicable to ground water, drinking,
surface, and saline waters, and domestic and Industrial wastes. The
applicable range 1s 1 to 250 mg Cl per liter of sample.
2.0 SUMMARY OF METHOD
2.1 Thlocyanate 1on (SCN) 1s liberated from mercuric thlocyanate through
sequestration of mercury by chloride 1on to form un-1on1zed mercuric chloride.
In the presence of ferric 1on, the liberated SCN forms highly colored ferric
thlocyanate 1n a concentration proportional to the original chloride
concentration.
3.0 INTERFERENCES
3.1 No significant Interferences.
4.0 APPARATUS AND MATERIALS
4.1 Automated continuous-flow analytical Instrument;
4.1.1 Sampler I.
4.1.2 Continuous filter.
4.1.3 Manifold.
4.1.4 Proportioning pump.
4.1.5 Colorimeter: equipped with 15-mm tubular flowcell and 480-nm
filters.
4.1.6 Recorder.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Ferric ammonium sulfate; Dissolve 60 g of FeNH4(S04)2*12H20 in
approximately 500 mL TypeIIwater. Add 355 mL of concentrated HN03 and
dilute to 1 liter with Type II water. Filter.
9250 - 1
Revision 0
Date September 1986
-------
5.3 Saturated mercuric thiocyanate; Dissolve 5 g of Hg(SCN)2 1n 1 liter
of Type II water.Decantancifiltera portion of the saturated supernatant
liquid to use as the reagent and refill the bottle with distilled water.
5.4 Sodium chloride stock solution (0.0141 N NaCl): Dissolve 0.8241 g
of pre-dried (140*C) NaCl in Type II water. Dilute to 1 liter in a volumetric
flask (1 ml = 0.5 mg Cl).
5.4.1 Prepare a series of standards by diluting suitable volumes of
stock solution to 100.0 ml with Type II water. The following dilutions
are suggested:
Stock
Solution (ml) Concentration (mg/L)
1.0 5.0
2.0 10.0
4.0 20.0
8.0 40.0
15.0 75.0
20.0 100.0
30.0 150.0
40.0 200.0
50.0 250.0
Choose three of the nine standard concentrations 1n such a way that the
chosen standards will bracket the expected concentration range of the
sample.
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 No special requirements for preservation.
7.0 PROCEDURE
7.1 No advance sample preparation 1s required. Set up manifold, as
shown 1n Figure 1. For water samples known to be consistently low 1n chloride
content, 1t 1s advisable to use only one Type II water Intake line.
7.2 Allow both colorimeter and recorder to warm up for 30 min. Run a
baseline with all reagents, feeding Type II water through the sample line.
Adjust dark current and operative opening on colorimeter to obtain stable
baseline.
9250 - 2
Revision
Date September 1986
-------
9250
3
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PROPORTIONING
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1.60 Ft NN 4 (SO 4)9
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2.50
WASTE
RPrnpncp SAMPLING TIME: 2.0 MINUTES
\A/AQW Tl IRPQ- OWP
FIGURE 1. CHLORIDE MANIFOLD AA-I
-------
7.3 Place Type II water wash tubes 1n alternate openings in sampler and
set sample timing at 2.0 min.
7.4 Place working standards in sampler in order of decreasing
concentrations. Complete filling of sampler tray with unknown samples.
7.5 Switch sample line from Type II water to sampler and begin analysis.
7.6 Calculation;
7.6.1 Prepare standard curve by plotting peak heights of processed
standards against known concentrations. Compute concentration of samples
by comparing sample peak heights with standard curve.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. Employ a minimum of one blank per sample batch to determine
if contamination has occurred.
8.3 Dilute samples if they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Verify calibration with an independently prepared check standard
every 15 samples.
8.5 Run one spike duplicate sample for every 10 samples. A duplicate
sample is a sample brought through the whole sample preparation and analytical
process.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 325.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. O'Brien, J.E., "Automatic Analysis of Chlorides in Sewage," Waste Engr.,
33, 670-672 (Dec. 1962).
2. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
p. 613, Method 602 (1975).
9250 - 4
Revision
Date September 1986
-------
METHOD 9290
CHLORIDE (COUORXNETRIC. AUTOMATED FCRRXCYANIOE AAX)
C
7.1
Set up manifold
enown In
Figure 1
7.2
Pleco
working
teneerdc and
unknown eemplee
in cempler trey
Warm up
colorimeter
end recorder:
obtein eteble
beeeline
7.5
Switch sample
line to
empler; enolyze
7.3
Piece
weter weซh
tube* in
empler;
et timing
7.6.11
I Prepere
tenderd
curve: compute
concentration
of eemplee
f Stop J
9250 - 5
Revision o
Date September 1986
-------
METHOD 9251
CHLORIDE (COLORIMETRIC. AUTOMATED FERRICYANIDE AAII)
1.0 SCOPE AND APPLICATION
1.1 This automated method 1s applicable to ground water, drinking,
surface, and saline waters, and domestic and Industrial wastes. The
applicable range 1s 1-200 mg Cl~ per liter of sample.
2.0 SUMMARY OF METHOD
2.1 Thlocyanate 1on (SCN) 1s liberated from mercuric thlocyanate through
sequestration of mercury by chloride 1on to form un-1on1zed mercuric chloride.
In the presence of ferric 1on, the liberated SCN forms highly colored ferric
thlocyanate 1n a concentration proportional to the original chloride
concentration.
3.0 INTERFERENCES
3.1 No significant Interferences.
4.0 APPARATUS AND MATERIALS
4.1 Automated continuous-flow analytical Instrument;
4.1.1 Sampler I.
4.1.2 Analytical cartridge.
4.1.3 Proportioning pump.
4.1.4 Colorimeter: Equipped with 15-mm tubular flowcell and 480-nm
filters.
4.1.5 Recorder.
4.1.6 Digital printer (optional).
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Mercuric thlocyanate solution; Dissolve 4.17 g of HgfSCN)? In 500
mL methanoTiDilute to 1 literwith methanol, mix, and filter through filter
paper.
9251 - 1
Revision 0
Date September 1986
-------
5.3 Ferric nitrate solution, 20.2%: Dissolve 202 g of Fe(N03)3'9H20 1n
500 ml of Type IIwater.Add 31.5 ml concentrated nitric acid, mix, and
dilute to 1 liter with Type II water.
5.4 Color reagent; Add 150 ml of mercuric thiocyanate solution
(Paragraph 5.2) to 150 ml of ferric nitrate solution (Paragraph 5.3), mix, and
dilute to 1 liter with Type II water. A combined color reagent is commer-
cially available.
5.5 Sodium chloride stock solution (0.0141 N NaCl): Dissolve 0.8241 g
of pre-dried (140*C) NaCl in Type II water. Dilute to 1 liter in a volumetric
flask (1 ml = 0.5 mg Cl').
5.5.1 Prepare a series of standards by diluting suitable volumes of
stock solution to 100.0 ml with Type II water. The following dilutions
are suggested:
Stock
Solution (ml) Concentration (mg/L)
1.0 5.0
2.0 10.0
4.0 20.0
8.0 40.0
15.0 75.0
20.0 100.0
30.0 150.0
40.0 200.0
Choose three of the nine standard concentrations 1n such a way that the
chosen standards will bracket the expected concentration range of the
sample.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.
6.2 No special requirements for preservation.
7.0 PROCEDURE
7.1 When particulate matter is present, the sample must be filtered
prior to the determination. The sample may be centrlfuged 1n place of
filtration. Set up the manifold, as shown 1n Figure 1.
9251 - 2
Revision
Date September 1986
-------
<ฃ>
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US 141
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PUR. PUR.
ORG. CRN.
BLK. BLK.
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GRY. GRY.
ORG. CRN.
GRY. GRY.
WHT. WHT.
GRY. GRY.
PROPOR
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3.40 OIL. WATER
0.32 AIR
2.50 OIL. WATER
0.10 SAMPLE
0.32 AIR
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1.00 COLOR REAGENT
0.60 SAMPLE WASTE
1.00 FROM F/C.
TIONING
MP
A4
to
oo
Figure 1. Chloride Manifold AATIO 200 mg C1/L.
-------
7.2 Allow both colorimeter and recorder to warm up for 30 min. Run a
baseline with all reagents, feeding Type II water through the sample line.
7.3 Place working standards in sampler in order of decreasing
concentrations. Complete filling of sampler tray with unknown samples.
7.4 When a stable baseline has been obtained, start the sampler.
t
7.5 Calculation: Prepare standard curve by plotting peak heights of
processed standards against known concentrations. Compute concentration of
samples by comparing sample peak heights with standard curve. Note that this
is not a linear curve, but a second order curve. (See Paragraph 8.2.)
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. Employ a minimum of one blank per sample batch to determine
if contamination has occurred.
8.3 Dilute samples if they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Verify calibration with an independently prepared check standard
every 15 samples.
8.5 Run one spike duplicate sample for every 10 samples. A duplicate
sample is a sample brought through the whole sample preparation and analytical
process.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
10.0 REFERENCES
1. O'Brien, J.E., "Automatic Analysis of Chlorides in Sewage," Waste Engr.,
33, 670-672 (Dec. 1962).
2. Technicon AutoAnalyzer II, Industrial Method No. 99-70W, Technicon
Industrial Systems, Tarrytown, New York, 10591 (Sept. 1973).
9251 - 4
Revision
Date September 1986
-------
METHOD 925J
CHLORIDE (COLORIMETRIC. AUTOMATED FERRICVANIOE AA II)
Yes
7.8
Warm up
i color-
imeter and
recorder; run
baseline with
all reagents
7.1
Filter
7.3 I
I Place
working
standards and
unknown samples
in sampler tray
7.4
Obtain stable
baseline: start
sampler
7. S.I
curs
cone
o<
Prepare
standard
e: compute
ntration
samples
f stop }
9251 - 5
Revision 0
Date September 1986
-------
METHOD 9252A
CHLORIDE (TITRIMETRIC, MERCURIC NITRATE)
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to ground water, drinking, surface, and
saline waters, and domestic and industrial wastes.
1.2 The method is suitable for all concentration ranges of chloride
content; however, in order to avoid large titration volume, a sample aliquot
containing not more than 10 to 20 mg Cl" per 50 ml is used.
1.3 Automated titration may be used.
2.0 SUMMARY OF METHOD
2.1 An acidified sample is titrated with mercuric nitrate in the
presence of mixed diphenylcarbazone-bromophenol blue indicator. The end point
of the titration is the formation of the blue-violet mercury diphenylcarbazone
complex.
3.0 INTERFERENCES
3.1 Anions and cations at concentrations normally found in surface
waters do not interfere. However, at the higher concentration often found in
certain wastes, problems may occur.
3.2 Sulfite interference can be eliminated by oxidizing the 50 ml of
sample solution with 0.5-1 ml of H202.
3.3 Bromide and iodide are also titrated with mercuric nitrate in the same
manner as chloride.
3.4 Ferric and chromate ions interfere when present in excess of 10 mg/L.
4.0 APPARATUS AND MATERIALS
4.1 Standard laboratory titrimetric equipment, including 1 mL or 5 mL
microburet with 0.01 mL gradations.
4.2 Class A volumetric flasks: 1 L and 100 mL.
4.3 pH Indicator paper.
4.4 Analytical balance: capable of weighing to 0.0001 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
9252A - 1 Revision 1
September 1994
-------
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 Standard sodium chloride solution, 0.025 N: Dissolve 1.4613 g
ฑ 0.0002 g of sodium chloride (dried at 600ฐC for 1 hr) in chloride-free water
in a 1 liter Class A volumetric flask and dilute to the mark with reagent water.
5.4 Nitric acid (HN03) solution: Add 3.0 mL concentrated nitric acid
to 997 mL of reagent water ("3 + 997" solution).
5.5 , Sodium hydroxide (NaOH) solution (lOg/L): Dissolve approximately
10 g of NaOH in reagent water and dilute to 1 L with reagent water.
5.6 Hydrogen peroxide (H202): 30%.
5.7 Hydroquinone solution (10 g/L): Dissolve 1 g of purified
hydroquinone in reagent water in a 100 mL Class A volumetric flask and dilute to
the mark.
5.8 Mercuric nitrate titrant (0.141 N): Dissolve 24.2 g Hg(N03)2 H20
in 900 mL of reagent water acidified with 5.0 mL concentrated HN03 in a 1 liter
volumetric flask and dilute to the mark with reagent water. Filter, if
necessary. Standardize against standard sodium chloride solution (Step 5.3)
using the procedures outlined in Sec. 7.0. Adjust to exactly 0.141 N and check.
Store in a dark bottle. A 1.00 mL aliquot is equivalent to 5.00 mg of chloride.
5.9 Mercuric nitrate titrant (0.025 N): Dissolve 4.2830 g Hg(N03)2
H20 in 50 mL of reagent water acidified with 0.05 mL of concentrated
HN03 (sp. gr. 1.42) in a 1 liter volumetric flask and dilute to the mark with
reagent water. Filter, if necessary. Standardize against standard sodium
chloride solution (Sec. 5.3) using the procedures outlined in Sec. 7.0. Adjust
to exactly 0.025 N and check. Store in a dark bottle.
5.10 Mercuric nitrate titrant (0.0141 N): Dissolve 2.4200 g Hg(N03)2
H20 in 25 mL of reagent water acidified with 0.25 mL of concentrated HN03 (sp.
gr. 1.42) in a 1 liter Class A volumetric flask and dilute to the mark with
reagent water. Filter, if necessary. Standardize against standard sodium
chloride solution (Sec. 5.3) using the procedures outlined in Sec. 7.0. Adjust
to exactly 0.0141 N and check. Store in a dark bottle. A 1 mL aliquot is
equivalent to 500 p,g of chloride.
5.11 Mixed indicator reagent: Dissolve 0.5 g crystalline diphenylcar-
bazone and 0.05 g bromophenol blue powder in 75 mL 95% ethanol in a 100 mL Class
A volumetric flask and dilute to the mark with 95% ethanol. Store in brown
bottle and discard after 6 months.
9252A - 2 Revision 1
September 1994
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5.12 Alphazurine indicator solution: Dissolve 0.005 g of alphazurine
blue-green dye in 95% ethanol or isopropanol in 100 mL Class A volumetric flask
and dilute to the mark with 95% ethanol or isopropanol.
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 There are no special requirements for preservation.
7.0 PROCEDURE
7.1 Place 50 mL of sample in a vessel for titration. If the concentra-
tion is greater than 20 mg/L chloride, use 0.141 N mercuric nitrate titrant (Sec.
5.8) in Sec. 7.6, or dilute sample with reagent water. If the concentration is
less than 2.5 mg/L of chloride, use 0.0141 N mercuric nitrate titrant (Sec. 5.10)
in Sec. 7.6. Using a 1 mL or 5 mL microburet, determine an indicator blank on
50 mL chloride-free water using Sec. 7.6. If the concentration is less than
0.1 mg/L of chloride, concentrate an appropriate volume to 50 mL.
7.2 Add 5 to 10 drops of mixed indicator reagent (Sec. 5.11); shake or
swirl solution.
7.3 If a blue-violet or red color appears, add HN03 solution (Sec. 5.4)
dropwise until the color changes to yellow. Proceed to Sec. 7.5.
7.4 If a yellow or orange color forms immediately on addition of the
mixed indicator, add NaOH solution (Sec. 5.5) dropwise until the color changes
to blue-violet; then add HN03 solution (Sec. 5.4) dropwise until the color
changes to yellow.
7.5 Add 1 mL excess HN03 solution (Sec. 5.4).
7.6 Titrate with 0.025 N mercuric nitrate titrant (Sec. 5.9) until a
blue-violet color persists throughout the solution. If volume of titrant exceeds
10 mL or is less than 1 mL, use the 0.141 N or 0.0141 N mercuric nitrate
solutions, respectively. If necessary, take a small sample aliquot. Alphazurine
indicator solution (Sec. 5.12) may be added with the indicator to sharpen the end
point. This will change color shades. Practice runs should be made.
Note: The use of indicator modifications and the presence of heavy
metal ions can change solution colors without affecting the
accuracy of the determination. For example, solutions containing
alphazurine may be bright blue when neutral, grayish purple when
basic, blue-green when acidic, and blue-violet at the chloride end
point. Solutions containing about 100 mg/L nickel ion and normal
mixed indicator are purple when neutral, green when acidic, and
gray at the chloride end point. ' When applying this method to
samples that contain colored ions or that require modified
indicator, it is recommended that the operator become familiar with
the specific color changes involved by experimenting with solutions
prepared as standards for comparison of color effects.
9252A - 3 Revision 1
September 1994
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7.6.1 If chromate is present at <100 mg/L and iron is not
present, add 5-10 drops of alphazurine indicator solution (Sec. 5.12) and
acidify to a pH of 3 (indicating paper). End point will then be an olive-
purple color.
7.6.2 If chromate is present at >100 mg/L and iron is not
present, add 2 ml of fresh hydroquinone solution (Sec. 5.7).
7.6.3 If ferric ion is present use a volume containing no more
than 2.5 mg of ferric ion or ferric ion plus chromate ion. Add 2 ml fresh
hydroquinone solution (Sec. 5.7).
7.6.4 If sulfite ion is present, add 0.5 mL of H202 solution
(Sec. 5.6) to a 50 ml sample and mix for 1 min.
7.7 Calculation:
(A - B)N x 35,450
mg chloride/liter =
ml of sample
where:
A = ml titrant for sample;
B = ml titrant for blank; and
N = normality of mercuric nitrate titrant.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for
easy reference or inspection. Refer to Chapter One for specific quality control
guidelines.
8.2 Analyze a standard reference material to ensure that correct
procedures are being followed and that all standard reagents have been prepared
properly.
8.3 Employ a minimum of one blank per analytical batch or twenty
samples, whichever is more frequent, to determine if contamination has occurred.
8.4 Run one matrix spike and matrix duplicate every analytical batch
or twenty samples, whichever is more frequent. Matrix spikes and duplicates are
brought through the whole sample preparation and analytical process.
9.0 METHOD PERFORMANCE
9.1 Water samplesA total of 42 analysts in 18 laboratories analyzed
synthetic water samples containing exact increments of chloride, with the results
shown in Table 1. In a single laboratory, using surface water samples at an
average concentration of 34 mg CV/L, the standard deviation was +1.0. A
9252A - 4 Revision 1
September 1994
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synthetic unknown sample containing 241 mg/L chloride, 108 mg/L Ca, 82 mg/L Mg,
3.1 mg/L K, 19.9 mg/L Na, 1.1 mg/L nitrate N, 0.25 mg/L nitrate N, 259 mg/L
sulfate and 42.5 mg/L total alkalinity (contributed by NaHC03) in reagent water
was analyzed in 10 laboratories by the mercurimetric method, with a relative
standard deviation of 3.3% and a relative error of 2.9%.
9.2 Oil combustates--These data are based on 34 data points obtained by
five laboratories who each analyzed four used crankcase oils and three fuel oil
blends with crankcase oil in duplicate. The samples were combusted using Method
5050. A data point represents one duplicate analysis of a sample. One data
point was judged to be an outlier and was not included in these results.
9.2.1 Precision and bias.
9.2.1.1 Precision. The precision of the method as determined
by the statistical examination of inter!aboratory test results is as
follows:
Repeatability - The difference between successive results
obtained by the same operator with the same apparatus under constant
operating conditions on identical test material would exceed, in the
long run, in the normal and correct operation of the test method, the
following values only in 1 case in 20 (see Table 2):
Repeatability = 7.61
*where x is the average of two results in
Reproducibility - The difference between two single and
independent results obtained by different operators working in
different laboratories on identical test material would exceed, in
the long run, the following values only in 1 case in 20:
Reproducibility = 20.02 /x*
*where x is the average value of two'results in p.g/g.
9.2.1.2 Bias. The bias of this method varies with
concentration, as shown in Table 3:
Bias = Amount found - Amount expected
9252A - 5 Revision 1
September 1994
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10.0 REFERENCES
1. Annual Book of ASTM Standards, Part 31, "Water," Standard D512-67, Method
A, p. 270 (1976).
2. Standard Methods for the Examination of Water and Wastewater, 15th ed.,
(1980).
3. U.S. Environmental Protection Agency, Methods for Chemical Analysis of
Water and Wastes, EPA 600/4-79-020 (1983), Method 325.3.
9252A - 6 Revision 1
September 1994
-------
TABLE 1. ANALYSES OF SYNTHETIC WATER SAMPLES
FOR CHLORIDE BY MERCURIC NITRATE METHOD
Increment as Precision as Accuracy as
Chloride Standard Deviation Bias Bias
(mg/L) (mg/L) (%) (mg/L)
17
18
91
97
382
398
1.54
1.32
2.92
3.16
11.70
11.80
+2.16
+3.50
+0.11
-0.51
-0.61
-1.19
+0.4
+0.6
+0.1
-0.5
-2.3
-4.7
TABLE 2. REPEATABILITY AND REPRODUCIBILITY
FOR CHLORINE IN USED OILS BY BOMB
OXIDATION AND MERCURIC NITRATE TITRATION
Average value, Repeatability, Reproducibility,
M9/9 M9/9 M9/9
500
1,000
1,500
2,000
2,500
3,000
170
241
295
340
381
417
448
633
775
895
1,001
1,097
9252A - 7 Revision 1
September 1994
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TABLE 3. RECOVERY AND BIAS DATA FOR CHLORINE IN
USED OILS BY BOMB OXIDATION AND
MERCURIC NITRATE TITRATION
Amount Amount
expected, found, Bias, Percent
M9/9 M9/9 Aig/9 bias
320 460 140 +44
480 578 98 +20
920 968 48 +5
1,498 1,664 166 +11
1,527 1,515 - 12 - 1
3,029 2,809 -220 - 7
3,045 2,710 -325 -11
9252A - 8 Revision 1
September 1994
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METHOD 9252A
CHLORIDE (TITRIMETRIC, MERCURIC NITRATE)
( START J
7 1 Place SO mL
sample in titration
vessel; determine
concentration of
mercuric nitrate
titrant to use in
Step 7.6; determine
an indicator blank
7.2 Add indicator
to iamplซ; shale*
7 . 4 Add sodium
hydroซidซ until
sanpl* is
bluซ-violซt; add
nitric acid until
sampl* is yซlloซ
7.3 Add nitric acid
until sampla is
7.5 Add 1 ml nitric
acid
7.6 Titrat* ซith
mercuric nitrate
until blue-violet
color persists
7.7 Calculate
concentration of
chloride in sample
( STOP J
9252A - 9
Revision 1
September 1994
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METHOD 9253
CHLORIDE (TITRIMETRIC. SILVER NITRATE)
1.0 SCOPE AND APPLICATION
1.1 This method is intended primarily for oxygen bomb combustates or
other waters where the chloride content is 5 mg/L or more and where interferences
such as color or high concentrations of heavy metal ions render Method 9252
impracticable.
2.0 SUMMARY OF METHOD
2.1 Water adjusted to pH 8.3 is titrated with silver nitrate solution
in the presence of potassium chromate indicator. The end point is indicated by
persistence of the orange-silver chromate color.
3.0 INTERFERENCES
3.1 Bromide, iodide, and sulfide are titrated along with the chloride.
Orthophosphate and polyphosphate interfere if present in concentrations greater
than 250 and 25 mg/L, respectively. Sulfite and objectionable color or turbidity
must be eliminated. Compounds that precipitate at pH 8.3 (certain hydroxides)
may cause error by occlusion.
3.2 Residual sodium carbonate from the bomb combustion may react with
silver nitrate to produce the precipitate, silver carbonate. This competitive
reaction may interfere with the visual detection of the end point. To remove
carbonate from the test solution, add small quantities of sulfuric acid followed
by agitation.
4.0 APPARATUS AND MATERIALS
4.1 Standard laboratory titrimetric equipment, including 1 mL or 5 mL
microburet with 0.01 mL gradations, and 25 mL buret.
4.2 Analytical balance: capable of weighing to 0.0001 g.
4.3 Class A volumetric flask: 1 L.
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 Hydrogen peroxide (30%), H202.
9253 - 1 Revision 0
September 1994
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5.4 Phenolphthalein indicator solution (10 g/L).
5.5 Potassium chromate indicator solution. Dissolve 50 g of potassium
chromate (K2Cr04) in 100 mL of reagent water and add silver nitrate (AgN03) until
a slightly red precipitate is produced. Allow the solution to stand, protected
from light, for at least 24 hours after the addition of AgN03. Then filter the
solution to remove the precipitate.and dilute to 1 L with reagent water.
5.6 Silver nitrate solution, standard (0.025N). Crush approximately
5 g of silver nitrate (AgNOJ crystals and dry to constant weight at 40ฐC.
Dissolve 4.2473 + 0.0002 g of the crushed, dried crystals in reagent water and
dilute to 1 L with reagent water. Standardize against the standard NaCl
solution, using the procedure given in Section 7.0.
5.7 Sodium chloride solution, standard (0.025N). Dissolve 1.4613 g
ฑ 0.0002 g of sodium chloride (dried at 600ฐC for 1 hr) in chloride-free water
in a 1 liter Class A volumetric flask and dilute to the mark with reagent water.
5.8 Sodium hydroxide solution (0.25N). Dissolve approximately 10 g of
NaOH in reagent water and dilute to 1 L with reagent water.
5.9 Sulfuric acid (1:19), H2S04. Carefully add 1 volume of concentrated
sulfuric acid to 19 volumes of reagent water, while mixing.
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 There are no special requirements for preservation.
7.0 PROCEDURE
7.1 Pour 50 mL or less of the sample, containing between 0.25 mg and
20 mg of chloride ion, into a white porcelain container. Dilute to approximately
50 mL with reagent water, if necessary. Adjust the pH to the phenolphthalein end
point (pH 8.3) using H2S04 (Sec. 5.9) or NaOH solution (Sec. 5.8).
7.2 Add approximately 1.0 mL of K_Cr04 indicator solution and mix. Add
standard AgN03 solution dropwise from a 25 mL buret until the orange color
persists throughout the sample when illuminated with a yellow light or viewed
with yellow goggles. Be consistent with endpoint recognition.
7.3 Repeat the procedure described in Sees. 7.1 and 7.2 using exactly
one-half as much original sample, diluted to 50 mL with halide-free water.
7.4 If sulfite ion is present, add 0.5 mL of H.02 to the samples
described in Sees. 7.2 and 7.3 and mix for 1 minute. Adjust tne pH, then proceed
as described in Sees. 7.2 and 7.3.
9253 - 2 Revision 0
September 1994
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7.5 Calculation
7.5.1 Calculate the chloride ion concentration in the original
sample, in milligrams per liter, as follows:
Chloride (mg/L) = [(Vj - V2) x N x 71,000] / S
where:
Vj = Milliliters of standard AgNO, solution added in titrating
the sample prepared in Sec. 7.1.
V2 = Milliliters of standard AgNO. solution added in titrating
the sample prepared in Sec. 7.3.
N = Normality of standard AgN03 solution.
S ป Milliliters of original sample in the 50. ml test sample
prepared in Sec. 7.1.
71,000 = 2 x 35,500 mg Cl'/equivalent, since \ll - 2V?.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for
easy reference or inspection. Refer to Chapter One for specific quality control
guidelines.
8.2 Analyze a standard reference material to ensure that correct
procedures are being followed and that all standard reagents have been prepared
properly.
8.3 Employ a minimum of one blank per analytical batch or twenty
samples, whichever is more frequent, to determine if contamination has occurred.
8.4 Run one matrix spike and matrix duplicate every analytical batch
or twenty samples, whichever is more frequent. Matrix spikes and duplicates are
brought through the whole sample preparation and analytical process.
9.0 METHOD PERFORMANCE
9.1 These data are based on 32 data points obtained by five
laboratories who each analyzed four used crankcase oils and three fuel oil blends
with crankcase in duplicate. The samples were combusted using Method 5050. A
data point represents one duplicate analysis of a sample. Three data points were
judged to be outliers and were not included in these results.
9.1.1 Precision. The precision of the method as determined by
the statistical examination of inter- laboratory test results is as
f ol 1 ows :
9253 - 3 Revision 0
September 1994
-------
Repeatability - The difference between successive results obtained
by the same operator with the same apparatus under constant operating
conditions on identical test material would exceed, in the long run, in
the normal and correct operation of the test method, the following values
only in 1 case in 20 (see Table 1):
Repeatability = 0.36 x*
*where x is the average of two results in M9/9-
Reproducibilitv - The difference between two single and independent
results obtained by different operators working in different laboratories
on identical test material would exceed, in the long run, the following
values only in 1 case in 20:
Reproducibility = 0.71 x*
where x is the average of two results in M9/9-
9.1.2 Bias. The bias of this method varies with concentration,
as shown in Table 2:
Bias = Amount found - Amount expected
10.0 REFERENCES
1. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; American Chemical Society: Washington, DC, 1986.
2. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
3. Gaskill, A.; Estes, E. 0.; 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.
68-01-7075, WA 80. July 1988.
9253 - 4 Revision 0
September 1994
-------
TABLE 1.
REPEATABILITY AND REPRODUCIBILITY FOR CHLORINE IN USED
OILS BY BOMB OXIDATION AND SILVER NITRATE TITRATION
Average value Repeatability Reproducibility
500
1,000
1,500
2,000
2,500
3,000
180
360
540
720
900
1,080
355
710
1,065
1,420
1,775
2,130
TABLE 2.
RECOVERY AND BIAS DATA FOR CHLORINE IN USED OILS BY
BOMB OXIDATION AND SILVER NITRATE TITRATION
Amount Amount
expected found Bias, Percent
(M9/g) (Mg/g) bias
320
480
920
1,498
1,527
3,029
3,045
645
665
855
1,515
1,369
2,570
2,683
325
185
-65
17
-158
-460
-362
+102
+39
-7
+1
-10
-15
-12
9253 - 5 Revision 0
September 1994
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METHOD 9253
CHLORIDE (TITRIMETRIC, SILVER NITRATE)
START
7.1 Place SO ml
sample in porcelain
container
74 Add hydrogen
peroxide; mn far 1
minute
Yes
741.
sulfite ion
present in
sample?
No
7.1 Adjust pH to
83
7.2 Add 10 ml
potassium chromate;
stir; add silver
nitrate until
orange color
persists
7.3 Repeat steps
7.1 and 72 ซith
1/2 as much sample
diluted to SO ml
7.S Calculate
concentration of
chloride in sampli
STOP
9253 - 6
Revision 0
Septenter 1994
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METHOD 9320
RADIUM-228
1.0 SCOPE AND APPLICATION
1.1 This method covers the measurement of radium-228 1n ground water
and, 1f desired, the determination of rad1um-226 on the same sample. If the
level of rad1um-226 1s above 3 pC1/L, the sample must also be measured for
rad1um-228.
1.2 This technique 1s devised so that the beta activity from actinium-
228, which 1s produced by decay of radium-228, can be determined and related
to the rad1um-228 that 1s present 1n the sample.
1.3 To quantify act1n1um-228 and thus determine rad1um-228, the
efficiency of the beta counter for measuring the very short half-lived
actin1um-228 (avg. beta energy of 0.404 keV) is to be calibrated with a beta
source of comparable average beta energy.
2.0 SUMMARY OF METHOD
2.1 The radium 1n the water sample is collected by coprec1p1tat1on with
barium and lead sulfate and purified by repredpitation from EDTA solution.
Both radium-226 and radium-228 are collected in this manner. After a 36-hr
ingrowth of actin1um-228 from radium-228, the actinium-228 is carried on
yttrium oxalate, purified and beta counted. If radium-226 1s also desired,
the activity in the supernatant can be reserved for coprecipltation on barium
sulfate, dissolving 1n EDTA and storing for Ingrowth in a sealed radon
bubbler.
3.0 INTERFERENCES
3.1 As evidenced by the results of the performance studies, the presence
of strontium-90 in the water sample gives a positive bias to the rad1um-228
activity measured. However, strontium-90 1s not likely to be found in ground
water, except possibly 1n monitoring wells around a radioactive burial site.
3.2 Excess barium in the water sample might result in a falsely high
chemical yield.
4.0 APPARATUS
4.1 Gas-flow proportional counting system (low-background beta <3 cpm).
4.2 Electric hot plate.
9320 - 1
Revision 0
Date September 1986
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4.3 Centrifuge.
4.4 Membrane filters; Matrlcel 47-mrn.
4.5 Drying lamp.
4.6 Glassware.
4.7 Stainless steel counting planchets.
4.8 Analytical balance.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water must be monitored for
Impurities.
5.2 Acetic add. 17.4 N: Glacial CFhCOOH (concentrated) sp. gr. 1.05,
99.8%.
5.3 Ammonium hydroxide. 15 N: NfyOH (concentrated) sp gr. 0.90, 56.6%.
5.4 Ammonium oxalate. 5%: Dissolve 5g (NH/j) 20304 '^O 1n Type II water
and dilute to 100 ml.
5.5 Ammonium sulfate, 200 mg/mL: Dissolve 20 g (NH4)2S04 1n Type II
water and dilute to 100 ml.
5.6 Ammonium sulflde. 2%: Dilute 10 ml (Nfy^S (20-24%), to 100 ml with
Type II water.
5.7 Barium carrier, 16 mg/mL, standardized: Dissolve 2.846 g BaCl2*2H20
1n Type II water, add 0.5 ml 16 N HN03, and dilute to 100 ml with Type II
water.
5.8 Citric add. 1 M: Dissolve 19.2 g C^HoOT-F^O 1n Type II water and
dilute to 100 ml.
5.9 EDTA reagent, basic (0.25 M): Dissolve 20 g NaOH 1n 750 ml Type II
water, heat, and slowly add 93 g disodlum ethylened1m'tr1loacetate dlhydrate
(Na2CioH1408N2ซ2H20) while stirring. After the salt is in solution, filter
through coarse filter paper, and dilute to 1 liter.
5.10 Lead carrier. 15 mg/mL: Dissolve 2.397 g Pb(N03)2 1n TyPe I I
water, add 0.5 mL 16 N HNOs, and dilute to 100 mL with Type II water.
5.11 Lead carrier. 1.5 mg/mL: Dilute 10 mL lead carrier (15 mg/mL) to
100 mL with Type II water.
9320 - 2
Revision
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected 1n a manner which addresses the
considerations discussed in Chapter Nine of this manual.
6.2 It is recommended that samples be preserved at the time of
collection by adding enough 1 N HN03 to the sample to bring 1t to pH 2
(15 mL 1 N HN03 per liter of sample is usually sufficient). If samples are to
be collected without preservation, they should be brought to the laboratory
within 5 days, then preserved, and held in the original container for a
minimum of 16 hr before analysis or transfer of the sample. See also Note to
Paragraph 7.2 below.
6.3 The container choice should be plastic (rather than glass) to
prevent loss due to breakage during transportation and handling.
7.0 PROCEDURE
7.1 Calibrations;
7.1.1 Counter efficiency: The beta counter may be calibrated with
actinium-228 or stront1um-89 (tj/2 =51 d). Strontium-89 has an average
beta energy of 0.589 KeV, while the average beta energy for actinium-228
is 0.404 KeV. A standard stront1um-89 tracer solution can be used to
determine beta efficiencies over a range of precipitate weights on the
stainless steel planchet.
7.2 For each liter of water, add 5 mL 1 M CsttQQffyO, and a few drops of
methyl orange indicator. The solution should be red.
NOTE: At the time of sample collection add 2 mL 16 N HN03 for each liter
of water.
7.3 Add 10 mL lead carrier (15 mg/mL), 2 mL strontium carrier
(10 mg/mL), 2.0 mL barium carrier (16 mg/mL), and 1 mL yttrium carrier
(18 mg/mL); stir well. Add 15 N NH/iOH until a definite yellow color is
obtained; then add a few drops excess. Heat to incipient boiling and maintain
at this temperature for 30 min.
7.4 Precipitate lead and barium sul fates by adding 18 N H2$OA until the
red color reappears; then add 0.25 mL excess. Add 5 mL (NH4)2S04 (200 mg/mL)
for each liter of sample. Stir frequently and keep at a temperature of about
90*C for 30 min.
7.5 Cool slightly; then filter with suction through a 47-mm matricel
membrane filter (GA6,0.45-m1cron pore size). Make a quantitative transfer of
precipitate to the filter by rinsing last particles out of beaker with a
strong jet of water.
7.6 Carefully place filter with precipitate 1n the bottom of a 250-mL
beaker. Add about 10 mL 16 N HNOs and heat gently until the filter completely
9320 - 3
Revision 0
Date September 1986
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dissolves. Transfer the precipitate Into a polypropylene centrifuge tube with
additional 16 N HN03. Centrifuge and discard supernatant.
7.7 Wash the precipitate with 15 mL 16 N HMOs, centrifuge, and discard
supernatant. Repeat this washing a second time.
7.8 Add 25 ml basic EDTA reagent, heat 1n a hot-water bath, and stir
well. Add a few drops 10 N NaOH 1f the precipitate does not readily dissolve.
7.9 Add 1 ml strontium-yttrium mixed carrier and stir thoroughly. Add a
few drops 10 N NaOH If any precipitate forms.
7.10 Add 1 ml (NH^SOi (200 mg/mL) and stir thoroughly. Add 17.4 N
acetic add until barium sulfate precipitates; then add 2 ml excess. Digest
in a hot water bath until precipitate settles. Centrifuge and discard
supernatant.
7.11 Add 20 ml basic EDTA reagent, heat 1n a hot-water bath, and stir
until precipitate dissolves. Repeat steps 7.9 and 7.10. (Note time of last
barium sulfate precipitation; this 1s the beginning of the act1nium-228
Ingrowth time.)
7.12 Dissolve the precipitate in 20 ml basic EDTA reagent as before;
then add 1.0 ml yttrium carrier (9 mg/mL) and 1 ml lead carrier (1.5 mg/mL).
If any precipitate forms, dissolve by adding a few drops 10 N NaOH. Cap the
polypropylene tube and age at least 36 hr.
7.13 Add 0.3 mL (NH4)?S and stir well. Add 10 N NaOH dropwise with
vigorous stirring until lead sulfide precipitates; then add 10 drops excess.
Stir Intermittently for about 10 mln. Centrifuge and decant supernatant Into
a clean tube.
7.14 Add 1 mL lead carrier (1.5 mg/mL), 0.1 mL (NHa^S, and a few drops
10 N, NaOH. Repeat precipitation of lead sulfide as before. Centrifuge and
filter supernate through Whatman #42 filter paper into a clean tube. Wash
filter with a few mL water. Discard residue.
7.15 Add 5 mL 18 N NaOH, stir well, and digest in a hot-water bath until
yttrium hydroxide coagulates. Centrifuge and decant supernate into a beaker.
Save for barium yield determination (step 7.20). (Note time of yttrium
hydroxide precipitation; this is the end of the act1nium-228 Ingrowth time and
beginning of actin1um-228 decay time.)
7.16 Dissolve the precipitate in 2 mL 6 N HN03. Heat and stir in a hot
water bath about 5 min. Add 5 mL water and reprecipltate yttrium hydroxide
with 3 mL 10 N NaOH. Heat and stir in a hot water bath until precipitate
coagulates. Centrifuge and add this supernate to the supernate produced in
step 7.15 1n order to determine barium yield.
7.17 Dissolve precipitate with 1 mL 1 N HN03 and heat in hot-water bath
a few minutes. Dilute to 5 mL and add 2 mL 5% (NH/^CeO/i^O. Heat to
coagulate, centrifuge, and discard supernatant.
9320 - 4
Revision 0
Date September 1986
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7.18 Add 10 mL water, 6 drops 1 N HN03 and 6 drops 5%
Heat and stir 1n a hot-water bath a few minutes. Centrifuge and~discard
supernatant.
7.19 To determine yttrium yield, transfer quantitatively to a tared
stainless steel planchet with a minimum amount of water. Dry under an
Infrared lamp to a constant weight and count in a low-background beta counter.
7.20 To the supernatant from step 7.15, add 4 mL 16 N HN03 and 2 mL
J2S04 (200 mg/mL), stirring well after each addition. Add 17.4 N acetic
acid until barium sulfate precipitates; then add 2 mL excess. Digest on a hot
plate until precipitate settles. Centrifuge and discard supernatant.
7.21 Add 20 mL basic EDTA reagent, rest 1n a hot-water bath, and stir
until precipitate dissolves. Add a few drops 10 N NaOH if precipitate does
not readily dissolve.
7.22 Add 1 mL (M^SOA (200 mg/mL) and stir thoroughly. Add 17.4 N
acetic acid until barium sulfate precipitates; then add 2 mL excess. Digest
in a hot-water bath until precipitate settles. Centrifuge and discard
supernatant.
7.23 Wash precipitate with 10 mL water. Centrifuge and discard
supernatant.
7.24 Transfer precipitate to a tared stainless steel planchet with a
minimum amount of water. Dry under an infrared lamp and weigh for barium
yield determination.
7.25 Calculation;
7.25.1 Calculate the rad1um-228 concentration, D, in picocurles per
liter as follows:
\+ *
r ?ll
x =r x 4
2.22 XEVR (1.e-Xt2)
is a factor to correct the average count rate to the count
-Xt, rate at the beginning of counting time.
Z)
9320 - 5
Revision
Date September 1986
-------
where:
C = Average net count rate, cpm;
E = Counter efficiency, for act1n1um-228, or comparable beta
energy nucllde;
V = Liters of sample used;
R = Fractional chemical yield of yttrium carrier (Step 7.19)
multiplied by fractional chemical yield of barrier
carrier (Step 7.24);
2.22 = Conversion factor from disintegrations/minute to
plcocurles;
X = The decay constant for actlnlum-228 (0.001884 mln'1);
tj = The time Interval (In m1n) between the first yttrium
hydroxide precipitation 1n Step 7.15 and the start of
the counting time;
t2 = The time Interval of counting In mln; and
13 = The Ingrowth time of act1n1um-228 1n m1n measured from
the last barium sulfate precipitation In Step 7.11 to
the first yttrium hydroxide precipitation 1n Step 7.15.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Employ a minimum of one blank per sample batch to determine If
contamination or any memory effects are occurring.
8.3 Run one spike duplicate sample for every 10 samples. A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
9.0 METHOD PERFORMANCE
9.1 No data provided.
9320 - 6
Revision
Date September 1986
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10.0 REFERENCES
1. Greenberg, A.E., J.J. Connors, and D.J. Jenkens, eds., Standard Methods
for the Examination of Water and Wastewater, 15th ed., American Public Health
Assoc., Washington, D.C., Method 707, p. 600, 1980.
2. Johnson, J.O., Determination of Radium 228 in Natural Waters.
Radiochemical Analysis of Water. U.S. Geol. Surv., Water Supply Paper 1696-G.
U.S. Govt. Printing Office, Washington, D.C., 1971.
3. Krieger, H.L., Prescribed Procedures for Measurement of Radioactivity in
Drinking Water, Environmental Monitoring and Support Laboratory, U.S. EPA,
Cincinnati, OH, EPA-600/4-75-008, 1976.
9320 - 7
Revision
Date September 1986
-------
METHOD 9320
RAOIUM-asa
C
Start
7.1.1
Calibrate
beta counter
Mltti Ac-228
or Sr-89
7.2
7.5
Cool slightly:
filter
Add
-ซHsฐ*ฐ Htฐ and
ffiethyl orange
indicator to
water
7.6 1
Put filter ana
precipitate in
beaker:
add HNOt:
heat: centrifuge:
discard
super-note
7.9
1 Add
strontium
yttrium nixed
carrier; add
Ma OH
7.3
Add
lead, strontium.
barium, and
yttrium
carriers; ctlr
7.7
Wash
precipitate:
centerfuge;
discard
super-note
7.3
Add NHซOH until
yellow color
obtained: heat
7.7
Repeat once
7.10
Add
(NH^)rSO<: add
CH COOH; digest:
centrifuge:
discard supern.
7.11
Add basic EOTA
reagent: heat:
tlr
7.4
Add
to
precipitate
lead and barium
ulfates; add
stir
7.8
Add basic EOTA
reagent: heat:
tlr
Repeat sections
7.9 and 7.1O
9320 - 8
Revision 0
Date September 1986
-------
METHOD 9320
RAOHJM-228
(Continued)
7. 12
Dissolve
precipitate
In EOTA; ooa
yttrium ana
lead carriers
Does
precipitate form?
Cap tube and
age at least
36 hours
7.H
Centrifuge and
filter
7. 17
Dilute:
1 add
(NHซ) 2CiOซ-H,.0:
heat:centrifuge
and discard
Gupernate
7.IS Add
NaOH;
stir; digest:
centrifuge
and decant
upernate
7. 16
Add water. HNO/.
(NH^)Z CiOVHj.0:
heat:centrlfuge ana
discard Bupernate
7.16
Dissolve precipitate:
heat and stir; add
water and
repreclpltate
yttrium hydroxide
7.191 Transfer
J to
planchet;
determine
yttrium yield
using counter
Add
-------
METHOD 9320
RAOIUM-ase
(Continued)
Old
precipitate
readily
dissolve?
Add (NHซ)iSO<: stir;
add CH3COOH; digest:
centrifuge: discard
supernate
7.23
Wash
precipitate:
centri fuge;
discard
supernate
7.24
precl
plane
we
Dar]
Transfer
pltate to
net: dry:
Ign for
urn yield
7.25
r
cone
uslr
Calculate
adlum-228
:entratlon
ig formula
in text
( Stop J
9320 - 10
Revision 0
Date September 1986
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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)
Cation-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
SIX - 1
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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 (i .e., those containing less than 0.5 % dry
solid material), the sample, after filtration through a 0.6 to 0.8 urn 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 jum 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 VITON*1 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
'VITONฎ 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-^m . 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 25ฐC.
4.6 ZHE Extract Collection Devices: TEDLARฎ2 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
2
TEDLAR* is a registered trademark of Du Pont.
1312 - 3 Revision 0
September 1994
-------
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 Initial liquid phase (i.e.. >1 % of total waste), the
syringe or the TEDLAR0 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 %
solidj^or has no significant solid phase (is <0.5% solid) , either the
TEDLAR* bag or the syringe may 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
September 1994
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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 ฑ 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 #2: 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 fluid 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
M .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 4ฐC
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 + 20ฐC
until two successive weighings yield the same value within + 1 %.
Record the final weight.
Caution: The drying oven should be vented to 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 #2 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 and/or soils,
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 multiphasic, 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 filtration, is defined as 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 48C 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 4ฐC 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 with a fresh filter under any circumstances. Use
only one filter.
7.2.9 If the sample contains <0.5% dry solids (see Step 7.1.2),
proceed to Step 7.2.13. 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
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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 (i.e., temperature of room in which extraction takes
place) shall be maintained at 23 ฑ 2ฐC 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 follows:
i
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
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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 (4ฐC) 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:
(V,) (C,) + (V2) (C2)
Final Analyte Concentration =
V, + V2
where:
V, = The volume of the first phase (L).
CT = 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 (4ฐC) 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
7.1.1), weigh out a 500 gram subsample of waste and record the
weight.
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.
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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 (liquid and solid
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 4ฐC 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 2-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 4ฐC 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
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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 + 2ฐC 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., TEDLAR0 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 TEDLAR
bag is used, if the extract is multiphasic, or if the waste contained an
initial liquid phase (see Steps 4.6 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 4ฐC
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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 (i.e., 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:
(V,) (C,) + (V2) (C2)
Final Analyte
Concentration , V, + V2
where:
V, = The volume of the first phases (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).
7.3.16 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 (Xs - Xu) / K
where:
X6 = 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.
i
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
-------
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 (davs)
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 time 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
-------
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.
2. Research Triangle Institute, "Interlaboratory Comparison of Methods 1310,
1311, and 1312 for Lead in Soil". U.S. EPA Contract 68-01-7075, November
1988.
1312 - 21 Revision 0
September 1994
-------
Table 1. Volatile Analytes1
Compound CAS No.
Acetone 67-64-1
Benzene 71-43-2
n-Butyl alcohol 71-36-3
Carbon disulfide 75-15-0
Carbon tetrachloride 56-23-5
Chlorobenzene 108-90-7
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
l,l,2-Trichloro-l,2,2-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
September 1994
-------
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
Mi Hi pore 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
(3740-2);
(3740-4);
(3740-6);
(3740-8);
12-vessel (3740-12);
24-vessel (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
ฑ2 rpm is acceptable.
1312 - 23
Revision 0
September 1994
-------
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
Whitmore Lake, MI
(313) 449-4116
Bedford, MA
(800) 225-3384
Lynchburg, VA
(804) 845-6424
C102, Mechanical
Pressure Device
3745-ZHE, Gas
Pressure Device
ZHE-11, Gas
Pressure Device
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 110 mm filter.
1312 - 24
Revision 0
September 1994
-------
Table 4. Suitable Filter Holders1
Company
Nucleopore Corporation
Micro Filtration
Systems
Millipore 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 mm size filter holder is
recommended.
Table 5. Suitable Filter Media1
Company
Millipore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Location Model
Bedford, MA AP40
(800) 225-3384
Pleasanton, CA 211625
(415) 463-2530
Clifton, NJ GFF
(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 Revision 0
September 1994
-------
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-Dichlorobenzene
1,2-Dichlorobenzene
2-Methylphenol
Nitrobenzene
2,4- Dime thy 1 phenol
Hexachlorobutadiene
Acenaphthene
2 ,4-Dinitrophenol
2 ,4-Dinitrotoluene
Hexachlorobenzene
famma BHC (Lindane)
eta BHC
METALS
Lead
Cadmium
Amount
Spiked
(Mg)
1040
1620
2000
8920
3940
1010
1460
6300
3640
1300
1900
1840
7440
640
5000
1000
Amount
Recovered*
(Mg)
834
1010
344
1010
1860
812
200
95
210
896**
1150
3.7
230
35
70
387
% RSD
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 (oH 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
September 1994
-------
TABLE 7 - METHOD 1312 PRECISION RESULTS FOR VOLATILES
Soil
No. 1
Soil
No. 2
Soil No
. 3
(Western and
(Western)
Compound Name
Acetone
Acrylonltrile
Benzene
n- Butyl Alcohol
(1-Butanol)
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1 , 2-Dichloroethane
1 , 1-Dichloroe thane
Ethyl acetate
Ethylbenzene
Ethyl ether
Isobutanol (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
Tetrachloroethene
Toluene
1,1,1-Trichloro-
e thane
1,1,2-Trichloro-
e thane
Trichloroethene
Trlchloro-
f luorome thane
1,1,2-Trichloro-
trlfluoroe 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
%RSD
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
(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
* %RSD
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
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
%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 33.9
15.3 24.8
11.8 25.4
* Triplicate analyses
** Six replicate analyses
*** Five replicate analyses
1312 - 27
Revision 0
September 1994
-------
Motor
(30ฑ 2 rpm)
Extraction Vessel Holder
Figure 1. Rotary Agitation Apparatus
Top Flange
Support Screen
Support Screen
Vlton
Bottom Flange*{_
Preuuriztd Gas -n
VUv*
Liquid Into/Outlet Valve
Sample
x "ซw a
Gas
Pressure
QauQe
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.
[ Start )
~^
Select
representative
sample.
Separate liquids
from solids,
filtrate
becomes SPLP
extract.
<0'5% ' Calculate \ >ฐ'5%
% solids.
Separate liquids
from solids.
particle N. Ves
reduction
required?
f Stop J
Extract w/
appropriate fluid via:
1. Bottle extraction
for non-volatiles,
2. ZHE for volatiles.
Reduce particle
size to <9.5 mm.
o
1312 - 29
Revision 0
September 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.
I
f Stop J
Prepare extract
according to
appropriate
methods.
Analyze extract.
f Stop J
1312 - 30
Revision 0
September 1994
-------
METHOD 1320
MULTIPLE EXTRACTION PROCEDURE
1.0 SCOPE AND APPLICATION
The Multiple Extraction Procedure (MEP) described In this method Is
designed to simulate the leaching that a waste will undergo from repetitive
precipitation of acid rain on an improperly designed sanitary landfill. The
repetitive extractions reveal the highest concentration of each constituent
that is likely to leach in a natural environment. Method 1320 is applicable
to liquid, solid, and multiphase samples.
2.0 SUMMARY OF METHOD
Waste samples are extracted according to the Extraction Procedure
Toxicity Test (Method 1310, Chapter 8) and analyzed for the constituents of
concern listed in Chapter 7, Table 7-1: Maximum Concentration of Contaminants
for Characteristic of EP Toxicity, using the 7000 and 8000 series methods.
Then the solid portions of the samples that remain after application of Method
1310 are re-extracted nine times using synthetic acid rain extraction fluid.
If the concentration of any constituent of concern increases from the 7th or
8th extraction to the 9th extraction, the procedure is repeated until these
concentrations decrease.
3.0 INTERFERENCES
Potential interferences that may be encountered during analysis are
discussed in the appropriate analytical methods.
4.0 APPARATUS AND MATERIALS
4.1 Refer to Method 1310.
5.0 REAGENTS
5.1 Refer to Method 1310.
5.2 Sulfuric acidtm'tric acid, 60/40 weight percent mixture: Cautiously
mix 60 g of concentrated sulfuric acid with 40 g of concentrated nitric acid.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Refer to Method 1310.
1320 - 1
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Run the Extraction Procedure (EP) test 1n Method 1310.
7.2 Analyze the extract for the constituents of interest.
7.3 Prepare a synthetic acid rain extraction fluid by adding the 60/40
weight percent sulfuric acid and nitric acid to distilled deionized water
until the pH is 3.0 + 0.2.
7.4 Take the solid phase of the sample remaining after the Separation
Procedure of the Extraction Procedure and weigh it. Measure an aliquot of
synthetic acid rain extraction fluid equal to 20 times the weight of the solid
sample. Do not allow the solid sample to dry before weighing.
7.5 Combine the solid phase sample and acid rain fluid in the same
extractor as used in the EP and begin agitation. Record the pH within 5-10
min after agitation has been started.
7.6 Agitate the mixture for 24 hr, maintaining the temperature at 20-
40*C (68-104'F). Record the pH at the end of the 24-hr extraction period.
7.7 Repeat the Separation Procedure as described in Method 1310.
7.8 Analyze the extract for the constituents of concern.
7.9 Repeat steps 7.4-7.8 eight additional times.
7.10 If, after completing the ninth synthetic rain extraction, the
concentration of any of the constituents of concern is increasing over that
found in the 7th and 8th extractions, then continue extracting with synthetic
acid rain until the concentration in the extract ceases to increase.
7.11 Report the initial and final pH of each extraction and the
concentration of each listed constituent of concern 1n each extract.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Employ a minimum of one blank per sample batch to determine 1f
contamination or any memory effects are occurring.
8.3 All quality control measures suggested 1n the referenced analytical
methods should be followed.
1320 - 2
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
1320 - 3
Revision
Date September 1986
-------
METHOD 1330
MULTIPLE EXTRACTION PROCEDURE
CEO O
7.1
Run extraction
procedure test
(Method 1310)
7.2
o
7.5
Combine
G agitate
BO lid phase
sample and acid
rain fluid:
record pH
Analyze metale
according to
Table l
7.3
7.7
Repeat
separation
procedure
(Method 1310)
Agitate
mixture for 24
hre; record pH
at end.
Prepare
nthetic acid
n extraction
fluid
7.8
Analyze
extract for
conatltuente
of concern
0
7.9 |
Repeat 8 times
1 weigh
solid phase
of sample;
oeasure acid
rain extraction
o
o
Is concentr. of
Sth extraction >
the 7th and
8th?
7.11
Report
initial
nd final
extraction
pH and concetr.
of constituents
-------
METHOD 1330A
EXTRACTION PROCEDURE FOR OILY WASTES
1.0 SCOPE AND APPLICATION
1.1 Method 1330 is used to determine the mobile metal concentration
(MMC) in oily wastes.
1.2 Method 1330 is applicable to API separator sludges, rag oils, slop
oil emulsions, and other oil wastes derived from petroleum refining.
2.0 SUMMARY OF METHOD
2.1 The sample is separated into solid and liquid components by
filtration.
2.2 The solid phase is placed in a Soxhlet extractor, charged with
tetrahydrofuran, and extracted. The THF is removed, the extractor is then
charged with toluene, and the sample is reextracted.
2.3 The EP method (Method 1310) is run on the dry solid residue.
2.4 The original liquid, combined extracts, and EP leachate are
analyzed for the EP metals.
3.0 INTERFERENCES
3.1 Matrix interferences will be coextracted from the sample. The
extent of these interferences will vary considerably from waste to waste,
depending on the nature and diversity of the particular refinery waste being
analyzed.
4.0 APPARATUS AND MATERIALS
4.1 Soxhlet extraction apparatus.
4.2 Vacuum pump or other source of vacuum.
4.3 Buchner funnel 12.
4.4 Electric heating mantle.
4.5 Paper extraction thimble.
4.6 Filter paper.
4.7 Muslin cloth disks.
4.8 Evaporative flask - 250-mL.
4.9 Balance - Analytical, capable of weighing to ฑ 0.5 mg.
1330A - 1 Revision 1
July 1992
-------
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.
X
5.2 Reagent water. All references to water in this method refer to
reagent water, as defined in Chapter One.
5.3 Tetrahydrofuran, C4H80.
5.4 Toluene, C6H5CH3.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 Samples must be collected in glass containers having a total volume
of at least 150 mL. No solid material should interfere with sealing the sample
container.
6.2 Sampling devices should be wiped clean with paper towels or
absorbent cloth, rinsed with a small amount of hexane followed by acetone rinse,
and dried between samples. Alternatively, samples can be taken with disposable
sampling devices in beakers.
7.0 PROCEDURE
7.1 Separate the sample (minimum 100 g) into its solid and liquid
components. The liquid component is defined as that portion of the sample which
passes through a 0.45 ium filter media under a pressure differential of 75 psi.
7.2 Determine the quantity of liquid (mL) and the concentration of the
toxicants of concern in the liquid phase (mg/L).
7.3 Place the solid phase into a Soxhlet extractor, charge the
concentration flask with 300 mL tetrahydrofuran, and extract for 3 hours.
7.4 Remove the flask containing tetrahydrofuran and replace it with one
containing 300 mL toluene.
7.5 Extract the solid a second time, for 3 hours, with the toluene.
7.6 Combine the tetrahydrofuran and toluene extracts.
7.7 Analyze the combined extracts for the toxicants of concern.
7.8 Determine the quantity of liquid (mL) and the concentration of the
toxicants of concern in the combined extracts (mg/L).
7.9 Take the solid material remaining in the Soxhlet thimble and dry
it at 100ฐC for 30 minutes.
1330A - 2 Revision 1
July 1992
-------
7.10 Run the EP (Method 1310) on the dried solid.
7.11 Calculate the mobile metal concentration (MMC) in mg/L using the
following formula:
MMC = 1,000 x
(Li + L2 + L3)
where:
Q, = Mass of toxicant in initial liquid phase of sample (amount
of liquid x concentration of toxicant) (mg).
Q2 = Mass of toxicant in combined organic extracts of sample
(amount of liquid x concentration of toxicant) (mg).
Q3 = Mass of toxicant in EP extract of solid (amount of extract
x concentration of toxicant) (mg).
L1 = Volume of initial liquid (ml).
L, = Volume of liquid in THF and toluene extract (Step 7.8)
(ml).
L3 = Volume of liquid in EP (mL) = 20 x [weight of dried solid
from Step 7.9 (g)].
8.0 QUALITY CONTROL
8.1 Any reagent blanks or replicates 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.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
1. Rohrbough, W.G.; et al . Reagent Chemicals, American Chemical Society
Specifications. 7th ed.; American Chemical Society: Washington, DC, 1986.
2. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
1330A - 3 Revision 1
July 1992
-------
Figure 1. Extractor
4.0
1
9.0
Non-Clogging Support Bushing
1-Inch Blade at 30' to Horizontal
1330A - 4
Revision 1
July 1992
-------
2-Liter Plastic or Glass Bottles
1/15-Horsepower Electric Motor
co
co
I
en
Screws for Holding Bottles
-I
ro
ft)
-J
O>
r>
ป
o
-5
*< JB
i/i
-
to o
ซO 3
ro
-------
Figure 3. EPRI Extractor
l-Gallon Plastic
or Glass Bottle
Totally Enclosed
Fan Cooled Motor
30 rpm, 1/8 HP
. Fฐam Bonded to Cover
Box Assembly
Plywood Construction
1330A - 6
Revision 1
July 1992
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Figure 4. Compaction Tester
m Combined Weight
0.33 kg (0.73 Ib)
3.15 cm
(1.25")
Sample
Elastomeric
Sample Holder
3.3 c
(1.3"
t
7.1cm
(2.8")
J.
1330A - 7
Revision 1
July 1992
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METHOD 1330A
EXTRACTION PROCEDURE FOR OILY WASTE
( START J
7.1 Separate sample
into liquid and
olid phases
7.8 Determine
quantity of liquid
and concentration
of toxicant* in
combined extracts
7.2 Determine
quantity of liquid
and concentration
of toxicants in
liquid phase
7.9 Remove solids
from thimble and
dry
7.3 Place solid
phase in extractor,
add THF to
concentration
flask, extract for
3 hours
7.10 Run EP (1310)
on dried solids .
-7.4 Replace THF
flask Kith toluene
concentration flask
1
7.5-7.7 Extract for
3 hours; combine
extracts; analyze
combined extracts
7.11 Calculate
mobile metal
concentration
( STOP J
1330A - 8
Revision 1
July 1992
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METHOD 9040A
pH ELECTROMETRIC MEASUREMENT
1.0 SCOPE AND APPLICATION
1.1 Method 9040 is used to measure the pH of aqueous wastes and those
multiphase wastes where the aqueous phase constitutes at least 20% of the total
volume of the waste.
1.2 The corrosivity of concentrated acids and bases, or of concentrated
acids and bases mixed with inert substances, cannot be measured. The pH
measurement requires some water content.
2.0 SUMMARY
2.1 The pH of the sample is determined electrometrically using either
a glass electrode in combination with a reference potential or a combination
electrode. The measuring device is calibrated using a series of standard
solutions of known pH.
3.0 INTERFERENCES
3.1 The glass electrode, in general, is not subject to solution
interferences from color, turbidity, colloidal matter, oxidants, reductants, or
moderate (<0.1 molar solution) salinity.
3.2 Sodium error at pH levels >10 can be reduced or eliminated by using
a low-sodium-error electrode.
3.3 Coatings of oily material or particulate matter can impair
electrode response. These coatings can usually be removed by gentle wiping or
detergent washing, followed by rinsing with distilled water. An additional
treatment with hydrochloric acid (1:10) may be necessary to remove any remaining
film.
3.4 Temperature effects on the electrometric determination of pH arise
from two sources. The first is caused by the change in electrode output at
various temperatures. This interference should be controlled with instruments
having temperature compensation or by calibrating the electrode-instrument system
at the temperature of the samples. The second source of temperature effects is
the change of pH due to changes in the sample as the temperature changes. This
error is sample-dependent and cannot be controlled. It should, therefore, be
noted by reporting both the pH and temperature at the time of analysis.
4.0 APPARATUS AND MATERIALS
4.1 pH meter: Laboratory or field model. Many instruments are commer-
cially available with various specifications and optional equipment.
4.2 Glass electrode.
9040A - 1 Revision 1
September 1994
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4.3 Reference electrode: A silver-silver chloride or other reference
electrode of constant potential may be used.
NOTE: Combination electrodes incorporating both measuring and
referenced functions are convenient to use and are available with
solid, gel-type filling materials that require minimal maintenance.
4.4 Magnetic stirrer and Teflon-coated stirring bar.
4.5 Thermometer and/or temperature sensor for automatic compensation.
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 Primary standard buffer salts are available from the National
Institute of Standards and Technology (NIST) and should be used in situations
where extreme accuracy is necessary. Preparation of reference solutions from
these salts requires some special precautions and handling, such as low-
conductivity dilution water, drying ovens, and carbon-dioxide-free purge gas.
These solutions should be replaced at least once each month.
5.3 Secondary standard buffers may be prepared from NIST salts or
purchased as solutions from commercial vendors. These commercially available
solutions have been validated by comparison with NIST standards and are
recommended for routine use.
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 of this manual.
6.2 Samples should be analyzed as soon as possible. ^
7.0 PROCEDURE
7.1 Calibration:
7.1.1 Because of the wide variety of pH meters and accessories,
detailed operating procedures cannot be incorporated into this method.
Each analyst must be acquainted with the operation of each system and
familiar with all instrument functions. Special attention to care of the
electrodes is recommended.
7.1.2 Each instrument/electrode system must be calibrated at a
minimum of two points that bracket the expected pH of the samples and are
approximately three pH units or more apart. (For corrosivity characteri-
zation, the calibration of the pH meter should include a buffer of pH 2
for acidic wastes and a pH 12 buffer for caustic wastes.) Various
9040At- 2 Revision 1
September 1994
-------
instrument designs may involve use of a dial (to "balance" or
"standardize") or a slope adjustment, as outlined in the manufacturer's
instructions. Repeat adjustments on successive portions of the two buffer
solutions until readings are within 0.05 pH units of the buffer solution
value.
7.2 Place the sample or buffer solution in a clean glass beaker using
a sufficient volume to cover the sensing elements of the electrodes and to give
adequate clearance for the magnetic stirring bar. If field measurements are
being made, the electrodes may be immersed directly into the sample stream to an
adequate depth and moved in a manner to ensure sufficient sample movement across
the electrode-sensing element as indicated by drift-free readings (<0.1 pH).
7.3 If the sample temperature differs by more than 2ฐC from the buffer
solution, the measured pH values must be corrected. Instruments are equipped
with automatic or manual compensators that electronically adjust for temperature
differences. Refer to manufacturer's instructions.
7.4 Thoroughly rinse and gently wipe the electrodes prior to measuring
pH of samples. Immerse the electrodes into the sample beaker or sample stream
and gently stir at a constant rate to provide homogeneity and suspension of
solids. Note and record sample pH and temperature. Repeat measurement on
successive aliquots of sample until values differ by <0.1 pH units. Two or three
volume changes are usually sufficient.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for the appropriate QC protoc'ols.
8.2 Electrodes must be thoroughly rinsed between samples.
9.0 METHOD PERFORMANCE
9.1 Forty-four analysts in twenty laboratories analyzed six synthetic
water samples containing exact increments of hydrogen-hydroxyl ions, with the
following results:
Accuracy as
Standard Deviation Bias . Bias
pH Units pH Units % pH Units
3.5
3.5
7.1
7.2
8.0
8.0
0.10
0.11
0.20
0.18
0.13
0.12
-0.29
-0.00
+1.01
-0.03
-0.12
+0.16
-0.01
+0.07
-0.002
-0.01
+0.01
10.0 REFERENCES
1. National Bureau of Standards, Standard Reference Material Catalog 1986-87,
Special Publication 260.
9040A - 3
Revision 1
September 1994
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METHOD 9040A
pH ELECTROMETRIC MEASUREMENT
7.1 Calibrate pH
meter.
7.2 Place sample
or buffer solution
in glass beaker.
7.3 Does
temperature
differ by more
than 2C from
buffer?
7.3 Correct
measured pH
values.
7.4 Immeroe
electrodes and
measure pH of
sample.
7.4 Note and record
pH and temperature;
repeat 2 or 3 times
with different
aliquots.
9040A - 4
Revision 1
September 1994
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METHOD 9041A
oH PAPER METHOD
1.0 SCOPE AND APPLICATION
1.1 Method 9041 may be used to measure pH as an alternative to Method
9040 (except as noted in Step 1.3) or in cases where pH measurements by Method
9040 are not possible.
1.2 Method 9041 is not applicable to wastes that contain components
that may mask or alter the pH paper color change.
1.3 pH paper is not considered to be as accurate a form of pH
measurement as pH meters. For this reason, pH measurements taken with Method
9041 cannot be used to define a waste as corrosive or noncorrosive (see RCRA
regulations 40 CFR ง261.22(a)(l).
2.0 SUMMARY OF METHOD
2.1 The approximate pH of the waste is determined with wide-range pH
paper. Then a more accurate pH determination is made using "narrow-range" pH
paper whose accuracy has been determined (1) using a series of buffers or (2) by
comparison with a calibrated pH meter.
3.0 INTERFERENCES
3.1 Certain wastes may inhibit or mask changes in the pH paper. This
interference can be determined by adding small amounts of acid or base to a small
aliquot of the waste and observing whether the pH paper undergoes the appropriate
changes.
CAUTION: THE ADDITION OF ACID OR BASE TO WASTES MAY RESULT IN VIOLENT
REACTIONS OR THE GENERATION OF TOXIC FUMES (e.g.. hydrogen
cyanide). Thus, a decision to take this step requires some
knowledge of the waste. See Step 7.3.3 for additional precautions.
4.0 APPARATUS AND MATERIALS
4.1 Wide-range pH paper.
4.2 Narrow-range pH paper: With a distinct color change for every 0.5
pH unit (e.g., Alkaacid Full-Range pH Kit, Fisher Scientific or equivalent).
Each batch of narrow-range pH paper must be calibrated versus certified pH
buffers or by comparison with a pH meter which has been calibrated with certified
pH buffers. If the incremental reading of the narrow-range pH paper is within
0.5 pH units, then the agreement between the buffer or the calibrated pH meter
with the paper must be within 0.5 pH units.
4.3 pH Meter (optional).
9041A - 1 Revision 1
July 1992
-------
5.0 REAGENTS
5.1 Certified pH buffers: To be used for calibrating the pH paper or
for calibrating the pH meter that will be used subsequently to calibrate the pH
paper.
5.2 Dilute acid (e.g.. 1:4 HC1).
5.3 Dilute base (e.g.. 0.1 N NaOH).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must be collected using a sampling plan which addresses
the considerations discussed in Chapter Nine of this manual.
7.0 PROCEDURE
7.1 A representative aliquot of the waste must be tested with wide-
range pH paper to determine the approximate pH.
7.2 The appropriate narrow-range pH paper is chosen and the pH of a
second aliquot of the waste is determined. This measurement should be performed
in duplicate.
7.3 Identification of interference:
7.3.1 Take a third aliquot of the waste, approximately 2 mL in
volume, and add acid dropwise until a pH change is observed. Note the
color change.
7.3.2 Add base dropwise to a fourth aliquot and note the color
change. (Wastes that have a buffering capacity may require additional
acid or base to result in a measurable pH change.)
7.3.3 The observation of the appropriate color change is a strong
indication that no interferences have occurred.
CAUTION ADDITION OF ACID OR BASE TO SAMPLES MAY RESULT IN VIOLENT REACTIONS
OR THE GENERATION OF TOXIC FUMES. PRECAUTIONS MUST BE TAKEN. THE
ANALYST SHOULD PERFORM THESE TESTS IN A WELL-VENTILATED HOOD WHEN
DEALING WITH UNKNOWN SAMPLES.
8.0 QUALITY CONTROL
8.1 All quality control data must be maintained and available for easy
reference or inspection.
8.2 All pH determinations must be performed in duplicate.
8.3 Each batch of pH paper must be calibrated versus certified pH
buffers or a pH meter which has been calibrated with certified pH buffers.
9041A - 2 Revision 1
July 1992
-------
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
9041A - 3 Revision 1
July 1992
-------
METHOD 9041A
pH PAPER METHOD
START
7.1 Determine
approximate pH with
ide-range pH paper
7.2 Select
appropriate
narrov range pH
paper; determine pH
in duplicate on 2nd
aliquot
7.3.1 Using 3rd
aliquot, add acid
to Haste until pH
changes; note color
change
7.3.2 Add base to
4th aliquot; note
color change
7.3.3 Determine if
interferences have
occurred
STOP
9041A - 4
Revision 1
July 1992
-------
METHOD 9045B
SOIL AND WASTE pH
1.0 SCOPE AND APPLICATION
1.1 Method 9045 is an electrometric procedure for measuring pH in
soils and waste samples. Wastes may be solids, sludges, or non-aqueous
liquids. If water is present, it must constitute less than 20% of the total
volume of the sample.
2.0 SUMMARY OF METHOD
2.1 The sample is mixed with reagent water, and the pH of the
resulting aqueous solution is measured.
3.0 INTERFERENCES
3.1 Samples with very low or very high pH may give incorrect
readings on the meter. For samples with a true pH of >10, the measured pH may
be incorrectly low. This error can be minimized by using a low-sodium-error
electrode. Strong acid solutions, with a true pH of <1, may give incorrectly
high pH measurements.
3.2 Temperature fluctuations will cause measurement errors.
3.3 Errors will occur when the electrodes become coated. If an
electrode becomes coated with an oily material that will not rinse free, the
electrode can (1) be cleaned with an ultrasonic bath, or (2) be washed with
detergent, rinsed several times with water, placed in 1:10 HC1 so that the
lower third of the electrode is submerged, and then thoroughly rinsed with
water, or (3) be cleaned per the manufacturer's instructions.
4.0 APPARATUS AND MATERIALS
4.1 pH Meter with means for temperature compensation.
4.2 Glass Electrode.
4.3 Reference electrode: A silver-silver chloride or other
reference electrode of constant potential may be used.
NOTE: Combination electrodes incorporating both measuring and
referenced functions are convenient to use and are available
with solid, gel-type filling materials that require minimal
maintenance.
4.4 Beaker: 50-mL.
4.5 Thermometer and/or temperature sensor for automatic
compensation.
4.6 Analytical balance: capable of weighing 0.1 g.
9045B - 1 Revision 2
September 1994
-------
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 Primary standard buffer salts are available from the National
Institute of Standards and Technology (NIST) and should be used in situations
where extreme accuracy is necessary. Preparation of reference solutions from
these salts requires some special precautions and handling, such as low-
conductivity dilution water, drying ovens, and carbon-dioxide-free purge gas.
These solutions should be replaced at least once each month.
5.4 Secondary standard buffers may be prepared from NIST salts or
purchased as solutions from commercial vendors. These commercially available
solutions, which have been validated by comparison with NIST standards, are
recommended for routine use.
6.0 SAMPLE PRESERVATION AND HANDLING
6.1 All samples must be collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.2 Samples should be analyzed as soon as possible.
7.0 PROCEDURE
7.1 Calibration:
7.1.1 Because of the wide variety of pH meters and
accessories, detailed operating procedures cannot be incorporated into
this method. Each analyst must be acquainted with the operation of each
system and familiar with all instrument-functions. Special attention to
care of the electrodes is recommended.
7.1.2 Each instrument/electrode system must be calibrated at a
minimum of two points that bracket the expected pH of the samples and
are approximately three pH units or more apart. Repeat adjustments on
successive portions of the two buffer solutions until readings are
within 0.05 pH units of the buffer solution value.
7.2 Sample preparation and pH measurement of soils:
7.2.1 To 20 g of soil in a 50-mL beaker, add 20 mL of reagent
water, cover, and continuously stir the suspension for 5 minutes. .
9045B - 2 Revision 2
September 1994
-------
Additional dilutions are allowed if working with hygroscopic soils and
salts or other problematic matrices.
7.2.2 Let the soil suspension stand for about 1 hour to allow
most of the suspended clay to settle out from the suspension or filter
or centrifuge off the aqueous phase for pH measurement.
7.2.3 Adjust the electrodes in the clamps of the electrode
holder so that, upon lowering the electrodes into the beaker, the glass
electrode will be immersed just deep enough into the clear supernatant
solution to establish a good electrical contact through the ground-glass
joint or the fiber-capillary hole. Insert the electrodes into the
sample solution in this manner. For combination electrodes, immerse
just below the suspension.
7.2.4 If the sample temperature differs by more than 2ฐC from
the buffer solution, the measured pH values must be corrected.
7.2.5 Report the results as "soil pH measured in water at
ฐC" where " ฐC" is the temperature at which the test was conducted.
7.3 Sample preparation and pH measurement of waste materials:
7.3.1 To 20 g of waste sample in a 50-mL beaker, add 20 ml of
reagent water, cover, and continuously stir the suspension for 5
minutes. . Additional dilutions are allowed if working with hygroscopic
wastes and salts or other problematic matrices.
7.3.2 Let the waste suspension stand for about 15 minutes to
allow most of the suspended waste to settle out from the suspension or
filter or centrifuge off aqueous phase for pH measurement.
NOTE: If the waste is hygroscopic and absorbs all the reagent
water, begin the experiment again using 20 g of waste and 40 mL
of reagent water.
NOTE: If the supernatant is multiphasic, decant the oily phase
and measure the pH of the aqueous phase. The electrode may need
to be cleaned (Step 3.3) if it becomes coated with an oily
material.
7.3.3 Adjust the electrodes in the clamps of the electrode
holder so that, upon lowering the electrodes into the beaker, the glass
electrode will be immersed just deep enough into the clear supernatant
to establish good electrical contact through the ground-glass joint or
the fiber-capillary hole. Insert the electrode into the sample solution
in this manner. For combination electrodes, immerse just below the
suspension.
7.3.4 If the sample temperature differs by more than 2ฐC from
the buffer solution, the measured pH values must be corrected.
7.3.5 Report the results as "waste pH measured in water at
ฐC" where " ฐC" is the temperature at which the test was conducted.
9045B - 3 Revision 2
September 1994
-------
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for the appropriate QC protocols.
8.2 Electrodes must be thoroughly rinsed between samples.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
1. Black, Charles Allen; Methods of Soil Analysis; American Society of
Agronomy: Madison, WI, 1973.
2. National Bureau of Standards, Standard Reference Material Catalog, 1986-
87, Special Publication 260.
9045B - 4 Revision 2
September 1994
-------
METHOD 9045B
SOIL AND WASTE pH
Start
J
7.1 Calibrate
each instrument/
electrode
system.
7.2.1 Add 20 mL
water to 20 g soil;
stir continuously
for 5 minutes.
Is the
sample soil
or waste?
7.3.1 Add 20 mL
water to 20 g waste;
stir continuously
for 5 minutes.
7.2.2 Let soil
suspension
stand for 1
hour or filter.
7.3.2 Let waste
suspension
stand for 15
minutes or filter.
Insert
electrodes
into sample
solution.
Do
sample
and buffer
sol'n temps
vary by
2C?
Correct
measured pH
values.
Report
results and
temperature
Is
supernatant
multiphasic?
Repeat experiment
with 20 g waste
and 40 mL water.
Decant oily
phase;
measure pH of
aqueous phase.
Aqueous
Phase
9045B - 5
Revision 2
September 1994
-------
METHOD 9050
SPECIFIC CONDUCTANCE
1.0 SCOPE AND APPLICATION
1.1 Method 9050 1s used to measure the specific conductance of drinking,
ground, surface, and saline waters and domestic and Industrial aqueous wastes.
Method 9050 1s not applicable to solid samples.
2.0 SUMMARY OF METHOD
2.1 The specific conductance of a sample 1s measured using a self-
contained conductivity meter (Wheatstone bridge-type or equivalent).
2.2 Whenever possible, samples are analyzed at 25*C. If samples are
analyzed at different temperatures, temperature corrections must be made and
results reported at 25*C.
3.0 INTERFERENCES
3.1 Platinum electrodes can degrade and cause erratic results. When
this happens, as evidenced by erratic results or flaking off of the platinum
black, the electrode should be replatlnlzed.
3.2 The specific conductance cell can become coated with oil and other
materials. It 1s essential that the cell be thoroughly rinsed and, 1f
necessary, cleaned between samples.
4.0 APPARATUS AND MATERIALS
4.1 Self-contained conductivity instruments; an Instrument consisting
of a source of alternating current, a Wheatstone bridge, null Indicator, and a
conductivity cell or other instrument measuring the ratio of alternating
current through the cell to voltage across 1t. The latter has the advantage
of a linear reading of conductivity. Choose an Instrument capable of
measuring conductivity with an error not exceeding IX or 1 umho/cm, whichever
is greater.
Platinum-electrode or non-platinum-electrode specific conductance
Water bath.
4.4 Thermometer; capable of being read to the nearest O.TC and
covering the range 23* to 27*C. An electrical thermometer having a small
thermistor sensing element 1s convenient because of Its rapid response.
9050 - 1
Revision 0
Date September 1986
-------
5.0 REAGENTS
5.1 Conductivity water; Pass distilled water through a mixed-bed
deionizer and discard first1,000 ml. Conductivity should be less than 1
umho/cm.
5.2 Standard potassium chloride (0.0100 M): Dissolve 0.7456 g anhydrous
KC1 in conductivity water and make up to 1,000 ml at 25*C. This solution will
have a specific conductance of 1,413 umho/cm at 25*C.
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 of this manual.
6.2 All sample containers must be prewashed and thoroughly rinsed. Both
plastic and glass containers are suitable.
6.3 Aqueous samples should be stored at 4*C and analyzed within 24 hr.
7.0 PROCEDURE
7.1 Determination of cell constant; Rinse conductivity cell with at
least three portions of 0.01 NKClsolution. Adjust temperature of a fourth
portion to 25.0 + 0.1'C. Measure resistance of this portion and note
temperature. Compute cell constant, C:
c = (o.001413)(Rซci) i + 0.0191 (t - 25)
where:
RKCI = measured resistance, ohms; and
t = observed temperature, *C.
7.2 Conductivity measurement; Rinse cell with one or more portions of
sample. Adjust temperatureofa final portion to 25.0 + 0.1'C. Measure
sample resistance or conductivity and note temperature.
7.3 Calculation; The temperature coefficient of most waters is only
approximately thesame as that of standard KCl solution; the more the
temperature of measurement deviates from 25.0*C, the greater the uncertainty
in applying the temperature correction. Report all conductivities at 25.0*C.
9050 - 2
Revision
Date September 1986
-------
7.3.1 When sample resistance is measured, conductivity at 25*C is
(l.OOO.OOOHC)
K =
where:
1 + 0.0191 (t - 25)
K = conductivity, umho/cm;
C = cell constant, cm-L;
Rm = measured resistance of sample, ohms; and
t = temperature of measurement.
7.3.2 When sample conductivity is measured, conductivity at 25'C
is:
1,000, ooo) (c)
* 1 + 0.0191 (t - 25)
where:
Km = measured conductivity, umho at t*C, and other units
are defined as above.
NOTE: If conductivity readout is in umho/cm, delete the factor 1,000,000
1n the numerator.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Analyze check standards after approximately every 15 samples.
8.3 Run 1 duplicate sample for every 10 samples.
9.0 METHOD PERFORMANCE
9.1 Three synthetic samples were tested with the following results:
Conduc-
tivity
umho s/ cm
147.0
303.0
228.0
No. of
Results
117
120
120
Relative
Standard
Deviation
%
8.6
7.8
8.4
Relative
Error
%
9.4
1.9
3.0
9050 - 3
Revision
Date September 1986
-------
10.0 REFERENCES
1. Standard Methods for the Examination of Water and Wastewater, 16th ed.
(1985), Method 205.
9050 - 4
Revision
Date September 1986
-------
METHOD 9OSO
SPECIFIC CONDUCTANCE
7. 1
r
and tt
solut
eel
Measure
esistance
;mp of KC1
on: cole.
1 constant
7.2
res
cor
<
ten
Measure
cample
ictance or
iductivity
ind note
nperetufe
7.3
Calculate
ample
conductivity
at 25 "C
f Stop J
9050 - 5
Revision o
Date September 1986
-------
METHOD 9080
CATION-EXCHANGE CAPACITY OF SOILS (AMMONIUM ACETATE)
1.0 SCOPE AND APPLICATION
1.1 Method 9080 1s used to determine the cation-exchange capacity of
soils. The method Is not applicable to soils containing appreciable amounts
of verm1cul1te clays, kaolin, halloyslte, or other l:l-type clay minerals.
They should be analyzed by the sodium acetate method (Method 9081). That
method (9081) 1s also generally the preferred method for very calcareous
soils. For distinctly acid soils, the cation-exchange capacity by summation
method (Chapman, p. 900; see Paragraph 10.1) should be employed.
2.0 SUMMARY
2.1 The soil 1s mixed with an excess of 1 N ammonium acetate solution.
This results in an exchange of the ammonium cations for exchangeable cations
present 1n the soil. The excess ammonium is removed, and the amount of
exchangeable ammonium 1s determined.
3.0 INTERFERENCES
3.1 Soils containing appreciable vermiculite clays, kaolin, halloyslte,
or other l:l-type clay minerals will often give lower values for exchange
capacity. See Paragraph 1.1 above.
3.2 With calcareous soils, the release of calcium carbonate from the
soil Into the ammonium acetate solution limits the saturation of exchange
sites by the ammonium ion. This results in artificially low cation-exchange
capacities.
4.0 APPARATUS AND MATERIALS
4.1 Erlenmeyer flask; 500-mL.
4.2 Buchner funnel or equivalent: 55-mm.
4.3 Sieve; 2-mm.
4.4 Aeration apparatus (assembled as in Figure 1):
4.4.1 Kjeldahl flask: 800-mL.
4.4.2 Erlenmeyer flask: 800-mL.
4.4.3 Glass wool filter.
9080 - 1
Revision
Date September 1986
-------
to Next Unit
From Air Scrubbers
Soil Sample
Plus 150 ml.
5% Na2C03
and
Few Drops
Paraffin Oil
Suction
(Aeration Rate of
450 to 500 Liters
Per Hour)
Orifice
in Glass
Tube
500-ml
Wide Mouth
Erlenmeyer
Flask
N/10
in 100 ml
Water
Figure 1. Diagram of aeration unit for determination of absorbed ammonia. Six to twelve
such units is a convenient number for routine work; they can be mounted on a portable rack.
(Apparatus as modified by Dr. A. P. Vanselow, Dept. of Soils & Plant Nutrition, Univerity of
California, Riverside, Calif.).
9080 - 2
Revision p
Date September 1986
-------
4.4.4 Glass tubing.
4.4.5 Flow meter.
5.0 REAGENTS
5.1 Ammonium acetate (N^OAc), 1 N: Dilute 114 ml of glacial acetic
acid (99.5%) with water to a volume of approximately 1 liter. Then add 138 mL
of concentrated ammonium hydroxide (NffyOH) and add water to obtain a volume of
about 1,980 ml. Check the pH of the resulting solution, add more NfyOH, as
needed, to obtain a pH of 7, and dilute the solution to a volume of 2 liters
with water.
5.2 Isopropyl alcohol; 99%.
5.3 Ammonium chloride (NfyCl), 1 N: Dissolve 53.49 g of NfyCl in Type
II water, adjust the pH to 7.0 with NfyOH, and dilute to 1 L.
5.4 Ammonium chloride (NfyCl), 0.25 N: Dissolve 13.37 g of N^Cl in
Type II water, adjust the pH to 7.0 with NfyOH, and dilute to 1 L.
5.5 Ammonium oxalate ((NfyJ^OV^O), 10%: Add 90 mL of Type II water
to 10 g of ammonium oxalate ((Nf^) 2^2ฐ4 '^O) and mix well.
5.6 Dilute ammonium hydroxide (NH/jOH): Add 1 volume of concentrated
NH40H to an equal volume of water.
5.7 Silver nitrate (AgNOs), 0.10 N: Dissolve 15.39 g of NgNOs in Type
II water, mix well, and dilute to 1 L.
5.8 Reagents for aeration option:
5.8.1 Sodium carbonate solution (^003) , 5%: Add 95 ml of Type II
water to 5 g of N32C03 and mix well.
5.8.2 Paraffin oil.
5.8.3 Sulfurlc acid (H2S04), 0.1 N standard: Add 2.8 ml
concentrated ^64 to Type II water and dilute to 1 L. Standardize
against a base of known concentration.
5.8.4 Sodium hydroxide (NaOH) , 0.1 N standard: Dissolve 4.0 g NaOH
1n Type II water and dilute to 1 L. Standardize against an add of known
concentration.
5.8.5 Methyl red Indicator, 0.1%: Dissolve 0.1 g in 99.9 ml of 95%
ethanol and mix well .
9080 - 3
Revision
Date September 1986
-------
5.9 Reagents for distillation option;
5.9.1 Sodium chloride, NaCl (acidified), 10%: Dissolve 100 g of
NaCl (ammonium-free) in 900 ml of Type II water; mix well. Add
approximately 0.42 ml of concentrated HC1 to make the solution
approximately 0.005 N.
5.9.2 Sodium hydroxide (NaOH), 1 N: Dissolve 40 g of NaOH in Type
II water and dilute to 1 L.
5.9.3 Boric add (H3B03), 2% solution: Dissolve 20 g H3B03 in 980
ml Type II water and mix well.
5.9.4 Standard sulfurlc add (1^04), 0.1 N: See Step 5.8.3.
5.9.5 Bromocresol green-methyl red mixed indicator: Triturate
0.1 g of bromocresol green with 2 ml 0.1 N NaOH in an agate mortar and
add 95% ethyl alcohol to obtain a total volume of 100 ml. Triturate
0.1 g of methyl red with a few mL of 95% ethyl alcohol in an agate
mortar. Add 3 ml of 0.1 N NaOH and dilute the solution to a volume of
100 ml with 95% ethyl alcohol. Mix 75 ml of the bromocresol green
solution with 25 mL of the methyl red solution and dilute the mixture to
200 ml with 95% ethyl alcohol.
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 of this manual.
7.0 PROCEDURE
7.1 Sieve a sample aliquot of the soil through a 2-mm screen and allow
the sieved soil to air dry (at a temperature of <60*C). Place 10 g of the
air-dried soil in a 500-mL Erlenmeyer flask and add 250 mL of neutral, 1 N
NH40Ac. (Use 25 g of soil if the exchange capacity is very low, e.g., 3-5 meq
per 100 g.) Shake the flask thoroughly and allow it to stand overnight.
7.2 Filter the soil with light suction using a 55-mm Buchner funnel or
equivalent. Do not allow the soil to become dry and cracked.
7.3 Leach the soil with the neutral NH40Ac reagent until no test for
calcium can be obtained in the effluent solution. (For the calcium test, add
a few drops each of 1 N NH4C1 and 10% ammonium oxalate, dilute NH40H to 10 mL
of the leachate in a test tube, and heat the solution to near the boiling
point. The presence of calcium is indicated by a white precipitate or
turbidity.)
7.4 Then leach the soil four times with neutral 1 N NH4C1 and once with
0.25 N NH4C1.
9080 - 4
Revision 0
Date September 1986
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7.5 Wash out the electrolyte with 150 to 200 ml of 99% Isopropyl
alcohol. When the test for chloride in the leachate (use 0.10 AgNOs) becomes
negligible, allow the soil to drain thoroughly.
7.6 Determine the adsorbed Nfy either by the aeration method (Paragraph
7.7) or by the acid-NaCl method (Paragraph 7.8).
7.7 Aeration method;
7.7.1 Place an excess of 0.1 N standard ^$04 in the 500-mL
Erlenmeyer flask on the aeration apparatus (50 ml is an ample quantity
for most soils) and add 10 drops of methyl red indicator and enough
distilled water to make the total volume about 100 ml.
7.7.2 Attach the flask to the apparatus. Then transfer the
ammonium-saturated sample of soil (from Paragraph 7.5) quantitatively to
the 800-mL Kjeldahl flask located in the flow line Just before the
Erlenmeyer flask with the standard acid. Use a rubber policeman and a
stream of distilled water from a wash bottle, as needed, to complete the
transfer.
7.7.3 Add 150 ml N32C03 solution and a few drops of paraffin oil
and attach the flask to the apparatus.
7.7.4 Apply suction to the outflow end of the apparatus and adjust
the rate of flow to 450 to 500 liters of air per hr. Continue the
aeration for 17 hr.
7.7.5 Shut off the suction and remove the flask. Titrate the
residual acid in the absorption solutions with standard 0.1 N NaOH from
the original red color through orange to yellow at the end point. From
the titration values obtained with the soil and blank solutions,
calculate the content of adsorbed ammonium in milligram equivalents per
100 g soil.
7.8 Acid-NaCl method;
7.8.1 Leach the ammonium-saturated soil from Paragraph 7.5 with 10%
acidified NaCl until 225 mL have passed through the sample. Add small
portions at a time, allowing each portion to pass through the sample
before adding the next portion.
7.8.2 Transfer the leachate quantitatively to an 800-mL Kjeldahl
flask, add 25 mL of 1 N NaOH, and distill 60 mL of the solution into
50 mL of 2% H3B03.
7.8.3 Add 10 drops of bromocresol green-methyl red mixed indicator
and titrate the boric acid solution with standard 0.1 N HgSCty. The color
change is from bluish green through bluish purple to pink at the end
point. Run blanks on the .reagents. Correct the titration figure for the
blanks and calculate the milliequivalents of ammonium in 100 g of soil.
9080 - 5
Revision 0
Date September 1986
-------
7.8.4 Results should be reported as "determined with ammonium
acetate" at pH 7.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or inspection.
8.2 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.3 Material of known cation-exchange capacity must be routinely
analyzed.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
1. This method is based on Chapman, H.D., "Cation-exchange Capacity,"
pp. 891-900, 1n C.A. Black (ed.), Method of Soil Analysis, Part 2: Chemical
and Microbiological Properties, Am. Soc. Agron., Madison, Wisconsin (1965).
9080 - 6
Revision
Date September 1986
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METHOD 9O80
CATION-EXCHANGE CAPACITY (AMMONIUM ACETATE)
C
7.1
Sieve ป
ample of coll
through 2mm
creen; dry
7. 1
Place
oil in
flack; mOO
NH OAC: let
tana overnight
7.2
Filter Boll
with light
uctlon
7.3
Leach soil with
neutral NHOAc
7.3
Tact for
calcium
Yes
7.3
Calcium
detected?
7.4
Leach soil
with NH^Cl
9080 - 7
Revision 0
Date September 1986
-------
METHOD 9060
CATION-EXCHANGE CAPACITY (AMMONIUM ACETATE!
(Continued)
7.5
ot
elect
e
Mash
t the
rolyte:
oil to
rain
Aeration method
'which method ls\. Acid-Nad method
' "".D determine ^
7.7.1
Place HtSO4 in
aeration apparatus
flack; add methyl
red indicator and
distilled Mater
7.8.1
Leach soil fron
Step 7.5 with
acidified Had
7.7.Z
Attach
1 flask to
apparatus:
transfer soil
ample (7.5) to
Kleldahl flack
7.B.2
Transfer
leachate
to KJeldahl
flack: add
NaOH. distill
into HBOj to] .
o
9080 - 8
Revision 0
Date September 1986
-------
METHOD 9O80
CATION-EXCHANGE CAPACITY (AMMONIUM ACETATE)
(Continued)
7.7.3 Add
I Na.COj
solution and
paraffin oil:
attach flask
to apparatus
7.6.31
Titrate H.BOt
solution <h
H,S04
7.7.41
Asrate for 17
hours
7.8.3
I Run
blanks; correct
tltratlon
figure for
blanks:
7.7.5J
Shut off
suction: remove
flask: titrate
residual acid
7.6.31
Calculate
wnonium
in soil
7.7.5
Calculate
content of
absorbed
9080 - 9
Revision 0
Date September 1986
-------
METHOD 9081
CATION-EXCHANGE CAPACITY OF SOILS (SODIUM ACETATE)
1.0 SCOPE AND APPLICATION
1.1 Method 9081 Is applicable to most soils, Including calcareous and
noncalcareous soils. The method of cation-exchange capacity by summation
(Chapman, 1965, p. 900; see Paragraph 10.1) should be employed for distinctly
add soils.
2.0 SUMMARY OF METHOD
2.1 The soil sample is mixed with an excess of sodium acetate solution,
resulting in an exchange of the added sodium cations for the matrix cations.
Subsequently, the sample is washed with isopropyl alcohol. An ammonium
acetate solution is then added, which replaces the adsorbed sodium with
ammonium. The concentration of displaced sodium is then determined by atomic
absorption, emission spectroscopy, or an equivalent means.
3.0 INTERFERENCES
3.1 Interferences can occur during analysis of the extract for sodium
content. Thoroughly investigate the chosen analytical method for potential
interferences.
4.0 APPARATUS AND MATERIALS
4.1 Centrifuge tube and stopper; 50-mL, round-bottom, narrow neck.
4.2 Mechanical shaker.
4.3 Volumetric flask; 100-mL.
5.0 REAGENTS
5.1 Sodium acetate (NaOAc), 1.0 N; Dissolve 136 g of NaC2H202'3H20 in
water and dilute 1t to 1,000 mL. The pH of this solution should be 8.2. If
needed, add a few drops of acetic acid or NaOH solution to bring the reaction
of the solution to pH 8.2.
5.2 Ammonium acetate (NH^Ac), 1 N: Dilute 114 mL of glacial acetic
acid (99.5%) with water to a volume of approximately 1 liter. Then add 138 mL
of concentrated ammonium hydroxide (NH40H) and add water to obtain a volume of
about 1,980 mL. Check the pH of the resulting solution, add more NH40H, as
needed, to obtain a pH of 7, and dilute the solution to a volume of 2 liters
with water.
9081 - 1
Revision 0
Date September 1986
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5.3 Isopropyl alcohol; 99%.
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 of this manual.
7.0 PROCEDURE
7.1 Weigh 4 g of medium- or fine-textured soil or 6 g of coarse-textured
soil and transfer the sample to a 50-mL, round-bottom, narrow-neck centrifuge
tube. (A fine soil has >50% of the particles <0.074 mm, medium soil has >50%
>0.425 mm, while a coarse soil has more than 50% of Its particles >2 mm.
7.2 Add 33 mL of 1.0 N NaOAc solution, stopper the tube, shake 1t In a
mechanical shaker for 5 m1n, and centrifuge 1t until the supernatant liquid Is
clear.
7.3 Decant the liquid, and repeat Paragraph 7.2 three more times.
7.4 Add 33 mL of 99% Isopropyl alcohol, stopper the tube, shake It 1n a
mechanical shaker for 5 m1n, and centrifuge 1t until the supernatant liquid Is
clear.
7.5 Repeat the procedure described 1n Paragraph 7.4 two more times.
7.6 Add 33 mL of NfyOAc solution, stopper the tube, shake It In a
mechanical shaker for 5 min, and centrifuge 1t until the supernatant liquid Is
clear. Decant the washing Into a 100-mL volumetric flask.
7.7 Repeat the procedure described 1n Paragraph 7.6 two more times.
7.8 Dilute the combined washing to the 100-mL mark with ammonium acetate
solution and determine the sodium concentration by atomic absorption, emission
spectroscopy, or-an equivalent method.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Employ a minimum of one blank per sample batch to determine 1f
contamination or any memory effects are occurring.
8.3 Materials of known cation-exchange capacity must be routinely
analyzed.
9081 - 2
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 This method 1s based on Chapman, H.D., "Cation-exchange Capacity,"
pp. 891-900, 1n C.A. Black (ed.), Method of Soil Analysis, Part 2: Chemical
and Microbiological Properties, Am. Soc. Agron., Madison, Wisconsin (1965).
9081 - 3
Revision
Date September 1986
-------
NCTMOD 9Oai
CAPACITY or SOILS (SODIUM ACETATE)
7.1 I
weigh
out aainoi*.
transfar to
cantrifuga tuba
Add
NaOAc aolutlon;
ahaka:
cantrifuga
7.3
Da cant liquid:
rapaat 3 aiora
tinas
7.4
Add laopropyl
alcohol: ahaka:
cantrifuga
7.S
8 wore
tiawa
CD
O
7.6 I Add
' NHdOAC
olution: ahaka:
centrifuga:
Decant Mashing
into flask
7.7
Repeat
procedure
Dilute
combined
7.8
with aMonlui
ecetete
aolutlon
7.a
Oateralna
odlun
cencantratien
r-o
9081 - 4
Revision 0
Date September 1986
-------
METHOD 9090A
COMPATIBILITY TEST FOR WASTES AND MEMBRANE LINERS
1.0 SCOPE AND APPLICATION
1.1 Method 9090 is intended for use in determining the effects of
chemicals in a surface impoundment, waste pile, or landfill on the physical
properties of flexible membrane liner (FML) materials intended to contain them.
Data from these tests will assist in deciding whether a given liner material is
acceptable for the intended application.
2.0 SUMMARY OF METHOD
2.1 In order to estimate waste/liner compatibility, the liner material
is immersed in the chemical environment for minimum periods of 120 days at room
temperature (23 + 2ฐC) and at 50 + 2ฐC. In cases where the FML will be used in
a chemical environment at elevated temperatures, the immersion testing shall be
run at the elevated temperatures if they are expected to be higher than 50ฐC.
Whenever possible, the use of longer exposure times is recommended. Comparison
of measurements of the membrane's physical properties, taken periodically before
and after contact with the waste fluid, is used to estimate the compatibility of
the liner with the waste over time.
3.0 INTERFERENCES (Not Applicable)
4.0 APPARATUS AND MATERIALS
NOTE: In general, the following definitions will be used in this method:
1. Sample - a representative piece of the liner material proposed for
use that is of sufficient size to allow for the removal of
all necessary specimens.
2. Specimen - a piece of material, cut from a sample, appropriately
shaped and prepared so that it is ready to use for a test.
4.1 Exposure tank - Of a size sufficient to contain the samples, with
provisions for supporting the samples so that they do not touch the bottom or
sides of the tank or each other, and for stirring the liquid in the tank. The
tank should be compatible with the waste fluid and impermeable to any of the
constituents they are intended to contain. The tank shall be equipped with a
means for maintaining the solution at room temperature (23 ฑ 2ฐC) and 50 ฑ 2ฐC
and for preventing evaporation of the solution (e.g., use a cover equipped with
a reflux condenser, or seal the tank with a Teflon gasket and use an airtight
cover). Both sides of the liner material shall be exposed to the chemical
environment. The pressure inside the tank must be the same as that outside the
tank. If the liner has a side that (1) is not exposed to the waste in actual use
and (2) is not designed to withstand exposure to the chemical environment, then
such a liner may be treated with only the barrier surface exposed.
9090A - 1 Revision 1
July 1992
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4.2 Stress-strain machine suitable for measuring elongation, tensile
strength, tear resistance, puncture resistance, modulus of elasticity, and ply
adhesion.
4.3 Jig for testing puncture resistance for use with FTMS 101C, Method
2065.
4.4 Liner sample labels and holders made of materials known to be
resistant to the specific wastes.
4.5 Oven at 105 ฑ 2ฐC.
4.6 Dial micrometer.
4.7 Analytical balance.
4.8 Apparatus for determining extractable content of liner materials.
NOTE: A minimum quantity of representative waste fluid necessary to conduct
this test has not been specified in this method because the amount will
vary depending upon the waste composition and the type of liner material.
For example, certain organic waste constituents, if present in the
representative waste fluid, can be absorbed by the liner material,
thereby changing the concentration of the chemicals in the waste. This
change in waste composition may require the waste fluid to be replaced
at least monthly in order to maintain representative conditions in the
waste fluid. The amount of waste fluid necessary to maintain
representative waste conditions will depend on factors such as the volume
of constituents absorbed by the specific liner material and the
concentration of the chemical constituents in the waste.
5.0 REAGENTS (Not Applicable)
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 For information on what constitutes a representative sample of the
waste fluid, refer to the following guidance document:
Permit Applicants' Guidance Manual for Hazardous Waste Land Treatment,
Storage, and Disposal Facilities; Final Draft; Chap. 5, pp. 15-17;
Chap. 6, pp. 18-21; and Chap. 8, pp. 13-16, May 1984.
7.0 PROCEDURE
7.1 Obtain a representative sample of the waste fluid. If a waste
sample is received in more than one container, blend thoroughly. Note any signs
of stratification. If stratification exists, liner samples must be placed in
each of the phases. In cases where the waste fluid is expected to stratify and
the phases cannot be separated, the number of immersed samples per exposure
period can be increased (e.g.. if the waste fluid has two phases, then 2 samples
per exposure period are needed) so that test samples exposed at each level of the
waste can be tested. If the waste to be contained in the land disposal unit is
in solid form, generate a synthetic leachate (see Step 7.9.1).
9090A - 2 Revision 1
July 1992
-------
7.2 Perform the following tests on unexposed samples of the polymeric
membrane liner material at 23 ฑ 2ฐC (see Steps 7.9.2 and 7.9.3 below for
additional tests suggested for specific circumstances). Tests for tear
resistance and tensile properties are to be performed according to the protocols
referenced in Table 1. See Figure 1 for cutting patterns for nonreinforced
liners, Figure 2 for cutting patterns for reinforced liners, and Figure 3 for
cutting patterns for semi crystal line liners. (Table 2, at the end of this method,
gives characteristics of various polymeric liner materials.)
1. Tear resistance, machine and transverse directions, three specimens
each direction for nonreinforced liner materials only. See Table
1 for appropriate test method, the recommended test speed, and the
values to be reported.
2. Puncture resistance, two specimens, FTMS 101C, Method 2065. See
Figure 1, 2, or 3, as applicable, for sample cutting patterns.
3. Tensile properties, machine and transverse directions, three
tensile specimens in each direction. See Table 1 for appropriate
test method, the recommended test speed, and the values to be
reported. See Figure 4 for tensile dumbbell cutting pattern
dimensions for nonreinforced liner samples.
4. Hardness, three specimens, Duro A (Duro D if Duro A reading is
greater than 80), ASTM D2240. The hardness specimen thickness for
Duro A is 1/4 in., and for Duro D it is 1/8 in. The specimen
dimensions are 1 in. by 1 in.
5. Elongation at break. This test is to be performed only on membrane
materials that do not have a fabric or other nonelastomeric support
as part of the liner.
6. Modulus of elasticity, machine and transverse directions, two
specimens each direction for semi crystalline liner materials only,
ASTM D882 modified Method A (see Table 1).
7. Volatiles content, SW 870, Appendix III-D.
8. Extractables content, SW 870, Appendix III-E.
9. Specific gravity, three specimens, ASTM D792 Method A.
10. Ply adhesion, machine and transverse directions, two specimens each
direction for fabric reinforced liner materials only, ASTM D413
Machine Method, Type A -- 180 degree peel.
11. Hydrostatic resistance test, ASTM D751 Method A, Procedure 1.
7.3 For each test condition, cut five pieces of the lining material of
a size to fit the sample holder, or at least 8 in. by 10 in. The fifth sample
is an extra sample. Inspect all samples for flaws and discard unsatisfactory
ones. Liner materials with fabric reinforcement require close inspection to
ensure that threads of the samples are evenly spaced and straight at 90*.
Samples containing a fiber scrim support may be flood-coated along the exposed
9090A - 3 Revision 1
July 1992
-------
edges with a solution recommended by the liner manufacturer, or another procedure
should be used to prevent the scrim from being directly exposed. The flood-
coating solution will typically contain 5-15% solids dissolved in a solvent. The
solids content can be the liner formula or the base polymer.
Measure the following:
1. Gauge thickness, in. -- average of the four corners.
2. Mass, Ib. -- to one-hundredth of a Ib.
3. Length, in. -- average of the lengths of the two sides plus the
length measured through the liner center.
4. Width, in. -- average of the widths of the two ends plus the width
measured through the liner center.
NOTE: Do not cut these liner samples into the test specimen shapes shown in
Figure 1, 2, or 3 at this time. Test specimens will be cut as specified
in Step 7.7, after exposure to the waste fluid.
7.4 Label the liner samples (e.g.. notch or use metal staples to
identify the sample) and hang in the waste fluid by a wire hanger or a weight.
Different liner materials should be immersed in separate tanks to avoid exchange
of plasticizers and soluble constituents when plasticized membranes are being
tested. Expose the liner samples to the stirred waste fluid held at room
temperature and at 50 + 2"C.
7.5 At the end of 30, 60, 90, and 120 days of exposure, remove one
liner sample from each test condition to determine the membrane's physical
properties (see Steps 7.6 and 7.7). Allow the liner sample to cool in the waste
fluid until the waste fluid has a stable room temperature. Wipe off as much
waste as possible and rinse briefly with water. Place wet sample in a labeled
polyethylene bag or aluminum foil to prevent the sample from drying out. The
liner sample should be tested as soon as possible after removal from the waste
fluid at room temperature, but in no case later than 24 hours after removal.
7.6 To test the immersed sample, wipe off any remaining waste and rinse
with deionized water. Blot sample dry and measure the following as in Step 7.3:
1. Gauge thickness, in.
2. Mass, Ib.
3. Length, in.
4. Width, in.
7.7 Perform the following tests on the exposed samples (see Steps 7.9.2
and 7.9.3 below for additional tests suggested for specific circumstances).
Tests for tear resistance and tensile properties are to be performed according
to the protocols referenced in Table 1. Die-cut test specimens following
suggested cutting patterns. See Figure 1 for cutting patterns for nonreinforced
9090A - 4 Revision 1
July 1992
-------
liners, Figure 2 for cutting patterns for reinforced liners, and Figure 3 for
semi crystal line liners.
1. Tear resistance, machine and transverse directions, three specimens
each direction for materials without fabric reinforcement. See
Table 1 for appropriate test method, the recommended test specimen
and speed of test, and the values to be reported.
2. Puncture resistance, two specimens, FTMS 101C, Method 2065. See
Figure 1, 2, or 3, as applicable, for sample cutting patterns.
3. Tensile properties, machine and transverse directions, three
specimens each direction. See Table 1 for appropriate test method,
the recommended test specimen and speed of test, and the values to
be reported. See Figure 4 for tensile dumbbell cutting pattern
dimensions for nonreinforced liner samples.
4. Hardness, three specimens, Duro A (Duro D if Duro A reading is
greater than 80), ASTM 2240. The hardness specimen thickness for
Duro A is 1/4 in., and for Duro D is 1/8 in. The specimen
dimensions are 1 in. by 1 in.
5. Elongation at break. This test is to be performed only on membrane
materials that do not have a fabric or other nonelastomeric support
as part of the liner.
6. Modulus of elasticity, machine and transverse directions, two
specimens each direction for semicrystalline liner materials only,
ASTM D882 modified Method A (see Table 1).
7. Volatiles content, SW 870, Appendix III-D.
8. Extractables content, SW 870, Appendix III-E.
9. Ply adhesion, machine and transverse directions, two specimens each
direction for fabric reinforced liner materials only, ASTM D413
Machine Method, Type A -- 180 degree peel.
10. Hydrostatic resistance test, ASTM D751 Method A, Procedure 1.
7.8 Results and reporting
7.8.1 Plot the curve for each property over the time period 0 to
120 days and display the spread in data points.
7.8.2 Report all raw, tabulated, and plotted data. Recommended
methods for collecting and presenting information are described in the
documents listed under Step 6.1 and in related agency guidance manuals.
7.8.3 Summarize the raw test results as follows:
1. Percent change in thickness.
2. Percent change in mass.
9090A - 5 Revision 1
July 1992
-------
3. Percent change in area (provide length and width
dimensions).
4. Percent retention of physical properties.
5. Change, in points, of hardness reading.
6. The modulus of elasticity calculated in pounds-force per
square inch.
7. Percent volatiles of unexposed and exposed liner material.
8. Percent extractables of unexposed and exposed liner
material.
9. The adhesion value, determined in accordance with ASTM
D413, Step 12.2.
10. The pressure and time elapsed at the first appearance of
water through the flexible membrane liner for the
hydrostatic resistance test.
7.9 The following additional procedures are suggested in specific
situations:
7.9.1 For the generation of a synthetic leachate, the Agency
suggests the use of the Toxicity Characteristic Leaching Procedure (TCLP)
that was finalized in the Federal Register on June 29, 1990, Vol. 55,
No. 126, p. 26986.
7.9.2 For semi crystal line membrane liners, the Agency suggests
the determination of the potential for environmental stress cracking. The
test that can be used to make this determination is either ASTM D1693 or
the National Institute of Standards and Technology Constant Tensile Load.
The evaluation of the results should be provided by an expert in this
field.
7.9.3 For field seams, the Agency suggests the determination of
seam strength in shear and peel modes. To determine seam strength in peel
mode, the test ASTM D413 can be used. To determine seam strength in shear
mode for nonreinforced FMLs, the test ASTM D3083 can be used, and for
reinforced FMLs, the test ASTM D751, Grab Method, can be used at a speed
of 12 in. per minute. The evaluation of the results should be provided by
an expert in this field.
8.0 QUALITY CONTROL
8.1 Determine the mechanical properties of identical nonimmersed and
immersed liner samples in accordance with the standard methods for the specific
physical property test. Conduct mechanical property tests on nonimmersed and
immersed liner samples prepared from the same sample or lot of material in the
same manner and run under identical conditions. Test liner samples immediately
after they are removed from the room temperature test solution.
9090A - 6 Revision 1
July 1992
-------
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
1. None required.
9090A - 7 Revision 1
July 1992
-------
Table t. Physical testing of e*ปsed
in llner-wuto Itcpld oepatlblllty test
Tjpe of cnpaund and
construction
Tensile properties Betted
Type of vectavn
Cross! Inked or wlcanlzed
ASTMD412
Tharaplastlc
ASTM063B
Duetto! 1b
Seal crystal line
ASTMD63B
Durtte1lb
Fabric-reinforced9
ASIป407bl. MsthodB
1-ln. wlda strip and 2- In. Jaw
Ntatorof
$wedof test
Values to to reported
3 In each dlractlon
20101
Tensile strength, psl
Elongation at break. 1
Tensile sat after break.
Stress at 100 and 2001
elongation, pst
3 In aach direction
20 Ipa
Tamil* strength, pst
Elongation at break. 1
Tensile set after break.
Stress at 100 and 2001
elongation, pst
tO
O
I
CO
Mxftilus of elasticity Mtnod
Tjpeof
Mater of spocleans
3>eadof test
Values reported
Tear resistance Mtnod
Type of *>ect
Mater of spec lewis
^>eadof test
Values reported
Puncture resistance avtted
ASTM0624
Diet
3 In aach direction
20 tpi
Stress, ppl
FT>6 101C. Nothod 2066
ASTN1004
3 In each direction
20 Ipa
Stress, ppt
FINS 101C. Method 2066
3 In each direction
Zip-
Tensile strength at yield, psl
Elongation at yield, X
Tensile set at break, psl
Elongation at break, psl
Tensile set after break. I
Stress at 100 and 200%
elongation, psl
AS1N DBB2. Method A
Strip: O.S In. wide and 6. In long
at a 2 In. Jaw separation
2 In each direction
0.2 HM
Greatest slope of Initial stress -
strain curve, psl
AS1M 01004
2 In each direction
21pป
Mntaua stress, ppl
FTMS 101C. Method 2066
separation
3 In each direction
12 Ipa
Tensile at fArtc break, ppi
Elongation at fabric break, 1
Tensile at ultlnte break, ppl
Elongation at ultleate break, ppl
Tensile set after break. I
Stress at 100 and 200X
elongation, psl
FTMS 101C. Method 2066
Tjpa of yeclean
Mater of vectaans
Speed of test
Values reported
2 In. sqare
2
201p>
Gage. .11
Stress, lb
Elongation, In.
2 In. square
2
20 Ipa
Gage. ซ1I
Stress. lb
Elongation. In.
2 In. sqare
2
20 Ipa
Gage, artl
Stress. lb
Elongation. In.
2 In. sojiare
2
20 Ipx
Gage. .11
Stress. lb
Elongation. In.
ID O
VO 3
r\>
Can to thermoplastic, crossl Inked, or vulcanized i
bSee Figure 4.
tear resistance test Is iwiaainrtBl for fatelc-ratnforcad sheetings In the taecrston study.
Saaa as AS1M 0624. Die C.
-------
TABLE 2.
POLYMERS USED IN FLEXIBLE MEMBRANE LINERS
Thermoplastic Materials (TP)
CPE (Chlorinated polyethylene)8
A family of polymers produced by a chemical reaction of chlorine on
polyethylene. The resulting thermoplastic elastomers contain 25 to 45%
chlorine by weight and 0 to 25% crystallinity.
CSPE (Chlorosulfonated polyethylene)8
A family of polymers that are produced by the reaction of polyethylene
with chlorine and sulfur dioxide, usually containing 25 to 43% chlorine
and 1.0 to 1.4% sulfur. Chlorosulfonated polyethylene is also known as
hypalon.
EIA (Ethylene interpolymer alloy)8
A blend of EVA and polyvinyl chloride resulting in a thermoplastic
elastomer.
PVC (Polyvinyl chloride)8
A synthetic thermoplastic polymer made by polymerizing vinyl chloride
monomer or vinyl chloride/vinyl acetate monomers. Normally rigid and
containing 50% of plasticizers.
PVC-CPE (Polyvinyl chloride - chlorinated polyethylene alloy)8
A blend of polyvinyl chloride and chlorinated polyethylene.
TN-PVC (Thermoplastic nitrile-polyvinyl chloride)8
An alloy of thermoplastic unvulcanized nitrile rubber and polyvinyl
chloride.
Vulcanized Materials (XL)
Butyl rubber8
A synthetic rubber based on isobutylene and a small amount of isoprene to
provide sites for vulcanization.
aAlso supplied reinforced with fabric.
9090A - 9 Revision 1
July 1992
-------
TABLE 2. (Continued)
EPDM (Ethylene propylene diene monomer)3'
A synthetic elastomer based on ethylene, propylene, and a small amount of
nonconjugated diene to provide sites for vulcanization.
CM (Cross-linked chlorinated polyethylene)
No definition available by EPA.
CO, ECO (Epichlorohydrin polymers)8
Synthetic rubber, including two epichlorohydrin-based elastomers that are
saturated, high-molecular-weight aliphatic polyethers with chloromethyl
side chains. The two types include homopolymer (CO) and a copolymer of
epichlorohydrin and ethylene oxide (ECO).
CR (Polychloroprene)8
Generic name for a synthetic rubber based primarily on chlorobutadiene.
Polychloroprene is also known as neoprene.
Semicrvstalline Materials (CX)
HOPE - (High-density polyethylene)
A polymer prepared by the low-pressure polymerization of ethylene as the
principal monomer.
HOPE - A (High-density polyethylene/rubber alloy)
A blend of high-density polyethylene and rubber.
LLDPE (Liner low-density polyethylene)
A low-density polyethylene produced by the copolymerization of ethylene
with various alpha olefins in the presence of suitable catalysts.
PEL (Polyester elastomer)
A segmented thermoplastic copolyester elastomer containing recurring long-
chain ester units derived from dicarboxylic acids and long-chain glycols
and short-chain ester units derived from dicarboxylic acids and low-
molecular-weight diols.
8Also supplied reinforced with fabric.
bAlso supplied as a thermoplastic.
9090A - 10 Revision 1
July 1992
-------
TABLE 2. (Continued)
PE-EP-A (Polyethylene ethylene/propylene alloy)
A blend of polyethylene and ethylene and propylene polymer resulting in a
thermoplastic elastomer.
T-EPDM (Thermoplastic EPDM)
An ethylene-propylene diene monomer blend resulting in a thermoplastic
elastomer.
9090A - 11 Revision 1
July 1992
-------
FIGURE 1. SUGGESTED PATTERN FOR CUTTING TEST SPECIMENS FROM
NONREINFORCED CROSSLINKED OR THERMOPLASTIC IMMERSED LINER SAMPLES.
Puncture test specimens
test specimens
Volatljes test specimen
Tensile test specimens
Hot to scale
9090A - 12
Revision 1
July 1992
-------
FIGURE 2. SUGGESTED PATTERN FOR CUTTING TEST SPECIMENS FROM
FABRIC REINFORCED IMMERSED LINER SAMPLES.
NOTE: TO AVOID EDGE EFFECTS, CUT SPECIMENS
1/8 - 1/4 INCH IN FROM EDGE OF IMMERSED SAMPLE.
VoUtlln test specimen
Puncture ttst specimens
Ply tdheslon ttst specimens
Tensile test specimens
Not to
9090A - 13
Revision 1
July 1992
-------
FIGURE 3. SUGGESTED PATTERN FOR CUTTING TEST SPECIMENS FROM
SEMICRYSTALLINE IMMERSED LINER SAMPLES.
NOTE: TO AVOID EDGE EFFECTS, CUT SPECIMENS
1/8 TO 1/4 INCH IN FROM EDGE OF IMMERSED SAMPLE.
Modulus of elasticity
ttst specimens
Tensile ttst specimens
Volitllts ttst sptclMn
Puncture ttst specimens
ttst specimens
HOC tO
9090A - 14
Revision 1
July 1992
-------
FIGURE 4. DIE FOR TENSILE DUMBBELL (NONREINFORCED LINERS)
HAVING THE FOLLOWING DIMENSIONS:
t
1
wo
1
1
N
s
1
\
w
t
1
LQ
X
V
W - Width of narrow section
L - Length of narrow section
WO - Width overall
LO - Length overall
G - Gage length
D - Distance between gaps
0.25
1.25
inches
inches
0.625 inches
50
00
2.00
inches
inches
inches
9090A - 15
Revision 1
July 1992
-------
METHOD 9090A
COMPATIBILITY TEST FOR WASTES AND MEMBRANE LINERS
START
7.1 Obtain sample
of waste fluid
7.2 Perform tests
on unexposed
samples of liner
material
7.3 Cut pieces of
lining material for
each test condition
7.4 Label test
specimens and
expose to waste
fluid
7.5 Determine
membrane physical
properties at 30
day intervals (30,
60. 90. 120 days)
7.6 To test exposed
specimens, measure
gauge thickness,
mass, length, and
width
7.7 Perform tests
on exposed samples
7 8 Report and
evaluate data
STOP
9090A - 16
Revision 1
July 1992
-------
METHOD 9095
PAINT FILTER LIQUIDS TEST
1.0 SCOPE AND APPLICATION
1.1 This method 1s used to determine the presence of free liquids 1n a
representative sample of waste.
1.2 The method 1s used to determine compliance with 40 CFR 264.314 and
265.314.
2.0 SUMMARY OF METHOD
2.1 A predetermined amount of material 1s placed In a paint filter. If
any portion of the material passes through and drops from the filter within
the 5-m1n test period, the material is deemed to contain free liquids.
3.0 INTERFERENCES
3.1 Filter media were observed to separate from the filter cone on
exposure to alkaline materials. This development causes no problem 1f the
sample is not disturbed.
4.0 APPARATUS AND MATERIALS
4.1 Conical paint filter; Mesh number 60 (fine meshed size). Available
at local paint stores such as Sherwin-Williams and Glidden for an approximate
cost of $0.07 each.
4.2 Glass funnel; If the paint filter, with the waste, cannot sustain
Its weight on the ring stand, then a fluted glass funnel or glass funnel with
a mouth large enough to allow at least 1 in. of the filter mesh to protrude
should be used to support the filter. The funnel 1s to be fluted or have a
large open mouth 1n order to support the paint filter yet not interfere with
the movement, to the graduated cylinder, of the liquid that passes through the
filter mesh.
4.3 Ring stand and ring, or tripod.
4.4 Graduated cylinder or beaker; 100-mL.
5.0 REAGENTS
5.1 None.
9095 - 1
Revision
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must be collected according to the directions in Chapter
Nine of this manual.
6.2 A 100-mL or 100-g representative sample is required for the test.
If it is not possible to obtain a sample of 100 mL or 100 g that is
sufficiently representative of the waste, the analyst may use larger size
samples in multiples of 100 mL or 100 g, i.e., 200, 300, 400 mL or g.
However, when larger samples are used, analysts shall divide the sample into
100-mL or 100-g portions and test each portion separately. If any portion
contains free liquids, the entire sample is considered to have free liquids.
7.0 PROCEDURE
7.1 Assemble test apparatus as shown in Figure 1.
7.2 Place sample in the filter. A funnel may be used to provide support
for the paint filter.
7.3 Allow sample to drain for 5 min into the graduated cylinder.
7.4 If any portion of the test material collects in the graduated
cylinder in the 5-min period, then the material is deemed to contain free
liquids for purposes of 40 CFR 264.314 and 265.314.
8.0 QUALITY CONTROL
8.1 Duplicate samples should be analyzed on a routine basis.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
9095 - 2
Revision 0
Date September 1986
-------
MINC STAND -
FUNNEL
PAINT FILTER
.^-GRADUATED CYLINDER
Figure 1. Paint filter test apparatus.
9095 - 3
Revision 0
Date September 1986
-------
METHOD 9095
PAINT FILTER LIQUIDS TEST
f Start J
7.1
Assemble test
apparatus
7.2
Place sample In
filter
7.3
Allow
cample to drain
into graduated
cylinder
Did any teat
material collect
in graduated
cylinder?
7.4
to cor
llqulc
CFR 21
Material
is deemed
itain free
Is; see 40
54.314 or
!6S.314
f Stop J
9095 - 4
Revision 0
Date September 1986
-------
METHOD 9096
LIQUID RELEASE TEST (LRT) PROCEDURE
1.0 SCOPE AND APPLICATION
1.1 The Liquid Release Test (LRT) is a laboratory test designed to
determine whether or not liquids will be released from sorbents when they are
subjected to overburden pressures in a landfill.
1.2 Any liquid-loaded sorbent that fails the EPA Paint Filter Free
Liquids Test (PFT) (SW-846 Method 9095), may be assumed to release liquids in
this test. Analysts should ensure that the material in question will pass the
PFT before performing the LRT.
2.0 SUMMARY OF METHOD
2.1 A representative sample of the liquid-loaded sorbent, standing 10
cm high in the device, is placed between twin stainless steel screens and two
stainless-steel grids, in a device capable of simulating landfill overburden
pressures. An absorptive filter paper is placed on the side of each stainless-
steel grid opposite the sample (i.e.. the stainless-steel screen separates the
sample and the filter paper, while the stainless-steel grid provides a small air
gap to prevent wicking of liquid from the sample onto the filter paper). A
compressive force of 50 psi is applied to the top of the sample. Release of
liquid is indicated when a visible wet spot is observed on either filter paper.
3.0 INTERFERENCES
3.1 When testing sorbents are loaded with volatile liquids (e.g..
solvents), any released liquid migrating to the filter paper may rapidly
evaporate. For this reason, filter papers should be examined immediately after
the test has been conducted.
3.2 It is necessary to thoroughly clean, and dry the stainless-steel
screens prior to testing to prevent false positive or false negative results.
Material caught in screen holes may impede liquid transmission through the screen
causing false negative results. A stiff bristled brush, like those used to clean
testing sieves, may be used to dislodge material from holes in the screens. The
screens should be ultrasonically cleaned with a laboratory detergent, rinsed with
deionized water, rinsed with acetone, and thoroughly dried.
When sorbents containing oily substances are tested, it may be necessary
to use solvents (e.g., methanol or methylene chloride) to remove any oily residue
from the screens and from the sample holder surfaces.
3.3 When placing the 76 mm screen on top of the loaded sample it is
important to ensure that no sorbent is present on top of the screen to contact
the filter paper and cause false positive results. In addition, some sorbent
residue may adhere to container sidewalls and contact the filter as the sample
9096 - 1 Revision 0
September 1994
-------
compresses under load, causing wet spots on the edges of the filter. This type
of false positive may be avoided by carefully centering the 76 mm filter paper
in the device prior to initiating the test.
3.4 Visual examination of the sample may indicate that a release is
certain (e.g., free standing liquid or a sample that flows like a liquid),
raising concern over unnecessary clean-up of the LRT device. An optional 5
minute Pre-Test, described in Appendix A of this procedure, may be used to
determine whether or not an LRT must be performed.
4.0 APPARATUS AND MATERIALS
4.1 LRT Device (LRTD): A device capable of applying 50 psi of pressure
continuously to the top of a confined, cylindrical sample (see Figure 1). The
pressure is applied by a piston on the top of the sample. All device components
contacting the sample (i.e., sample-holder, screens, and piston) should be
resistant to attack by substances being tested. The LRTD consists of two basic
components, described below.
4.1.1 Sample holder: A rigid-wall cylinder, with a bottom plate,
capable of holding a 10 cm high by 76 mm diameter sample.
4.1.2 Pressure Application Device: In the LRTD (Figure 1),
pressure is applied to the sample by a pressure rod pushing against a
piston that lies directly over the sample. The rod may be pushed against
the piston at a set pressure using pneumatic, mechanical, or hydraulic
pressure. Pneumatic pressure application devices should be equipped with
a pressure gauge accurate to within +1 psi, to indicate when the desired
pressure has been attained and whether or not it is adequately maintained
during the test. Other types of pressure application devices (e.g.,
mechanical or hydraulic) may be used if they can apply the specified
pressure continuously over the ten minute testing time. The pressure
application device must be calibrated by the manufacturer, using a load
cell or similar device placed under the piston, to ensure that 50 + 1 psi
is applied to the top of the sample. The pressure application device
should be sufficiently rugged to deliver consistent pressure to the sample
with repeated use.
4.2 Stainless-Steel Screens: To separate the sample from the filter,
thereby preventing false positive results from particles falling on the filter
paper. The screens are made of stainless steel and have hole diameters of 0.012
inches with 2025 holes per square inch. Two diameters of screens are used: a
larger (90 mm) screen beneath the sample and a smaller (76 mm) screen that is
placed on top of the sample in the sample-holding cylinder.
4.3 Stainless-Steel Grids: To provide an air gap between the
stainless-steel screen and filter paper, preventing false positive results from
capillary action. The grids are made of 1/32" diameter, woven, stainless steel
wire cut to two diameters, 90 mm and 76 mm.
9096 - 2 Revision 0
September 1994
-------
4.4 Filter Papers: To detect released liquid. Two sizes, one 90 mm
and one 76 mm, are placed on the side of the screen opposite the sample. The
76 mm diameter filter paper has the outer 6 mm cut away except 3 conical points
used for centering the paper (see Figure 2). Blue, seed-germination filter paper
manufactured by Schleicher and Schuell (Catalog Number 33900) is suitable. Other
colored, absorptive papers may be used as long as they provide sufficient wet/dry
contrast for the operator to clearly see a wet spot.
4.5 Spatula: To assist in loading and removing the sample.
4.6 Rubber or wooden mallet: To tap the sides of the device to settle
and level the sample.
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 Acetone.
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
6.1 All samples should be collected using a sampling plan that
addresses the considerations discussed in "Test Methods for Evaluating Solid
Wastes (SW-846)." The sampling plan should be designed to detect and sample any
pockets of liquids that may be present in a container (i.e., in the bottom or top
of the container).
6.2 Preservatives should not be added to samples.
6.3 Samples should be tested as soon as possible after collection, but
in no case after more than three days after collection. If samples must be
stored, they can be stored in sealed containers and maintained under dark, cool
conditions (temperature ranging between 35ฐ and 72ฐ F). Samples should not be
frozen.
7.0 PROCEDURE
The procedure below was developed for the original LRTD, manufactured by
Associated Design and Manufacturing Company (ADM). Procedures for other LRTDs,
along with evidence for equivalency to the ADM device, should be supplied by the
manufacturer.
9096 - 3 Revision 0
September 1994
-------
7.1 Disassemble the LRTD and make sure that all parts are clean and
dry.
7.2 Invert the sample-holding cylinder and place the large stainless-
steel screen, the large stainless-steel grid, then a 90 mm filter paper on the
cylinder base (bottom-plate side).
7.3 Secure the bottom plate (plate with a hole in the center and four
holes located on the outer circumference) to the flange on the bottom of the
sample-holding cylinder using four knob screws.
7.4 Turn the sample holder assembly to the right-side-up position
(bottom-plate-side down). Fill the sample holder with a representative sample
until the sample height measures 10 cm (up to the etched line in the cylinder).
7.5 Tap the sides of the sample holder with a rubber or wooden mallet
to remove air pockets and to settle and level the sample.
7.6 Repeat filling, and tapping until a sample height of 10 cm is
maintained after tapping.
7.7 Smooth the top of the sample with a spatula to create a horizontal
surface.
7.8 Place the small stainless-steel screen, then the small stainless-
steel grid on top of the sample.
NOTE: Prior to placing the stainless-steel grid on top of the
screen, make sure that no sorbent material is on the grid side of
the stainless-steel screen.
7.9 Place the 76 mm filter paper on top of the small stainless-steel
grid, making sure the filter paper is centered in the device.
7.10 Using the piston handle (screwed into the top of the piston) lower
the piston into the sample holder until it sits on top of the filter paper.
Unscrew and remove the handle.
7.11 Place the loaded sample holder into position on the baseplate and
lock into place with two toggle clamps.
7.12 Place the pressure application device on top of the sample-holder.
Rotate the device to lock it into place and insert the safety key.
7.13 Connect air lines.
7.14 Initiate rod movement and pressure application by pulling the air-
valve lever toward the operator and note time on data sheet. The pressure gauge
at the top of the pressure application device should read as specified in the
factory calibration record for the particular device. If not, adjust regulator
to attain the specified pressure.
9096 - 4 Revision 0
September 1994
-------
NOTE: After pressure application, the air lines can be disconnected, the
toggle clamps can be released, and the LRTD can be set aside for 10
minutes while other LRTDs are pressurized. LRTD pressures should be
checked every 3 minutes to ensure that the specified pressure is being
maintained. If the specified pressure is not being maintained to within
+ 5 psi, the LRTD must be reconnected to the air lines and pressure
applied throughout the 10 minute test.
7.15 After 10 minutes place the LRTD on the baseplate, reconnect air
lines and toggle clamps, and turn off pressure (retract the rod) by pushing the
air-valve lever away from the operator. Note time on data sheet.
7.16 When the air gauge reaches 0 psi, disconnect the air lines and
remove the pressure-application device by removing the safety key, rotating the
device, and lifting it away from the sample holder.
7.17 Screw the piston handle into the top of the piston.
7.18 Lift out the piston.
7.19 Remove the filter paper and immediately examine it for wet spots
(wet area on the filter paper). The presence of a wet spot(s) indicates a
positive test (i.e., liquid release). Note results on data sheet.
7.20 Release toggle clamps and remove sample holder from baseplate.
Invert sample holder onto suitable surface and remove the knob screws holding the
bottom plate.
7.21 Remove the bottom plate and immediately examine the filter paper
for wet spots as described in Step 7.19. Note results on data sheet. Wet
spot(s) on either filter indicates a positive test.
8.0 QUALITY CONTROL
8.1 Duplicate samples should be analyzed every twenty samples or every
analytical batch, whichever is more frequent. Refer to Chapter One for
additional QC protocols.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
10.0 REFERENCES
1. Hoffman, P., G. Kingsbury, B. Lesnik, M. Meyers, "Background Document for
the Liquid Release Test (LRT) Procedure"; document submitted to the Environmental
Protection Agency by Research Triangle Institute: Research Triangle Park, NC
under Contract No. 68-01-7075, Work Assignment 76 and Contract No. 68-WO-0032,
Work Assignment 12.
9096 - 5 Revision 0
September 1994
-------
FIGURE 1.
LRT DEVICE
Pressure
Application
Device
50 psi
Sample-Holding Cylinder
Filter
Separator Plate
9096 - 6
Separator Plate
Filter
Bottom Plate
Revision 0
September 1994
-------
76
FIGURE 2.
DIAMETER FILTER PAPER
9096 - 7
Revision 0
September 1994
-------
FIGURE 3.
GLASS GRID SPECIFICATIONS.
0.25 inchf
glass rodt
i. Sen-*
1.7cm
^
4.0 cm
9.7 cm
9096 - 8
Revision 0
September 1994
-------
FIGURE 4.
POSITIONING OF DYE ON GLASS PLATE
Methylene Blue
Anthraquinone
7.5 cm
7.5 cm
9096 - 9
Revision 0
September 1994
-------
METHOD 9096
LIQUID RELEASE TEST (LRT) PROCEDURE
START
J
7.6 Add mori
ample
7 .1 Di*a**amble
LRTD to en*ure
cleanline** and
dryne**
7.2 Place
*creen, grid
and filter
paper on
cylinder bate
7.3 Secure
ample holder
7.4 - 7.5
Fill cylinder
xith (ample;
tap to remove
air
7.8 Place
tainle**-*teel
and grid on top
ox *ample
7.9 Place
filter paper
on grid and
center in the
device
7.10 Lower
piston into
ample holder
7.11 Place
ample holder
on baซe plate
and ซecure
7.12 Lock
preซ*ure
device on top
of *ample
holder
7 .13 Connect
air line*
7.14 Pre**uriie
LRTD and
maintain
preปซure for 10
minute*
7.15 - 7.16
Depre**urize
and remove
LRTD from
ample holder
7.18 Remove
pi*ton
7.19 - 7.21
Di*a**emble and
check filter
paper for wet
ซpot(.)
C STOP J
9096 - 10
Revision 0
September 1994
-------
APPENDIX A
LIQUID RELEASE TEST PRE-TEST
1.0 SCOPE AND APPLICATION
1.1 The LRT Pre-Test is an optional, 5 minute laboratory test designed
to determine whether or not liquids will be definitely released from sorbents
before applying the LRT. This test is performed to prevent unnecessary cleanup
and possible damage to the LRT device.
1.2 This test is purely optional and completely up to the discretion
of the operator as to when it should be used.
2.0 SUMMARY OF METHOD
A representative sample will be loaded into a glass grid that is placed on
a glass plate already stained with 2 dyes (one water soluble and one oil
soluble). A second glass plate will be placed on top and a 2 Ib. weight placed
on top for 5 minutes. At the end of 5 minutes the base of the glass grid is
examined for any dye running along the edges, this would indicate a liquid
release.
3.0 INTERFERENCES
A liquid release can be detected at lower Liquid Loading Levels with
extremely clean glassware. The glass plates and glass grid should be cleaned
with a laboratory detergent, rinsed with Deionized water, rinsed with acetone,
and thoroughly dried.
4.0 APPARATUS AND MATERIALS
4.1 Glass Plate: 2 glass plates measuring 7.5 cm x 7.5 cm.
4.2 Glass Grid: See Figure 3.
4.3 Paint Brush: Two small paint brushes for applying dyes.
4.4 Spatula: To assist in loading the sample.
4.5 Weight: 2.7 kg weight to apply pressure to the sample.
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 Methylene Blue dye in methanol.
9096 - 11
Revision 0
September 1994
-------
5.3 Anthraquinone dye in toluene.
6.0 SAMPLE COLLECTION, PRESERVATION AND HANDLING
See LRT Procedure.
7.0 PROCEDURE
7.1 Paint one strip, approximately 1 cm wide, of methylene blue dye
across the center of a clean and dry glass plate (see Figure 4). The dye is
allowed to dry.
7.2 Paint one strip, approximately 1 cm wide, of anthraquinone dye
across the center of the same glass plate (see Figure 4). This strip should be
adjacent to and parallel with the methylene blue strip. The dye is allowed to
dry.
7.3 Place the glass grid in the center of the dye-painted glass plate.
7.4 Place a small amount of sample into the glass-grid holes, pressing
down gently until the holes are filled to slightly above the grid top.
7.5 Place a second, clean and dry, glass plate on top of the sample and
grid.
7.6 Place a 2.7 kg weight on top of the glass for 5 minutes.
7.7 After 5 minutes remove the weight and examine the base of the grid
extending beyond the sample holes for any indication of dyed liquid. The entire
assembly may be turned upside down for observation. Any indication of liquid
constitutes a release and the LRT does not need to be performed.
8.0 QUALITY CONTROL
8.1 Refer to Chapter One for specific quality control procedures.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
10.0 REFERENCES
1. Research Triangle Institute. "Background Document for the Liquid Release
Test: Single Laboratory Evaluation and 1988 Collaborative Study".
Submitted to the Environmental Protection Agency under Contract No. 68-01-
7075, Work Assignment 76 and Contract No. 68-WO-0032, Work Assignment 12.
September 18, 1991.
9096 - 12 Revision 0
September 1994
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METHOD 9096
APPENDIX A
START
7.1 Paint methylene
blue atrip on
glasi; dry
7.2 Paint
anthraquinone strip
on glass parallel
to firat atrip; dry
7.3 Place grid in
center of glass
plate
7.4 Fill holea of
grid with aample
7.5 Place second
glasa plate on top
of sample
7.6 Apply weight on
glaaa for 5 minutes
7.7 Remove weight
and check for *ซt
apot(a)
STOP
9096 - 13
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September 1994
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METHOD 9100
SATURATED HYDRAULIC CONDUCTIVITY,
SATURATED LEACHATE CONDUCTIVITY, AND
INTRINSIC PERMEABILITY
1.0 INTRODUCTION
1.1 Scope and Application; This section presents methods available to
hydrogeologists and and geotechnical engineers for determining the saturated
hydraulic conductivity of earth materials and conductivity of soil liners to
leachate, as outlined by the Part 264 permitting rules for hazardous-waste
disposal facilities. In addition, a general technique to determine intrinsic
permeability is provided. A cross reference between the applicable part of
the RCRA Guidance Documents and associated Part 264 Standards and these test
methods is provided by Table A.
1.1.1 Part 264 Subpart F establishes standards for ground water
quality monitoring and environmental performance. To demonstrate
compliance with these standards, a permit applicant must have knowledge
of certain aspects of the hydrogeology at the disposal facility, such as
hydraulic conductivity, in order to determine the compliance point and
monitoring well locations and in order to develop remedial action plans
when necessary.
1.1.2 In this report, the laboratory and field methods that are
considered the most appropriate to meeting the requirements of Part 264
are given in sufficient detail to provide an experienced hydrogeologlst
or geotechnical engineer with the methodology required to conduct the
tests. Additional laboratory and field methods that may be applicable
under certain conditions are included by providing references to standard
texts and scientific journals.
1.1.3 Included in this report are descriptions of field methods
considered appropriate for estimating saturated hydraulic conductivity by
single well or borehole tests. The determination of hydraulic
conductivity by pumping or injection tests is not included because the
latter are considered appropriate for well field design purposes but may
not be appropriate for economically evaluating hydraulic conductivity for
the purposes set forth in Part 264 Subpart F.
1.1.4 EPA is not Including methods for determining unsaturated
hydraulic conductivity at this time because the Part 264 permitting
standards do not require such determinations.
1.2 Definitions; This section provides definitions of terms used in
the remainderofthis report. These definitions are taken from U.S.
Government publications when possible.
9100 - 1
Revision
Date September 1986
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TABLE A
HYDRAULIC AND LINER CONDUCTIVITY DETERMINATION
METHODS FOR SURFACE IMPOUNDMENT,
WASTE PILE, AND LANDFILL COMPONENTS, AS CITED
IN RCRA GUIDANCE DOCUMENTS AND DESCRIBED IN SW-846
Guidance Cite* Corresponding
Surface Impoundments Associated Regulation SW-846 Section
Soil liner hydraulic Guidance section D(2)(b)(l) 2.0
conductivity and D(2)(c)(l)/Section
264.221(a),(b)
Soil Uner leachate Guidance section D(2)(b)(2) 2.11
conductivity and D(2)(c)(2)
Leak detection Guidance section C(2)(a)/ 2.0
Section 264.222
Final cover drain Guidance section E(2)(d)(l) 2.0
layer Section 264.228
Final cover low Guidance section E(2)(e)(2)(A)/ 2.0
permeability layer Section 264.228
General hydrogeologic 264 subpart F 3.0
site investigation
1 RCRA Guidance Document: Surface Impoundments, Liner Systems, Final Cover,
and Freeboard Control. Issued July, 1982.
(continued on next page)
9100 - 2
Revision
Date September 1986
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TABLE A (continued)
Guidance Cite2 Corresponding
Waste Piles Associated Regulation SW-846 Section
Soil liner hydraulic Guidance section D(2)(b)(i) 2.0
conductivity and D(2)(c)(1)/
Section 264.251(a)(1)
Soil liner leachate Guidance section D(2)(b)(ii) 2.11
conductivity and D(2)(c)(1i)
Leak detection Guidance section C(2)(a)/ 2.0
system Section 264.252(a)
Leachate collection Guidance section C(2)(a)/ 2.0
and renewal system Section 264.251(a)(2)
General hydrogeologic 264 subpart F 3.0
site investigation
2 RCRA Guidance Document: Waste Pile Design, Liner Systems.
Issued July, 1982.
(continued on next page)
9100 - 3
Revision 0
Date September 1986
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TABLE A (continued)
Landf111s
Guidance Cite3
Associated Regulation
Corresponding
SW-846 Section
Soil liner hydraulic
conductivity
Soil liner leachate
conductivity
Leak detection
system
Leachate collection and
removal system
Final cover drain
layer
Final cover low
permeability layer
General hydrogeologic
site investigation
Guidance section D(2)(b)(l)/ 2.0
Section 264.301(a)(l)
Guidance section D(2)(b)(2) 2.11
Guidance section C(2)(a)/ 2.0
Section 264.302(a)(3)
Guidance section C(2)(a)/ 2.0
Section 264.301(a)(2)
Guidance section E(2)(d)(l)/ 2.0
Section 264.310(a)(b)
Guidance section E(2)(e)(2)(A) 2.0
Section 264.310(a)(b)
264 subpart F 3.0
3 RCRA Guidance Document:
Issued July, 1982.
Landfill Design, Liner Systems and Final Cover.
9100 - 4
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1.2.1 Units: This report uses consistent units in all equations.
The symbols used are:
Length = L,
Mass = M, and
Time = T.
1.2.2 Fluid potential or head (h): A measure of the potential
energy required to move fluid from a point in the porous medium to a
reference point. For virtually all situations expected to be found in
disposal sites and in ground water systems, h is defined by the following
equation:
h = hp + hz (1)
where:
h is the total fluid potential, expressed as a height of
fluid above a reference datum, L;
hp, the pressure potential caused by the weight of fluid
above the point in question, L, is defined by hp = P//KJ,
where:
P is the fluid pressure at the point in question, ML~^T~2,
p is the fluid density at the prevailing temperature, ML~3,
and
g is the acceleration of gravity, LT~2; and
hz is the height of the point in question above the reference
datum, L.
By knowing hp and hz at two points along a flow path and by knowing
the distance between these points, the fluid potential gradient can be
determined.
1.2.3 Hydraulic potential or head: The fluid potential when water
is the fluid.
1.2.4 Hydraulic conductivity: The fluid potential when water is
the fluid. The generic term, fluid conductivity, is discussed below in
1.2.5.
1.2.5 Fluid conductivity (K): Defined as the volume of fluid at
the prevailing density and dynamic viscosity that will move in a unit
time under a unit fluid potential gradient through a unit area measured
at right angles to the direction of flow. It is a property of both the
fluid and the porous medium as shown by the following equation:
9100 - 5
Revision
Date September 1986
-------
K - SJfl ; (2)
where:
K is the fluid conductivity, IT"1;
k is the intrinsic permeability, a property of the porous medium
alone, L^; and
u is the dynamic viscosity of the fluid at the prevailing
temperature, ML~1 T~l.
The fluid conductivity of a porous material is also defined by Darcy's
law, which states that the fluid flux (q) through a porous medium is
proportional to the first power of the fluid potential across the unit
area:
q = J = -KI (3)
where:
q = the specific fluid flux, LT'l,
Q is the volumetric fluid flux, L3!'1,
A is the cross-sectional area, L2, and
I is the fluid potential gradient, Lฐ.
Darcy's law provides the basis for all methods used to determine
hydraulic conductivity in this report. The range of validity of Darcy's
law is discussed in Section 1.5 (Lohman, 1972).
1.2.6 Leachate conductivity: The fluid conductivity when leachate
is the fluid.
1.2.7 Aquifer: A geologic formation, group of formations, or part
of a formation capable of yielding a significant amount of ground water
to wells or springs (40 CFR 260.10).
1.2.8 Confining layer: By strict definition, a body of impermeable
material stratigraphically adjacent to one or more aquifers. In nature,
however, its hydraulic conductivity may range from nearly zero to some
value distinctly lower than that of the aquifer. Its conductivity
relative to that of the aquifer it confines should be specified or
indicated by a suitable modifier, such as "slightly permeable" or
"moderately permeable" (Lohman, 1972).
1.2.9 Transm1ss1y1ty, T [L2, I"1]: The rate at which water of the
prevailing kinematic viscosity is transmitted through a unit width of the
aquifer under a unit hydraulic gradient. Although spoken of as a
9100 - 6
Revision
Date September 1986
-------
property of the aquifer, the term also Includes the saturated thickness
of the aquifer and the properties of the fluid. It 1s equal to an
Integration of the hydraulic conductivities across the saturated part of
the aquifer perpendicular to the flow paths (Lohman, 1972).
1.3 Temperature and viscosity corrections; By using Equation (2),
corrections to conditions different from those prevailing during the test can
be made. Two types of corrections can commonly be made: a correction for a
temperature that varies from the test temperature, and a correction for fluids
other than that used for the test. The temperature correction 1s defined by:
K u
where:
#
the subscript f refers to field conditions, and
the subscript t refers to test conditions.
Most temperature corrections are necessary because of the dependence of
viscosity on temperature. Fluid density variations caused by temperature
changes are usually very small for most liquids. The temperature correction
for water can be significant. Equation (4) can also be used to determine
hydraulic conductivity if fluids other than water are used. It is assumed,
however, when using Equation (4) that the fluids used do not alter the
intrinsic permeability of the porous medium during the test. Experimental
evidence shows that this alteration does occur with a wide range of organic
solvents (Anderson and Brown, 1981). Consequently, it is recommended that
tests be run using fluids, such as leachates, that might occur at each
particular site. Special considerations for using non-aqueous fluids are
given in Section 3.3 of this report.
1.4 Intrinsic permeability (k) : Rearrangement of Equation 2 results in
a definition of intrinsic permeability:
Since this is a property of the medium alone, if fluid properties change, the
fluid conductivity must also change to keep the intrinsic permeability a
constant. By using measured fluid conductivity, and values of viscosity and
density for the fluid at the test temperature, intrinsic permeability can be
determined.
1.5 Range of validity of Darcy's law; Determination of fluid
conductivities using both laboratory and field methods requires assuming the
validity of Darcy's law. Experimental evidence has shown that deviations from
the linear dependence of fluid flux on potential gradient exist for both
extremely low and extremely high gradients (Hillel, 1971; Freeze and Cherry,
1979). The lower limits are the result of the existence of threshold
9100 - 7
Revision 0
Date September 1986
-------
gradients required to Initiate flow (Swartzendruber, 1962). The upper limits
to the validity of Darcy's law can be estimated by the requirements that the
Reynolds number, Re, In most cases be kept below 10 (Bear, 1972). The
Reynolds number Is defined by:
Re = (6)
where:
d 1s some characteristic dimension of the system, often represented
by the median grain size diameter, DSQ, (Bouwer, 1978), and
q 1s the fluid flux per unit area, LT'1.
For most field situations, the Reynolds number 1s less than one, and Darcy's
law 1s valid. However, for laboratory tests 1t may be possible to exceed the
range of validity by the Imposition of high potential gradients. A rough
check on acceptable gradients can be made by substituting Darcy's law 1n
Equation (6) and using an upper limit of 10 for Re:
T
/*D50
where:
K is the approximate value of fluid conductivity determined at
gradient I.
A more correct check on the validity of Darcy's law or the range of gradients
used to determine fluid conductivity is performed by measuring the conduc-
tivity at three different gradients. If a plot of fluid flux versus gradient
is linear, Darcy's law can be considered to be valid for the test conditions.
1.6 Method Classification; This report classifies methods of
determining fluid conductivity into two divisions: laboratory and field
methods. Ideally, and whenever possible, compliance with Part 264 disposal
facility requirements should be evaluated by using field methods that test the
materials under 1n-s1tu conditions. Field methods can usually provide more
representative values than laboratory methods because they test a larger
volume of material, thus integrating the effects of macrostructure and
heterogeneities. However, field methods presently available to determine the
conductivity of compacted fine-grained materials 1n reasonable times require
the tested interval to be below a water table or to be fairly thick, or
require excavation of the material to be tested at some point in the test.
The Integrity of liners and covers should not be compromised by the
installation of boreholes or piezometers required for the tests. These
restrictions generally lead to the requirement that the fluid conductivity of
Uner and cover materials must be determined in the laboratory. The transfer
value of laboratory data to field conditions can be maximized for liners and
covers because it is possible to reconstruct relatively accurately the desired
9100 - 8
Revision
Date September 1986
-------
field conditions 1n the laboratory. However, field conditions that would
alter the values determined 1n the laboratory need to be addressed 1n permit
applications. These conditions Include those that would Increase conductivity
by the formation of mlcrocracks and channels by repeated wetting and drying,
and by the penetration of roots.
1.6.1 Laboratory methods are categorized 1n Section 2.0 by the
methods used to apply the fluid potential gradient across the sample.
The discussion of the theory, measurement, and computations for tests run
under constant and falling-head conditions is followed by a detailed
discussion of tests using specific types of laboratory apparatus and the
applicability of these tests to remolded compacted, fine-grained
uncompacted, and coarse-grained porous media. Section 2.3 provides a
discussion of the special considerations for conducting laboratory tests
using non-aqueous permeants. Section 2.10 gives a discussion of the
sources of error and guidance for establishing the precision of
laboratory tests. Laboratory methods may be necessary to measure
vertical fluid conductivity. Values from field tests reflect effects of
horizontal and vertical conductivity.
1.6.2 Field methods are discussed in Section 3.0 and are limited to
those requiring a single bore hole or piezometer. Methods requiring
multiple bore holes or piezometers and areal methods are Included by
reference. Because of the difficulties 1n determining fluid conductivity
of in-place liner and cap materials under field conditions without
damaging their integrity, the use of field methods for fine-grained
materials will be generally restricted to naturally occurring materials
that may serve as a barrier to fluid movement. Additional field methods
are referenced that allow determination of saturated hydraulic
conductivity of the unsaturated materials above the shallowest water
table. General methods for fractured media are given In Section 3.8. A
discussion of the Important considerations in well Installation,
construction, and development 1s Included as an introduction to Section
3.0.
2.0 LABORATORY METHODS
2.1 Sample collection for laboratory method; To assure that a
reasonable assessment 1s made of fieldconditionsat a disposal site, a site
investigation plan should be developed to direct sampling and analysis. This
plan generally requ1res$the professional judgement of an experienced
hydrogeologist or geotechnical engineer. General guidance 1s provided for
plan development in the Guidance Manual for Preparation of a Part 264 land
Disposal Facility Permit Application (EPA, in press).The points listed below
should be followed:
o The hydraulic conductivity of a soil Uner should be determined either
from samples that are processed to simulate the actual Uner, or from an
undisturbed sample of the complete liner.
9100 - 9
Revision 0
Date September 1986
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o To obtain undisturbed samples, the thin-walled tube sampling method (ASTM
Method # D1587-74) or a similar method may be used. Samples
representative of each 11ft of the liner should be obtained, and used in
the analyses. If actual undisturbed samples are not used, the soil used
1n liner construction must be processed to represent accurately the
liner's Initial water content and bulk density. The method described in
Section 2.7.3 or ASTM Method #0698-70 (ASTM, 1978) can be used for this
purpose.
o For purpose of the general site investigation, the general techniques
presented in ASTM method #0420-69 (ASTM, 1978) should be followed. This
reference establishes practices for soil and rock investigation and
sampling, and incorporates various detailed ASTM procedures for
Investigation, sampling, and material classification.
2.2 Constant-head methods: The constant-head method is the simplest
method of determining hydraulic conductivity of saturated soil samples. The
concept of the constant-head method is schematically Illustrated in Figure 1.
The Inflow of fluid is maintained at a constant head (h) above a datum and
outflow (Q) is measured as a function of time (t). Using Darcy's law, the
hydraulic conductivity can be determined using the following equation after
the outflow rate has become constant:
K = QL/hA, (8)
where:
K = hydraulic conductivity, LT"1;
L = length of sample, L;
A = cross-sectional area of sample, L^;
Q = outflow rate, L^T'l; and
h = fluid head difference across the sample, L.
Constant-head methods should be restricted to tests on media having high fluid
conductivity.
2.3 Falling-head methods; A schematic diagram of the apparatus for the
falling-head method is shown in Figure 2. The head of inflow fluid decreases
from hj to \\2 as a function of time (t) in a standpipe directly connected to
the specimen. The fluid head at the outflow 1s maintained constant. The
quantity of outflow can be measured as well as the quantity of Inflow. For
the setup shown in Figure 2a, the hydraulic conductivity can be determined
using the following equation:
v 2.3 aL, hO
K = -AtIog10 h '
9100 - 10
Revision
Date September 1986
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WATER SUPPLY
OVERFLOW
TO MAINTAIN
CONSTANT HEAD
OMAOUATIIO
C VLINOE R
Figure 1.Principle of the constant head method
9100 - 11
Revision 0
Date September 1986
-------
STANDPIPE-
OVERFLOW^- _,
^T^
(a)
OVERFLOW
(b)
Figure 2.Principle of the falling head method
using a small (a) and large (b) standpipe,
9100 - 12
Revision p
Date September 1986
-------
where:
a = the cross-sectional area of the standplpe, L2;
A = the cross-sectional area of the specimen, L2;
L = the length of the specimen, L; and
t = elapsed time from ti to t2, T.
For the setup in Figure 2b, the term a/A in Equation (9) is replaced by 1.0.
Generally, falling-head methods are applicable to fine-grained soils because
the testing time can be accelerated.
2.4 General test considerations;
2.4.1 Fluid supplies to be used: For determining hydraulic
conductivity and leachate conductivity, the supplies of permeant fluid
used should be de-a1red. A1r coming out of solution in the sample can
significantly reduce the measured fluid conductivity. Deairing can be
achieved by boiling the water supply under a vacuum, bubbling helium gas
through the supply, or both.
2.4.1.1 Significant reductions in hydraulic conductivity can
also occur in the growth and multiplication of microorganisms
present in the sample. If it is desirable to prevent such growth, a
bactericide or fungicide, such as 2000 ppm formaldehyde or 1000 ppm
phenol (Olsen and Daniel, 1981), can be added to the fluid supply.
2.4.1.1 Fluid used for determining hydraulic conductivity in
the laboratory should never be distilled water. Native ground water
from the aquifer underlying the sampled area or water prepared to
simulate the native ground water chemistry should be used.
2.4.2 Pressure and Fluid Potential Measurement: The equations in
this report are all dimenslonally correct; that is, any consistent set of
units may be used for length, mass, and time. Consequently, measurements
of pressure and/or fluid potential using pressure gages and manometers
must be reduced to the consistent units used before applying either
Equation 8 or 9. Pressures or potentials should be measured to within a
few tenths of one percent of the gradient applied across the sample.
2.5 Constant-head test with conventional permeameter;
2.5.1 Applicability: This method covers the determination of the
hydraulic conductivity of soils by a constant-head method using a
conventional permeameter. This method 1s recommended for disturbed
coarse-grained soils. If this method 1s to be used for fine-grained
soils, the testing time may be prohibitively long. This method was taken
from the Engineering and Design, Laboratory Soils Testing Manual (U.S.
Army, 1980). It parallels ASTM Method D2434-68 (ASTM.1978). The ASTM
9100 - 13
Revision 0
Date September 1986
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method gives extensive discussion of sample preparation and applicability
and should be reviewed before conducting constant-head tests. Lambe
(1951) provides additional information on sample preparation and
equipment procedures.
2.5.2 Apparatus: The apparatus 1s shown schematically in Figure 3.
It consists of the following:
1. A permeameter cylinder having a diameter at least 8 times the
diameter of the largest particle of the material to be tested;
2. Constant-head filter tank;
3. Perforated metal disks and circular wire to support the sample;
4. Filter materials such as Ottawa sand, coarse sand, and gravel of
various gradations;
5. Manometers connected to the top and bottom of the sample;
6. Graduated cylinder, 100-mL capacity;
7. Thermometer;
8. Stop watch;
9. Deal red water;
10. Balance sensitive to 0.1 gram; and
11. Drying oven.
2.5.3 Sample preparation:
1. Oven-dry the sample. Allow it to cool, and weigh to the nearest
0.1 g. Record the oven-dry weight of material. The amount of
material should be sufficient to provide a specimen in the
permeameter having a minimum length of about one to two times
the diameter of the specimen.
2. Place a wire screen, with openings small enough to retain the
specimen, over a perforated disk near the bottom of the
permeameter above the Inlet. The screen opening should be
approximately equal to the 10 percent size of the specimen.
3. Allow deal red water to enter the water inlet of the permeameter
to a height of about 1/2 1n. above the bottom of the screen,
taking care that no air bubbles are trapped under the screen.
9100 - 14
Revision
Date September 1986
-------
K- ป-.
i
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-
i
~
=
-
Sc
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T
H
i
1MB*
en
Perforated .
D He A Screen
V
Conttent ft
Heed Tank B
V Id
Vnj
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M tl.
ซ
PI
// I I*
/:'!-"ป
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A**- L "
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Ah
1 ' ' JLH
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-
-
-
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. Perforeted
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constant head
Watte
(b)
falling head
Figure 3. Apparatus setup for the constant head (a)
and falling head (b) methods.
9100 - 15
Revision 0
Date September 1986
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4. Mix the material thoroughly and place 1n the permeameter to
avoid segregation. The material should be dropped just at the
water surface, keeping the water surface about 1/2 1n. above the
top of the soil during placement. A funnel or a spoon 1s
convenient for this purpose.
5. The placement procedure outlined above will result 1n a
saturated specimen of uniform density although 1n a relatively
loose condition. To produce a higher density 1n the specimen,
the sides of the permeameter containing the soil sample are
tapped uniformly along Its circumference and length with a
rubber mallet to produce an increase 1n density; however,
extreme caution should be exercised so that fines are not put
Into suspension and segregated within the sample. As an
alternative to this procedure, the specimen may be placed using
an appropriate sized funnel or spoon. Compacting the specimen
in layers is not recommended, as a film of dust which might
affect the permeability results may be formed at the surface of
the compacted layer. After placement, apply a vacuum to the top
of the specimen and permit water to enter the evacuated specimen
through the base of the permeameter.
6. After the specimen has been placed, weigh the excess material,
if any, and the container. The specimen weight 1s the
difference between the original weight of sample and the weight
of the excess material. Care must be taken so that no material
is lost during placement of the specimen. If there 1s evidence
that material has been lost, oven-dry the specimen and weigh
after the test as a check.
7. Level the top of the specimen, cover with a wire screen similar
to that used at the base, and fill the remainder of the
permeameter with a filter material.
8. Measure the length of the specimen, inside diameter of the
permeameter, and distance between the centers of the manometer
tubes (L) where they enter the permeameter.
2.5.4 Test procedure:
1. Adjust the height of the constant-head tank to obtain the
desired hydraulic gradient. The hydraulic gradient should be
selected so that the flow through the specimen 1s laminar.
Hydraulic gradients ranging from 0.2 to 0.5 are recommended.
Too high a hydraulic gradient may cause turbulent flow and also
result in piping of soils. In general, coarser soils require
lower hydraulic gradients. See Section 1.5 for further
discussion of excessive gradients.
2. Open valve A (see Figure 3a) and record the initial piezometer
readings after the flow has become stable. Exercise care in
building up heads in the permeameter so that the specimen Is not
disturbed.
9100 - 16
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Date September 1986
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3. After allowing a few minutes for equilibrium conditions to be
reached, measure by means of a graduated cylinder the quantity
of discharge corresponding to a given time Interval. Measure
the piezometric heads (hj and h2) and the water temperature in
the permeameter.
4. Record the quantity of flow, piezometer readings, water
temperature, and the time interval during which the quantity of
flow was measured.
2.5.5 Calculations: By plotting the accumulated quantity of
outflow versus time on rectangular coordinate paper, the slope of the
linear portion of the curve can be determined, and the hydraulic
conductivity can be calculated using Equation (8). The value of h in
Equation (8) 1s the difference between hi and \\2*
2.6 Falling-head test with conventional permeameter;
2.6.1 Applicability: The falling-head test can be used for all
soil types, but 1s usually most widely applicable to materials having low
permeability. Compacted, remolded, fine-grained soils can be tested with
this method. This method presented 1s taken from the Engineering and
Design, Laboratory Soils Testing Manual (U.S. Army, 1980).
2.6.2 Apparatus: The schematic diagram of the falling-head
permeameter 1s shown in Figure 3b. The permeameter consists of the
following equipment:
1. Permeameter cylinder, a transparent acrylic cylinder having a
diameter at least 8 times the diameter of the largest particles;
2. Porous disk;
3. Wire screen;
4. Filter materials;
5. Manometer;
6. Timing device; and
2.6.3 Sample Preparation: Sample preparation for coarse-grained
soils is similar to that described previously 1n Section 2.4.3. For
fine-grained soils, samples are compacted to the desired density using
methods described 1n ASTM Method D698-70.
2.6.4 Test Procedure:
1. Measure and record the height of the specimen, L, and the cross-
sectional area of the specimen, A.
9100 - 17
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Date September 1986
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2. With valve B open (see Figure 3b), crack valve A, and slowly
bring the water level up to the discharge level of the
permeameter.
3. Raise the head of water in the standpipe above the discharge
level of the permeameter. The difference in head should not
result in an excessively high hydraulic gradient during the
test. Close valves A and B.
4. Begin the test by opening valve B. Start the timer. As the
water flows through the specimen, measure and record the height
of water in the standpipe above the discharge level, hi, at time
ti, and the height of water above the discharge level, h2 at
time t2.
2.6.5 Calculation*. From the test data, plot the logarithm of head
versus time on rectangular coordinate paper, or use semi-log paper. The
slope of the linear part of the curve is used to determine
Iogio(hi/h2)/t. Calculate the hydraulic conductivity using Equation (9).
2.7 Modified compaction permeameter method;
2.7.1 Applicability: This method can be used to determine the
hydraulic conductivity of a wide range of materials. The method is
generally used for remolded fine-grained soils. The method is generally
used under constant-head conditions. The method was taken from Anderson
and Brown, 1981, and EPA (1980). It should be noted that this method
method of Section 2.9.
2.7.2 Apparatus: The apparatus is shown in Figure 4 and consists
of equipment and accessories as follows:
1. Soil chamber, a compaction mold having a diameter 8 times larger
than the diameter of the largest particles (typically, ASTM
standard mold, Number CN405, is used);
2. Fluid chamber, a. compaction mold sleeve having the same diameter
as the soil chamber;
3. 2-kg hammer;
4. Rubber rings used for sealing purposes;
5. A coarse porous stone having higher permeability than the tested
sample;
6. Regulated source of compressed air; and
7. Pressure gage or manometer to determine the pressure on the
fluid chamber.
9100 - 18
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Date September 1986
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TO REGULATED PRESSURE SOURCE AND
PRESSURE GAGE OR MANOMETER USED TO
MEASURE H .
PRESSURE RELEASE VALVE
TOP PLATE
RUBBER "0' RING SEALS
BASE PLATE
I POROUS STONE
OUTFLOW TO VOLUMETRIC MEASURING DEVICE.
PRESSURE SHOULD BE ATMOSPHERIC OR ZERO
GAGE PRESSURE
Figure 4.Modified compaction permeameter.
Note: h in Equation 8 is the difference
between the regulated inflow pressure
and the outflow pressure. Source:
Anderson and Brown, 1981.
9100 - 19
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Date September 1986
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2.7.3 Sample preparation:
1. Obtain sufficient representative soil sample. Air dry the
sample at room temperature. Do not oven dry.
2. Thoroughly mix the selected representative sample with water to
obtain a desired moisture content.
3. Compact the sample to the desired density within the mold using
the method described as part of ASTM Method D698-70.
4. Level the surface of the compacted sample with straight edge,
weigh and determine the density of the sample.
5. Measure the length and diameter of the sample.
6. Assemble the apparatus, make sure that there are no leaks, and
then connect the pressure line to the apparatus.
2.7.4 Test procedure:
1. Place sufficient volume of water in the fluid chamber above the
soil chamber.
2. Apply air pressure gradually to flush water through the sample
until no air bubbles in the outflow are observed. For fine-
grained soils, the saturation may take several hours to several
days, depending on the applied pressure.
3. After the sample is saturated, measure and record the quantity
of outflow versus time.
4. Record the pressure reading (h) on the top of the fluid chamber
when each reading is made.
5. Plot the accumulated quantity of outflow versus time on
rectangular coordinate paper.
6. Stop taking readings as soon as the linear position of the curve
is defined.
2.7.5 Calculations: The hydraulic conductivity can be calculated
using Equation (8).
2.8 Triaxial-cell method with back pressure:
2.8.1 Applicability: This method is applicable for all soil types,
but especially for fine-grained, compacted, cohesive soils in which full
fluid saturation of the sample is difficult to achieve. Normally, the
test is run under constant-head conditions.
9100 - 20
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Date September 1986
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2.8.2 Apparatus: The apparatus is similar to conventional triaxial
apparatus. The schematic diagram of this apparatus is shown in Figure 5.
2.8.3 Sample preparation: Disturbed or undisturbed samples can be
tested. Undisturbed samples must be trimmed to the diameter of the top
cap and base of the triaxial cell. Disturbed samples should be prepared
in the mold using either kneading compaction for fine-grained soils, or
by the pouring and vibrating method for coarse-grained soils, as
discussed in Section 2.5.3.
2.8.4 Test procedure:
1. Measure the dimensions and weight of the prepared sample.
2. Place one of the prepared specimens on the base.
3. Place a rubber membrane in a membrane stretcher, turn both ends
of the membrane over the ends of the stretcher, and apply a
vacuum to the stretcher. Carefully lower the stretcher and
membrane over the specimen. Place the specimen and release the
vacuum on the membrane stretcher. Turn the ends of the membrane
down around the base and up around the specimen cap and fasten
the ends with 0-rings.
4. Assemble the triaxial chamber and place it in position in the
loading device. Connect the tube from the pressure reservoir to
the base of the triaxial chamber. With valve C (see Figure 5)
on the pressure reservoir closed and valves A and B open,
increase the pressure inside the reservoir, and allow the
pressure fluid to fill the triaxial chamber. Allow a few drops
of the pressure fluid to escape through the vent valve (valve B)
to insure complete filling of the chamber with fluid. Close
valve A and the vent valve.
5. Place saturated filter paper disks having the same diameter as
that of the specimen between the specimen and the base and cap;
these disks will also facilitate removal of the specimen after
the test. The drainage lines and the porous inserts should be
completely saturated with deaired water. The drainage lines
should be as short as possible and made of thick-walled, small-
bore tubing to insure minimum elastic changes in volume due to
changes in pressure. Valves in the drainage lines (valves E, F,
and G in Figure 5) should preferably be of a type which will
cause no discernible change of internal volume when operated.
While mounting the specimen in the compression chamber, care
should be exercised to avoid entrapping any air beneath the
membrane or between the specimen and the base and cap.
9100 - 21
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Date September 1986
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>-*
-------
6. For ease and uniformity of saturation, as well as to allow
volume changes during consolidation to be measured with the
burette, specimens should be completely saturated before any
appreciable consolidation is permitted; therefore, the
difference between the chamber pressure and the back pressure
should not exceed 5 psi during the saturation phase. To insure
that a specimen is not prestressed during the saturation phase,
the back pressure must be applied in small increments, with
adequate time between increments to permit equalization of pore
water pressure throughout the specimen.
7. With all valves closed, adjust the pressure regulators to a
chamber pressure of about 7 psi and a back pressure of about 2
psi. Now open valve A to apply the preset pressure to the
chamber fluid and simultaneously open valve F to apply the back
pressure through the specimen cap. Immediately open valve G and
read and record the pore pressure at the specimen base. When
the measured pore pressure becomes essentially constant, close
valves F and G and record the burette reading.
8. Using the technique described in Step 3, increase the chamber
pressure and the back pressure in increments, maintaining the
back pressure at about 5 psi less than the chamber pressure.
The size of each increment might be 5, 10, or even 20 psi,
depending on the compressibility of the soil specimen and the
magnitude of the desired consolidation pressure. Open valve G
and measure the pore pressure at the base immediately upon
application of each increment of back pressure and observe the
pore pressure until it becomes essentially constant. The time
required for stabilization of the pore pressure may range from a
few minutes to several hours depending on the permeability of
the soil. Continue adding increments of chamber pressure and
backpressure until, under any increment, the pore pressure
reading equals the applied back pressure immediately upon
opening valve G.
9. Verify the completeness of saturation by closing valve F and
increasing the chamber pressure by about 5 psi. The specimen
shall not be considered completely saturated unless the increase
in pore pressure immediately equals the increase in chamber
pressure.
10. When the specimen is completely saturated, increase the chamber
pressure with the drainage valves closed to attain the desired
effective consolidation pressure (chamber pressure minus back
pressure). At zero elapsed time, open valves E and F.
11. Record time, dial indicator reading, and burette reading at
elapsed times of 0, 15, and 30 sec, 1, 2, 4, 8, and 15 min, and
1, 2, 4, and 8 hr, etc. Plot the dial indicator readings and
9100 - 23
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Date September 1986
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burette readings on an arithmetic scale versus elapsed time on a
log scale. When the consolidation curves indicate that primary
consolidation is complete, close valves E and F.
12. Apply a pressure to burette B greater than that 1n burette A.
The difference between the pressures in burettes B and A 1s
equal to the head loss (h); h divided by the height of the
specimen after consolidation (L) is the hydraulic gradient. The
difference between the two pressures should be kept as small as
practicable, consistent with the requirement that the rate of
flow be large enough to make accurate measurements of the
quantity of flow within a reasonable period of time. Because
the difference in the two pressures may be very small in
comparison to the pressures at the ends of the specimen, and
because the head loss must be maintained constant throughout the
test, the difference between the pressures within the burettes
must be measured accurately; a differential pressure gage is
very useful for this purpose. The difference between the
elevations of the water within the burettes should also be
considered (1 in. of water = 0.036 psi of pressure).
13. Open valves D and F. Record the burette readings at any zero
elapsed time. Make readings of burettes A and B and of
temperature at various elapsed times (the interval between
successive readings depends upon the permeability of the soil
and the dimensions of the specimen). Plot arithmetically the
change 1n readings of both burettes versus time. Continue
making readings until the two curves become parallel and
straight over a sufficient length of time to determine
accurately the rate of flow as Indicated by the slope of the
curves.
2.8.5 Calculations: The hydraulic conductivity can be calculated
using Equation (8).
2.9 Pressure-chamber permeameter method:
2.9.1 Applicability: This method can be used to determine
hydraulic conductivity of a wide range of soils. Undisturbed and
disturbed samples can be tested under falling-head conditions using this
method. This method is also applicable to both coarse- and fine-grained
soils, including remolded, fine-grained materials.
2.9.2 Apparatus: The apparatus, shown in Figure 6, consists of
1. Pressure chamber;
2. Standpipe;
3. Specimen cap and base; and
4. Coarse porous plates.
9100 - 24
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Date September 1986
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,-tevfciNC tuti
COADUATCD
STAND*! ปf
OVTLIT WU.VC
.wmc HUT
MM UMO fOซ
NICMfd LATIKAL
0' LlVtLINC BULB
Figure 6.-
Pressure'chamber for hydraulic
conductivity.
Source: U.S. Army Corps of Engineers,
1980.
9100 - 25
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Date September 1986
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The apparatus is capable of applying confining pressure to simulate field
stress conditions.
2.9.3 Sample preparation: The sample preparation of disturbed and
undisturbed conditions can be prepared in the chamber and enclosed within
the rubber membrane, as discussed in Section 2.8.4.
2.9.4 Test procedure:
1. By adjusting the leveling bulb, a confining pressure 1s applied
to the sample such that the stress conditions represent field
conditions. For higher confining pressure, compressed air may
be used.
2. Allow the sample to consolidate under the applied stress until
the end of primary consolidation.
3. Flush water through the sample until no indication of air
bubbles is observed. For higher head of water, compressed air
may be used.
4. Adjust the head of water to attain a desired hydraulic gradient.
5. Measure and record the head drop 1n the standpipe along with
elapsed time until the plot of logarithm of head versus time is
linear for more than three consecutive readings.
2.9.5 Calculations: The hydraulic conductivity can be determined
using Equation (9).
2.10 Sources of error for laboratory test for hydraulic conductivity;
There are numerouspotentialsourcesoferror1n laboratorytests for
hydraulic conductivity. Fixed-wall permeameters may have problems with
sidewall leakage, causing higher values of hydraulic conductivity. Flexible-
membrane permeameters may yield misleadingly low values for hydraulic
conductivity when testing with a leachate that causes contraction and
shrinkage cracks in the sample because the membrane shrinks with the sample.
Table B summarizes some potential errors that can occur. 01 sen and Daniel
(1981) provide a more detailed explanation of sources of these errors and
methods to minimize them. If the hydraulic conductivity does not fall within
the expected range for the soil type, as given in Table C, the measurement
should be repeated after checking the source of error in Table B.
9100 - 26
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Date September 1986
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TABLE B
SUMMARY OF PUBLISHED DATA ON POTENTIAL ERRORS
IN USING DATA FROM
LABORATORY PERMEABILITY TESTS ON SATURATED SOILS
Measured K
Source of Error (References)
Too Low or Too High?
1. Voids formed in sample preparation
(01 sen and Daniel, 1981).
2. Smear zone formed during trimming
(Olsen and Daniel, 1981).
3. Use of distilled water as a
permeant (Fireman, 1944; and
Wilkinson, 1969).
4. Air in sample (Johnson, 1954)
5. Growth of micro-organisms
(Allison, 1947).
6. Use of excessive hydraulic
gradient (Schwartzendruber, 1968;
and Mitchell and Younger, 1967).
7. Use of temperature other than the
test temperature.
8. Ignoring volume change due to
stress change, with no confining
pressure used.
9. Performing laboratory rather
than in-situ tests (Olsen and
Daniel, 1981),
10. Impedance caused by the test
apparatus, including the
resistance of the screen or
porous stone used to support
the sample.
High
Low
Low
Low
Low
Low or High
Varies
High
Usually Low
Low
9100 - 27
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Date September 1986
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TABLE C
HYDRAULIC CONDUCTIVITIES ESTIMATED FROM GRAIN-SIZE DESCRIPTIONS
(In Feet Per Day)
Grain-Size Class or Range Degree of Sorting Silt Content
From Sample Description Poor Moderate Well Slight Moderate High
Fine-Grained Materials
Clay
Silt, clayey
Silt, slightly sandy
Silt, moderately sandy
Silt, very sandy
Sandy silt
Silty sand
Sands and gravel s(!)
Very fine sand
Very fine to fine sand
Very fine to medium sand
Very fine to coarse sand
Very fine to very coarse sand
Very fine sand to fine gravel
Very fine sand to medium gravel
Very fine sand to coarse gravel
Fine sand
Fine to medium sand
Fine to coarse sand
Fine to very coarse sand
Fine sand to fine gravel
Fine sand to medium gravel
Fine sand to coarse gravel
Medium sand
Medium to coarse sand
Medium to very coarse sand
Medium sand to fine gravel
Medium sand to medium gravel
Medium sand to coarse gravel
Coarse sand
Coarse to very coarse sand
Coarse sand to fine gravel
Coarse sand to medium gravel
Coarse sand to coarse gravel
Less than .001
1 - 4
5
7-8
9-11
11
13
13
27
36
48
59
76
99
128
27
53
57
70
88
114
145
67
74
84
103
131
164
80
94
116
147
184
20 27
27
41-47
-
-
-
-
-
40 53
67
65-72
-
-
-
-
80 94
94
98-111
-
-
-
107 134
134
136-156
-
-
23
24
32
40
51
67
80
107
33
48
53
60
74
94
107
64
72
71
84
114
134
94
94
107
114
134
19
20
27
31
40
52
66
86
27
39
43
47
59
75
87
51
57
61
68
82
108
74
75
88
94
100
13
13
21
24
29
38
49
64
20
30
32
35
44
57
72
40
42
49
52
66
82
53
57
68
74
92
Reduce by 10 percent if grains are subangular.
Source: Lappala (1978).
(continued)
9100 - 28
Revision
Date September 1986
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TABLE C (Continued)
Grain-Size Class or Range Degree of Sorting Silt Content
From Sample Description Poor Moderate Well Slight Moderate High
Sands and Gravels(*)
Very coarse sand
Very coarse sand to fine
Very coarse sand to medi
gravel
urn gravel
Very coarse sand to coarse gravel
Fine gravel
Fine to medium gravel
Fine to coarse gravel
Medium gravel
Medium to coarse gravel
Coarse gravel
107
134
1270
207
160
201
245
241
294
334
147
214
199-227
-
214
334
289-334
231
468
468
187
-
-
-
267
-
-
401
-
602
114
120
147
160
227
201
234
241
294
334
94
104
123
132
140
167
189
201
243
284
74
87
99
104
107
134
144
160
191
234
Reduce by 10 percent if grains are subangular.
Source: Lappala (1978).
9100 - 29
Revision
Date September 1986
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2.11 Leachate conductivity using laboratory methods; Many primary and
secondary leachates found at disposal sites may be nonaqueous liquids or
aqueous fluids of high ionic strength. These fluids may significantly alter
the intrinsic permeability of the porous medium. For example, Anderson and
Brown (1981) have demonstrated increases in hydraulic conductivity of
compacted clays of as much as two orders of magnitude after the passage of a
few pore volumes of a wide range of organic liquids. Consequently, the
effects of leachate on these materials should be evaluated by laboratory
testing. The preceding laboratory methods can all be used to determine
leachate conductivity by using the following guidelines.
2.11.1 Applicability: The determination of leachate conductivity
may be required for both fine-grained and coarse-grained materials.
Leachates may either increase or decrease the hydraulic conductivity.
Increases are of concern for compacted clay liners, and decreases are of
concern for drain materials. The applicability sections of the preceding
methods should be used for selecting an appropriate test for leachate
conductivity. The use of the modified compaction method (Section 2.7)
for determining leachate conductivity is discussed extensively in EPA
Publication SW870 (EPA 1980).
2.11.2 Leachate used: A supply of leachate must be obtained that
is as close in chemical and physical properties to the anticipated
leachate at the disposal site as possible. Methods for obtaining such
leachate are beyond the scope of this report. However, recent
publications by EPA (1979) and Conway and Malloy (1981) give
methodologies for simulating the leaching environment to obtain such
leachate. Procedures for deal ring the leachate supply are given 1n
Section 2.4. The importance of preventing bacterial growth in leachate
tests will depend on the expected conditions at the disposal site. The
chemical and physical properties that may result in corrosion,
dissolution, or encrustation of laboratory hydraulic conductivity
apparatus should be determined prior to conducting a leachate
conductivity test. Properties of particular importance are the pH and
the vapor pressure of the leachate. Both extremely acidic and basic
leachates may corrode materials. In general, apparatus for leachate
conductivity tests should be constructed of Inert materials, such as
acrylic plastic, nylon, or Teflon. Metal parts that might come in
contact with the leachate should be avoided. Leachates with high vapor
pressures may require special treatment. Closed systems for fluid supply
and pressure measurement, such as those in the modified tr1axial-cell
methods, should be used.
2.11.3 Safety: Tests involving the use of leachates should be
conducted under a vented hood, and persons conducting the tests should
wear appropriate protective clothing and eye protection. Standard
laboratory safety procedures such as those as given by Manufacturing
Chemists Association (1971) should be followed.
2.11.4 Procedures: The determination of leachate conductivity
should be conducted immediately following the determination of hydraulic
9100 - 30
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Date September 1986
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conductivity (Anderson and Brown, 1981). This procedure maintains fluid
saturation of the sample, and allows a comparison of the leachate and
hydraulic conductivities under the same test conditions. This procedure
requires modifications of test operations as described below.
2.11.5 Apparatus: In addition to a supply reservoir for water as
shown 1n Figures 3 through 6, a supply reservoir for leachate 1s
required. Changing the Inflow to the test cell from water to leachate
can be accomplished by providing a three-way valve 1n the Inflow line
that 1s connected to each of the reservoirs.
2.11.6 Measurements: Measurements of fluid potential and outflow
rates are the same for leachate conductivity and hydraulic conductivity.
If the leachate does not alter the Intrinsic permeability of the sample,
the criteria for the time required to take measurements is the same for
leachate conductivity tests as for hydraulic conductivity tests.
However, 1f significant changes occur in the sample by the passage of
leachate, measurements should be taken until either the shape of a curve
of conductivity versus pore volume can be defined, or until the leachate
conductivity exceeds the applicable design value for hydraulic
conductivity.
2.11.7 Calculations: If the leachate conductivity approaches a
constant value, Equations (8) and (9) can be used. If the conductivity
changes continuously because of the action of the leachate, the following
modifications should be made. For constant-head tests, the conductivity
should be determined by continuing a plot of outflow volume versus time
for the constant rate part of the test conducted with water. For
falling-head tests, the slope of the logarithm of head versus time should
be continued.
2.11.7.1 If the slope of either curve continues to change
after the flow of leachate begins, the leachate is altering the
Intrinsic permeability of the sample. The leachate conductivity in
this case is not a constant. In this case, values of the slope of
the outflow curve to use in Equation (8) or (9) must be taken as the
tangent to the appropriate outflow curve at the times of
measurement.
3.0 FIELD METHODS
This section discusses methods available for the determination of fluid
conductivity under field conditions. As most of these tests will use water as
the testing fluid, either natural formation water or water added to a borehole
or piezometer, the term hydraulic conductivity will be used for the remainder
of this section. However, if field tests are run with leachate or other
fluids, the methods are equally applicable.
The location of wells, selection of screened intervals, and the
appropriate tests that are to be conducted depend upon the specific site under
9100 - 31
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Date September 1986
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Investigation. The person responsible for such selections should be a
qualified hydrogeologist or geotechnical engineer who is experienced in the
application of established principles of contaminant hydrogeology and ground
water hydraulics. The following are given as general guidelines.
1. The bottom of the screened interval should be below the lowest
expected water level.
2. Wells should be screened in the lithologic units that have the
highest probability of either receiving contaminants or
conveying them down gradient.
3. Wells up gradient and down gradient of sites should be screened
in the same lithologic unit.
Standard reference texts on ground water hydraulics and contaminant
hydrogeology that should be consulted include: Bear (1972), Bouwer (1978),
Freeze and Cherry (1979), Stallman (1971), and Walton (1970).
The success of field methods in determining hydraulic conductivity is
often determined by the design, construction, and development of the well or
borehole used for the tests. Details of these methods are beyond the scope of
this report; however, important considerations are given in Sections 3.1 and
3.2. Detailed discussions of well installation, construction, and development
methods are given by Bouwer, pp. 160-180 (1978), Acker (1974), and Johnson
(1972).
The methods for field determination of hydraulic conductivity are
restricted to well or piezometer type tests applicable below existing water
tables. Determinations of travel times of leachate and dissolved solutes
above the water table usually require the application of unsaturated flow
theory and methods which are beyond the scope of this report.
3.1 Well-construct!on considerations: The purpose of using properly
constructed wells for hydraulicconductivity testing is to assure that test
results reflect conditions in the materials being tested, rather than
conditions caused by well construction. In all cases, diagrams showing all
details of the actual well or borehole constructed for the test should be
made. Chapter 3 of the U.S. EPA, RCRA Ground Water Monitoring Technical
Enforcement Guidance Document (TEGD) should be consulted.
3.1.1 Well Installation methods: Well installation methods are
listed below in order of preference for ground water testing and
monitoring. The order was determined by the need to minimize side-wall
plugging by drilling fluids and to maximize the accurate detection of
saturated zones. This order should be used as a guide, combined with the
judgment of an experienced hydrogeologist in selecting a drilling method.
The combined uses of wells for hydraulic conductivity testing, water-
level monitoring, and water-quality sampling for organic contaminants
were considered in arriving at the ranking.
9100 - 32
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Date September 1986
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1. Hollow-stem auger;
2. Cable tool;
3. A1r rotary;
4. Rotary drilling with non-organic drilling fluids;
5. A1r foam rotary; and
6. Rotary with organic-based drilling fluids.
Although the hollow stem-auger method 1s usually preferred for the
Installation of most shallow wells (less than 100 feet), care must be
taken 1f the tested zone Is very fine. Smearing of the borehole walls by
drilling action can effectively seal off the borehole from the adjacent
formation. Scarification can be used to remedy this.
3.1.2 Wells requiring well screens: Well screens placed opposite
the Interval to be tested should be constructed of materials that are
compatible with the fluids to be encountered. Generally an Inert plastic
such as PVC is preferred for ground .water contamination studies. The
screen slot size should be determined to minimize the Inflow of fine-
oral ned material to the well during development and testing. Bouwer
(1978) and Johnson (1972) give a summary of guidelines for sizing well
screens.
3.1.2.1 The annul us between the well screen and the borehole
should be filled with an artificial gravel pack or sand filter.
Guidelines for sizing these materials are given by Johnson (1972).
For very coarse materials, it may be acceptable to allow the
materials from the tested zone to collapse around the screen forming
a natural gravel pack.
3.1.2.2 The screened Interval should be Isolated from
overlying and underlying zones by materials of low hydraulic
conductivity. Generally, a short bentonite plug 1s placed on top of
the material surrounding the screen, and cement grout 1s placed in
the borehole to the next higher screened Interval (in the case of
multiple screen wells), or to the land surface for single screen
wells.
3.1.2.3 Although considerations for sampling may dictate
minimum casing and screen diameters, the recommended guideline is
that wells to be tested by pumping, balling, or injection in coarse-
grained materials should be at least 4-1nches Inside diameter.
Wells to be used for testing materials of low hydraulic conductivity
by sudden removal or Injection of a known volume of fluid should be
constructed with as small a casing diameter as possible to maximize
measurement resolution of fluid level changes. Casing sizes of 1.25
to 1.50 inches usually allow this resolution while enabling the
efficient sudden withdrawal of water for these tests.
9100 - 33
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Date September 1986
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3.1.3 Wells not requiring well screens: If the zone to be tested
1s sufficiently Indurated that a well screen and casing are not required
to prevent caving in, it is preferable to use a borehole open to the zone
to be tested. These materials generally are those having low to
extremely low hydraulic conductivities. Consolidated rocks having high
conductivity because of the presence of fractures and solution openings
may also be completed without the use of a screen and gravel pack.
Uncased wells may penetrate several zones for which hydraulic
conductivity tests are to be run. In these cases, the zones of interest
can be isolated by the use of inflatable packers.
3.2 Well development; For wells that are constructed with well screens
and gravel packs, and for all wells in which drilling fluids have been used
that may have penetrated the materials to be tested, adequate development of
the well is required to remove these fluids and to remove the fine-grained
materials from the zone around the well screen. Development is carried out by
methods such as intermittent pumping, jetting with water, surging, and
bailing. Adequate development is required to assure maximum communication
between fluids in the borehole and the zone to be tested. Results from tests
run in wells that are inadequately developed will Include an error caused by
loss of fluid potential across the undeveloped zone, and computed hydraulic
conductivities will be lower than the actual value. Bouwer (1978) and Johnson
(1975) give further details on well development including methods to determine
when adequate development has occurred. The U.S. EPA TEGD should also be
consulted.
3.3 Data interpretation and test selection considerations; Hydraulic
conductivity may be determined in wells that are either cased or uncased as
described in Section 3.1. The tests all Involve disturbing the existing fluid
potential in the tested zone by withdrawal from or injection of fluid into a
well, either as a slug over an extremely short period of time, or by
continuous withdrawal or injection of fluid. The hydraulic conductivity is
determined by measuring the response of the water level or pressure in the
well as a function of time since the start of the test. Many excellent
references are available that give the derivation and use of the methods that
are outlined below, including Bouwer (1978), Walton (1969), and Lohman (1972).
3.3.1 The selection of a particular test method and data analysis
technique requires the consideration of the purposes of the test, and the
geologic framework in which the test is to be run. Knowledge of the
stratigraphic relationships of the zone to be tested and both overlying
and underlying materials should always be used to select appropriate test
design and data interpretation methods.
3.3.2 The equations given for all computational methods given here
and in the above references are based on idealized models comprising
layers of materials of different hydraulic conductivities. The water-
level response caused by disturbing the system by the addition or removal
of water can be similar for quite different systems. For example, the
response of a water-table aquifer and a leaky, confined aquifer to
9100 - 34
Revision 0
Date September 1986
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pumping can be very similar. Consequently, 1t 1s not considered
acceptable practice to obtain data from a hydraulic conductivity test and
interpret the type of hydraulic system present without supporting
geologic evidence.
3.3.3 The primary use of hydraulic conductivity data from tests
described subsequently will usually be to aid In siting monitoring wells
for facility design as well as for compliance with Subpart F of Part 264.
As such, the methods are abbreviated to provide guidance in determining
hydraulic conductivity only. Additional analyses that may be possible
with some methods to define the storage properties of the aquifer are not
included. The U.S. EPA TEGD has an expanded discussion on the
relationship between K tests and siting design (Chapter 1) and should be
consulted.
3.3.4 The well test methods are discussed under the following two
categories: 1) methods applicable to coarse-grained materials and tight
to extremely tight materials under confined conditions; and 2) methods
applicable to unconflned materials of moderate permeability. The single
well tests integrate the effects of heterogeneity and anlsotropy. The
effects of boundaries such as streams or less permeable materials usually
are not detectable with these methods because of the small portion of the
geologic unit that is tested.
3.4 Single well tests; The tests for determining hydraulic conductivity
with a single wellaredTscussed below based on methods for confined and
unconfined conditions. The methods are usually called slug tests because the
test involves removing a slug of water instantaneously from a well and
measuring the recovery of water in the well. The method was first developed
by Hvorslev (1951), whose analysis did not consider the effect of fluid stored
in the well. Cooper and others (1967) developed a method that considers well
bore storage. However, their method only applied to wells that are open to
the entire zone to be tested and that tap confined aquifers. Because of the
rapid water-level response 1n coarse materials, the tests are generally
limited to zones with a transmissivity of less than about 70 cm^/sec (Lohman,
1972). The method has been extended to allow testing of extremely tight
formations by Bredehoeft and Papadopulos (1980). Bouwer and Rice (1976)
developed a method for analyzing slug tests for unconflned aquifers.
3.4.1 Method for moderately permeable formations under confined
conditions:
3.4.1.1 Applicability; This method is applicable for testing
zones to which the entire zone is open to the well screen or open
borehole. The method usually is used in materials of moderate
hydraulic conductivity which allow measurement of water-level
response over a period of a hour to a few days. More permeable
zones can be tested with rapid response water-level recording
equipment. The method assumes that the tested zone is uniform in
all radial directions from the test well. Figure 7 illustrates the
test geometry for this method.
9100 - 35
Revision
Date September 1986
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WELL CASING
WELL SCREEN
x CONFINING LAYER
Figure 7.Geometry and variable definition for
slug tests in confined aquifers.
9100 - 36
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Date September 1986
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3.4.1.2 Procedures; The slug test 1s run by utilizing some
method of removing or adding a known volume of water from the well
bore 1n a very short time period and measuring the recovery of the
water level 1n the well. The procedures are the same for both
unconfined and confined aquifers. Water Is most effectively removed
by using a bailer that has been allowed to fill and stand 1n the
well for a sufficiently long period of time so that any water-level
disturbance caused by the Insertion of the bailer will have reached
equilibrium. In permeable materials, this recovery time may be as
little as a few minutes. An alternate method of effecting a sudden
change 1n water level Is the withdrawal of a weighted float. The
volume of water displaced can be computed using the known submersed
volume of the float and Archimedes' principle (Lohman, 1972).
Water-level changes are recorded using either a pressure
transducer and a strip chart recorder, a weighted steel tape, or an
electric water-level probe. For testing permeable materials that
approach or exceed 70 cm^/sec, a rapid-response transducer/recorder
system 1s usually used because essentially full recovery may occur
1n a few minutes. Because the rate of water-level response decays
with time, water-level or pressure changes should be taken at
increments that are approximately equally spaced in the logarithm of
the time since fluid withdrawal. The test should be continued until
the water level in the well has recovered to at least 85 percent of
the initial pre-test value.
3.4.1.3 Calculations; Calculations for determining hydraulic
conductivity for moderately permeable formations under confined
conditions can be made using the following procedure:
1. Determine the transmisslvity of the tested zone by plotting the
ratio h/h0 on an arithmetic scale against time since removal of
water (t) on a logarithmic scale. The observed fluid potential
1n the well during the test as measured by water level or
pressure is h, and the fluid potential before the instant of
fluid withdrawal is h0. The data plot is superimposed on type
curves, such as those given by Lohman (1972), Plate 2, or
plotted from Appendix A, with the h/h0 and time axes coincident.
The data plot 1s moved horizontally until the data fits one of
the type curves. A value of time on the data plot corresponding
to a dlmenslonless time (/O on the type curve plot 1s chosen,
and the transmissivity 1s computed from the following:
(10)
where:
rc 1s the radius of the casing (Lohman, p. 29 (1972)).
9100 - 37
Revision
Date September 1986
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The type curves plotted using data 1n Appendix A are not to be
confused with those commonly referred to as "Theis Curves" which
are used for pumping tests in confined aquifers (Lohman, 1972).
The type curve method is a general technique of determining
aquifer parameters when the solution to the descriptive flow
equation involves more than one unknown parameter. Although
both the storage coefficient and transmissivity of the tested
interval can be determined with the type curve method for slug
tests, determination of storage coefficients is beyond the scope
of this report. See Section 3.4.1.4 for further discussion of
the storage coefficient.
If the data in Appendix A are used, a type curve for each
value of a is prepared by plotting F(a,/7) on the arithmetic
scale and dimensionless time (/?) on the logarithmic scale of
semi-log paper.
2. Determine the hydraulic conductivity by dividing the
transmissivity (T) calculated above by the thickness of the
tested zone.
3.4.1.4 Sources of error; The errors that can arise in
conducting slug tests can beof three types: those resulting from
the well or borehole construction; measurement errors; and data
analysis error.
Well construction and development errors; This method assumes that
the entire thickness of the zone of interest is open to the well
screen or boreholes and that flow is principally radial. If this is
not the case, the computed hydraulic conductivity may be too high.
If the well is not properly developed, the computed conductivity
will be too low.
Measurement errors; Determining or recording the fluid level in the
boreholeandthe time of measurement incorrectly can cause
measurement errors. Water levels should be measured to an accuracy
of at least 1 percent of the initial water-level change. For
moderately permeable materials, time should be measured with an
accuracy of fractions of minutes, and, for more permeable materials,
the time should be measured in terms of seconds or fractions of
seconds. The latter may require the use of a rapid-response
pressure transducer and recorder system.
Data analysis errors; The type curve procedure requires matching
the data tooneof a family of type curves, described by the
parameter , which is a measure of the storage in the well bore and
aquifer. Papadopulos and others (1973) show that an error of two
orders of magnitude in the selection of would result in an error
of less than 30 percent in the value of transmissivity determined.
Assuming no error in determining the thickness of the zone tested,
this is equivalent to a 30 percent error in the hydraulic
conductivity.
9100 - 38
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Date September 1986
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3.4.2 Methods for extremely tight formations under confined
conditions:
3.4.2.1 Applicability; This test is applicable to materials
that have low to extremely low permeability such as silts, clays,
shales, and indurated lithologic units. The test has been used to
determine hydraulic conductivities of shales of as low as 10~10
cm/sec.
3.4.2.2 Procedures; The test described by Bredehoeft and
Papadopulos (1980) andmodified by Neuzil (1982) is conducted by
suddenly pressurizing a packed-off zone in a portion of a borehole
or well. The test 1s conducted using a system such as shown in
Figure 8. The system is filled with water to a level assumed to be
equal to the prevailing water level. (This step is required if
sufficiently large times have not elapsed since the drilling of the
well to allow full recovery of water levels.) A pressure transducer
and recorder are used to monitor pressure changes in the system for
a period prior to the test to obtain pressure trends preceding the
test. The system is pressurized by addition of a known volume of
water with a high-pressure pump. The valve is shut and the pressure
decay is monitored. Neuzil's modification uses two packers with a
pressure transducer below the bottom packer to measure the pressure
change in the cavity and one between the two packers to monitor any
pressure change caused by leakage around the bottom packer.
3.4.2.3 Calculations; The modified slug test as developed by
Bredehoeft and Papadopulos (1980) considered compresslve storage of
water in the borehole. These authors considered that the volume of
the packed-off borehole did not change during the test and that all
compressive storage resulted in compression of water under the
pressure pulse. Neuzil (1980) demonstrated that under some test
conditions this is not a valid assumption. The computational from
either Lohman, Plate 2 (1972) or plotted from data given in Appendix
A as described in Section 3.4.1.3. The values of time (t) and
dimensionless time (/J) are determined in the same manner as for the
conventional tests. If compression of water only is considered,
transmissivity is computed by replacing rc by the quantity
(VwCw/>g/ir) in Equation 10:
0(VU Cu pj*)2
T - P W p (10)
where:
Vy is the volume of water in the packed-off cavity, L3;
CN is the compressibility of water, U^M"1;
p is the density of water, ML"3; and
g is the acceleration of gravity, LT~2.
9100 - 39
Revision 0
Date September 1986
-------
Valve
Pressure Gage
System Filled
with Water ซv
Pump
Pressure Gage
Land Surface
Initial Head
? - ? -in Tested ? - ?
Casing Interval
------ ,
'WellPoint
__j
to--
Tested ^
Pump
^ Tight
11. FormatiorQrinnnnr
(a)
(b)
Figure 8.Schematic diagram for pressurized slug
test method in unconsolidated (a) and
consolidated (b) materials. Source:
Papadopulos and Bredehoeft, 1980.
9100 - 40
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Date September 1986
-------
If the compresslve storage 1s altered by changing the volume of the
packed-off cavity (V), then the combined compressibility of the
water and the expansion of the cavity (C0) is used. C0 1s computed
by measuring the volume of water injected during pressurization (AV)
and the pressure change (AP) for the pressurization:
co -w (11)
(Neuzll, p. 440 (1982)). Use of C0 requires an accurate method of
metering the volume of water Injected and the volume of the cavity.
3.4.2.4 Sources of error; The types of errors 1n this method
are the same as those for th~e conventional slug test. Errors may
also arise by inaccurate determination of the cavity volume and
volume of water injected. An additional assumption that 1s required
for this method is that the hydraulic properties of the Interval
tested remain constant throughout the test. This assumption can
best be satisfied by limiting the initial pressure change to a value
only sufficiently large enough to be measured (Bredehoeft and
Papadopulos, 1980).
3.4.3 Methods for moderately permeable materials under unconflned
conditions:
3.4.3.1 Applicability; This method 1s applicable to wells
that fully or partiallypenetrate the interval of Interest (Figure
9). The hydraulic conductivity determined will be principally the
value in the horizontal direction (Bouwer and Rice, 1976).
3.4.3.2 Procedures; A general method for testing cased wells
that partly or fully penetrate aquifers that have a water table as
the upper boundary of the zone to be tested was developed by Bouwer
and Rice (1976). The geometry and dimensions that are required to
be known for the method are shown in Figure 9. The test is
accomplished by effecting a sudden change in fluid potential in the
well by withdrawal of either a bailer or submerged float as
discussed in Section 3.4.1.2. Water-level changes can be monitored
with either a pressure transducer and recorder, a wetted steel tape,
or an electric water-level sounder. For highly permeable
formations, a rapid-response transducer and recorder system Is
required. The resolution of the transducer should be about 0.01 m.
3.4.3.3 Calculations; The hydraulic conductivity 1s
calculated using the following equation from Bouwer and Rice (1976),
in the notation of this report:
r,,2 In R"/r Yrt
* In ^ (12)
2Let
9100 - 41
Revision 0
Date September 1986
-------
WELL CASING
() CASED WITH SCREEN
(b) CASED. NO SCREEN, NO
CAVITY ENLARGEMENT
(c) OPEN BOREHOLE
Figure 9.Variable definitions for slug tests in
unconfined materials. Cased wells are
open at the bottom.
9100 - 42
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Date September 1986
-------
where rc, rw, Le, t, Y, and K have been previously defined or are
defined 1n Figure 8a. Y0 1s the value of Y Immediately after
withdrawal of the slug of water. The term "R is an effective radius
for wells that do not fully penetrate the aquifer that is computed
using the following equation given by Bouwer and Rice (1976):
.. A + B ln[(H -L )/r ] ,1 -1
1J: 1+ . ฐฃ SL 'y (13}
In (L/rJ (L/r ) I, u<3;
W W G W J
If the quantity (H0-Lw)/rw) is larger than 6, a value of 6 should be
used.
For wells that completely penetrate the aquifer, the following
equation is used:
-1
(14)
(Bouwer, 1976). The values of the constants A, B, and C are given
by Figure 10 (Bouwer and Rice, 1976).
For both cases, straight-line portions of plots of the logarithm of
Y or Y0/Y against time should be used to determine the slope,
(In Y0/Y)/t.
Additional methods for tests under unconfined conditions are
summarized by Bower (1976) on pages 117-122. These methods are
modifications of the cased-well method described above that apply
either to an uncased borehole or to a well or piezometer in which
the diameter of the casing and the borehole are the same (Figures ,9b
and 9c.)
3.4.3.4 Sources of error; The method assumes that flow of
water from above is negligible. If this assumption cannot be met,
the conductivities may be 1n error. Sufficient flow from the
unsaturated zone by drainage would result in a high conductivity
value. Errors caused by measuring water levels and recording time
are similar to those discussed in Sections 3.4.1.4 and 3.4.2.4.
3.5 Multiple well tests; Hydraulic conductivity can also be determined
by conventional pumpingtests in which water is continuously withdrawn or
injected using one well, and the water-level response is measured over time 1n
or near more observation wells. The observation wells must be screened in the
same strata as the injection or pumping well. These methods generally test
larger portions of aquifers than the single well tests discussed 1n Section
3.4. For some circumstances these tests may be appropriate in obtaining data
to use in satisfying requirements of Part 264 Subpart F. However, the large
possibility for non-uniqueness in interpretation, problems involved 1n pumping
contaminated fluids, and the expense of conducting such tests generally
9100 - 43
Revision
Date September 1986
-------
A
and
C
12
10
10
50 100
500 1000
5000
Figure 10. Curves defining coefficients A, B,
and C in equations 13 and 14 as
a function of the ratio L/rw.
Source: Bower and Rice, 1976.
9100 - 44
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Date September 1986
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preclude their use in problems of contaminant hydrogeology. The following
references give excellent discussions of the design and interpretation of
these tests: Lohman (1972), Stallman (1971), and Walton (1970).
3.6 Estimates of hydraulic conductivity for coarse-grained materials;
The characterization of ground water flow systems to satisfy the Intent of
Part 264 Subpart F is preferably done with flow nets based on borehole
measurements rather than relying on interpolation from grain-size analyses.
An empirical approach that has been used by the U.S. Geological Survey
(Lappala, 1978) in several studies relates conductivity determined by aquifer
testing to grain-size, degree of sorting and silt content. Table C provides
the estimates of hydraulic conductivity.
Although estimates of K from analysis of grain-size and degree of sorting
do provide a rough check on test values of K, repeated slug tests provide a
better check on the accuracy of results.
3.7 Consolidation tests: As originally defined by Terzagi (Terzaghi and
Peck, 1967) the coefficient of consolidation (Cv) of a saturated,
compressible, porous medium is related to the hydraulic conductivity by:
Cv
where:
K is the hydraulic conductivity, LT~;
p is the fluid density, ML~3;
g is the gravitational constant, LT~2; and
a is the soil's compressibility, LM'iT2.
The compressibility can be determined in the laboratory with several types of
consolidometers, and is a function of the applied stress and the previous
loading history. Lambe (1951) describes the testing procedure.
3.7.1 The transfer value of results from this testing procedure is
influenced by the extent to which the laboratory loading simulates field
conditions and by the consolidation rate. The laboratory loadings will
probably be less than the stress that remolded clay liner will
experience; therefore, the use of an already remolded sample in the
consolidometer will probably produce no measurable results. This
suggests that the test is of little utility in determining the hydraulic
conductivity of remolded or compacted, fine-grained soils. Second, the
consolidation rate determines the length of the testing period. For
granular soils, this rate is fairly rapid. For fine-grained soils, the
rate may be sufficiently slow that the previously described methods,
9100 - 45
Revision
Date September 1986
-------
which give faster results, will be preferable. Cohesive soils (clays)
must be trimmed from undisturbed samples to fit the mold, while
cohesionless sands can be tested using disturbed, repacked samples
(Freeze and Cherry, 1979).
3.7.2 In general, EPA believes that consolidation tests can provide
useful information for some situations, but prefers the previously
described methods because they are direct measurements of hydraulic
conductivity. Hydraulic conductivity values determined using
consolidation tests are not to be used in permit applications.
3.8 Fractured media: Determining the hydraulic properties of fractured
media is always adifficult process. Unlike the case with porous media,
Darcy's Law is not strictly applicable to flow through fractures, although it
often can be applied empirically to large bodies of fractured rock that
incorporate many fractures. Describing local flow conditions in fractured
rock often poses considerable difficulty. Sowers (1981) discusses
determinations of hydraulic conductivity of rock. This reference should be
consulted for guidance in analyzing flow through fractured media.
3.8.1 Fine-grained sediments, such as glacial tills, are commonly
fractured in both saturated and unsaturated settings. These fractures
may be sufficiently interconnected to have a significant influence on
ground water flow, or they may be of very limited connection and be of
little practical significance.
3.8.2 Frequently, a laboratory test of a small sample of clay will
determine hydraulic conductivity to be on the order of 10~8 cm/sec. A
piezometer test of the same geologic unit over an interval containing
fractures may determine a hydraulic conductivity on the order of perhaps
10-5 or 10-6 cm/sec. To assess the extent of fracture interconnection,
and hence the overall hydraulic conductivity of the unit, several
procedures can be used. Closely spaced piezometers can be installed; one
can be used as an observation well while water is added to or withdrawn
from the other. Alternately, a tracer might be added to one piezometer,
and the second could be monitored. These and other techniques are
discussed by Sowers (1981).
3.8.3 For situations that may involve flow through fractured media,
1t is Important to note in permit applications that an apparent hydraulic
conductivity determined by tests on wells that intersect a small number
of fractures may be several orders others of magnitude lower or higher
than the value required to describe flow through parts of the ground
water system that Involve different fractures and different stress
conditions from those used during the test.
4.0 CONCLUSION
4.1 By following laboratory and field methods discussed or referenced in
this report, the user should be able to determine the fluid conductivity of
materials used for liners, caps, and drains at waste-disposal facilities, as
9100 - 46
Revision 0
Date September 1986
-------
well as materials composing the local ground water flow system. If fluid-
conductivity tests are conducted and Interpreted properly, the results
obtained should provide the level of information necessary to satisfy
applicable requirements under Part 264.
5.0 REFERENCES
1. Acker, W. L., Ill, Basic Procedures for Soil Sampling and Core Drilling,
Acker Drill Co., 246 p., 1974.
2. Allison, I.E., Effect of Microorganisms on Permeability of Soil under
Prolonged Submergence, Soil Science, 63, pp. 439-450 (1947).
i
3. American Society for Testing and Materials >(ASTM), Annual Book of ASTM
Standards, Part 19, 1978.
4. Anderson, D., and K. W. Brown, Organic Leachate Effects on the
Permeability of Clay Liners, iji Proceedings of Solid Waste Symposium, U.S.
EPA, p. 119-130, 1981.
5. Bear, J., Dynamics of Fluids 1n Porous Media, American Elsevler, 764 p.,
1972.
6. Bouwer, H., and R. C. Rice, A Slug Test for Determining Hydraulic
Conductivity of Unconflned Aquifers with Completely or Partially Penetrating
Wells, Water Resources Research, 12, p. 423-428 (1976).
7. Bredehoeft, J. D., and S. S. Papadopulos, A Method for Determining the
Hydraulic Properties of Tight Formations, Water Resources Research, 16, p.233-
238 (1980).
8. Conway, R. A., and B. C. Malloy, eds., Hazardous Solid Waste Testing:
First conference, ASTM Special Technical Publication 760, 1981.
9. Cooper, H. H., J. D. Bredehoeft, and I. S. Papadopulos, Response of a
Finite Diameter Well to an Instantaneous Charge of Water, Water Resources
Research, 3, p. 263-269 (1967).
10. Dakessian, S., et al., Lining of Waste Impoundment and Disposal
Facilities, Municipal Environment Research Laboratory, U.S. EPA, Cincinnati,
OH, EPA-530/SW-870C, pp. 264-269, 1980.
11. Fireman, M., Permeability Measurements on Disturbed Soil Samples, Soil
Science, 58, pp. 337-355 (1944).
12. Freeze, R. A., and J. A. Cherry, Ground Water, Prentice Hall, 604 p.,
1979.
9100 - 47
Revision
Date September 1986
-------
13. Gordon, B.B., and, M. Forrest, Permeability of Soil Using Contaminated
Permeant, iji Permeability and Ground Water Contaminant Transport, ed. T. F.
Zimmie and C. 0. R1ggs, ASTM Special Technical Publication 746, p. 101-120,
1981.
14. Hlllel, D., Soil and Water, Academic Press, 288 p., 1971.
15. Hvorslev, M. J., Time Lag and Soil Permeability 1n Ground Water
Observations, U.S. Army Corps of Engineers Waterways Experiment Station Bull.
36, 1951.
16. Johnson, A. I., Symposium on Soil Permeability, ASTM STP 163, American
Society of Testing and Materials, Philadelphia, pp. 98-114, 1954.
17. Johnson, E. E., Inc., Ground Water and Wells, Johnson Division, UOP,
440 p., 1975.
18. Lappala, E. G., Quantitative Hydrogeology of the Upper Republican Natural
Resources District, Southwest Nebraska, U.S. Geological Survey Water Resources
Investigations 78-38.
19. Lambe, T. W., Soil Testing for Engineers, John Wiley, N.Y., 1951.
20. Lohman, S. W., Ground Water Hydraulics, U.S. Geological Survey
Professional Paper 708, 70 p., 1972.
21. Lohman, S. W., et al., Definitions of Selected Ground Water Terms -
Revisions and Conceptual Refinements, U.S. Geological Survey Water Supply
Paper 1988, 1972.
22. Manufacturing Chemists Association, Guide for Safety in the Chemical
Laboratory, Van Nostrand, Reinhold Co, N.Y., 1971.
23. Mitchell, A.K., and J. S. Younger, Permeability and Capillarity of Soils,
ASTM STP 417, American Society for Testing and Materials, Philadelphia,
pp.106-139, 1967.
24. Neuzil, C. E., On Conducting the Modified 'Slug1 Test in Tight
Formations, Water Resources Research, 18(2), pp. 439-441 (1982).
25. 01 sen, R. E., and D. E. Daniel, Measurement of the Hydraulic Conductivity
of Fine-Grained Soils, 1_n Permeability and Ground Water Transport, ed. T.F.
Zimmie and C. 0. Riggs, ASTM Special Publication 746, p. 18-64, 1981.
26. Papadopulos, S. S., J. D. Bredehoeft, and H. H. Cooper, Jr., On the
Analysis of 'Slug Test' Data, Water Resources Research, 9, p. 1087-1089
(1973).
27. Schwartzendruber, D., The Applicability of Darcy's Law, Soil Science
Society of America Proceedings, 32(1), pp. 11-18 (1968).
9100 - 48
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Date September 1986
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28. Sowers, G. F., Rock Permeability or Hydraulic Conductivity -- An
Overview, Jhi Permeability and Ground Water Transport, ed. T. F. Zlmrnle and Co.
0. R1ggs, ASTM Special Technical Publication 746, 1981.
29. Stallman, R. W., Aquifer-Test Design, Observation and Data Analysis,
TWRI, Chap. Bl, Book 3, U.S. Geological Survey, U.S. Govt. Printing Office,
Washington, D.C., 1971.
30. Terzaghl, K., and R. B. Peck, Soil Mechanics 1n Engineering Practice, 2nd
ed., John Wiley & Sons, N.Y., 729 p., 1967.
31. Walton, W. C., Ground Water Resource Evaluation, McGraw Hill, 664 p.,
1970.
32. Wilkinson, W. B., In S1tu Investigation 1n Soils and Rocks, British and
Geotechnlcal Society, Institution of C1v1l Engineers, London, pp. 311-313,
1969.
33. U.S. Army Corps of Engineers, Laboratory Soil Testing, Waterways
Experiment Station, Vlcksburg, Mississippi, Publication EM 1110-2-2-1906,
1970.
34. U.S. Environmental Protection Agency, Hazardous Waste Guidelines and
Regulations (proposed), Federal Register, Part IV, Dec. 18, 1978.
35. U.S. Environmental Protection Agency, RCRA Ground Water Monitoring
Technical Enforcement Guidance Document, Draft Final.
9100 - 49
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Date September 1986
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METHOD 9100 (Part)
HYDRAULIC COONDUCTIVITV OF SOIL SAMPLES:
CONSTANT-HEAD TEST WITH CONVENTIONAL PEPMEAMETER
a.s.3
o
Oven-dry ปno
weigh sample
2.5.3
2.5.4
Open
valve A;
stabilize flow;
obtain initial
piezometer
readings
Admit de-airea
water to
permeameter
2.5.4
Allow flow to
reach
eaullibrulm
2.5.31
Place
specimen
In permeameter.
taking care to
avoid
segregat ion
2.5.3
2.5.4 I
Record
quantity of flow.
piezometrlc readings.
and water temperature
over an Interval
of time
Obtain
weight and
dimensions
of specimen
2.5.S
Plot
outflow
ve time:
obtain slope of
linear portion
of curve
2.5.4 Adjust
halght
of tank to
obtain desired
hydraulic
gradient
2.5.51
Calculate
conductivity
using
Equation (a)
0
( stop J
9100 - 50
Revision 0
Date September 1986
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METHOD 9100
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
FALLING-HEAD TEST WITH CONVENTIONAL PERMEAMETEH
CED O
2.5.3
Oven-dry end
weigh sample
2.5.3
2.6.4
o
Slowly
bring water
up to discharge
level of
permeameter
Admit
de-elred water
to permeanieter
2.5.3
2.6.4
2.6.4
Record water
temperature
Raise head of water
In stardplpe above
discharge level of
permeameter
Place
specimen
In permeameter.
taking care
to avoid
segregation
2.E.5
Plot
head ve time;
obtain slope of
linear portion
of curve
2.6.4
Open valve B: Record
height of water In
stardplpe above
discharge level at
times t, and t,
2.5.31
Obtain weight
and dimensions
of specimen
2.6.5
Calculate
conductivity
using
Equation (9)
(
o
9100 - 51
Revision 0
Date September 1986
-------
METHOD 91OO
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
MODIFIED COMPACTION PARAMETER METHOD
2.7.3
o
Air dry
sample:
mix with water
for desired
moisture
content
2.7.3
2.7.4
Flush
water through
sample until It
Is saturated
Compact sample: level
the surface, weigh.
and determine
density: measure
length and density
2.7.3
2.7.4
Record quantity of
outflow VG time:
record pressure at
times out is measured
Assemble
apparatus
2.7.4
2.7.4
Plot cumulative
outflow vs time: stop
when linear protlon
of curve is defined
Place water in
fluid chamber
2.7.5
Calculate
conductivity
using
equation (8)
Q
f Stop J
9100 - 52
Revision 0
Date September 1986
-------
METHOD 9tOO
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
TRIAXIAL CELL METHOD WITH BACK PRESSURE
o
Trim sample
to diameter
of top cap of
trlaxial cell
2.8.4
o
Z. 8. 4
Saturate specimen
by applying chamber
pressure and back
pressure In small
Increments
No
Does
pore
pressure Incr.
immediately -
chamber
pressure
incr.
2.8.4 Maintain
minimum
head loss
corns Istent with
a measureable
flow rate
2.6.4
Open valves 0 and F:
record burette
readings and
temperature as a
function of time
Measure
dimension
nd weigh
of sample:
place specimen
on base
2.6.4
Increase chamber
pressure to attain
desired effective
ancolidation pressure
2.8.41
Secure membrane
over specimen
2.6.4
Determine flow
rate from slope
of curves
2.6.4
Open valves E and F;
record and plot dial
indicator and burette
readings as a
function of time
2.8.4
Assemble trlaxlal
chamber and fill with
fluid: insert filter
paper disks
2.8.5
Calculate
conductivity
using
Equation (8)
0
O
9100 - 53
Revision 0
Date September 1986
-------
METHOD 9100
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
PRESSURE-CHAMBER PARAMETER METHOD
Trim sample
to diameter
of top cap of
trlaxlal cell
o
2.8.41 Measure
'dimension
and weigh
of sample;
place specimen
on base
2.8.4
Secure membrane
over specimen
2.8.4
Assemble trlaxlal
chamber and fill with
fluid: insert filter
paper disks
o
2.9.4 Apply
confining
pressure by
adjusting
leveling held
or compress air
2.9.4
Allow sample to
consolidate
2.9.4
Flush
ample
with water
until no air
bubbles are
observed
2.9.4
Adjust
head of
water to
attain desired
hydraulic
gradient
O
o
2.94.
p
he
in st
as f
of
ecord
ad drop
andpipe
unction
time
Is log vs time
linear for >3
consecutive
readings?
Calculate
conductivity
using
Equation (9)
9100 - 54
Revision 0
Date September 1986
-------
METHOD 9100
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
FIELD METHODS FOR EXTREMELY TIGHT FORMATIONS UNDER CONFINED CONDITIONS
Start
3.4.2.2
Fill
borehole
with water to
prevailing
water level
3.4.2.2 Add a
known
' volume of
water with a
highpressure
pump
3.4.2.2
Shut valve
and monitor
pressure decay
Has pressure
reached 85X of
initial
value?
o
3.4.2.3
tronem
of test
uslr
curve
3.4.2.2
for
in vc
pat
(
3.4.2.3
Condi
transml
by thick
testc
Oetei
mine
Lsetvity
,ed zone
ig type
! method
Correct
changes
ilume of
:ked-of f
:avlty
Deter-
mine
ictivlty
Lseivity
cnesE of
d zone
f Stop J
9100 - 55
Revision 0
Date September 1986
-------
METHOD 9100
HYRAULIC CONDUCTIVITY OF SOIL SAMPLES
FIELD METHODS FOR MODERATELY PERMEABLE MATERIALS UNDER UNCONFINED CONDITIONS
3. 4. a. a
Rapidly
remove a volume
of water from
the well bore
3
4.3.8
Record
watei level
Changes over
time
3.4.3.3
condi
using i
Bouwer e
(<
Calcu-
late
jctlvity
iquatlon
ind Rice
1976)
f Stop }
9100 - 56
Revision p
Date September 1986
-------
METHOD 910C
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
FIELD METHOD FOR MODERATELY PERMEABLE FORMATIONS UNDER CONFINED CONDITIONS
Start
3
.4.1.2
Rapidly
remove a volume
O' water from
the well bore
3
.4.1.2
Record
water-level
changes over
time
Has water
level reached 65X
of Initial
value?
transmlssIvlty
of tested zone
using type
Curve method
Determine
conductivity by
dividing
tranซmlsslvlty by
thickness of
tested zone
9100 - 57
Revision 0
Date September 1986
-------
METHOD 9310
GROSS ALPHA AND GROSS BETA
1.0 SCOPE AND APPLICATION
1.1 This method covers the measurement of gross alpha and gross beta
particle activities in surface and ground waters.
1.2 The method is applicable to the measurement of alpha emitters having
energies above 3.9 mega electron volts (MeV) and beta emitters having maximum
energies above 0.1 MeV.
1.3 The minimum limit of concentration to which this method is
applicable depends on sample size, counting-system characteristics,
background, and counting time.
1.4 Because, in this method for gross alpha and gross beta measurement,
the radioactivity of the sample is not separated from the solids of the
sample, the solids concentration is very much a limiting factor in the
sensitivity of the method for any given water sample. Also, for samples with
very low concentrations of radioactivity, it 1s essential to analyze as large
a sample aliquot as is needed to give reasonable times.
1.5 The largest sample aliquot that should be counted for gross alpha
activity 1s that size aliquot which gives a solids density thickness of
5 mg/cm^ in the counting planchet. For a 2-1n. diameter counting planchet
(20 crn^), an aliquot containing 100 mg of nitrated dissolved solids would be
the maximum aliquot size for that sample which should be evaporated and
counted for gross alpha activity.
1.6 When the concentration of total solids (TS) is known for a given
water sample and the alpha background and the counting efficiency of a given
counting system are known, the counting time that 1s needed to meet the
required sensitivity (3 pCi/L) can be determined by equations given in
Appendix C.
1.7 For the counting of gross beta activity in a water sample, the TS is
not as limiting as for gross alpha activity because beta particles are not
stopped in solids as easily as are alpha particles. Very often a single
sample aliquot is evaporated and counted for both gross alpha and gross beta
activity. In that case, the sample aliquot size would be dictated by the
solids limitations for alpha particles. For water samples that are to be
counted for gross beta activity, equations in Appendix C can also be used to
determine the necessary counting time to meet a sensitivity for gross beta
activity (4 pC1/L).
1.8 Radionuclides that are volatile under the sample preparation
conditions of this method will not be measured. In some areas of the country
the nitrated water solids (sample evaporated with nitric acid present) will
9310 - 1
Revision 0
Date September 1986
-------
not remain at a constant weight after being dried at 105*C for 2 hr and then
exposed to the atmosphere before and during counting. Other radioactivities
(such as some chemical forms of radloiodlne) may also be lost during the
sample evaporation and drying at 105*C. Those types of water samples need to
be heated to a dull red heat for a few minutes to convert the salts to oxides.
Sample weights are then usually sufficiently stable to give consistent
counting rates, and a correct counting efficiency can then be assigned. Some
radioactivities, such as the cesium radioisotopes, may be lost when samples
are heated to a dull red color. Such losses are limitations of the test
method.
1.9 This method provides a rapid screening measurement to indicate
whether specific analyses are required. When the gross alpha particle
activity exceeds 5 pCi/L, the same or an equivalent sample shall be analyzed
for alpha-emitting radium isotopes (Method 9315) or an alternative measurement
of radium-226 alpha emission (Standard Methods for the Examination of Water
and Wastewater, 15th edition, Method 705 or 706, respectively). Gross beta
particle emissions exceeding 15 pC1/L in a sample shall be analyzed for
strontium-89 and cesium-134 (Standard Methods for the Examination of Water and
Wastewater, 15th edition, Methods 704 and 709, respectively). If gross beta
activity exceeds 50 pC1/L, the identity of the major radioactive constituents
must be evaluated and the appropriate organ and total body doses determined.
2.0 SUMMARY OF METHOD
2.1 An aliquot of a preserved water sample is evaporated to a small
volume and transferred quantitatively to a tared 2-1n. stainless steel
counting planchet. The sample residue is dried to constant weight, rewelghed
to determine dry residue weight, and then counted for alpha and/or beta
radioactivity.
2.2 Counting efficiencies for both alpha and beta particle activities
are selected according to the amount of sample sol Ids from counting efficiency
vs. sample sol Ids standard curves.
3.0 INTERFERENCES
3.1 Moisture absorbed by the sample residue is an interference because
it obstructs counting and self-absorption characteristics. If a sample is
counted in an internal proportional counter, static charge on the sample
residue can cause erratic counting, thereby preventing an accurate count.
3.2 Nonunlformity of the sample residue in counting planchet Interferes
with the accuracy and precision of the method.
3.3 Sample density on the planchet area should be not more than 10
mg/cm2 for gross alpha and not more than 20 mg/cm2 for gross beta.
9310 - 2
Revision 0
Date September 1986
-------
3.4 When counting alpha and beta particle activity by a gas-flow
proportional counting system, counting at the alpha plateau discriminates
against beta particle activity, whereas counting at the beta plateau is
sensitive to alpha particle activity present in the sample. This latter
effect should be determined and compensated for during the calibration of the
specific instrument being used.
4.0 APPARATUS AND MATERIALS
4.1 Gas-flow proportional counting system, or
4.2 Scintillation detection system, or
4.3 Stainless steel counting planchets.
4.4 Electric hot plate.
4.5 Drying oven.
4.6 Drying lamp.
4.7 Glass desiccator.
4.8 Glassware.
4.9 Analytical balance.
5.0 REAGENTS
5.1 All chemicals should be of "reagent-grade" or equivalent whenever
they are commercially available.
5.2 Distilled or deionized water (Type II) having a resistance value
between 0.5 and 2.0 megaohms (2.0 to 0.5 mhos)/cm at 25ฐC.
5.3 Nitric acid. 1 N: Mix 6.2 ml 16 N HN03 (cone.) with deionized or
distilled water and dilute to 100 ml.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected in a manner which addresses the
considerations discussed in Chapter Nine of this manual.
6.2 It is recommended that samples be preserved at the time of collec-
tion by adding enough 1 N HN03 to the sample to bring it to pH 2 (15 mL 1 N
HN03 per liter of sample is usually sufficient). If samples are to be
collected without preservation, they should be brought to the laboratory
within 5 days and then preserved and held in the original "container for a
minimum of 16 hr before analysis or transfer of the sample.
9310 - 3
Revision 0
Date September 1986
-------
6.3 The container choice should be plastic rather than glass to prevent
loss due to breakage during transportation and handling.
7.0 PROCEDURE
7.1 Calibration;
7.1.1 For absolute gross alpha and gross beta measurement, the
detectors must be calibrated to obtain the ratio of count rate to
disintegration rate. Amer1c1um-24l (used for alpha activity 1n the
collaborative test of this method) has higher alpha particle energy and
rad1um-226 radlonuclldes but 1s close to the energy of the alpha
particles emitted by naturally occurring thorlum-228 and rad1um-224.
Standards should be prepared In the geometry and weight ranges to be
encountered 1n these gross analyses. It 1s, therefore, the prescribed
radlonucllde for gross alpha calibration. NBS or NBS-traceable
amerldum-241 1s available from Standard Reference Materials Catalog, NBS
Special Publications 260, U.S. Department of Commerce (1976) and from
Quality Assurance Branch, EMSL-LV, P.O. Box 15027, Las Vegas, Nevada
89114.
7.1.2 Stront1um-90 and ceslum-137 have both been used quite
extensively as standards for gross beta activity. Standard solutions of
each of these radlonuclldes are readily available. Cesium 1s volatile at
elevated temperatures (above 450*C). Some water supplies have dissolved
sol Ids (salts) that, when converted to nitrate salts, are quite
hygroscopic and need to be converted to oxides by heating to red heat to
obtain sample allquots that are weight-stable. Sample weight stability
1s essential to gross alpha and gross beta measurements to ensure the
accuracy of the self-absorption counting efficiency factor to be used for
the samples. Stront1um-90 In equilibrium with its daughter yttr1um-90 1s
the prescribed radionucllde for gross beta calibrations.
7.1.3 For each counting instrument to be used, the analyst should
prepare separate alpha and beta particle self-absorption graphs showing
water sample residue weight (mg) vs. the efficiency factor (cpm/dpm),
using standard alpha and beta emitter solutions and tap water. For the
alpha graph standard, alpha activity is added to varying sizes of
allquots of tap water such that the aliquot residue weight is varied
between 0 and 100 mg (for a 2-in. counting planchet). A similar graph 1s
prepared with standard beta activity and tap-water allquots, varying the
residue weight between 0 and 300 mg (for a 2-in. planchet). If it 1s
planned to use water-sample aliquot volumes that always contain 100 mg of
dried water solids, then only the efficiency factor for that residue
weight needs to be established.
7.1.4 Tap water allquots, with added americium-241 or stront1um-90
standard, should be acidified with a few ml 16 N HN03, evaporated to a
small volume in a beaker on a hot plate, transferred quantitatively 1n 5-
mL portions or less to a tared counting planchet, evaporated to dryness,
and finally dried at 105*C for 1 hr (or flamed to a red heat if dried
9310 - 4
Revision 0
Date September 1986
-------
solids appear to be noticeably hygroscopic). Weight-stable aliquot
residues should then be alpha and/or beta counted until at least 10,000
total counts have been accumulated. A single set of reference standards
prepared 1n this way can be used for each counting Instrument for
separate graph preparations and can be stored for reverlflcation whenever
needed.
7.2 Transfer to a beaker an aliquot of water sample of a volume that
contains no more than 100 mg (for alpha only or alpha and beta determination)
or 200 mg (for beta only determination) of total water solids. Evaporate the
aliquot to near dryness on a hot plate. If water samples are known or
suspected to contain chloride salts, those chloride salts should be converted
to nitrate salts before the sample residue is transferred to a stainless steel
planchet (chlorides will attack stainless steel and ' Increase the sample
solids, and no correction can be made for those added solids). Chloride salts
can be converted to nitrate salts by adding 5-mL portions of 16 N HN03 to the
sample residue and evaporating to near dryness. (Two treatments are usually
sufficient.) Add 10 ml 1 N HN03 to the beaker and swirl to dissolve the
residue. Quantitatively transfer the aliquot concentrate 1n small portions
(not more than 5 ml at a time) to a tared planchet, evaporating each portion
to dryness.
7.3 Dry the sample residue in a drying oven at 105*C for at least 1 hr,
cool in a desiccator, weigh, and count. Store the sample residue in a
desiccator until ready for counting.
7.4 Some types of water-dissolved solids, when converted to nitrate
salts, are quite hygroscopic even after being dried at 105*C for 1 hr. When
such hygroscopic salts are present with samples that are put Into an automatic
counting system, those samples gain weight while they are waiting to be
counted, and Inaccurate counting data result. When there is evidence of
hygroscopic salts 1n sample counting planchets, 1t 1s recommended that they be
flamed to a dull red heat with a Meeker burner for a few minutes to convert
the nitrate salts to oxides before weighing and counting. (It 1s possible to
have a loss of cesium during the flaming of the samples.)
7.5 Count for alpha and beta activity at their respective voltage
plateaus. If the sample is to be recounted for reverification, store 1t in a
desiccator.
NOTE: As long as counting chambers are capable of handling the same size
planchet, alpha and beta activities can be determined at their
respective voltage plateaus in the designated counting
Instruments. Keep the planchet in the desiccator until ready to
count because vapors from moist residue can damage detector and
window and can cause erratic measurements. If the gas-flow
internal proportional counter does not discriminate for the higher
energy alpha pulses at the beta plateau, the alpha activity must
be subtracted from the beta plus alpha activity. This is
particularly Important for samples with high alpha activity.
9310 - 5
Revision 0
Date September 1986
-------
7.6 Calculations;
7.6.1 Calculate the alpha radioactivity by the following equation:
Alpha (pd/liter) = jj^
where:
A = net alpha count rate (gross alpha count rate minus the
background count rate) at the alpha voltage plateau;
C = alpha efficiency factor, read from the graph (Paragraph
7.1.3) of efficiency vs. mg of water sol Ids per cm2 of
planchet area, cpm/dpm);
V = volume of sample aliquot (ml); and
2.22 = conversion factor from dpm/pC1.
7.6.2 Calculate the beta radioactivity by the following equations:
7.6.2.1 If there are no significant alpha counts when the
sample 1s counted at the alpha voltage plateau, the beta activity
can be determined from the following equation:
Beta (pC1/Hter) =
where:
B = net beta count rate (gross alpha count rate minus the
background count rate at the beta voltage plateau),
D = beta efficiency factor, read from the graph (Paragraph
7.1.3) of efficiency vs. mg of water solids per cm2 of
planchet area, (cpm/dpm).
V = volume of sample aliquot (ml).
2.22 = conversion factor from dpm/pd.
7.6.3 When counting beta radioactivity 1n the presence of alpha
radioactivity by gas-flow proportional counting systems (at the beta
plateau), alpha particles are also counted. Because alpha particles are
more readily absorbed by increasing sample thickness than beta particles,
the alpha/beta count ratios vary with Increasing sample thickness.
Therefore, 1t is necessary to prepare a calibration curve by counting
standards containing amer1cium-24l with increasing thickness of solids on
9310 - 6
Revision
Date September 1986
-------
the alpha plateau and then on the beta plateau, plotting the ratios of
the two counts vs. density thickness. The alpha amplification factor (E)
from that curve 1s used to correct the amplified alpha count on the beta
plateau. When significant alpha activity is indicated by the sample
count at the alpha voltage plateau, the beta activity of the sample can
be determined by counting the sample at the beta voltage plateau and
calculating the activity from the following equation:
Beta (pel/liter)
-------
9.0 METHOD PERFORMANCE
9.1 In a collaborative study of two sets of paired water samples
containing known additions of radlonuclldes, 15 laboratories determined the
gross alpha activity and 16 analyzed gross beta activity. The samples
contained simulated water minerals of approximately 350 mg fixed sol1ds/L.
The alpha results of one laboratory were rejected as outliers.
The average recoveries of added gross alpha activity were 86, 87, 84, and
82%. The precision (random error) at the 95% confidence level was 20 and 24%
for the two sets of paired samples. The method was biased low, but not
seriously.
The average recoveries of added gross beta activity were 99, 100, 100,
and 100%. The precision (random error) at the 95% confidence level was 12 and
18% for the two sets of paired samples. The method showed no bias.
10.0 REFERENCES
10.1 None required.
9310 - 8
Revision
Date September 1986
-------
METHOD 9310
GROSS ALPHA AND GROSS BETA
7. 1
Calibrate using
Am-241 for gross
lone activity: Sr-go
or Cs-137 for gross
bata activity
7.1.3
Prepare
separate
alpha and
beta particle
elfabsorption
graphs
7.1.4
Does water
ample contain
chloride
alts?
o
7.6. 1
Calculate alpha
radioactivity
Add
HNOj:
swirl: transfer
each aliquot to
tard planchet;
avaporate
Acidify
tap water
aliguots with
HNOi; evaporate:
transfer to
planchet
7.1.4
7.3
7.6.Z
^-M>MซJ
Calculate bete
radioactivity
Dry ample
residue: weigh
and count
f Stop j
Evaporate
and dry:
count alpha.
beta residue
for reference
tandard
7.2
i Transfer
aliquot of
water sample
to beaker;
vaporate
Flame to a dull
red neat
9310 - 9
Revision 0
Date September 1986
-------
METHOD 9315
ALPHA-EMITTING RADIUM ISOTOPES
1.0 SCOPE AND APPLICATION
1.1 This method covers the measurement of the total soluble alpha-
emitting radioisotopes of radium, namely radium-223, radium-224, and radium-
226, in surface and ground waters.
1.2 Although the method does not always give an accurate measurement of
the radium-226 content of the sample (when other radium alpha emitters are
present), it can be used to screen samples. When the total radium alpha
activity of a drinking water sample is greater than 5 pC1/L, then the radium-
226 analysis 1s required. If the level of rad1um-226 exceeds 3 pC1/L, the
sample must also be measured for rad1um-228 (Method 9320).
1.3 Because this method provides for the separation of radium from other
water-dissolved sol Ids in the sample, the sensitivity of the method is a
function of sample size, reagent and Instrument background, counting
efficiency, and counting time.
1.4 Absolute measurement can be made by calibrating the alpha detector
with standard radium-226 in the geometry obtained with the final precipitate.
2.0 SUMMARY OF METHOD
2.1 The radium 1n the surface water or ground water sample 1s collected
by coprecipitatlon with barium and lead sulfate and purified by repredpi-
tation from EDTA solution. Citric acid is added to the water sample to assure
that complete Interchange occurs before the first precipitation step. The
final BaS04 precipitate, which Includes radium-226, radium-224, and radium-
223, 1s alpha counted to determine the total disintegration rate of the radium
isotopes.
2.2 The radium activities are counted 1n an alpha counter where
efficiency for determining radium-226 has been calibrated with a standard of
known radium-226 activity. By making a correction for the Ingrowth of alpha
activity in radium-226 for the elapsed time after separation, one can
determine radium activity 1n the sample. Because some daughter Ingrowth can
occur before the separated radium 1s counted, it 1s necessary to make activity
corrections for the count rate. A table of ingrowth factors for various times
after radium separation is provided in Paragraph 7.14.
t
3.0 INTERFERENCES
3.1 Inasmuch as the radlochemical yield of the radium activity 1s based
on the chemical yield of the BaS04 precipitate, the presence of significant
natural barium in the sample will result 1n a falsely high chemical yield.
9315 - 1
Revision 0
Date September 1986
-------
3.2 Radium Isotopes are separated from other alpha-emitting
radlonuclldes by this method.
3.3 The alpha count of the separated radium must be corrected for Its
partially Ingrown alpha-emitting daughters.
4.0 APPARATUS AND MATERIALS
4.1 Alpha scintillation or a gas-flow proportional alpha particle
counting system with low background ซ1 cpm).
4.2 Stainless steel counting planchets.
4.3 Electric hot plate.
4.4 Drying oven and/or drying lamp.
4.5 Glass desiccator.
4.6 Analytical balance.
4.7 Centrifuge.
4.8 Glassware.
5.0 REAGENTS
5.1 Distilled or delonlzed water (Type II).
5.2 Acetic acid. 17.4 N: glacial CHaCOOH (cone.), sp. gr. 1.05, 99.8%.
5.3 Ammonium sulfate, 200 mg/mL: Dissolve 20 g (NH^SCty 1n a minimum
of water and dilute to 100 ml.
5.4 Barium carrier, 16 mg/mL, standardized:
5.4.1 Dissolve 2.846 g BaCl2-2H20 1n water, add 0.5 mL 16 N HN03,
and dilute to 100 mL with water.
5.4.2 To perform standardization (1n triplicate): Pipette 2.0 mL
carrier solution Into a centrifuge tube containing 15 mL water. Add 1 mL
18 N HgSOA with stirring and digest precipitate 1n a water bath for 10
m1n. Cool, centrifuge, and decant the supernatant. Wash precipitate
with 15 mL water. Transfer the precipitate to a tared stainless steel
planchet with a'minimum of water. Dry under Infrared lamp, store 1n
desiccator, and weigh as BaSCty.
5.5 Citric acid. 1 M: Dissolve 19.2 g WsOffyO In water and dilute to
100 mL.
9315 - 2
Revision
Date September 1986
-------
5.6 EDTA reagent, basic (0.25 M): Dissolve 20 g NaOH 1n 750 mL water,
heat and slowly add 93 g d1sodium ethylened1n1tr1loacetate d1hydrate
(Na2CioHu08N2*2H20). Heat and stir until dissolved; filter through coarse
filter paper and dilute to 1 liter.
5.7 Lead carrier, 15 mg/mL: Dissolve 2.397 g Pb(N03)2 1n water, add 0.5
mL 16 N HN03, and dilute to 100 mL with water.
5.8 Sodium hydroxide, 6 N: Dissolve 24 g NaOH 1n 80 mL water and dilute
to 100 mL.
5.9 Sulfurlc add. 18 N: Cautiously mix 1 volume 36 N H2S04 (concen-
trated) with 1 volume of water.
5.10 Sulfurlc add. 0.1 N: Mix 1 volume 18 N ^04 with 179 volumes
of water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected 1n a manner which addresses the
considerations discussed 1n Chapter Nine of this manual.
6.2 It 1s recommended that samples be preserved at the time of
collection by adding enough 1 N HN03 to the sample to bring It to pH 2 (15 mL
1 N HN03 per liter of sample 1s usually sufficient). If samples are to be
collected without preservation, they should be brought to the laboratory
within 5 days and then preserved and held 1n the original container for a
minimum of 16 hr before analysis or transfer of the sample.
6.3 The container choice should be plastic rather than glass to prevent
loss due to breakage during transportation and handling.
7.0 PROCEDURE
7.1 Calibration;
7.1.1 The counting efficiency for radium alpha particles with
barium sulfate carrier present must be determined using a standard
(known) radium alpha activity and 32 mg of barium carrier as 6aS04 (same
carrier amount used 1n samples). This 1s done with spiked distilled
water samples, and the procedure for regular samples 1s followed. Note
the time of the Ra-BaS04 precipitation.
7.1.2 The radium alpha counting efficiency, E, 1s calculated as
fol1ows;
E (cpm/dpm) = ^-j
9315 - 3
Revision
Date September 1986
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where:
C = sample net cpm (gross counts minus background divided
by the counting time in minutes).
A = dpm of rad1um-226 added to sample.
I = Ingrowth factor for the elapsed time from Ra-BaS04,
precipitation to midpoint of counting time.
7.2 To a 1,000-mL surface water or ground water sample, add 5 ml 1 M
1 mL lead carrier, and 2.0 ml barium carrier, and heat to boiling.
7.3 Cautiously, with vigorous stirring, add 20 ml 18 N ^04. Digest 5
to 10 m1n and let the mixed BaS04-PbS04 precipitate settle overnight. Decant
and discard supernate.
7.4 Transfer the precipitate to a centrifuge tube with a minimum amount
of 0.1 N H2S04. Centrifuge and discard supernate.
7.5 Wash the precipitate twice with 0.1 N ^$04. Centrifuge and discard
washes.
7.6 Dissolve the precipitate by adding 15 mL basic EDTA reagent; heat in
a hot-water bath and add a few drops 6 N NaOH until solution Is complete.
7.7 Add 1 ml (NH4)2S04 (200 mg/mL) and stir thoroughly. Add 17.4 N
dropwlse until precipitation begins and then add 2 ml extra. Digest 5
to 10 mln.
7.8 Centrifuge, discard the supernate, and record time.
NOTE: At this point, the separation of the BaSCty 1s complete, and the
Ingrowth of radon (and daughters) commences.
7.9 Wash the BaS04 precipitate with 15 ml water, centrifuge, and discard
wash.
7.10 Transfer the precipitate to a tared stainless steel planchet with a
minimum of water and dry under Infrared lamps.
NOTE: Drying should be rapid, but not too vigorous, to minimize any loss
of radon-222 that has already grown Into the precipitate.
7.11 Cool, weigh, and store In desiccator.
7.12 Count 1n a gas-flow Internal proportional counter or an alpha
scintillation counter to determine the alpha activity.
9315 - 4
Revision
Date September 1986
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7.13 Calculation;
7.13.1 Calculate the rad1um-226 concentration, D (which would
Include any rad1um-224 and rad1um-223 that 1s present), 1n plcocurles per
liter as follows:
D
2.22 xExVxRxI
where:
C = net count rate, cpm.
E = counter efficiency, for rad1um-226 1n BaS04 predetermined
for this procedure (see Paragraph 7.1.2).
V = liters of sample used.
R - fractional chemical yield.
I = Ingrowth correction factor (see Paragraph 7.14).
2.22 = conversion factor from dpm/pC1.
7.14 It 1s not always possible to count the BaSCty precipitate
Immediately after separation; therefore, corrections must be made for the
Ingrowth of the rad1um-226 daughters between the time of separation and
counting, according to the following table:
Hours from separation Ingrowth correction
to counting factor
0 1.00
1 1.02
2 1.04
3 1.06
4 1.08
5 1.10
6 1.12
24 1.49
48 1.91
72 2.25
96 2.54
120 2.78
144 2.99
192 3.29
240 3.51
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Revision
Date September 1986
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8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Employ a minimum of one blank per sample batch to determine 1f
contamination or any memory effects are occurring.
8.3 Run one duplicate sample for every 10 samples. A duplicate sample
1s a sample brought through the whole sample-preparation process.
8.4 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment 1s operating properly.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
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Revision
Date September 1986
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METHOD 9315
ALPHA-EMITTING RADIUM ISOTOPES
7. 1. J
Calibrate
detectors for
radium (lob*
measurement
7.Z
7.6
Dissolve
precipitate
In EOTA; heat:
dd NปOH
Add C,H.cv Hto.
and barium carrie
to water sample
heat to Dolling
7.3
7.7
Cool. weigh.
and ctore in
aaalccator
Add CNH4>zS04:
tlr; aao
CHjCOOM; digact
Add HiSOซ whil*
stirring: digest:
precipitate:
discard supernste
7.12
Uae counter to
determine alpha
activity
7.8
Centrifuge:
discard
suparnate:
record time
Centrifuge:
discard
supernate
7.13.1
Calculate
raajium-226
concentration
7.9
I Mash
BSS04
precipitate:
centrifuge:
dlacnard wash
Maoh
precipitate:
centrifuge:
discard Mashes
7.14
Correct
for ingrowth
of redium-226
daughtera
7.101
Transfer
precipitate
to planchat:
dry
f Start 1
9315 - 7
Revision o
Date September 1986
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PART II CHARACTERISTICS
Revision 0
Date September 1986
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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 งง 173.300 and
173.151).
Characteristics Of Iqnitabilitv 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 < 60ฐC (140ฐF), 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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September 1994
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lonitable Compressed Gas
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 (70ฐF) or, regardless of the pressure at
. 21ฐC (70eF), having an absolute pressure exceeding 104 psi at 54ฐC
(130ฐF), or any liquid flammable material having a vapor pressure
exceeding 40 psi absolute at 38ฐC (100ฐF), as determined by ASTM
Test D-323.
2. Ignitable 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.
Oxidizer (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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Septenter 1994
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7.2 CORROSIVITY
7.2.1 Introduction
The corrosivity 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 260.21.
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 55ฐC (130ฐF), 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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September 1994
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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 B 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.
SEVEN - 4 Revision 2
Septenterl994
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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
Septenter 1994
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4.5 Flexible tubing - For connection from nitrogen supply to
apparatus.
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 H2SO. to
reagent water and dilute to 1 L. WUndraw 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 AgN03. 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 40ฐC.
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
SEVEN - 6 Revision 2
Septennber 1994
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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 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. 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 (mg/kg) = R x S
SEVEN - 7 Revision 2
September 1994
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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.
SEVEN - 8 Revision 2
September 1994
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FIGURE 1.
APPARATUS TO DETERMINE HYDROGEN CYANIDE RELEASED FROM WASTES
Flowmeter
N, In
Reaction Flask
Gas Scrubber
Waste Sample
SEVEN - 9
Revision 2
September 1994
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7.3.4 Interim Guidance For 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 upon 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 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.
4.5 Flexible tubing - For connection from nitrogen supply to
apparatus.
SEVEN - 10 Revision 2
September 1994
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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 H2S04.
5.4 Sulfide reference solution - Dissolve 4.02 g of Na2S ShU) in
1.0 L of reagent water. This solution contains 570 mg/L hydrogen sulfide.
Dilute this stock solution to cover the analytical range required (100-570
mg/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
September 1994
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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 HJS in scrubber (mg/L)
(This is obtained from Method 9030.)
L = Volume of solution in scrubber (L)
W = Weight of waste used (kg)
S = Time of experiment (sec.) = Time N2 stopped - Time N2 started
X L
R = specific rate of release (mg/kg/sec.)
W S
Total releasable H?S (mg/kg) = R x S
SEVEN - 12 Revision 2
September 1994
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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
September 1994
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FIGURE 2.
APPARATUS TO DETERMINE HYDROGEN SULFIDE RELEASED FROM WASTES
Stirrer
Flowmeter
N2ln
Reaction Rask
Gas Scrubber
Waste Sample
SEVEN - 14
Revision 2
Septenter 1994
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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 ฑ 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
ง268.41 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 ง261.24, 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 ง268.41, the treatment standard for that
waste has not been met, and further treatment is necessary prior to land
disposal.
7.4.2 Summary of Procedure
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 /im 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.
2. Particle Size Reduction
Prior to extraction, the solid material must pass through a 9.5-mm
(0.375-in.) standard sieve, have a surface area per gram of material equal to
or greater than 3.1 cm , 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
-------
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 ง268.41 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 ง268.41 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.
SEVEN - 16 Revision 2
Septwter 1994
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TABLE 7-1.
MAXIMUM CONCENTRATION OF CONTAMINANTS FOR TOXICITY CHARACTERISTIC
Contaminant
Arsenic
Barium
Benzene
Cadmium
Carbon tetrachloride
Chlordane
Chlorobenzene
Chloroform
Chromium
o-Cresol
m-Cresol
p-Cresol
Cresol
2,4-D
1,4-Dichlorobenzene
1,2-Dichloroethane
1,1-Dichloroethylene
2,4-Dinitrotoluene
Endrin
Heptachlor (and its hydroxide)
Hexachlorobenzene
Hexachloro-l,3-butadiene
Hexachloroethane
Lead
Lindane
Mercury
Methoxychlor
Methyl ethyl ketone
Nitrobenzene
Pentachlorophenol
Pyridine
Selenium
Silver
Tetrachl oroethyl ene
Toxaphene
SEVEN - 17
Regulatory Level
(ซg/L)
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
September 1994
-------
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
llf o-, m-, and p-cresol concentrations cannot be differentiated, the total
cresol (0026) 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
September 1994
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FIGURE 3.
TOXICITY CHARACTERISTIC LEACHATE PROCEDURE FLOWCHART
Separata
liquids fro*
olid. Kith 0.6
- 0.8 un glau
fibar filtar
Saparata
liquid* from
solid* ซith 0.6
- 0.8 ua gUซa
fibar filtar
Solid
Diicatd
olida
Extract /
appropriata fluid
1) Bottla aitractor
for non-volatilai
2) ZHE daviea for
volatila*
Raduca
particla tiza
to <9 5 mm
SEVEN - 19
Revision 2
Septaiter 1994
-------
FIGURE 3
(continued)
Diicard
olid*
Solid
Separate
tract from
olidt "/ 0.6
0.8 un glaปป
fiber filter
Meaaure amount of
liquid and analyze
(ma thematiea11y
combine retull /
reiult of extract
analytn)
I
liquid
Liquid /compatible "V No
ith the
tract?
Combine
extract /
liquid phase
of "atte
SEVEN - 20
Revision 2
Septaiter 1994
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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
September 1994
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8.1 Ignitability
The following methods are found in Section 8.1:
Method 1010: Pensky-Martens Closed-Cup Method for Determining
Ignitability
Method 1020A: Setaflash Closed-Cup Method for Determining
Ignitability
EIGHT - 2 Revision 1
September 1994
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METHOD 1010
PENSKY-MARTENS CLOSED-CUP METHOD FOR DETERMINING IGNITABILITY
1.0 SCOPE AND APPLICATION
1.1 Method 1010 uses the Pensky-Martens closed-cup tester to determine
the flash point of liquids Including those that tend to form a surface film
under test conditions. Liquids containing non-filterable, suspended solids
shall also be tested using this method.
2.0 SUMMARY OF METHOD
2.1 The sample 1s heated at a slow, constant rate with continual
stirring. A small flame is directed into the cup at regular Intervals with
simultaneous Interruption of stirring. The flash point 1s the lowest
temperature at which application of the test flame Ignites the vapor above the
sample.
For further information on how to conduct a test by this method, see
Reference 1 below.
3.0 METHOD PERFORMANCE
3.1 The Pensky-Martens and Setaflash Closed Testers were evaluated using
five industrial waste mixtures and p-xylene. The results of this study are
shown below in *F along with other data.
Pensky-
Sample Martens Setaflash
I2 143.7 + 1.5 139.3 + 2.1
22 144.7 + 4.5 129.7 + 0.6
32 93.7 + 1.5 97.7 + 1.2
42 198.0 + 4.0 185.3 + 0.6
52 119.3 + 3.1 122.7 + 2.5
p-xylene2 81.3 + 1.1 79.3 + 0.6
p-xylene3 77.7 + 0.5a
Tanker oil 125, 135
Tanker oil 180, 180
Tanker oil 110, 110
DIBK/xylene 102 + 4b 107
^75/25 v/v analyzed by four laboratories.
a!2 determinations over five-day period.
1010 - 1
Revision
Date September 1986
-------
4.0 REFERENCES
1. D 93-80, Test Methods for Flash Point by Pensky-Martens Closed Tester,
American Society for Testing and Materials, 1916 Race Street, Philadelphia, PA
19103, 04.09, 1986.
2. Umana, M., Gutknecht, W.f Salmons, C.t et al., Evaluation of Ignitability
Methods (Liquids), EPA/600/S4-85/053, 1985.
3. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
1010 - 2
Revision
Date September 1986
-------
METHOD 1020A
SETAFLASH CLOSED-CUP METHOD FOR DETERMINING IGNITABILITY
1.0 SCOPE AND APPLICATION
1.1 Method 1020 makes use of the Setaflash Closed Tester to determine
the flash point of liquids that have flash points between 0ฐ and 110'C (32ฐ and
230ฐF) and viscosities lower than 150 stokes at 25ฐC (77ฐF).
1.2 The procedure may be used to determine whether a material will or
will not flash at a specified temperature or to determine the finite temperature
at which a material will flash.
1.3 Liquids that tend to form surface films under test conditions or
those that contain non-filterable suspended solids shall be tested for
ignitability using Method 1010 (Pensky-Martens Closed-Cup).
2.0 SUMMARY OF METHOD
2.1 By means of a syringe, 2-mL of sample is introduced through a leak-
proof entry port into the tightly closed Setaflash Tester or directly into the
cup which has been brought to within 3ฐC (5ฐF) below the expected flash point.
2.2 As a flash/no-flash test, the expected flash-point temperature may
be a specification (e.g., 60ฐC). For specification testing, the temperature of
the apparatus is raised to the precise temperature of the specification flash
point by slight adjustment of the temperature dial. After 1 minute, a test flame
is applied inside the cup and note is taken as to whether the test sample flashes
or not. If a repeat test is necessary, a fresh sample should be used.
2.3 For a finite flash management, the temperature is sequentially
increased through the anticipated range, the test flame being applied at 5ฐC
(9"F) intervals until a flash is observed. A repeat determination is then made
using a fresh sample, starting the test at the temperature of the last interval
before the flash point of the material and making tests at increasing 0.5ฐC (1ฐF)
intervals.
For further information on how to conduct a test with this method, see
Reference 1 below.
3.0 METHOD PERFORMANCE
See Method 1010.
4.0 REFERENCES
1. D-3278-78, Test Method for Flash Point of Liquids by Setaflash Closed
Tester, American Society for Testing and Materials, 1916 Race Street,
Philadelphia, PA 19103.
2. Umana, M., Gutknecht, W., Salmons, C., et al., Evaluation of Ignitability
Methods (Liquids), EPA/600/S4-85/053, 1985.
1020A - 1 Revision 1
July 1992
-------
3. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
1020A - 2 Revision 1
July 1992
-------
8.2 Corrosivity
The following method is found in Section 8.2:
Method 1110: Corrosivity Toward Steel
EIGHT - 3 Revision 1
September 1994
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METHOD 1110
CORROSIVITY TOWARD STEEL
1.0 SCOPE AND APPLICATION
1.1 Method 1110 is used to measure
aqueous and nonaqueous liquid wastes.
the corroslvlty toward steel of both
2.0 SUMMARY OF METHOD
2.1 This test exposes coupons of SAE Type 1020 steel to the liquid waste
to be evaluated and, by measuring the degree to which the coupon has been
dissolved, determines the corroslvlty of the waste.
3.0 INTERFERENCES
3.1 In laboratory tests, such as
coupons 1s usually reproducible to within
corrosion rates may occasionally occur
surfaces become passlvated. Therefore,
corrosion rate should be made.
this one, corrosion of duplicate
10%. However, large differences 1n
under conditions where the metal
at least duplicate determinations of
4.0 APPARATUS AND MATERIALS
4.1 An apparatus should be used, consisting of a kettle or flask of
suitable size (usually 500 to 5,000 mL), a reflux condenser, a thermowell and
temperature regulating device, a heating device (mantle, hot plate, or bath),
and a specimen support system. A typical resin flask set up for this type of
test is shown in Figure 1.
4.2 The supporting device and container shall be constructed of
materials that are not affected by, or cause contamination of, the waste under
test.
4.3 The method of supporting the coupons will vary with the apparatus
used for conducting the test, but it should be designed to Insulate the
coupons from each other physically and electrically and to Insulate the
coupons from any metallic container or other device used 1n the test. Some
common support materials include glass, fluorocarbon, or coated metal.
4.4 The shape and form of the
with the waste.
coupon support should ensure free contact
1110 - 1
Revision 0
Date September 1986
-------
Jl
Figure 1. Typical resin flask that can be used as a versatile and
convenient apparatus to conduct simple immersion tests. Configuration of the
flask top is such that more sophisticated apparatus can be added as required
by the specific test being conducted. A = thermowell, B = resin flask, C =
specimens hung on supporting device, D = heating mantle, E = liquid interface,
F = opening in flask for additional apparatus that may be required, and G =
reflux condenser.
1110 - 2
Revision 0
Date September 1986
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4.5 A circular specimen of SAE 1020 steel of about 3.75 cm (1.5 1n.)
diameter is a convenient shape for a coupon. With a thickness of
approximately 0.32 cm (0.125 in.) and a 0.80-cm (0.4-1n.)-d1ameter hole for
mounting, these specimens will readily pass through a 45/50 ground-glass joint
of a distillation kettle. The total surface area of a circular specimen is
given by the following equation:
A = 3.14/2(D2-d2) + (t)(3.14)(D) + (t)(3.14)(d)
where:
t = thickness.
D = diameter of the specimen.
d = diameter of the mounting hole.
If the hole is completely covered by the mounting support, the last term in
the equation, (t)(3.14)(d), is omitted.
4.5.1 All coupons should be measured carefully to permit accurate
calculation of the exposed areas. An area calculation accurate to +1% 1s
usually adequate.
4.5.2 More uniform results may be expected 1f a substantial layer
of metal is removed from the coupons prior to testing the corrosivlty of
the waste. This can be accomplished by chemical treatment (pickling), by
electrolytic removal, or by grinding with a coarse abrasive. At least
0.254 mm (0.0001 in.) or 2-3 mg/cm2 should be removed. Final surface
treatment should include finishing with #120 abrasive paper or cloth.
Final cleaning consists of scrubbing with bleach-free scouring powder,
followed by rinsing in distilled water and then in acetone or methanol,
and finally by air-drying. After final cleaning, the coupon should be
stored in a desiccator until used.
4.5.3 The minimum ratio of volume of waste to area of the metal
coupon to be used in this test 1s 40 ml/cm2.
5.0 REAGENTS
5.1 Sodium hydroxide (NaOH), (20%): Dissolves 200 g NaOH 1n 800 ml Type
II water and mix well.
5.2 Z1nc dust.
5.3 Hydrochloric add (HC1): Concentrated.
5.4 Stannous chloride (SnCl2).
5.5 Antimony chloride
1110 - 3
Revision
Date September 1986
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6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples should be collected using a sampling plan that address
the considerations discussed in Chapter Nine of this manual.
7.0 PROCEDURE
7.1 Assemble the test apparatus as described 1n Paragraph 4.0, above.
7.2 Fill the container with the appropriate amount of waste.
7.3 Begin agitation at a rate sufficient to ensure that the liquid is
kept well mixed and homogeneous.
7.4 Using the heating device, bring the temperature of the waste to 55*C
(130*F).
7.5 An accurate rate of corrosion 1s not required; only a determination
as to whether the rate of corrosion Is less than or greater than 6.35 nun per
year is required. A 24-hr test period should be ample to determine whether or
not the rate of corrosion 1s >6.35 mm per year.
7.6 In order to determine accurately the amount of material lost to
corrosion, the coupons have to be cleaned after Immersion and prior to
weighing. The cleaning procedure should remove all products of corrosion
while, removing a minimum of sound metal. Cleaning methods can be divided into
three general categories: mechanical, chemical, and electrolytic.
7.6.1 Mechanical cleaning Includes scrubbing, scraping, brushing,
and ultrasonic procedures. Scrubbing with a bristle brush and mild
abrasive 1s the most popular of these methods. The others are used in
cases of heavy corrosion as a first step 1n removing heavily encrusted
corrosion products prior to scrubbing. Care should be taken to avoid
removing sound metal.
7.6.2 Chemical cleaning implies the removal of material from the
surface of the coupon by dissolution In an appropriate solvent. Solvents
such as acetone, dichloromethane, and alcohol are used to remove oil,
grease, or resinous materials and are used prior to immersion to remove
the products of corrosion. Solutions suitable for removing corrosion
from the steel coupon are:
Solution Soaking Time Temperature
20% NaOH + 200 g/L zinc dust 5 min Boiling
or
Cone. HC1 + 50 g/L SnCl2 + 20 g/L SbCl3 Until clean Cold
1110 - 4
Revision 0
Date September 1986
-------
7.6.3 Electrolytic cleaning should be preceded by scrubbing to
remove loosely adhering corrosion products. One method of electrolytic
cleaning that can be employed uses:
Solution: 50 g/L
Anode: Carbon or lead
Cathode: Steel coupon
Cathode current density: 20 amp/cm2 (129 amp/1n.2)
Inhibitor: 2 cc organic Inhibitor/liter
Temperature: 74* C (165*F)
Exposure Period: 3 m1n.
NOTE: Precautions must be taken to ensure good electrical contact with
the coupon to avoid contamination of the cleaning solution with easily
reducible metal Ions and to ensure that Inhibitor decomposition has not
occurred. Instead of a proprietary Inhibitor, 0.5 g/L of either
dlorthotolyl thlourea or quinolln eth Iodide can be used.
7.7 Whatever treatment 1s employed to clean the coupons, Its effect 1n
removing sound metal should be determined by using a blank (I.e., a coupon
that has not been exposed to the waste). The blank should be cleaned along
with the test coupon and Its waste loss subtracted from that calculated for
the test coupons.
7.8 After corroded specimens have been cleaned and dried, they are
rewelghed. The weight loss 1s employed as the principal measure of corrosion.
Use of weight loss as a measure of corrosion requires making the assumption
that all weight loss has been due to generalized corrosion and not localized
pitting. In order to determine the corrosion rate for the purpose of this
regulation, the following formula 1s used:
Corrosion Rate (mmpy) -
where: weight loss 1s 1n milligrams,
area 1n square centimeters,
time 1n hours, and
corrosion rate 1n millimeters per year (mmpy).
8.0 QUALITY CONTROL
8.1 All quality control data should be filed and available for auditing.
8.2 Duplicate samples should be analyzed on a routine basis.
1110 - 5
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
1. National Association of Corrosion Engineers, "Laboratory Corrosion
Testing of Metals for the Process Industries/ NACE Standard TM-01-69 (1972
Revision), NACE, 3400 West Loop South, Houston, TX 77027.
1110 - 6
Revision
Date September 1986
-------
METHOD itSO
CORROSIVITY TOWARD STEEL
C
7.1
Aaaenola test
apparatus
7.2
Fill container
with waste
7.3
Agitate
7.4
Heat
o
7.6
Clean
coupons
by necnenlcal.
chemical ana/or
electrolytic
methods
7.7 I Check
i effect
of cleaning
treatment on
removing sound
metal
7.8
Determine
corroaion rate
( Stop J
o
1110 - 7
Revision 0
Date September 1986
fr U.S. GOVERNMENT pRINTIMrs OFFICE:! 993-342-139/83251
-------
8.3 Reactivity
Refer to guidance given in Chapter Seven, especially Section 7.3.3 and
7.3.4.
EIGHT - 4 Revision 1
September 1994
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8.4 Toxicity
The following methods are found in Section 8.4:
Method 1310A: Extraction Procedure (EP) Toxicity Test Method
and Structural Integrity Test
Method 1311: Toxicity Characteristic Leaching Procedure
EIGHT - 5 Revision- 1
September 1994
*U.S. G.P.O.;1995-386-824:33251
-------
METHOD 1310A
EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
AND STRUCTURAL INTEGRITY TEST
1.0 SCOPE AND APPLICATION
1.1 This method is an interim method to determine whether a waste
exhibits the characteristic of Extraction Procedure Toxicity.
1.2 The procedure may also be used to simulate the leaching which a
waste may undergo if disposed of in a sanitary landfill. Method 1310 is
applicable to liquid, solid, and multiphase samples.
2.0 SUMMARY OF METHOD
2.1 If a representative sample of the waste contains > 0.5% solids, the
solid phase of the sample is ground to pass a 9.5 mm sieve and extracted with
deionized water which is maintained at a pH of 5 + 0.2, with acetic acid. Wastes
that contain < 0.5% filterable solids are, after filtering, considered to be the
EP extract for this method. Monolithic wastes which can be formed into a
cylinder 3.3 cm (dia) x 7.1 cm, or from which such a cylinder can be formed
which is representative of the waste, may be evaluated using the Structural
Integrity Procedure instead of being ground to pass a 9.5-mm sieve.
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 Extractor - For purposes of this test, an acceptable extractor is
one that will impart sufficient agitation to the mixture to (1) prevent
stratification of the sample and extraction fluid and (2) ensure that all sample
surfaces are continuously brought into contact with well-mixed extraction fluid.
Examples of suitable extractors are shown in Figures 1-3 of this method and are
available from: Associated Designs & Manufacturing Co., Alexandria, Virginia;
Glas-Col Apparatus Co., Terre Haute, Indiana; Millipore, Bedford, Massachusetts;
and Rexnard, Milwaukee, Wisconsin.
4.2 pH meter or pH controller - Accurate to 0.05 pH units with
temperature compensation.
4.3 Filter holder - Capable of supporting a 0.45-jim filter membrane and
of withstanding the pressure needed to accomplish separation. Suitable filter
holders range from simple vacuum units to relatively complex systems that can
exert up to 5.3 kg/cm (75 psi) of pressure. The type of filter holder used
depends upon the properties of the mixture to be filtered. Filter holders known
to EPA and deemed suitable for use are listed in Table 1.
1310A - 1 Revision 1
July 1992
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4.4 Filter membrane - Filter membrane suitable for conducting the
required filtration shall be fabricated from a material that (1) is not
physically changed by the waste material to be filtered and (2) does not absorb
or leach the chemical species for which a waste's EP extract will be analyzed.
Table 2 lists filter media known to the agency to be suitable for solid waste
testing.
4.4.1 In cases of doubt about physical effects on the filter,
contact the filter manufacturer to determine if the membrane or the
prefilter is adversely affected by the particular waste. If no
information is available, submerge the filter in the waste's liquid phase.
A filter that undergoes visible physical change after 48 hours (i.e.,
curls, dissolves, shrinks, or swells) is unsuitable for use.
4.4.2 To test for absorption or leaching by the filter:
4.4.2.1 Prepare a standard solution of the chemical
species of interest.
4.4.2.2 Analyze the standard for its concentration of
the chemical species.
4.4.2.3 Filter the standard and reanalyze. If the
concentration of the filtrate differs from that of the original
standard, then the filter membrane leaches or absorbs one or more
of the chemical species and is not usable in this test method.
4.5 Structural integrity tester - A device meeting the specifications
shown in Figure 4 and having a 3.18-cm (1.25-in) diameter hammer weighing 0.33
kg (0.73 Ib) with a free fall of 15.24 cm (6 in) shall be used. This device is
available from Associated Design and Manufacturing Company, Alexandria, VA
22314, as Part No. 125, or it may be fabricated to meet these specifications.
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 Acetic acid (0.5N), CHปCOOH. This can be made by diluting
concentrated glacial acetic acid (17.5N) by adding 57 ml glacial acetic acid to
1,000 mL of water and diluting to 2 liters. The glacial acetic acid must be of
high purity and monitored for impurities.
5.4 Analytical standards should be prepared according to the applicable
analytical methods.
1310A - 2 Revision 1
July 1992
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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 of this manual.
6.2 Preservatives must not be added to samples.
6.3 Samples can be refrigerated if it is determined that refrigeration
will not affect the integrity of the sample.
7.0 PROCEDURE
7.1 If the waste does not contain any free liquid, go to Step 7.9. If
the sample is liquid or multiphase, continue as follows. Weigh filter membrane
and prefilter to ฑ 0.01 g. Handle membrane and prefilters with blunt curved-tip
forceps or vacuum tweezers, or by applying suction with a pipet.
7.2 Assemble filter holder, membranes, and prefilters following the
manufacturer's instructions. Place the 0.45-jitn membrane on the support screen
and add prefilters in ascending order of pore size. Do not prewet filter
membrane.
7.3 Weigh out a representative subsample of the waste (100 g minimum).
7.4 Allow slurries to stand, to permit the solid phase to settle.
Wastes that settle slowly may be centrifuged prior to filtration.
7.5 Wet the filter with a small portion of the liquid phase from the
waste or from the extraction mixture. Transfer the remaining material to the
filter holder and apply vacuum or gentle pressure (10-15 psi) until all liquid
passes through the filter. Stop filtration when air or pressurizing gas moves
through the membrane. If this point is not reached under vacuum or gentle
pressure, slowly increase the pressure in 10-psi increments to 75 psi. Halt
filtration when liquid flow stops. This liquid will constitute part or all of
the extract (refer to Step 7.16). The liquid should be refrigerated until time
of analysis.
NOTE: Oil samples or samples containing oil are treated in exactly the same way
as any other sample. The liquid portion of the sample is filtered and
treated as part of the EP extract. If the liquid portion of the sample
will not pass through the filter (usually the case with heavy oils or
greases), it should be carried through the EP extraction as a solid.
7.6 Remove the solid phase and filter media and, while not allowing
them to dry, weigh to + 0.01 g. The wet weight of the residue is determined by
calculating the weight difference between the weight of the filters (Step 7.1)
and the weight of the solid phase and the filter media.
7.7 The waste will be handled differently from this point on, depending
on whether it contains more or less than 0.5% solids. If the sample appears to
have < 0.5% solids, determine the percent solids exactly (see Note below) by the
following procedure:
1310A - 3 Revision 1
July 1992
-------
7.7.1 Dry the filter and residue at 80ฐC until two successive
weighings yield the same value.
7.7.2 Calculate the percent solids, using the following
equation:
weight of tared weight
filtered solid - of filters
and filters
initial weight of waste material
x 100 = % solids
NOTE: This procedure is used only to determine whether the solid must be
extracted or whether it can be discarded unextracted. It is not used in
calculating the amount of water or acid to use in the extraction step. Do
not extract solid material that has been dried at 80ฐC. A new sample will
have to be used for extraction if a percent solids determination is
performed.
7.8 If the solid constitutes < 0.5% of the waste, discard the solid and
proceed immediately to Step 7.17, treating the liquid phase as the extract.
7.9 The solid material obtained from Step 7.5 and all materials that
do not contain free liquids shall be evaluated for particle size. If the solid
material has a surface area per g of material > 3.1 cm2 or passes through a 9.5-
mm (0.375-in.) standard sieve, the operator shall proceed to Step 7.11. If the
surface area is smaller or the particle size larger than specified above, the
solid material shall be prepared for extraction by crushing, cutting, or grinding
the material so that it passes through a 9.5-mm (0.375-in.) sieve or, if the
material is in a single piece, by subjecting the material to the "Structural
Integrity Procedure" described in Step 7.10.
7.10 Structural Integrity Procedure (SIP)
7.10.1 Cut a 3.3-cm diameter by 7.1-cm long cylinder from the
waste material. If the waste has been treated using a fixation process,
the waste may be cast in the form of a cylinder and allowed to cure for 30
days prior to testing.
7.10.2 Place waste into sample holder and assemble the tester.
Raise the hammer to its maximum height and drop. Repeat 14 additional
times.
7.10.3 Remove solid material from tester and scrape off any
particles adhering to sample holder. Weigh the waste to the nearest 0.01
g and transfer it to the extractor.
7.11 If the sample contains > 0.5% solids, use the wet weight of the
solid phase (obtained in Step 7.6) to calculate the amount of liquid and acid to
employ for extraction by using the following equation:
W = Wf - Wt
1310A - 4 Revision 1
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where :
W = Wet weight in g of solid to be charged to extractor.
Wf = Wet weight in g of filtered solids and filter media.
Wt = Weight in g of tared filters.
If the waste does not contain any free liquids, 100 g of the material will be
subjected to the extraction procedure.
7.12 Place the appropriate amount of material (refer to Step 7.11) into
the extractor and add 16 times its weight with water.
7.13 After the solid material and water are placed in the extractor, the
operator shall begin agitation and measure the pH of the solution in the
extractor. If the pH is > 5.0, the pH of the solution should be decreased to 5.0
ฑ 0.2 by slowly adding 0.5N acetic acid. If the pH is < 5.0, no acetic acid
shou.ld be added. The pH of the solution should be monitored, as described below,
during the course of the extraction, and, if the pH rises above 5.2, 0.5N acetic
acid should be added to bring the pH down to 5.0 ฑ 0.2. However, in no event
shall the aggregate amount of acid added to the solution exceed 4 ml of acid per
g of solid. The mixture should be agitated for 24 hours and maintained at 20-
40ฐC (68-104ฐF) during this time. It is recommended that the operator monitor
and adjust the pH during the course of the extraction with a device such as the
Type 45-A pH Controller, manufactured by Chemtrix, Inc., Hillsboro, Oregon
97123, or its equivalent, in conjunction with a metering pump and reservoir of
0.5N acetic acid. If such a system is not available, the following manual
procedure shall be employed.
NOTE: Do not add acetic acid too quickly. Lowering the pH to below the target
concentration of 5.0 could affect the metal concentrations in the
leachate.
7.13.1 A pH meter should be calibrated in accordance with the
manufacturer's specifications.
7.13.2 The pH of the solution should be checked, and, if
necessary, 0.5 N acetic acid should be manually added to the extractor
until the pH reaches 5.0 ฑ 0.2. The pH of the solution should be adjusted
at 15-, 30-, and 60-minute intervals, moving to the next longer interval
if the pH does not have to be adjusted > 0.5 pH units.
7.13.3 The adjustment procedure should be continued for at least
6 hours.
7.13.4 If, at the end of the 24-hour extraction period, the pH
of the solution is not below 5.2 and the maximum amount of acid (4 ml per
g of solids) has not been added, the pH should be adjusted to 5.0 + 0.2
and the extraction continued for an additional 4 hours, during which the
pH should be adjusted at 1-hour intervals.
1310A - 5 Revision 1
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7.14 At the end of the extraction period, water should be added to the
extractor in an amount determined by the following equation:
where:
V = (20)(W) - 16(W) - A
V = ml water to be added.
W = Weight in g of solid charged to extractor.
A = ml of 0.5N acetic acid added during extraction.
7.15 The material in the extractor should be separated
component liquid and solid phases in the following manner:
into its
7.15.1 Allow slurries to stand to permit the solid phase to
settle (wastes that are slow to settle may be centrifuged prior to
filtration) and set up the filter apparatus (refer to Steps 4.3 and 4.4).
7.15.2 Wet the filter with a small portion of the liquid phase
from the waste or from the extraction mixture. Transfer the remaining
material to the filter holder and apply vacuum or gentle pressure (10-
15 psi) until all liquid passes through the filter. Stop filtration when
air or pressurizing gas moves through the membrane. If this point is not
reached under vacuum or gentle pressure, slowly increase the pressure in
10-psi increments to 75 psi. Halt filtration when liquid flow stops.
7.16 The liquids resulting from Steps 7.5 and 7.15 should be combined.
This combined liquid (or waste itself, if it has < 0.5% solids, as noted in Step
7.8) is the extract.
7.17 The extract is then prepared and analyzed using the appropriate
analytical methods described in Chapters Three and Four of this manual.
NOTE:
If the EP extract includes two phases, concentration of contaminants is
determined by using a simple weighted average. For example: An EP
extract contains 50 ml of oil and 1,000 ml of an aqueous phase.
Contaminant concentrations are determined for each phase. The final
contamination concentration is taken to be:
50 x contaminant cone.
in oil
1,000 x contaminant cone
of aqueous phase
NOTE:
1050
In cases where a contaminant was not detected, use the MDL in the
calculation. For example, if the MDL in the oily phase is 100 mg/L and 1
mg/L in the aqueous phase, the reporting limit would be 6 mg/L (rounded to
the nearest mg). If the regulatory threshold is 5 mg/L, the waste may be
EP toxic and results of the analysis are inconclusive.
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8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for
easy reference or inspection.
8.2 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.3 All quality control measures described in Cnapter One and in the
referenced analytical methods should be followed.
9.0 METHOD PERFORMANCE
9.1 The data tabulated in Table 3 were obtained from records of state
and contractor laboratories and are intended to show the precision of the entire
method (1310 plus analysis method).
10.0 REFERENCES
1. Rohrbough, W.G.; et al. Reagent Chemicals. American Chemical Society
Specifications. 7th ed.; American Chemical Society: Washington, DC, 1986.
2. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification for
Reagent Water"; ASTM: Philadelphia, PA, 1985; D1193-77.
3. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
1310A - 7 Revision 1
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TABLE 1. ERA-APPROVED FILTER HOLDERS
Manufacturer
Size
Model No.
Comments
Vacuum Filters
Gel man
Nalgene
Nuclepore
Millipore
Pressure Filters
Nuclepore
47 mm
500 mL
Micro Filtration
Systems
Millipore
47 mm
47 mm
142 mm
142 mm
142 mm
4011
44-0045
410400
XX10 047 00
425900
302300
YT30 142 HW
Disposable plastic unit,
including prefilter, filter
pads, and reservoir; can be
used when solution is to be
analyzed for inorganic
constituents.
1310A - 8
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TABLE 2. ERA-APPROVED FILTRATION MEDIA
Supplier
Filter to be used
for aqueous systems
Filter to be used
for organic systems
Coarse prefilter
Gel man
Nuclepore
Millipore
Medium prefliters
Gel man
Nuclepore
Millipore
Fine prefilters
Gel man
Nuclepore
Millipore
Fine filters (0.45 urn)
Gel man
Pall
Nuclepore
Millipore
Selas
61631, 61635
210907, 211707
AP25 035 00,
AP25 127 50
61654, 61655
210905, 211705
AP20 035 00,
AP20 124 50
64798, 64803
210903, 211703
AP15 035 00,
AP15 124 50
63069, 66536
NX04750, NX14225
142218
HAWP 047 00,
HAWP 142 50
83485-02,
83486-02
61631, 61635
210907, 211707
AP25 035 00,
AP25 127 50
210905, 211705
AP20 035 00,
AP20 124 50
64798, 64803
210903, 211703
APIS 035 00,
APIS 124 50
60540 or 66149,
66151
1422188
FHUP 047 00,
FHLP 142 50
83485-02,
83486-02
Susceptible to decomposition by certain polar organic solvents.
1310A - 9
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TABLE 3. PRECISIONS OF EXTRACTION-ANALYSIS
PROCEDURES FOR SEVERAL ELEMENTS
Element
Arsenic
Barium
Cadmium
Sample Matrix
1.
2.
3.
1.
2.
3.
1.
2.
3.
4.
5.
Auto fluff
Barrel sludge
Lumber treatment
company sediment
Lead smelting emission
control dust
Auto fluff
Barrel sludge
Lead smelting emission
control dust
Wastewater treatment
sludge from
electroplating
Auto fluff
Barrel sludge
Oil refinery
tertiary pond sludge
Analysis
Method
7060
7060
7060
6010
7081
7081
3010/7130
3010/7130
7131
7131
7131
Laboratory
Replicates
1.8,
0.9,
28,
0.12
791,
422,
120,
360,
470,
1100
3.2,
1.5 M9/L
2.6 M9/L
42 mg/L
, 0.12 mg/L
780 M9/L
380 M9/L
120 mg/L
290 mg/L
610 M9/L
, 890 M9/L
1.9 M9/L
Chromium
Mercury
1. Wastewater treatment 3010/7190
sludge from
electroplating
2. Paint primer 7191
3. Paint primer filter 7191
4. Lumber treatment 7191
company sediment
5. Oil refinery 7191
tertiary pond sludge
1. Barrel sludge 7470
2. Wastewater treatment 7470
sludge from
electroplating
3. Lead smelting emission 7470
control dust
1.1, 1.2 mg/L
61, 43 Mg/L
0.81, 0.89 mg/L
0.15, 0.09
1.4, 0.4
0.4, 0.4 M9/L
1310A - 10
Revision 1
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TABLE 3 (Continued)
Element
Lead
Sample Matrix
1.
2.
3.
4.
5.
Lead smelting emission
control dust
Auto fluff
Incinerator ash
Barrel sludge
Oil refinery
tertiary pond sludge
Analysis
Method
3010/7420
7421
7421
7421
7421
Laboratory
Replicates
940, 920 mg/L
1540, 1490/ug/
1000, 974 jug/
2550, 2800 M9/
31, 29 M9/L
Nickel
Chromium(VI)
1. Sludge
2. Wastewater treatment
sludge from
electroplating
1. Wastewater treatment
sludge from
electroplating
7521
3010/7520
7196
2260, 1720
130, 140 mg/L
18, 19 Mg/L
1310A - 11
Revision 1
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FIGURE 1.
EXTRACTOR
5.0H
^" *
-------
2-Liter Plastic or Glass Bottles
1/15-Horsepower Electric Motor
CO
o
J>
Screws for Holding Bottles
o
73
CL, 73
Vฃ>
ro
-------
FIGURE 3.
EPRI EXTRACTOR
l-Gallon Plastic
or Glass Bottle
Hinged Cover
Foam Bonded to Cover
Totally Enclosed
Fan Cooled Motor
30 rpm, 1/8 HP
Box Assembly
Plywood Construction
1310A - 14
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FIGURE 4.
COMPACTION TESTER
m Combined Weight
0.33 kg (0.73 Ib)
Sample
Elastomeric
Sample Holder
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METHOD 1310A
EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
AND STRUCTURAL INTEGRITY TEST
7.1 Weigh filter
membrane and
prefliter
7.2 Assemble filter
holder, membranes,
and prefi1ters
7.3 Weigh out
subsample of waste
7.4 Let solid phase
settle: centrifuge
if necessary
7.5 Filter out
liquid phase and
refrigerate it
7.6 Weigh net solid
phase
7.7.1 Dry filter
and weigh
7.7.2 Calculate
percent solids
1310A - 16
7.7 Does
waste appear
to contain
<0.5*
soilds?
Revision 1
July 1992
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METHOD 1310A
(Continued)
7.8 Discard solids
Area >
3.1 cm2/g
Area < 3.1
cm2/g or
par ticle
size > 9.5
mm sieve
Material is
in single
place
7.10.1 Cut or cast
cylinder from waste
material for
Structural
Integrity Procedure
7.9 Prepare
material for
eMtraction by
crushing, cutting.
or grinding
7 10.2 Assemble
tester; drop hammer
IS times
7 .10.3 Remove solid
material; weigh;
transfer to
ex tractor
1310A - 17
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METHOD 1310A
(Continued)
7.15 Allow slurries
to stand; set up
filter apparatus;
filter
7.11 Calculate
amount of liquid
and acid to use for
extraction
7.12 Place material
into extractor; add
deionized water
7.11 Use 100 g of
material for
extraction
procedure
7.16 Combine
liquids from
Sections 7.S and
7.15 to analyze for
contaminants
7 .13 Agitate for 24
hours and monitor
pH of solution
7.17 Obtain
analytical method
from Chapters 3 and
4
7 13 Calibrate and
adjust pH meter
7.18 Compare
ex t ract
concentration to
maximum
contamina tion
limits to determine
EP toxicity
7.14 At end of
extraction period,
add deionized water
STOP
1310A - 18
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METHOD 1311
TOXICITY CHARACTERISTIC LEACHING PROCEDURE
1.0 SCOPE AND APPLICATION
1.1 The TCLP is designed to determine the mobility of both organic and
inorganic analytes present in liquid, solid, and multiphasic wastes.
1.2 If a total analysis of the waste demonstrates that individual
analytes are not present in the waste, or that they are present but at such low
concentrations that the appropriate regulatory levels could not possibly be
exceeded, the TCLP need not be run.
1.3 If an analysis of any one of the liquid fractions of the TCLP
extract indicates that a regulated compound is present at such high concentra-
tions that, even after accounting for dilution from the other fractions of the
extract, the concentration would be above the regulatory level for that compound,
then the waste is hazardous and it is not necessary to analyze the remaining
fractions of the extract.
1.4 If an analysis of extract obtained using a bottle extractor shows
that the concentration of any regulated volatile analyte exceeds the regulatory
level for that compound, then the waste is hazardous and extraction using the ZHE
is not necessary. However, extract from a bottle extractor cannot be used to
demonstrate that the concentration of volatile compounds is below the regulatory
level.
2.0 SUMMARY OF METHOD
2.1 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 jum glass fiber
filter, is defined as the TCLP extract.
2.2 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;
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 alkalinity
of the solid phase of the waste. 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 jitm 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.
1311-. 1 Revision 0
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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 waste 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
vessel (see Section 4.3.1). The vessels shall have an internal volume of
500-600 ml, and be equipped to accommodate a 90-110 mm filter. The devices
contain VITON*1 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 psi 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
TCLP 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 psi, 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 psi, 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 Section 7.3) refers to pounds per square inch (psi), 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.
1 VITON* is a trademark of Du Pont.
1311- 2 Revision 0
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4.2.2 Bottle Extraction Vessel. When the waste 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
Section 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 Section 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 Extractor Vessel (ZHE): When the waste is
evaluated for volatiles, the zero-headspace extraction vessel described in
Section 4.2.1 is used for filtration. The device shall be capable of
supporting and keeping in place the glass fiber filter and be able to
withstand the pressure needed to accomplish .separation (50 psi).
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 waste is evaluated for other than
volatile analytes, any 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 psi
or more. The type of filter holder used depends on the properties of the
material to be filtered (see Section 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 shown 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 waste components. 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. Borosili-
cate glass bottles are recommended for use over other types of glass
bottles, especially when inorganics are analytes of concern.
1311- 3 Revision 0
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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 urn, or equivalent. 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 deionized distilled 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 of the waste when using the ZHE device. The 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
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 initial 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)aor has no significant solid phase (is 100% liquid), either the
TEDLAR* bag or the syringe may 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 Section 4.3.2), or other
ZHE device).
4.8 Laboratory Balance: Any laboratory balance accurate to within
ฑ0.01 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.
TEDLAR* is a registered trademark of Du Pont.
1311- 4 Revision 0
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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).
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 Hydrochloric acid (IN), HC1, made from ACS reagent grade.
5.4 Nitric acid (IN), HN03, made from ACS reagent grade.
5.5 Sodium hydroxide (IN), NaOH, made from ACS reagent grade.
5.6 Glacial acetic acid, CH3CH2OOH, ACS reagent grade.
5.7 Extraction fluid.
5.7.1 Extraction fluid # 1: Add 5.7 ml glacial CH3CH2OOH to
500 ml of reagent water (See Section 5.2), add 64.3 ml of IN NaOH, and
dilute to a volume of 1 liter. When correctly prepared, the pH of this
fluid will be 4.93 ฑ 0.05.
5.7.2 Extraction fluid # 2: Dilute 5.7 ml glacial CH3CH2OOH with
reagent water (See Section 5.2) to a volume of 1 liter. When correctly
prepared, the pH of this fluid will be 2.88 + 0.05.
1311- 5 Revision 0
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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 fluid shall be
discarded and fresh extraction fluid prepared.
5.8 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 The TCLP may place 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 preliminary evaluation of which extraction
fluid is to be used for the nonvolatile analyte extraction procedure. Another
aliquot may be needed to actually conduct the nonvolatile extraction (see Section
1.4 concerning the use of this extract for volatile organics). 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 waste 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
ฐC. Samples should be opened only immediately prior to extraction).
6.6 TCLP 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 Section 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 Section 8.0 (QA
requirements) for acceptable sample and extract holding times.
7.0 PROCEDURE
7.1 Preliminary Evaluations
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Perform preliminary TCLP evaluations on a minimum 100 gram aliquot of
waste. This aliquot may not actually undergo TCLP extraction. These preliminary
evaluations include: (1) determination of the percent solids (Section 7.1.1);
(2) determination of whether the waste contains insignificant solids and is,
therefore, its own extract after filtration (Section 7.1.2); (3) determination
of whether the solid portion of the waste requires particle size reduction
(Section 7.1.3); and (4) determination of which of the two extraction fluids are
to be used for the nonvolatile TCLP extraction of the waste (Section 7.1.4).
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 waste will obviously yield no liquid when
subjected to pressure filtration (i.e., is 100% solids) proceed to
Section 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
described in Section 4.3.2 and is outlined in Sections 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 the 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. Wastes 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 waste sample to the
filter holder (liquid and solid phases). Spread the waste sample
evenly over the surface of the filter. If filtration of the waste
at 4 ฐC 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.
NOTE: If waste 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
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subtract it from the sample weight determined in Section 7.1.1.5 to
determine the weight of the waste sample that will be filtered.
Gradually apply vacuum or gentle pressure of 1-10 psi,
until air or pressurizing gas moves through the filter. If this
point is not reached under 10 psi, and if no additional liquid has
passed through the filter in any 2 minute interval, slowly increase
the pressure in 10 psi increments to a maximum of 50 psi. After
each incremental increase of 10 psi, 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 psi increment. When the pressurizing gas begins to move
through the filter, or when liquid flow has ceased at 50 psi (i.e..
filtration does not result in any additional filtrate within any 2
minute period), stop the filtration.
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 waste, and the filtrate is defined as the
liquid phase.
NOTE: Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material that appears to be a liquid. Even
after applying vacuum or pressure filtration, as outlined in
Section 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 Section
7.1.1.3) from the total weight of the filtrate-filled container.
Determine the weight of the solid phase of the waste sample by
subtracting the weight of the liquid phase from the weight of the
total waste sample, as determined in Section 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 (Section 7.1.1.9)
Percent solids = x 100
Total weight of waste (Section 7.1.1.5 or 7.1.1.7)
7.1.2 If the percent solids determined in Section 7.1.1.9 is
equal to or greater than 0.5%, then proceed either to Section 7.1.3 to
determine whether the solid material requires particle size reduction or
to Section 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
Section 7.1.1.9 is less than 0.5%, then proceed to Section 7.2.9 if the
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nonvolatile TCLP is to be performed and to Section 7.3 with a fresh
portion of the waste if the volatile TCLP 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 ฐC
until two successive weighing yield the same value within + 1%.
Record the final weight.
NOTE: Caution should be taken to ensure that the subject solid will not
flash upon heating. It is recommended that the drying oven be
vented to a hood or other appropriate device.
7.1.2.3 Calculate the percent dry solids as follows:
(Wt. of dry waste + filter) - tared wt. of filter
Percent dry solids = x 100
Initial wt. of waste (Section 7.1.1.5 or 7.1.1.7)
7.1.2.4 If the percent dry solids is less than 0.5%,
then proceed to Section 7.2.9 if the nonvolatile TCLP is to be
performed, and to Section 7.3 if the volatile TCLP is to be
performed. If the percent dry solids is greater than or equal to
0.5%, and if the nonvolatile TCLP is to be performed, return to the
beginning of this Section (7.1) and, with a fresh portion of waste,
determine whether particle size reduction is necessary (Section
7.1.3) and determine the appropriate extraction fluid (Section
7.1.4). If only the volatile TCLP is to be performed, see the note
in Section 7.1.4.
7.1.3 Determination of whether the waste requires particle size
reduction (particle size is reduced during this step): Using the solid
portion of the waste, 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 waste
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
Section 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.
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7.1.4 Determination of appropriate extraction fluid: If the
solid content of the waste is greater than or equal to 0.5% and if the
sample will be extracted for nonvolatile constituents (Section 7.2),
determine the appropriate fluid (Section 5.7) for the nonvolatiles
extraction as follows:
NOTE: TCLP extraction for volatile constituents uses only extraction
fluid #1 (Section 5.7.1). Therefore, if TCLP extraction for
nonvolatiles is not required, proceed to Section 7.3.
7.1.4.1 Weigh out a small subsample of the solid phase
of the waste, reduce the solid (if necessary) to a particle size of
approximately 1 mm in diameter or less, and transfer 5.0 grams of
the solid phase of the waste to a 500 ml beaker or Erlenmeyer
flask.
7.1.4.2 Add 96.5 ml of reagent water to the beaker,
cover with a watchglass, and stir vigorously for 5 minutes using a
magnetic stirrer. Measure and record the pH. If the pH is <5.0,
use extraction fluid #1. Proceed to Section 7.2.
7.1.4.3 If the pH from Section 7.1.4.2 is >5.0, add
3.5 ml IN HC1, slurry briefly, cover with a watchglass, heat to 50
ฐC, and hold at 50 ฐC for 10 minutes.
7.1.4.4 Let the solution cool to room temperature and
record the pH. If the pH is <5.0, use extraction fluid #1. If the
pH is >5.0, use extraction fluid #2. Proceed to Section 7.2.
7.1.5 If the aliquot of the waste used for the preliminary
evaluation (Sections 7.1.1 - 7.1.4) was determined to be 100% solid at
Section 7.1.1.1, then it can be used for the Section 7.2 extraction
(assuming at least 100 grams remain), and the Section 7.3 extraction
(assuming at least 25 grams remain). If the aliquot was subjected to the
procedure in Section 7.1.1.7, then another aliquot shall be used for the
volatile extraction procedure in Section 7.3. The aliquot of the waste
subjected to the procedure in Section 7.1.1.7 might be appropriate for use
for the Section 7.2 extraction if an adequate amount of solid (as
determined by Section 7.1.1.9) 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 Section 7.2.10 of the nonvolatile TCLP extraction.
7.2 Procedure When Volatiles are not Involved
A minimum sample size of 100 grams (solid and liquid phases) is recommend-
ed. In some cases, a larger sample size may be appropriate, depending on the
solids content of the waste sample (percent solids, See Section 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 TCLP extract will be sufficient to support all
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of the analyses required. If the amount of extract generated by a single TCLP
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 waste will obviously yield no liquid when subjected
to pressure filtration (i.e.. is 100% solid, see Section 7.1.1), weigh out
a subsample of the waste (100 gram minimum) and proceed to Section 7.2.9.
7.2.2 If the sample is liquid or multiphasic, liquid/solid
separation is required. This involves the filtration device described in
Section 4.3.2 and is outlined in Sections 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
Section 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 waste (100 gram minimum) and
record the weight. If the waste contains <0.5% dry solids (Section
7.1:2), the liquid portion of the waste, after filtration, is defined as
the TCLP 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 TCLP extract. For wastes containing >0.5% dry solids
(Sections 7.1.1 or 7.1.2), use the percent solids information obtained in
Section 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 TCLP extract.
7.2.6 Allow slurries to stand to permit the solid phase to
settle. Wastes that settle slowly may be centrifuged prior to filtration.
Use centrifugation only as an aid to filtration. If the waste is
centrifuged, the liquid should be decanted and filtered followed by
filtration of the solid portion of the waste through the same filtration
system.
7.2.7 Quantitatively transfer the waste sample (liquid and solid
phases) to the filter holder (see Section 4.3.2). Spread the waste sample
evenly over the surface of the filter. If filtration of the waste at 4 ฐC
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.
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
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subtract it from the sample weight determined in Section 7.2.5, to
determine the weight of the waste sample that will be filtered.
Gradually apply vacuum or gentle pressure of 1-10 psi, until air or
pressurizing gas moves through the filter. If this point is not reached
under 10 psi, and if no additional liquid has passed through the filter in
any 2 minute interval, slowly increase the pressure in 10 psi increments
to a maximum of 50 psi. After each incremental increase of 10 psi, 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 psi increment. When the pressurizing gas begins to move
through the filter, or when the liquid flow has ceased at 50 psi (i .e..
filtration does not result in any additional filtrate within a 2 minute
period), stop the filtration.
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 waste, and the filtrate is defined as the liquid phase.
Weigh the filtrate. The liquid phase may now be either analyzed (See
Section 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 that appears to be a liquid. Even
after applying vacuum or pressure filtration, as outlined in
Section 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 with a fresh filter under any circumstances. Use
only one filter.
7.2.9 If the waste contains <0.5% dry solids (see Section
7.1.2), proceed to Section 7.2.13. If the waste contains >0.5% dry solids
(see Section 7.1.1 or 7.1.2), and if particle size reduction of the solid
was needed in Section 7.1.3, proceed to Section 7.2.10. If the waste 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 Section 7.2.11.
7.2.10 Prepare the solid portion of the waste for extraction by
crushing, cutting, or grinding the waste to a surface area or particle
size as described in Section 7.1.3. When the surface area or particle
size has been appropriately altered, quantitatively transfer the solid
material 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.
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manipulation of these materials should be done when cold (4 ฐC) to minimize loss
of volatiles.
7.3.1 Pre-weigh the (evacuated) filtrate cojlection container
(See Section 4.6) and set aside. If using a TEDLAR1" 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 Section 4.6 are recommended for
use under the conditions stated in Sections 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 Section
7.3, Section 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 waste is 100% solid (see Section 7.1.1), weigh out
a subsample (25 gram maximum) of the waste, record weight, and proceed to
Section 7.3.5.
7.3.4 If the waste contains < 0.5% dry solids (Section 7.1.2),
the liquid portion of waste, after filtration, is defined as the TCLP
extract. Filter enough of the sample so that the amount of filtered
liquid will support all of the volatile analyses required. For wastes
containing > 0.5% dry solids (Sections 7.1.1 and/or 7.1.2), use the
percent solids information obtained in Section 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 wastes containing < 5% solids (see Section
7.1.1), weigh out a 500 gram subsample of waste and record the
weight.
7.3.4.2 For wastes containing > 5% solids (see Section
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 (Section 7.1.1)
Weigh out a subsample of the waste of the appropriate size and
record the weight.
7.3.5 If particle size reduction of the solid portion of the
waste was required in Section 7.1.3, proceed to Section 7.3.6. If
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particle size reduction was not required in Section 7.1.3, proceed to
Section 7.3.7.
7.3.6 Prepare the waste for extraction by crushing, cutting, or
grinding the solid portion of the waste to a surface area or particle size
as described in Section 7.1.3. Wastes and appropriate reduction equipment
should be refrigerated, if possible, to 4 ฐC 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 Section 7.3.7.
7.3.7 Waste slurries need not be allowed to stand to permit the
solid phase to settle. Do not centrifuge wastes prior to filtration.
7.3.8 Quantitatively transfer the entire sample (liquid and
solid phases) quickly to the ZHE. Secure the filter and support screens
onto 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 extract collection device to the
top plate.
NOTE: If waste 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 Section 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 psi (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 ฐC reduces the
amount of expressed liquid over what would be expressed at room tempera-
ture, then allow the sample to warm up to room temperature in the device
before filtering. If the waste is 100% solid (see Section 7.1.1), slowly
increase the pressure to a maximum of 50 psi to force most of the
headspace out of the device and proceed to Section 7.3.12.
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7.2.11 Determine the amount of extraction fluid to add to the
extractor vessel as follows:
20 x percent solids (Section 7.1.1) x weight of waste
filtered (Section 7.2.5 or 7.2.7)
Weight of =
extraction fluid 100
Slowly add this amount of appropriate extraction fluid (see Section
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 agitation device, and rotate at 30 + 2 rpm for 18 + 2 hours.
Ambient temperature (i.e., temperature of room in which extraction takes
place) shall be maintained at 23 ฑ2 ฐC during the extraction period.
NOTE: As agitation continues, pressure may build up within the extractor
bottle for some types of wastes (e.g., limed or calcium carbonate
containing waste 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
Section 7.2.7. For final filtration of the TCLP extract, the glass fiber
filter may be changed, if necessary, to facilitate filtration. Filter(s)
shall be acid-washed (see Section 4.4) if evaluating the mobility of
metals.
7.2.13 Prepare the TCLP extract as follows:
7.2.13.1 If the waste contained no initial liquid
phase, the filtered liquid material obtained from Section 7.2.12 is
defined as the TCLP extract. Proceed to Section 7.2.14.
7.2.13.2 If compatible (e.g., multiple phases will not
result on combination), combine the filtered liquid resulting from
Section 7.2.12 with the initial liquid phase of the waste obtained
in Section 7.2.7. This combined liquid is defined as the TCLP
extract. Proceed to Section 7.2.14.
7.2.13.3 If the initial liquid phase of the waste, as
obtained from Section 7.2.7, is not or may not be compatible with
the filtered liquid resulting from Section 7.2.12, do not combine
these liquids. Analyze these liquids, collectively defined as the
TCLP extract, and combine the results mathematically, as described
in Section 7.2.14.
7.2.14 Following collection of the TCLP 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
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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 ฐC) until analyzed. The TCLP extract shall be prepared
and analyzed according to appropriate analytical methods. TCLP 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:
(V,) (C,) -f (V2) (C2)
Final Analyte Concentration =
V + V
V1 + V2
where:
V, = 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 TCLP 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 TCLP extract for analysis of volatile
compounds only. Extract resulting from the use of the ZHE shall not be used to
evaluate the mobility of nonvolatile 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 psi), due to the need to add an amount of extraction fluid equal to 20
times the weight of the solid phase.
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 waste, the initial liquid phase, or the extract to be
exposed to the atmosphere for any more time than is absolutely necessary. Any
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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 psi 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 psi increments to a maximum of 50 psi. After each
incremental increase of 10 psi, if no additional liquid has passed through
the filter in any 2 minute interval, proceed to the next 10 psi increment.
When liquid flow has ceased such that continued pressure filtration at 50
psi 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 waste and the filtrate is defined as the liquid phase.
NOTE: Some wastes, such as oily wastes and some paint wastes, will
obviously contain some material that 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 TCLP extraction as a
solid.
If the original waste contained <0.5% dry solids (see Section
7.1.2), this filtrate is defined as the TCLP extract and is analyzed
directly. Proceed to Section 7.3.15.
7.3.11 The liquid phase may now be either analyzed immediately
(See Sections 7.3.13 through 7.3.15) or stored at 4 ฐC under minimal
headspace conditions until time of analysis. Determine the weight of
extraction fluid #1 to add to the ZHE as follows:
20 x percent solids (Section 7.1.1) x weight
of waste filtered (Section 7.3.4 or 7.3.8)
Weight of extraction fluid =
100
7.3.12 The following Sections 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 #1 is used in all cases
(See Section 5.7).
7.3.12.1 With the ZHE in the vertical position, attach
a line from the extraction fluid reservoir to the liquid in-
let/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,
1311- 17 Revision 0
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and begin transferring extraction fluid (by pumping or similar
means) into 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 liqu'id inlet/outlet valve on top.
Pressurize the ZHE to 5-10 psi (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 psi and check all ZHE fittings to ensure that they
are closed.
7.3.12.3 Place the ZHE in the rotary agitation appara-
tus (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 ฐC during agita-
tion.
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 device is leaking.
Check the ZHE for leaking as specified in Section 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 Section 7.3.9. All extract shall be filtered and collected if the
TEDLAR" bag is used, if the extract is multiphasic, or if the waste
contained an initial liquid phase (see Sections 4.6 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 waste contained no initial liquid phase,
the filtered liquid material obtained from Section 7.3.13 is defined as
the TCLP extract. If the waste contained an initial liquid phase, the
1311- 18 Revision 0
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filtered liquid material obtained from Section 7.3.13 and the initial
liquid phase (Section 7.3.9) are collectively defined as the TCLP extract.
7.3.15 Following collection of the TCLP extract, immediately
prepare the extract for analysis and store with minimal headspace at 4 ฐC
until analyzed. Analyze the TCLP extract according to the appropriate
analytical methods. If the individual phases are to be analyzed
separately (i.e., 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:
(VJ (C,) + (V2) (C2)
Final Analyte
Concentration V,+ V2
where:
V, = The volume of the first phases (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
7.3.16 Compare the analyte concentrations in the TCLP extract
with the levels identified in the appropriate regulations. Refer to
Section 8.0 for quality assurance requirements.
8.0 QUALITY ASSURANCE
8.1 A minimum of one blank (using the same extraction fluid as used for
the samples) must be analyzed for every 20 extractions that have been conducted
in an extraction vessel.
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 are 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 TCLP
extract and before preservation. Matrix spikes should not be added prior
to TCLP extraction of the sample.
8.2.2 In most cases, matrix spikes 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 concentra-
tion, but may not be not less than five times the method detection limit.
In order to avoid differences in matrix effects, the matrix spikes must be
1311- 19 Revision 0
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added to the same nominal volume of TCLP 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
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 TCLP 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 (X8 - XJ/K
where:
X8 = 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
TCLP extract is not at least 50% and the concentration does not exceed the
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
standard as the independent variable (x-axis). Solve for the intercept of
1311- 20 Revision 0
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the abscissa (the independent variable, x-axis) which is the concentration
in the unknown.
8.4.4 Alternately, subtract the instrumental signal or external -
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-
tions as the dependant variable versus the independent variable. Derive
concentrations for unknowns using the internal calibration curve as if it
were an external calibration curve.
8.5
periods:
Samples must undergo TCLP extraction within the following time
SAMPLE MAXIMUM HOLDING TIMES [Days]
Volatiles
Semi-volatiles
Mercury
Metals, except
mercury
From:
Field
collection
To:
TCLP
extraction
14
14
28
180
From:
TCLP
extraction
To:
Preparative
extraction
NA
7
NA
NA
From:
Preparative
extraction
To:
Determinative
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 time will not invalidate characterization if the waste exceeds the
regulatory level.
9.0 METHOD PERFORMANCE
9.1 Ruggedness. Two ruggedness studies have been performed to determine
the effect of various perturbations on specific elements of the TCLP protocol.
Ruggedness testing determines the sensitivity of small procedural variations
which might be expected to occur during routine laboratory application.
9.1.1 Metals - The following conditions were used when leaching
a waste for metals analysis:
1311- 21
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Varying Conditions
Liquid/Solid ratio
Extraction time
Headspace
Buffer n acidity
Acid-washed filters
Filter type
Bottle type
19:1 vs. 21:1
16 hours vs. 18 hours
20% vs. 60%
190 meq vs. 210 meq
yes vs. no
0.7 /tun glass fiber vs. 0.45 /urn
vs. polycarbonate
borosilicate vs. flint glass
Of the seven method variations examined, acidity of the extraction
fluid had the greatest impact on the results. Four of 13 metals from an
API separator sludge/electroplating waste (API/EW) mixture and two of
three metals from an ammonia lime still bottom waste were extracted at
higher levels by the more acidic buffer. Because of the sensitivity to pH
changes, the method requires that the extraction fluids be prepared so
that the final pH is within + 0.05 units as specified.
9.1.2 Volatile Organic Compounds - The following conditions were
used when leaching a waste for VOC analysis:
Varying Conditions
Liquid/Solid ratio
Headspace
Buffer n acidity
Method of storing extract
Aliquotting
Pressure behind piston
19:1 vs. 21:1
0% vs. 5%
60 meq vs. 80 meq
Syringe vs. Tedlarฎ
bag
yes vs. no
0 psi vs. 20 psi
None of the parameters had a significant effect on the results of
the ruggedness test.
9.2 Precision. Many TCLP precision (reproducibility) studies have been
performed, and have shown that, in general, the precision of the TCLP is
comparable to or exceeds that of the EP toxicity test and that method precision
is adequate. One of the more significant contributions to poor precision appears
to be related to sample homogeneity and inter-laboratory variation (due to the
nature of waste materials).
1311- 22
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9.2.1 Metals - The results of a multi-laboratory study are shown
in Table 6, and indicate that a single analysis of a waste may not be
adequate for waste characterization and identification requirements.
9.2.2 Semi-Volatile Organic Compounds - The results of two
studies are shown in Tables 7 and 8. Single laboratory precision was
excellent with greater than 90 percent of the results exhibiting an RSD
less than 25 percent. Over 85 percent of all individual compounds in the
multi-laboratory study fell in the RSD range of 20 - 120 percent. Both
studies concluded that the TCLP provides adequate precision. It was also
determined that the high acetate content of the extraction fluid did not
present problems (i.e., column degradation of the gas chromatograph) for
the analytical conditions used.
9.2.3 Volatile Organic Compounds - Eleven laboratories
participated in a collaborative study of the use of the ZHE with two waste
types which were fortified with a mixture of VOCs. The results of the
collaborative study are shown in Table 9. Precision results for VOCs tend
to occur over a considerable range. However, the range and mean RSD
compared very closely to the same collaborative study metals results in
Table 6. Blackburn and Show concluded that at the 95% level of signifi-
cance: 1) recoveries among laboratories were statistically similar, 2)
recoveries did not vary significantly between the two sample types, and 3)
each laboratory showed the same pattern of recovery for each of the two
samples.
10.0 REFERENCES
1. Blackburn, W.B. and Show, I. "Collaborative Study of the Toxicity
Characteristics Leaching Procedure (TCLP)." Draft Final Report, Contract No. 68-
03-1958, S-Cubed, November 1986.
2. Newcomer, L.R., Blackburn, W.B., Kimmell, T.A. "Performance of the
Toxicity Characteristic Leaching Procedure." Wilson Laboratories, S-Cubed, U.S.
EPA, December 1986.
3. Williams, L.R., Francis, C.W.; Maskarinec, M.P., Taylor D.R.,, and Rothman,
N. "Single-Laboratory Evaluation of Mobility Procedure for Solid Waste." EMSL,
ORNL, S-Cubed, ENSECO.
1311- 23 Revision 0
July 1992
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Table 1.
Volatile Analytes1'2
Compound CAS No.
Acetone
Benzene
n-Butyl alcohol
Carbon disulfide
Carbon tetrachloride
Chlorobenzene
Chloroform
1,2-Dichloroethane
1,1-Dichloroethylene
Ethyl acetate
Ethyl benzene
Ethyl ether
Isobutanol
Methanol
Methylene chloride
Methyl ethyl ketone
Methyl isobutyl ketone
Tetrachl oroethyl ene
Toluene
1,1,1,-Trichloroethane
Trichloroethylene
Tri chl orof 1 uoromethane
l,l,2-Trichloro-l,2,2-trifluoroethane
Vinyl chloride
Xylene
67-64-1
71-43-2
71-36-3
75-15-0
56-23-5
108-90-7
67-66-3
107-06-2
75-35-4
141-78-6
100-41-4
60-29-7
78-83-1
67-56-1
75-09-2
78-93-3
108-10-1
127-18-4
108-88-3
71-55-6
79-01-6
75-69-4
76-13-1
75-01-4
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.
2 Benzene, carbon tetrachloride, chlorobenzene, chloroform,
1,2-dichloroethane, 1,1-dichloroethylene, methyl ethyl ketone,
tetrachloroethylene, and vinyl chloride are toxicity characteristic
constituents.
1311- 24 Revision 0
July 1992
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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
Warrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Environmental Machine and
Design, Inc.
IRA Machine Shop and
Laboratory
Lars Lande Manufacturing
Mi Hi pore Corp.
Lynchburg, VA
(804) 845-6424
Santurce, PR
(809) 752-4004
Whitmore Lake,
(313) 449-4116
Bedford, MA
(800) 225-3384
4-vessel extractor (DC20S)
8-vessel extractor (DC20)
12-vessel extractor (DC20B)
24-vessel extractor (DC24C)
2-vessel
4-vessel
6-vessel
8-vessel
12-vessel
24-vessel
MI
(3740-2-BRE)
(3740-4-BRE)
(3740-6-BRE)
(3740-8-BRE)
(3740-12-BRE)
(3740-24-BRE)
8-vessel (08-00-00)
4-vessel (04-00-00)
8-vessel (.011001)
10-vessel
5-vessel
6-vessel
(10VRE)
(5VRE)
(6VRE)
4-ZHE or
4 2-liter bottle
extractor (YT310RAHW)
1 Any device that rotates the extraction vessel in an end-over-end fashion at 30
+ 2 rpm is acceptable.
1311- 25
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July 1992
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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.
Gelman Science
Warrington, PA
(215) 343-4490
Alexandria, VA
(703) 549-5999
Whitmpre Lake, MI
(313) 449-4116
Bedford, MA
(800) 225-3384
Lynchburg, VA
(804) 845-6424
Ann Arbor, MI
(800) 521-1520
C102, Mechanical
Pressure Device
3745-ZHE, Gas
Pressure Device
ZHE-11, Gas
Pressure Device
YT30090HW, Gas
Pressure Device
VOLA-TOX1, Gas
Pressure Device
15400 Gas Pressure
Device
1 Any device that meets the specifications listed in Section 4.2.1 of the method
is suitable.
2 This device uses a 110 mm filter.
1311- 26
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July 1992
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Table 4.
Suitable Filter Holders1
Model/
Company
Nucleopore Corporation
Micro Filtration
Systems
Location
Pleasanton, CA
(800) 882-7711
Dublin, CA
(800) 334-7132
(415) 828-6010
Catalogue No.
425910
410400
302400
311400
Size
142 mm
47 mm
142 mm
47 mm
Millipore Corporation Bedford, MA YT30142HW 142 mm
(800) 225-3384 XX1004700 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 mm size filter holder is
recommended.
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July 1992
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Table 5.
Suitable Filter Media1
Company
Millipore Corporation
Nucleopore Corporation
Whatman Laboratory
Products, Inc.
Micro Filtration
Systems
Gelman Science
Location
Bedford, MA
(800) 225-3384
Pleasanton, CA
(415) 463-2530
Clifton, NJ
(201) 773-5800
Dublin, CA
(800) 334-7132
(415) 828-6010
Ann Arbor, MI
(800) 521-1520
Model
AP40
211625
GFF
GF75
66256 (90mm)
66257 (142mm)
Pore
Size
(M"i)
0.7
0.7
0.7
0.7
0.7
1 Any filter that meets the specifications in Section 4.4 of the Method is
suitable.
1311- 28
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July 1992
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Table 6. Multi-Laboratory TCLP Metals, Precision
Waste
Ammonia
Lime Still
Bottoms
API/EW
Mixture
Fossil
Fuel Fly
Ash
v
Extraction
Fluid
#1
#2
#1
n
n
n
#1
n
n
n
n
n
n
n
n
n
n
n
Metal
Cadmium
Chromium
Lead
Cadmium
Chromium
Lead
Cadmium
Chromium
Lead
X
0.053
0.023
0.015
0.0032
0.0030
0.0032
0.0046
0.0005
0.0561
0.105
0.0031
0.0124
0.080
0.093
0.017
0.070
0.0087
0.0457
S
0.031
0.017
0.0014
0.0037
0.0027
0.0028
0.0028
0.0004
0.0227
0.018
0.0031
0.0136
0.069
0.067
0.014
0.040
0.0074
0.0083
%RSD
60
76
93
118
90
87
61
77
40
17
100
110
86
72
85
57
85
18
%RSD Range = 17 - 118
Mean %RSD = 74
NOTE: X = Mean results from 6-12 different laboratories
Units = mg/L
Extraction Fluid #1 = pH 4.9
#2 o pH 2.9
1311- 29
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July 1992
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Table 7. Single-Laboratory Semi-Volatiles, Precision
Waste
Ammonia
Lime Still
Bottoms
API/EW
Mixture
Compound
Phenol
2-Methyl phenol
4-Methyl phenol
2, 4-Dimethyl phenol
Naphthalene
2-Methyl naphthalene
Dibenzofuran
Acenaphthylene
Fluorene
Phenanthrene
Anthracene
Fluoranthrene
Phenol
2,4-Dimethylphenol
Naphthalene
2-Methyl naphthalene
Extraction
Fluid
#1
#2
#1
n
n
n
n
n
n
n
n
#2
#1
n
n
n
n
n
#i
n
n
n
n
#2
n
n
n
n
n
n
n
n
X
19000
19400
2000
1860
7940
7490
321
307
3920
3827
290
273
187
187
703
663
151
156
241
243
33.2
34.6
25.3
26.0
40.7
19.0
33.0
43.3
185
165
265
200
S
2230
929
297
52.9
1380
200
46.8
45.8
413
176
44.8
19.3
22.7
7.2
89.2
20.1
17.6
2.1
22.7
7.9
6.19
1.55
1.8
1.8
13.5
1.76
9.35
8.61
29.4
24.8
61.2
18.9
%RSD
11.6
4.8
14.9
2.8
17.4
2.7
14.6
14.9
10.5
4.6
15.5
7.1
12.1
3.9
12.7
3.0
11.7
1.3
9.4
3.3
18.6
4.5
7.1
7.1
33.0
9.3
28.3
19.9
15.8
15.0
23.1
9.5
%RSD Range =1-33
Mean %RSD = 12
NOTE: Units = /xg/L
Extractions were performed in triplicate
All results were at least 2x the detection limit
Extraction Fluid #1 = pH 4.9
n = pH 2.9
1311- 30
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July 1992
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Table 8. Multi-Laboratory Semi-Volatiles, Precision
Waste
Ammonia Lime
Still Bottoms (A)
API/EW
Mixture (B)
Fossil Fuel
Fly Ash (C)
Compound
BNAs
BNAs
BNAs
Extraction
Fluid
n
n
#1
#2
#1
n
X
10043
10376
1624
2074
750
739
S
7680
6552
675
1463
175
342
%RSD
76.5
63.1
41.6
70.5
23.4
46.3
Mean %RSD = 54
NOTE:
Units =
X = Mean results from 3-10 labs
Extraction Fluid #1 = pH 4.9
n = pH 2.9
%RSD Range for Individual Compounds
A, #1 0 - 113
A, #2 28 - 108
B, #1 20 - 156
B, n 49 - 128
C, n 36 - 143
C, n 61 - 164
1311- 31
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July 1992
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Table 9. Multi-Laboratory (11 Labs) VOCs, Precision
Waste
Mine
Tailings
Ammonia
Lime Still
Bottoms
Compound
Vinyl chloride
Methylene chloride
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
Chloroform
1,2-Dichloroethane
2-Butanone
1,1,1 -Tri chl oroethane
Carbon tetrachloride
Trichloroethene
1 , 1 , 2-Tri chl oroethene
Benzene
1,1,2 , 2-Tetrachl oroethane
Toluene
Chlorobenzene
Ethyl benzene
Tri chl orof 1 uoromethane
Acrylonitrile
Vinyl chloride
Methylene chloride
Carbon disulfide
1,1-Dichloroethene
1,1-Dichloroethane
Chloroform
1,2-Dichloroethane
2-Butanone
1,1,1 -Tri chl oroethane
Carbon tetrachloride
Trichloroethene
1,1, 2-Tri chl oroethene
Benzene
1,1, 2, 2-Tetrachl oroethane
Toluene
Chlorobenzene
Ethyl benzene
Tri chl orof 1 uoromethane
Acrylonitrile
X
6.36
12.1
5.57
21.9
31.4
46.6
47.8
43.5
20.9
12.0
24.7
19.6
37.9
34.9
29.3
35.6
4.27
3.82
76.7
5.00
14.3
3.37
52.1
52.8
64.7
43.1
59.0
53.6
7.10
57.3
6.7
61.3
3.16
69.0
71.8
3.70
4.05
29.4
S
6.36
11.8
2.83
27.7
25.4
29.2
33.6
36.9
20.9
8.2
21.2
10.9
28.7
25.6
11.2
19.3
2.80
4.40
110.8
4.71
13.1
2.07
38.8
25.6
28.4
31.5
39.6
40.9
6.1
34.2
4.7
26.8
2.1
18.5
12.0
2.2
4.8
34.8
%RSD
100
98
51
127
81
63
70
85
100
68
86
56
76
73
38
54
66
115
144
94
92
61
75
49
44
73 .
67
76
86
60
70
44
66
27
17
58
119
118
%RSD Range =17-144
Mean %RSD = 75
NOTE: Units = M9/L
1311- 32
Revision 0
July 1992
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Motor
(30ฑ 2 rpm)
Extraction Vessel Holder
Figure 1. Rotary Agitation Apparatus
Top Flange
Support Screen-
Filter
Support Screen'
Liquid Inlet/Outlet Valve
Viton o-rings
Bottom Flange*{_
Pressurized Gas
Inlet/Outlet Valve
.'-;.-. .Sample
Piston
Gas
Pressure
Gauge
Figure 2. Zero-Headspace Extractor (ZHE)
1311- 33
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July 1992
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METHOD 1311
TOXICITY CHARACTERISTIC LEACHATE PROCEDURE
Separate
liquids from
solids with 0.6
- 0.8 um glass
fiber filter
Separate
liquids from
solids with 0.6
- 0.8 um glass
fiber filter
Discard
solids
Must the
solid be
milled?
Solid
En tract ป/
appropriate fluid
1) Bottle extractor
for non- vola ti les
2) 2HE device for
volatiles
Reduce
particle size
to <9 . 5 mm
1311- 34
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July 1992
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METHOD 1311 (CONTINUED)
TOXICITY CHARACTERISTIC LEACHATE PROCEDURE
Discard
sol ids
Solid
Separate
extract from
solids w/ 0.6 -
0 . 8 urn glass
fiber filter
Liquid Sw
V
Store
at
1 iquid
4 C
Is
1iquid
compatible
ith the
extract?
Measure amount of
liquid and analyze
(math etna tical 1 y
combine result w/
result of extract
analysis)
Combine
extract w/
liquid phase
of waste
Analyze
1 iquid
STOP
1311- 35
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July 1992
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APPENDIX
COMPANY REFERENCES
The following listing of frequently-used addresses is provided for the
convenience of users of this manual. No endorsement is intended or implied.
Ace Glass Company
1342 N.W. Boulevard
P.O. Box 688
Vine!and, NJ 08360
(609) 692-3333
Aldrich Chemical Company
Department T
P.O. Box 355
Milwaukee, WI 53201
Alpha Products
5570 - T W. 70th Place
Chicago, IL 60638
(312) 586-9810
Barneby and Cheney Company
E. 8th Avenue and N. Cassidy Street
P.O. Box 2526
Columbus, OH 43219
(614) 258-9501
Bio - Rad Laboratories
2200 Wright Avenue
Richmond, CA 94804
(415) 234-4130
Burdick & Jackson Lab Inc.
1953 S. Harvey Street
Muskegon, MO 49442
Calgon Corporation
P.O. Box 717
Pittsburgh, PA 15230
(412) 777-8000
Conostan Division
Conoco Speciality Products, Inc.
P.O. Box 1267
Ponca City, OK 74601
(405) 767-3456
COMPANIES - 1
Revision 0
Date September 1986
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Corning Glass Works
Houghton Park
Corning, NY 14830
(315) 974-9000
Dohrmann, Division of Xertex Corporation
3240 - T Scott Boulevard
Santa Clara, CA 95050
(408) 727-6000
(800) 538-7708
E. M. Laboratories, Inc.
500 Executive Boulevard
Elmsford, NY 10523
Fisher Scientific Co.
203 Fisher Building
Pittsburgh, PA 15219
(412) 562-8300
General Electric Corporation
3135 Easton Turnpike
Fairfield, CT 06431
(203) 373-2211
Graham Manufactory Co., Inc.
20 Florence Avenue
Batavia, NY 14020
(716) 343-2216
Hamilton Industries
1316 18th Street
Two Rivers, WI 54241
(414) 793-1121
ICN Life Sciences Group
3300 Hyland Avenue
Costa Mesa, CA 92626
Johns - Manville Corporation
P.O. Box 5108
Denver, CO 80217
Kontes Glass Company
8000 Spruce Street
Vineland, NJ 08360
MilUpore Corporation
80 Ashby Road
Bedford, MA 01730
(617) 275-9200
(800) 225-1380
COMPANIES - 2
Revision
Date September 1986
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National Bureau of Standards
U.S. Department of Commerce
Washington, DC 20234
(202) 921-1000
Pierce Chemical Company
Box 117
Rockford, IL 61105
(815) 968-0747
Scientific Glass and Instrument, Inc.
7246 - T Wynnwood
P.O. Box 6
Houston, TX 77001
(713) 868-1481
Scientific Products Company
1430 Waukegon Road
McGaw Park, IL 60085
(312) 689-8410
Spex Industries
3880 - T and Park Avenue
Edison, NJ 08820
Waters Associates
34 - T Maple Street
Mllford, MA 01757
(617) 478-2000
(800) 252-4752
Whatman Laboratory Products, Inc.
Clifton, NJ 07015
(201) 773-5800
COMPANIES - 3
Revision
Date September 1986
U. S. GOVERNMENT PRINTING OFFICE : 1986 O - 169-934
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