United States
Environmental Protection
Agency
Office of Solid Waste
and Emergency Response
Washington, DC 20460
November 1986
SW-846
Third Edition
Solid Waste
Test Methods
for Evaluating Solid Waste
Volume 1C: Laboratory Manual
Physical/Chemical Methods
-------
VOLUME ONE,
SECTION C
Revision 0
Date September 1986
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For sale by the Superintendent of Documents, U.S. Government Printing Office Washington. D.C. 20402
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ABSTRACT
This manual provides test procedures which may be used to evaluate those
properties of a solid waste which determine whether the waste 1s a hazardous
waste within the definition of Section 3001 of the Resource Conservation and
Recovery Act (PL 94-580). These methods are approved for obtaining data to
satisfy the requirement of 40 CFR Part 261, Identification and Listing of
Hazardous Waste. This manual encompasses methods for collecting
representative samples of solid wastes, and for determining the reactivity,
corrosivlty, 1gnitabil1ty, and composition of the waste and the mobility of
toxic species present in the waste.
ABSTRACT - 1
Revision
Date September 1986
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TABLE OF CONTENTS
VOLUME ONE,
SECTION A
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
ACKNOWLEDGEMENTS
PART I METHODS FOR ANALYTES AND PROPERTIES
CHAPTER ONE — QUALITY CONTROL
1.1 Introduction
1.2 Quality Control
1.3 Detection Limit and Quantification Limit
1.4 Data Reporting
1.5 Quality Control Documentation
1.6 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
CONTENTS - 1
Revision
Date September 1986
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CHAPTER THREE — METALLIC ANALYTES
3.1 Sampling Considerations
3.2 Sample Preparation Methods
Method 3005:
Method 3010:
Method 3020:
Method 3040:
Method 3050:
Acid Digestion of Waters for Total Recoverable
or Dissolved Metals for Analysis by Flame
Atomic Absorption Spectroscopy or
Inductively Coupled Plasma Spectroscopy
Acid Digestion of Aqueous Samples and Extracts
for Total Metals for Analysis by Flame
Atomic Absorption Spectroscopy or
Inductively Coupled Plasma Spectroscopy
Acid Digestion of Aqueous Samples and Extracts
for Total Metals for Analysis by Furnace
Atomic Absorption Spectroscopy
Dissolution Procedure for Oils, Greases, or
Waxes
Acid Digestion of Sediments, Sludges, and Soils
3.3 Methods for Determination of Metals
Method 6010:
Method 7000:
Method 7020:
Method 7040:
Method 7041:
Method 7060:
Method 7061:
Method 7080:
Method 7090:
Method 7091:
Method 7130:
Method 7131:
Method 7140:
Method 7190:
Method 7191:
Method 7195:
Method 7196:
Method 7197:
Method 7198:
Method 7200:
Method 7201:
Method 7210:
Method 7380:
Method 7420:
Method 7421:
Method 7450:
Method 7460:
Inductively Coupled Plasma Atomic Emission
Spectroscopy
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Antimony (AA, Direct Aspiration)
Antimony (AA, Furnace Technique)
Arsenic (AA, Furnace Technique)
Arsenic (AA, Gaseous Hydride)
Barium (AA, Direct Aspiration)
Beryllium (AA, Direct Aspiration)
Beryllium (AA, Furnace Technique)
Cadmium (AA, Direct Aspiration)
Cadmium (AA, Furnace Technique)
Calcium (AA, Direct Aspiration)
Chromium (AA, Direct Aspiration)
Chromium (AA, Furnace Technique)
Chromium, Hexavalent (Copreclpitation)
Chromium, Hexavalent (Colorimetric)
Chromium, Hexavalent (Chelati on/Extraction)
Chromium, Hexavalent (Differential Pulse
Pol arography)
Cobalt (AA, Direct Aspiration)
Cobalt (AA, Furnace Technique)
Copper (AA, Direct Aspiration)
Iron (AA, Direct Aspiration)
Lead (AA, Direct Aspiration)
Lead (AA, Furnace Technique)
Magnesium (AA, Direct Aspiration)
Manganese (AA, Direct Aspiration)
CONTENTS -" 2
Revision 0
Date September 1986
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Method 7470:
Method 7471:
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
7480:
7481:
7520:
7550:
7610:
7740:
7741:
7760:
7770:
7840:
7841:
7870:
7910:
7911:
7950:
Mercury 1n Liquid Waste (Manual Cold-Vapor
Technique)
Mercury 1n Solid or Semi solid 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)
Selenium (AA, Gaseous Hydride)
Silver (AA, Direct Aspiration)
Sodium (AA, Direct Aspiration)
Thallium (AA, Direct Aspiration)
Thallium (AA, Furnace Technique)
Tin (AA, Direct Aspiration)
Vanadium (AA, Direct Aspiration)
Vanadium (AA, Furnace Technique)
Z1nc (AA, Direct Aspiration)
APPENDIX — COMPANY REFERENCES
CONTENTS - 3
Revision 0
Date September 1986
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VOLUME ONE,
SECTION B
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
CHAPTER ONE. REPRINTED — QUALITY CONTROL
1.1 Introduction
1.2 Quality Control
1.3 Detection Limit and Quantification Limit
1.4 Data Reporting
1.5 Quality Control Documentation
1.6 References
CHAPTER FOUR — ORGANIC ANALYTES
4.1 Sampling Considerations
4.2 Sample Preparation Methods
4.2.1 Extractions and Preparations
Method 3500: Organic Extraction And Sample Preparation
Method 3510: Separatory Funnel Liquid-Liquid Extraction
Method 3520: Continuous Liquid-Liquid Extraction
Method 3540: Soxhlet Extraction
Method 3550: Sonication Extraction
Method 3580: Waste Dilution
Method 5030: Purge-and-Trap
Method 5040: Protocol for Analysis of Sorbent Cartridges from
Volatile Organic Sampling Train
4.2.2 Cleanup
Method 3600: Cleanup
Method 3610: Alumina Column Cleanup
Method 3611: Alumina Column Cleanup And Separation of
Petroleum Wastes
Method 3620: Florisil Column Cleanup
Method 3630: Silica Gel Cleanup
Method 3640: Gel-Permeation Cleanup
Method 3650: Acid-Base Partition Cleanup
Method 3660: Sulfur Cleanup
CONTENTS - 4
Revision 0
Date September 1986
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4.3 Determination of Organic Analytes
4.3.1 Gas Chromatographic Methods
Method 8000: Gas Chromatography
Method 8010: Halogenated Volatile Organlcs
Method 8015: Nonhalogenated Volatile Organics
Method 8020: Aromatic Volatile Organics
Method 8030: Acrolein, Acrylonitrile, Acetonitrile
Method 8040: Phenols
Method 8060: Phthalate Esters
Method 8080: Organochlorine Pesticides and PCBs
Method 8090: Nitroaromatics and Cyclic Ketones
Method 8100: Polynuclear Aromatic Hydrocarbons
Method 8120: Chlorinated Hydrocarbons
Method 8140: Organophosphorus Pesticides
Method. 8150: Chlorinated Herbicides
4.3.2 Gas Chromatograph1c/Mass Spectroscoplc Methods
Method 8240: Gas Chromatography/Mass Spectrometry for
Volatile Organics
Method 8250: Gas Chromatography/Mass Spectrometry for
Semi volatile Organics: Packed Column
Technique
Method 8270: Gas Chromatography/Mass Spectrometry for
Semi volatile Organics: 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 PCDD's/PCDF's
4.3.3 High Performance Liquid Chromatographic Methods
Method 8310: Polynuclear Aromatic Hydrocarbons
4.4 Miscellaneous Screening Methods
Method 3810: Headspace
Method 3820: Hexadecane Extraction and Screening of Purgeable
Organics
APPENDIX — COMPANY REFERENCES
CONTENTS - 5
Revision
Date September 1986
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VOLUME ONE,
SECTION C
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
CHAPTER ONE. REPRINTED — QUALITY CONTROL
1.1 Introduction
1.2 Quality Control
1.3 Detection Limit and Quantification Limit
1.4 Data Reporting
1.5 Quality Control Documentation
1.6 References
CHAPTER FIVE — MISCELLANEOUS TEST METHODS
Method 9010:
Method 9012:
Method 9020:
Method 9022:
Method 9030:
Method 9035:
Method 9036:
Method 9038:
Method 9060:
Method 9065:
Method 9066:
Method 9067:
Method 9070:
Method 9071:
Total and Amenable Cyanide (Colorimetric,
Manual)
Total and Amenable Cyanide (Color1metr1c,
Automated UV)
Total Organic Hal ides (TOX)
Total Organic Hal ides (TOX) by Neutron
Activation Analysis
Sulfides
Sulfate (Colorimetric, Automated, Chloranilate)
Sulfate (Colorimetric, Automated, Methyl thymol
Blue, AA II)
Sulfate (Turbidimetrlc)
Total Organic Carbon
Phenolics (Spectrophotometric, Manual 4-AAP with
Distillation)
Phenolics (Colorimetric, Automated 4-AAP with
Distillation)
Phenol1cs (Spectrophotometric, MBTH with
Distillation)
Total Recoverable Oil & Grease (Gravimetric,
Separatory Funnel Extraction)
Oil & Grease Extraction Method for Sludge
Samples
CONTENTS - 6
Revision 0
Date September 1986
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Method 9131:
Method 9132:
Method 9200:
Method 9250:
Method 9251:
Method 9252:
Method 9320:
Total Coliform: Multiple Tube Fermentation
Technique
Total Coliform: Membrane Filter Technique
Nitrate
Chloride (Colorimetric, Automated Ferricyanide
AAI)
Chloride (Colorimetric, Automated Ferricyanide
AAI I)
Chloride (Titrimetric, Mercuric Nitrate)
Radium-228
CHAPTER SIX — PROPERTIES
Method
Method
Method
Method
Method
Method
Method
1320:
1330:
9040:
9041:
9045:
9050:
9080:
Method 9081:
Method 9090:
Method 9095:
Method 9100:
Method 9310:
Method 9315:
Multiple Extraction Procedure
Extraction Procedure for Oily Wastes
pH Electrometric Measurement
pH Paper Method
Soil 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
Saturated Hydraulic Conductivity, Saturated
Leachate Conductivity, and Intrinsic
Permeability
Gross Alpha & Gross Beta
Alpha-Emitting Radium Isotopes
PART II CHARACTERISTICS
CHAPTER SEVEN — INTRODUCTION AND REGULATORY DEFINITIONS.
7.1 Ignitability
7.2 Corrositivity
7.3 Reactivity
Section 7.3.3.2: Test Method to Determine Hydrogen Cyanide
Released from Wastes
Section 7.3.4.1: Test Method to Determine Hydrogen Sulfide
Released from Wastes
7.4 Extraction Procedure Toxicity
CONTENTS - 7
Revision 0
Date September 1986
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CHAPTER EIGHT — METHODS FOR DETERMINING CHARACTERISTICS
8.1 Ignllability
Method 1010: Pensky-Martens Closed-Cup Method for Determining
Ign1tab1l1ty
Method 1020: Setaflash Closed-Cup Method for Determining
Ign1tab1l1ty
8.2 Corros1v1ty
Method 1110: Corroslvlty Toward Steel
8.3 Reactivity
8.4 Toxlclty
Method 1310: Extraction Procedure (EP) Toxlclty Test Method
and Structural Integrity Test
APPENDIX — COMPANY REFERENCES
CONTENTS - 8
Revision
Date September 1986
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VOLUME TWO
ABSTRACT
TABLE OF CONTENTS
METHOD INDEX AND CONVERSION TABLE
PREFACE
CHAPTER ONE. REPRINTED — QUALITY CONTROL
1.1 Introduction
1.2 Quality Control
1.3 Detection Limit and Quantification Limit
1.4 Data Reporting
1.5 Quality Control Documentation
1.6 References
PART III SAMPLING
CHAPTER NINE — SAMPLING PLAN
9.1 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
CONTENTS - 9
Revision
Date September 1986
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PART IV MONITORING
CHAPTER ELEVEN — GROUND WATER MONITORING
11.1 Background and Objectives
11.2 Relationship to the Regulations and to Other Documents
11.3 Revisions and Additions
11.4 Acceptable Designs and Practices
11.5 Unacceptable Designs and Practices
CHAPTER TWELVE — LAND TREATMENT MONITORING
12.1 Background
12.2 Treatment Zone
12.3 Regulatory Definition
12.4 Monitoring and Sampling Strategy
12.5 Analysis
12.6 References and Bibliography
CHAPTER THIRTEEN — INCINERATION
13.1 Introduction
13.2 Regulatory Definition
13.3 Waste Characterization Strategy
13.4 Stack-Gas Effluent Characterization Strategy
13.5 Additional Effluent Characterization Strategy
13.6 Selection of Specific Sampling and Analysis Methods
13.7 References
APPENDIX — COMPANY REFERENCES
CONTENTS - 10
Revision
Date September 1986
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METHOD INDEX AND CONVERSION TABLE
Method Number,
Third Edition
0010
0020
0030
1010
1020
1110
1310
1320
1330
3005
3010
3020
3040
3050
3500
3510
3520
3540
3550
3580
3600
3610
3611
3620
3630
3640
3650
3660
3810
3820
5030
5040
6010
7000
7020
Chapter Number.
Third Edition
Ten
Ten
Ten
Eight
Eight
Eight
Eight
Six
Six
Three
Three
Three
Three
Three
(8.1)
(8.1)
8.2
8.4
Four (4.2.
Four
Four
4.2.
4.2.
Four (4.2.
Four (4.2.
Four (4.2.
Four
Four
Four
Four
Four
4.2.
4.2.
4.2.
4.2.
4.2.
Four (4.2.
)
)
1)
i!
ij
1)
2l
2)
2)
2)
2)
2)
Four (4.2.2)
Four (4.2.2)
Four
Four
(4.4)
(4.4)
Four (4.2.
Four (4.2,
Three
Three
Three
1)
1)
Method Number,
Current Revision
Second Edition
0010
0020
0030
1010
1020
1110
1310
1320
1330
3005
3010
3020
3040
3050
None (new method)
3510
3520
3540
3550
None (new method)
None (new method)
None (new method)
3570
None (new method)
None (new method)
None (new method)
None (new method)
None (new method)
5020
None (new method)
5030
3720
6010
7000
7020
Number
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 1
Revision 0
Date September 1986
-------
METHOD INDEX AND CONVERSION TABLE
(Continued)
Method Number,
Third Edition
Chapter Number,
Third Edition
Method Number,
Second Edition
Current Revision
Number
7040
7041
7060
7061
7080
7090
7091
7130
7131
7140
7190
7191
7195
7196
7197
7198
7200
7201
7210
7380
7420
7421
7450
7460
7470
7471
7480
7481
7520
7550
7610
7740
7741
7760
7770
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Tnree
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
7040
7041
7060
7061
7080
7090
7091
7130
7131
7140
7190
7191
7195
7196
7197
7198
7200
7201
7210
7380
7420
7421
7450
7460
7470
7471
7480
7481
7520
7550
7610
7740
7741
7760
7770
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
METHOD INDEX - 2
Revision 0
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 (4.3.1)
Four (
Four (
Four |
Four 1
4.3.1)
4.3.1)
4.3.1)
4.3.1)
Four (4.3.1)
Four (4.3.1)
Four (4.3.1)
Four 1
Four (
4.3.1)
4.3.1
Four (4.3.1
Four (4.3.1
Four (4.3.2
Four
Four
Four
Four
Five
Five
Five
Five
Five
Five
Five
Six
Six
Six
Six
4.3.2)
4.3.2]
4.3.2)
4.3.3]
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
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) 1s Intended to provide a
unified, up-to-date source of Information on sampling and analysis related to
compliance with RCRA regulations. It brings together Into one reference all
sampling and testing methodology approved by the Office of Solid Waste for use
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 1n
sampling and analytical situations require a certain amount of flexibility.
The solutions to these problems will depend, in part, on the skill, training,
and experience of the analyst. For some situations, 1t 1s possible to use
this manual 1n rote fashion. In other situations, 1t will require a
combination of technical abilities, using the manual as guidance rather than
in a step-by-step, word-by-word fashion. Although this puts an extra burden
on the user, 1t 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 1n evaluating the waste
characteristics. Volume II deals with sample acquisition and includes quality
control, sampling plan design and Implementation, and field sampling methods.
Included for the convenience of sampling personnel are discussslons 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
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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 1n 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 1s hazardous because it
exhibits a particular characteristic.
Volume II gives background Information on statistical and nonstatlstlcal
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
1n developing data quality objectives, sampling plans, and laboratory SOP's.
Significant interferences, or other problems, may be encountered with
certain samples. In these situations, the analyst 1s advised to contact the
Chief, Methods Section (WH-562B) Technical Assessment Branch, Office of Solid
Waste, US EPA, Washington, DC 20460 (202-382-4761) for assistance. The
manual is 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
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CHAPTER ONE,
REPRINTED
QUALITY CONTROL
1.1 INTRODUCTION
Appropriate use of data generated under the great range of analytical
conditions encountered in RCRA analyses requires reliance on the quality
control practices incorporated into the methods and procedures. The
Environmental Protection Agency generally requires using approved methods for
sampling and analysis operations fulfilling regulatory requirements, but the
mere approval of these methods does not guarantee adequate results.
Inaccuracies can result from many causes, including unanticipated matrix
effects, equipment malfunctions, and operator error. Therefore, the quality
control component of each method is indispensable.
The data acquired from quality control procedures are used to estimate
and evaluate the information content of analytical data and to determine the
necessity or the effect of corrective action procedures. The means used to
estimate information content include precision, accuracy, detection limit, and
other quantifiable and qualitative indicators.
1.1.1 Purpose of this Chapter
This chapter defines the quality control procedures and components that
are mandatory 1n the performance of analyses, and indicates the quality
control information which must be generated with the analytical data. Certain
activities in an Integrated program to generate quality data can be classified
as management (QA) and other as functional (QC). The presentation given here
1s an overview of such a program.
The following sections discuss some minimum standards for QA/QC programs.
The chapter 1s not a guide to constructing quality assurance project plans,
quality control programs, or a quality assurance organization. Generators who
are choosing contractors to perform sampling or analytical work, however,
should make their choice only after evaluating the contractor's QA/QC program
against the procedures presented in these sections. Likewise, laboratories
that sample and/or analyze solid wastes should similarlly evaluate their QA/QC
programs.
Most of the laboratories who will use this manual also carry out testing
other than that called for 1n SW-846. Indeed, many user laboratories have
multiple mandates, Including analyses of drinking water, wastewater, air and
industrial hygiene samples, and process samples. These laboratories will, In
most cases, already operate under an organizational structure that Includes
QA/QC. Regardless of the extent and history of their programs, the users of
this manual should consider the development, status, and effectiveness of
their QA/QC program 1n carrying out the testing described here.
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1.1.2 Program Design
The Initial step for any sampling or analytical work should be strictly
to define the program goals. Once the goals have been defined, a program must
be designed to meet them. QA and QC measures will be used to monitor the
program and to ensure that all data generated are suitable for their intended
use. The responsibility of ensuring that the QA/QC measures are properly
employed must be assigned to a knowledgeable person who is not directly
involved in the sampling or analysis.
One approach that has been found to provide a useful structure for a
QA/QC program 1s the preparation of both general program plans and project-
specific QA/QC plans.
The program plan for a laboratory sets up basic laboratory policies,
Including QA/QC, and may Include standard operating procedures for specific
tests. The program plan serves as an operational charter for the laboratory,
defining its purposes, Its organization and its operating principles. Thus,
1t is an orderly assemblage of management policies, objectives, principles,
and general procedures describing how an agency or laboratory intends to
produce data of known and accepted quality. The elements of a program plan
and Us preparation are described in QAMS-004/80.
Project-specific QA/QC plans differ from program plans 1n that specific
details of a particular sampling/analysis program are addressed. For example,
a program plan might state that all analyzers will be calibrated according to
a specific protocol given in written standard operating procedures for the
laboratory (SOP), while a project plan would state that a particular protocol
will be used to calibrate the analyzer for a specific set of analyses that
have been defined in the plan. The project plan draws on the program plan or
its basic structure and applies this management approach to specific
determinations. A given agency or laboratory would have only one quality
assurance program plan, but would have a quality assurance project plan for
each of Its projects. The elements of a project plan and its preparation are
described 1n QAMS/005/80 and are listed 1n Figure 1-1.
Some organizations may find 1t Inconvenient or even unnecessary to
prepare a new project plan for each new set of analyses, especially analytical
laboratories which receive numerous batches of samples from various customers
within and outside their organizations. For these organizations, 1t 1s
especially Important that adequate QA management structures exist and that any
procedures used exist as standard operating procedures (SOP), written
documents which detail an operation, analysis or action whose mechanisms are
thoroughly prescribed and which is commonly accepted as the method for
performing certain routine or repetitive tasks. Having copies of SW-846 and
all Its referenced documents 1n one's laboratory 1s not a substitute for
having In-house versions of the methods written to conform to specific
Instrumentation, data needs, and data quality requirements.
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FIGURE 1-1
ESSENTIAL ELEMENTS OF A QA PROJECT PLAN
1. Title Page
2. Table of Contents
3. Project Description
4. Project Organization and Responsibility
5. QA Objectives
6. Sampling Procedures
7. Sample Custody
8. Calibration Procedures and Frequency
9. Analytical Procedures
10. Data Reduction, Validation, and Reporting
11. Internal Quality Control Checks
12. Performance and System Audits
13. Preventive Maintenance
14. Specific Routine Procedures Used to Assess Data
Precision, Accuracy, and Completeness
15. Corrective Action
16. Quality Assurance Reports to Management
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1.1.3 Organization and Responsibility
As part of any measurement program, activities for the data generators,
data reviewers/approvers, and data users/requestors must be clearly defined.
While the specific titles of these Individuals will vary among agencies and
laboratories, the most basic structure will Include at least one
representative of each of these three types. The data generator 1s typically
the Individual who carries out the analyses at the direction of the data
user/requestor or a designate within or outside the laboratory. The data
reviewer/approver 1s responsible for ensuring that the data produced by the
data generator meet agreed-upon specifications.
Responsibility for data review 1s sometimes assigned to a "Quality
Assurance Officer" or "QA Manager." This Individual has broad authority to
approve or disapprove project plans, specific analyses and final reports. The
QA Officer is Independent from the data generation activities. In general,
the QA Officer is responsible for reviewing and advising on all aspects of
QA/QC, including:
Assisting the data requestor in specifying the QA/QC procedure to be used
during the program;
Making on-s1te evaluations and submitting audit samples to assist in
reviewing QA/QC procedures; and,
f problems are detected, making recommendations to the data requestor and
upper corporate/institutional management to ensure that appropriate
corrective actions are taken.
In programs where large and complex amounts of data are generated from
both field and laboratory activities, 1t is helpful to designate sampling
monitors, analysis monitors, and quality control/data monitors to assist 1n
carrying out the program or project.
The sampling monitor 1s responsible for field activities. These include:
Determining (with the analysis monitor) appropriate sampling equipment
and sample containers to minimize contamination;
Ensuring that samples are collected, preserved, and transported as
specified in the workplan; and
Checking that all sample documentation (labels, field notebooks, chaln-
of-custody records, packing lists) 1s correct and transmitting that
Information, along with the samples, to the analytical laboratory.
The analysis monitor 1s responsible for laboratory activities. These
Include:
Training and qualifying personnel 1n specified laboratory QC and
analytical procedures, prior to receiving samples;
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Receiving samples from the field and verifying that incoming samples
correspond to the packing list or chain-of-custody sheet; and
Verifying that laboratory QC and analytical procedures are being followed
as specified in the workplan, reviewing sample and QC data during the
course of analyses, and, 1f questionable data exist, determining which
repeat samples or analyses are needed.
The quality control and data monitor is responsible for QC activities and
data management. These include:
Maintaining records of all incoming samples, tracking those samples
through subsequent processing and analysis, and, ultimately,
appropriately disposing of those samples at the conclusion of the
program;
Preparing quality control samples for analysis prior to and during the
program;
Preparing QC and sample data for review by the analysis coordinator and
the program manager; and
Preparing QC and sample data for transmission and entry into a computer
data base, if appropriate.
1.1.4 Performance and Systems Audits
The QA Officer may carry out performance and/or systems audits to ensure
that data of known and defensible quality are produced during a program,.
Systems audits are qualitative evaluations of all components of field and
laboratory quality control measurement systems. They determine 1f the
measurement systems are being used appropriately. The audits may be carried
out before all systems are operational, during the program, or after the
completion of the program. Such audits typically Involve a comparison of the
activities given 1n the QA/QC plan with those actually scheduled or performed.
A special type of systems audit 1s the data management audit. This audit
addresses only data collection and management activities.
The performance audit 1s a quantitative evaluation of the measurement
systems of a program. It requires testing the measurement systems with
samples of known composition or behavior to evaluate precision and accuracy.
The performance audit is carried out by or under the auspices of the QA
Officer without the knowledge of the analysts. Since this is seldom
achievable, many variations are used that Increase the awareness of the
analyst as to the nature of the audit material.
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1.1.5 Corrective Action
Corrective action procedures should be addressed 1n the program plan,
project, or SOP. These should include the following elements:
The EPA predetermined limits for data acceptability beyond which
corrective action 1s required;
Procedures for corrective action; and,
For each measurement system, identification of the individual responsible
for initiating the corrective action and the individual responsible for
approving the corrective action, if necessary.
The need for corrective action may be Identified by system or performance
audits or by standard QC procedures. , The essential steps in the corrective
action system are:
Identification and definition of the problem;
Assignment of responsibility for investigating the problem;
Investigation and determination of the cause of the problem;
Determination of a corrective action to eliminate the problem;
Assigning and accepting responsibility for implementing the corrective
action; .
Implementing the corrective action and evaluating Its effectiveness; and
Verifying that the corrective action has eliminated the problem.
The QA Officer should ensure that these steps are taken and that the
problem which led to the corrective action has been resolved.
1.1.6 QA/QC Reporting to Management
QA Project Program or Plans should provide a mechanism for periodic
reporting to management (or to the data user) on the performance of the
measurement system and the data quality. Minimally, these reports should
include:
Periodic assessment of measurement quality indicators, i.e., data
accuracy, precision and completeness;
Results of performance audits;
Results of system audits; and
Significant QA problems and recommended solutions.
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The individual responsible within the organization structure for
preparing the periodic reports should be identified in the organizational or
management plan. The final report for each project should also include a
separate QA section which summarizes data quality information contained in the
periodic reports.
Other guidance on quality assurance management and organizations is
available from the Agency and professional organizations such as ASTM, AOAC,
APHA and FDA.
1.1.7 Quality Control Program for the Analysis of RCRA Samples
An analytical quality control program develops information which can be
used to:
Evaluate the accuracy and precision of analytical data in order to
establish the quality of the data;
Provide an indication of the need for corrective actions, when comparison
with existing regulatory or program criteria or data trends shows that
activities must be changed or monitored to a different degree; and
To determine the effect of corrective actions.
1.1.8 Definitions
ACCURACY:
ANALYTICAL BATCH:
BLANK:
Accuracy means the nearness of a result or the mean (7) of
a set of results to the true value. Accuracy is assessed
by means of reference samples and percent recoveries.
The basic unit for analytical quality control is the
analytical batch. The analytical batch is defined as
samples which are analyzedtogether with the same method
sequence and the same lots of reagents and with the
manipulations common to each sample within the same time
period or in continuous sequential time periods. Samples
in each batch should be of similar composition.
A blank is an artificial sample designed to monitor the
introduction of artifacts Into the process. For aqueous
samples, reagent water is used as a blank matrix; however,
a universal blank matrix does not exist for solid samples,
and therefore, no matrix is used. The blank is taken
through the appropriate steps of the process.
A reagent blank is an aliquot of analyte-free water or
solvent analyzed with the analytical batch. Field blanks
are aliquots of analyte-free water or solvents brought to
the field in sealed containers and transported back to the
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CALIBRATION
CHECK:
CHECK SAMPLE:
laboratory with the sample containers. Trip blanks and
equipment blanks are two specific types of field blanks.
Trip blanks are not opened in the field. They are a check
on sample contamination originating from sample transport,
shipping and from site conditions. Equipment blanks are
opened in the field and the contents are poured
appropriately over or through the sample collection device,
collected in a sample container, and returned to the
laboratory as a sample. Equipment blanks are a check on
sampling device cleanliness.
Verification of the ratio of instrument response to analyte
amount, a calibration check, is done by analyzing for
appropriate solvent. Calibration
from a stock solution which is
analyte standards 1n an
check solutions are made
different from the stock used to prepare standards.
A blank which has been spiked with the analyte(s) from an
independent source 1n order to monitor the execution of the
analytical method 1s called a check sample. The level of
the spike shall be at the regulatory action level when
applicable. Otherwise, the spike shall be at 5 times the
estimate of the quantification
shall be phase matched with
characterized: for an example,
appropriate for an aqueous sample.
limit. The matrix used
the samples and well
reagent grade water is
ENVIRONMENTAL
SAMPLE:
An environmental sample or field sample Is a representative
sample of any material (aqueous, nonaqueous, or multimedia)
collected from any source for which determination of
composition or contamination is requested or required. For
the purposes of this manual, environmental samples shall be
classified as follows:
Surface Water and Ground Water;
Drinking Water — delivered (treated or untreated) water
designated as potable water;
Water/Wastewater — raw source waters for public drinking
water supplies, ground waters, municipal Influents/
effluents, and Industrial Influents/effluents;
Sludge — municipal sludges and Industrial sludges;
Waste — aqueous and nonaqueous liquid wastes, chemical
solids, contaminated soils, and industrial liquid and solid
wastes.
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MATRIX/SPIKE-
DUPLICATE
ANALYSIS:
MQL:
PRECISION:
PQL:
RCRA:
REAGENT GRADE:
In matrix/spike duplicate analysis, predetermined quantl-
ties of stock solutions of certain analytes are added to a
added to a sample matrix prior to sample extraction/
digestion and analysis. Samples are split into duplicates,
spiked and analyzed. Percent recoveries are calculated for
each of the analytes detected. The relative percent
difference between the samples is calculated and used to
assess analytical precision. The concentration of the
spike should be at the regulatory standard level or the
estimated or actual method quantification limit. When the
concentration of the analyte in the sample is greater than
0.1%, no spike of the analyte 1s necessary.
The method' quantification limit (MQL) is the minimum
concentration of a substance that can be measured and
reported.
Precision means the measurement of agreement of a set of
replicate results among themselves without assumption of
any prior information as to the true result. Precision 1s
assessed by means of duplicate/replicate sample analysis.
The practical quantisation limit (PQL) is the lowest level
that can be reliably achieved within specified limits of
precision and accuracy during routine laboratory operating
conditions.
The Resource Conservation and Recovery Act.
Analytical reagent (AR) grade, ACS
reagent grade are synonomous terms
fit
reagent grade, and
for reagents which
of the Committee on
REPLICATE SAMPLE:
orm to the current specifications
Analytical Reagents of the American Chemical Society.
A replicate sample 1s a sample prepared by dividing a
sample Into two or more separate aliquots. Duplicate
samples are considered to be two replicates.
STANDARD CURVE: A standard curve 1s a
known analyte standard
the analyte.
curve which plots concentrations of
versus the Instrument response to
SURROGATE:
Surrogates are organic compounds which are similar to
analytes of Interest 1n chemical composition, extraction,
and chromatography, but which are not normally found in
environmental samples. These compounds are spiked Into all
blanks, standards, samples and spiked samples prior to
analysis. Percent recoveries are calculated for each
surrogate.
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WATER: Reagent, analyte-free, or laboratory pure water means
distilled or deionized water or Type II reagent water which
1s free of contaminants that may interfere with the
analytical test in question.
1.2 QUALITY CONTROL
The procedures indicated below are to be performed for all analyses.
Specific instructions relevant to particular analyses are given in the
pertinent analytical procedures.
1.2.1 Field Quality Control
The sampling component of the Quality Assurance Project Plan (QAPP) shall
include:
Reference to or incorporation of accepted sampling techniques in the
sampling plan;
Procedures for documenting and justifying any field actions contrary to
the QAPP; :
Documentation of all pre-field activities such as equipment check-out,
calibrations, and container storage and preparation;
Documentation of field measurement quality control data (quality control
procedures for such measurements shall be equivalent to corresponding
laboratory QC procedures);
Documentation of field activities;
Documentation of post-field activities including sample shipment and
receipt, field team de-briefing and equipment check-in;
Generation of quality control samples Including duplicate samples, field
blanks, equipment blanks, and trip blanks; and
The use of these samples in the context of data evaluation, with details
of the methods employed (including statistical methods) and of the
criteria upon which the information generated will be judged.
1.2.2 Analytical Quality Control
A quality control operation or component is only useful 1f it can be
measured or documented. The following components of analytical quality
control are related to the analytical batch. The procedures described are
intended to be applied to chemical analytical procedures; although the
principles are applicable to radio-chemical or biological analysis, the
procedures may not be directly applicable to such techniques.
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All quality control data and records required by this section shall be
retained by the laboratory and shall be made available to the data requestor
as appropriate. The frequencies of these procedures shall be as stated below
or at least once with each analytical batch.
1.2.2.1 Spikes. Blanks and Duplicates
General Requirements
These procedures shall be performed at least once with each analytical
batch with a minimum of once per twenty samples.
1.2.2.1.1 Duplicate Spike
A split/spiked field sample sha]l be analyzed with every analytical batch
or once intwentysamples, whichever is the greater frequency. Analytes
stipulated by the analytical method, by applicable regulations, or by other
specific requirements must be spiked into the sample. Selection of the sample
to be spiked and/or split depends on the information required and the variety
of conditions within a typical matrix. In some situations, requirements of
the site being sampled may dictate that the sampling team select a sample to
be spiked and split based on a pre-visit evaluation or the on-s1te inspection.
This does not preclude the laboratory's spiking a sample of its own selection
as well. In other situations the laboratory may select the appropriate
sample. The laboratory's selection should be guided by the objective of
spiking, which is to determine the extent of matrix bias or Interference on
analyte recovery and sample-to-sample precision. For soil/sediment samples,
spiking is performed at approximately 3 ppm and, therefore, compounds in
excess of this concentration in the sample may cause Interferences for the
determination of the spiked analytes.
1.2.2.1.2 Blanks
Each batch shall be accompanied by a reagent blank. The reagent blank
shall be carried through the entire analytical procedure.
1.2.2.1.3 Field Samples/Surrogate Compounds
Every blank, standard, and environmental sample (Including matrix
spike/matrix duplicate samples) shall be spiked with surrogate compounds prior
to purging or extraction. Surrogates shall be spiked into samples according
to the appropriate analytical methods. Surrogate spike recoveries shall fall
within the control limits set by the laboratory (in accordance with procedures
specified in the method or within +20%) for samples falling within the
quantification limits without dilution? Dilution of samples to bring the
analyte concentration Into the linear range of calibration may dilute the
surrogates below the quantification limit; evaluation of analytical quality
then will rely on the quality control embodied 1n the check, spiked and
duplicate spiked samples.
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1.2.2.1.4 Check Sample
Each analytical batch shall contain a check sample. The analytes
employed shall be a representative subset of the analytes to be determined.
The concentrations of these analytes shall approach the estimated
quantification limit in the matrix of the check sample. In particular, check
samples for metallic analytes shall be matched to field samples in phase and
in generaT~matrix composition.
1.2.2.2 Clean-Ups
Quality control procedures described here are Intended for adsorbent
chromatography and back extractions applied to organic extracts. All batches
of adsorbents (Florisil, alumina, silica gel, etc.) prepared for use shall be
checked for analyte recovery by running the elution pattern with standards as
a column check. The elution pattern shall be optimized for maximum recovery
of analytes and maximum rejection of contaminants.
1.2.2.2.1 Column Check Sample
The elution pattern shall be reconfirmed with a column check of standard
compounds after activating or deactivating a batch of adsorbent. These
compounds shall be representative of each elution fraction. Recovery as
specified in the methods 1s considered an acceptable column check. A result
lower than specified indicates that the procedure is not acceptable or has
been misapplied.
1.2.2.2.2 Column Check Sample Blank
The check blank shall be run after activating or deactivating a batch of
adsorbent.
1.2.2.3 Determinations
1.2.2.3.1 Instrument'Adjustment; Tuning, Alignment, etc.
Requirements and procedures are instrument- and method-specific.
Analytical Instrumentation shall be tuned and aligned in accordance with
requirements which are specific to the Instrumentation procedures employed.
Individual determinative procedures shall be consulted. Criteria for Initial
conditions and for continuing confirmation conditions for methods within this
manual are found 1n the appropriate procedures.
1.2.2.3.2 Calibration .
Analytical Instrumentation shall be calibrated 1n accordance with
requirements which are specific to the Instrumentation and procedures
employed. Introductory Methods 7000 and 8000 and appropriate analytical
procedures shall be consulted for criteria for Initial and continuing
calibration.
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1.2.2.3.3 Additional QC Requirements for Inorganic Analysis
Standard curves used In the determination of Inorganic analytes shall be
prepared as follows:
Standard curves derived from data consisting of one reagent blank and
four concentrations shall be prepared for each analyte. The response for each
prepared standard shall be based upon the average of three replicate readings
of each standard. The standard curve shall be used with each subsequent
analysis provided that the standard curve is verified by using at least one
reagent blank and one standard at a level normally encountered or expected 1n
such samples. The response for each standard shall be based upon the average
of three replicate readings of the standard. If the results of the
verification are not within +10% of the original curve, a new standard shall
be prepared and analyzed. If the results of the second verification are not
within +10% of the original standard curve, a reference standard should be
employeH to determine if the discrepancy 1s with the standard or with the
Instrument. New standards should also be prepared on a quarterly basis at a
minimum. All data used 1n drawing or describing the curve shall be so
Indicated on the curve or its description. A record shall be made of the
verification.
Standard deviations and relative standard deviations shall be calculated
for the percent recovery of analytes from the spiked sample duplicates and
from the check samples. These values shall be established for the twenty most
recent determinations in each category.
1.2.2.3.4 Additional Quality Control Requirements for
Organic Analysis ~
The following requirements shall be applied to the analysis of samples by
gas chromatography, liquid chromatography and gas chromatography/mass
spectrometry.
The calibration of each instrument shall be verified at frequencies
specified 1n the methods. A new standard curve must be prepared as specified
1n the methods.
The tune of each GC/MS system used for the determination of organic
analytes shall be checked with 4-bromofluorobenzene (BFB) for determinations
of volatiles and with decafluorotriphenylphosphlne (DFTPP) for determinations
of seml-volatiles. The required ion abundance criteria shall be met before
determination of any analytes. If the system does not meet the required
specification for one or more of the required Ions, the Instrument must be
retuned and rechecked before proceeding with sample analysis. The tune
performance check criteria must be achieved daily or for each 12 hour
operating period, whichever 1s more frequent.
Background subtraction should be straightforward and designed only to
eliminate column bleed or instrument background ions. Background subtraction
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actions resulting 1n spectral distortions for the sole purpose of meeting
special requirements are contrary to the objectives of Quality Assurance and
are unacceptable.
For determinations by HPLC or GC, the Instrument calibration shall be
verified as specified in the methods.
1.2.2.3.5 Identification
Identification of all analytes must be accomplished with an authentic
standard of the analyte. When authentic standards are not available,
identification 1s tentative.
For gas chromatographlc determinations of specific analytes, the relative
retention time of the unknown must be compared with that of an authentic
standard. For compound confirmation, a sample and standard shall be re-
analyzed on a column of different selectivity to obtain a second
characteristic relative retention time. Peaks must elute within daily
retention time windows to be declared a tentative or confirmed identification.
For gas chromatographic/mass spectrometric determinations of specific
analytes, the spectrum of the analyte should conform to a literature
representation of the spectrum or to a spectrum of the authentic standard
obtained after satisfactory tuning of the mass spectrometer and within the
same twelve-hour working shift as the analytical spectrum. The appropriate
analytical methods should be consulted for specific criteria for matching the
mass spectra, relative response factors, and relative retention times to those
of authentic standards.
1.2.2.3.6 Quantification
The procedures for quantification of analytes are discussed 1n the
appropriate general procedures (7000, 8000) and the specific analytical
methods.
In some situations in the course of determining metal analytes. matrix-
matched calibration standards may be required. These standards shall be
composed of the pure reagent, approximation of the matrix, and reagent
addition of major Interferents in the samples. This will be stipulated in the
procedures.
Estimation of the concentration of an organic compound not contained
within the calibration standard may be accomplished by comparing mass spectral
response of the compound with that of an internal standard. The procedure 1s
specified in the methods.
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1.3 DETECTION LIMIT AND QUANTIFICATION LIMIT
The detection limit and quantification limit of analytes shall be
evaluated by determining the noise level of response for each sample 1n the
batch. If analyte 1s present, the noise level adjacent 1n retention time to
the analyte peak may be used. For wave-length dispersive Instrumentation,
multiple determinations of dlgestates with no detectable analyte may be used
to establish the noise level. The method of standard additions should then be
used to determine the calibration curve using one digestate or extracted
sample 1n which the analyte was not detected. The slope of the calibration
curve, m, should be calculated using the following relations:
m = slope of calibration line
SB = standard deviation of the average noise level
MDL = KSB/m
For K = 3; MDL = method detection limit.
For K = 5; MQL = method quantisation limit.
1.4 DATA REPORTING
The requirement of reporting analytical results on a wet-weight or a dry-
weight basis 1s dictated by factors such as: sample matrix; program or
regulatory requirement; and objectives of the analysis.
Analytical results shall be reported with the percent moisture or percent
solid content of the sample.
1.5 QUALITY CONTROL DOCUMENTATION
The following sections list the QC documentation which comprises the
complete analytical package. This package should be obtained from the data
generator upon request. These forms, or adaptations of these forms, shall be
used by the data generator/reporter for Inorganics (I), or for organics (0) or
both (I/O) types of determinations.
1.5.1 Analytical Results (I/O: Form I)
Analyte concentration.
Sample weight.
Percent water (for non-aqueous samples when specified).
Final volume of extract or diluted sample.
Holding times (I: Form X).
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1.5.2 Calibration (I: Form II; 0: Form V, VI, VII, IX)
Calibration curve or coefficients of the linear equation which
describes the calibration curve.
Correlation coefficient of the linear calibration.
Concentration/response data (or relative response data) of the
calibration check standards, along with dates on which they were
analytically determined.
1.5.3 Column Check (0: Form X)
Results of column chromatography check, with the chromatogram.
1.5.4 Extraction/Digestion (I/O: Form I)
Date of the extraction for each sample.
1.5.5 Surrogates (0: Form II)
Amount of surrogate spiked, and percent recovery of each surrogate.
1.5.6 Matrix/Duplicate Spikes (I: Form V, VI; 0: Form III)
Amount spiked, percent recovery, and relative percent difference for
each compound 1n the spiked samples for the analytical batch.
1.5.7 Check Sample (I: Form VII; 0: Form VIII)
Amount spiked, and percent recovery of each compound spiked.
1.5.8 Blank (I: Form III; 0: Form IV)
Identity and amount of each constituent.
1.5.9 Chromatograms (for organic analysis)
All chromatograms for reported results, properly labeled with:
- Sample Identification
- Method Identification
- Identification of retention time of analyte on the chromatograms.
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1.5.10 Quantitative Chromatogram Report (0: Forms VIII, IX, X)
Retention time of analyte.
Amount Injected.
Area of appropriate calculation of detection response.
Amount of analyte found.
Date and time of Injection.
1.5.11 Mass Spectrum
Spectra of standards generated from authentic standards (one for
each report for each compound detected).
Spectra of analytes from actual analyses.
Spectrometer Identifier.
1.5.12 Metal Interference Check Sample Results (I: Form IV)
1.5.13 Detection Limit (I: Form VII; 0: Form I)
Analyte detection limits with methods of estimation.
1.5.14 Results of Standard Additions (I: Form VIII)
1.5.15 Results of Serial Dilutions (I: Form IX)
1.5.16 Instrument Detection Limits (I: Form XI)
1.5.17 ICP Interelement Correction Factors and ICP Linear Ranges
(when applicable) (I; Form XII. Form XIII).
1.6 REFERENCES
1. Guidelines and Specifications for Preparing Quality Assurance Program
Plans, September 20, 1980, Office of Monitoring Systems and Quality Assurance,
ORD, U.S. EPA, QAMS-004/80, Washington, DC 20460.
2. Interim Guidelines and Specifications for Preparing Quality Assurance
Project Plans, December 29, 1980, Office of Monitoring Systems and Quality
Assurance, ORD, U.S. EPA, QAMS-005/80, Washington, DC 20460.
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Lat Kaz
COVLK PACL
INURGAN'IC ANALYSES L-AlA FACKAvL
Q.C. Kepori I.'o.
EPA No.
Sar.ple N'ur.c.<. r.^
Lab ID No. EKA No. . Lab 1U No.
Concents:
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Forn 1
Sarcplc No.
Date
LA* NAME
INOkCAMC ANALYSIS DATA SHLE1
CASE NO.
LAb SAMPLE 1L). No.
Lab Receipt Date
QC REPORT NO.
Llenc-nts Identified and Measured
Matrix: Uater
11. Iron
12. Lead
Cyanide
Soil
Sludge
uther
uj:/L or iib/kt dry weight (Circle One)
1.
2.
3.
5.
6.
7.
b.
9.
10.
Aluninur
AntiBor.v
Arsenic
bariurt
Bervlliur;
Cadiriuir.
Calciur
Chror.iur.
Cobalt
Copper
n.
14.
15."
16.
17.
16.
IV.
2u.
21.
22.
Magnesiu:
Manganese
Mercurv
Nickel
Potassiur
Seleniur
Silver
Sodiuc
Thalliur
Vanadium
26. Zinc
Precent Solids (:'.)
Commonts:
Lab
ONE - 19
Revision 0
Date September 1986
-------
LAB
Fore II
Q. C. .Report No.
INITIAL AND CONTINUING CALlbRATlUN VLKlFlCATlUN
CASL Nu.
DATE
Compound
Metals:
1. Alurcinur,
2. Antimony
3. Arsenic
4. barium
5. Beryiliun;
t>. Cadrr.iur
7. Calcium
b. Chroniuci
V. Cobalt
JO. Copper
JJ. Iron
12. Lead
13. Magnesium
14. Manganese
15. fiercury
It. Nickel
UNITS: ug/L
Initial CalibJ Continuing Calibration2
True Value
17. Potassiun|
lo. Seleniur,
IV. Silver
20. Sodium
21. Thallium
22. Vanadium |
23. ^inc
Otlicr :
Cyanide
Found
•
XR
I
True Value
•
i
i
i
Found
XR
Found
t
|
ik
1
1
Method-
1
/ 1!
1 Initial Calibration Source ^ cjoiuinuinn Calibration Source
Indicate Analytical Method Used: V - 1CP; A -.Fianw AA; F - Furnace AA
ONE - 20
Revision 0
Date September 1986
-------
Fonr. Ill
C. Report No.
BLANKS
LAB NAMŁ
UATt.
CASE
UNI 7
Compound
Metals:
1. Aluminur.
2. Antimonv
3. Arsenic
A. bariur
5. berylliur
b. Cadciu-
7. Calcium
8. Chror.iur
9. Cobalt
10. Copper
11. Iron
12. Lead
1J. hagnesiur,
K. Manganese
13. Mercury
lt>. Nickel
17. Potassiu-r,
16. Selenium
IV. Silver
2(j. Sodium
^1. Thallium
22. Vanadium
iJ. Zinc
Ot he r :
Cyanide
Initial
Call brat ion
Blank Value
Continuing Calibration
Blank Value
1
1
2
3
i
I
Preparation Elar.;
Matrix: Matrix:
1 2
1 Reporting Units: aqueous, u&/L; solid
ONE - 21
Revision 0
Date September 1986
-------
Fore IV
Q. C. Report No.
LAB NAMI
1CF 1NTEKFERENCL CHECK SAT.f'Lt
CASL NO.
Check Sacple l.L.
DATL
Check Sample Source
Units: ug/L
Compound
Metals:
1. Alur.inuTr,
2. An.timonv
3. Arsenic
4. Bariuc
3. berylliur,
fc. Cadtr.iur
7. Calciur.
b. Chrooiun
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
13. Mercury
16. Nickel
17. Potassium
18. Selenium
IV. Silver
20. Sodium
Control Limits'
Mean
21. Thallium j
22. Vanadium
2J. Zinc
Other:
Std. Dev.
•-
True^
1
'•
Initial
Observed
XF.
Final
Observed
HP,
i
Mean value based on n =
True value of LPA 1CP Interference Check Sample or contfactor.standard.
ONE - 22
Revision 0
Date September 1986
-------
Fore V
Q- C. Report No.
SPIKZ SAMPLE RECOVERY-
LAB KAMI
DATE
CASE NO.
Sample he.
Lab Sarspie ID No.
Units
Matrix
Compound
Metals:
1. Aluminuc
2. Antlmonv
3. Arsenic
4. Bariuc
5. Beryllium
6. Cadtiun
7. Calciuc
6. Chrociur.
9. Cobslt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassiuc
Ib. Seleniutr
19. Silver
20. Sodiuc
21. Thalliuc
22. Vanadium
23. Zinc
Other:
Cyanide
Control Limit
IK
Spiked Sample
Result (SSR)
Sample
Result (SR)
Spiked
Added (SA)
,R1
1 XR » |(SSR - SK)/SAj x 100
"N"- out of control
NK" - Not required
Comments:
ONE - 23
Revision 0
Date September 1986
-------
LAB NAME
DATt
fore VI
Q. C. Report No.
DUPLICATES
CASE NO. __
Sample No.
Lab Sample ID No.
Units
Matrix
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Bariutr
5. Bervlliur.
6. Cadeiui
7. Calciur.
8. ChroEiur
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesiur
14. Manganese
15. Mercury
16. Nickel
17. Potassiur
Ib. Seleniuc
1*. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide
Control Limit1
Sample (S)
Duplicate (0)
RPD2
* Out of Control
1 To be added at a later date. 2 RPD • I|S - D|/((S + D)/2)J x 100
NC - Non calculable KP1J due to value(s) less than CROL
ONE - 24
Revision 0
Date September 1986
-------
LAB NAME
Forr.- VII
Q.C. Report No.
INSTRUMENT DETECTION LIMITS ANL
LABORATORY CONTROL SAMPLE
CASE NO.
DATL _
LCS NO.
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
Ł• fiariuc.
5. Beryllium
t>. Cadniur
7. CalciuE
fc. Chrociur
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesiutr.
1A. ilanganese
15. Mercury
16. Nickel
17. Potassiutr.
18. Seleniuo
IV. Silver
20. Sodium
21. Thai Hun
22. Vanadium
23. Zinc
Other:
Cyanide
Required Detection
Licits (CRDL)-UK/1
1('
Instrument Detection
Lioits (IDL)-ug/! '
ICP/AA Furnace
1D< IDf
NR
l.K
Lab Control Sample
ug/L np/kf
(circle one)
True Found 21%
1
- Kot required
ONE - 25
Revision 0
Date September 1986
-------
Fore VIII
O..C. Report No.
SlANDAKi; AUDITION RISl'Llb
LAB NAMt
UATt
CASE NO.
UMTS .'
tPA
Sample V
Llenent
Natrix
0 ADD
Abb.
J
CON.
ADD
ABb-
2
CON .
ADD
ABS.^
3
CON.
I^DL-
At: .^
FINAL
CON. 3
r*
CON is the concentration added, Abb. is the instrument readout in absorbance or
concentration.
J Concentration aŁ determined by .S
*"r" is the correlation coefficient.
+ - correlation coefficient is outsid..- ol control window of O.yy5.
ONE - 26
Revision 0
Date September 1986
-------
LAB NAV.il
DA7L
Terr I>.
Q- C. Report No.
SERIAL DlJ.f710.'.i
CAŁi N'«-!.
Sample No.
La 1: Sasplt 1L *,o.
Units: ug/L
Matrix
Compound
Metals :
1. Aluainur
2. Antirconv
3. Arsenic
* . bariur
i. bervlliur:
t. Cadr.iuTr.
7. Calciur
b. Chror.iur.
V. Cobalt .
Ju. Copper
11. Iron
12. Lead
12. Ma^nesiur
14. Manganese
li. Nickel
lt>. Fotassiur.
17. Seleniur
ib. Silver
IV. Sodiur
20. Thallium
^J. Vanadiun
tl. /Cine
Ot he r :
Initial Sacple
Concentration( 1 )
Serial Dilution
Result(S)
'
X Difference4
..
' Diluted sample concentration corrected tor 1:4 dilution (see Exhibit D)
'*• Percent Difference « M " sl x
NK - Not Required, initial sample concentration less than lu times 1UL
NA - Not Applicable, analyte not determined by 1CP
ONE - 27
Revision 0
Date September 1986
-------
Forp
QC Report No.
HOLDING J1KLH-
LAB KAMI
DATE
CASL Nu.
LPA
Sample No.
..
Matrix
Dace
Received
Mercury
Prep Date
• ^_
Mercury
Holding Time *
(Davs)
CN Prep
Date
CN
Holding Tio;
(Davs)
I
'Holding time is defined as number of days between the date received and the
sample preparation date.
ONE - 28
Revision 0
Date September 1986
-------
LAti NAME
Fore XI
INSTRUMENT DE1LCTION LIMITS
DATE
ICP/Flame AA (Circle One)
Element
1 . Aluninurc
2. Antimonv
3. Arsenic
*. bariutr
i. berylliuc
0. Cadciur.
7 . Ca 1 c i ur:
6. ChroEiur.
V. Cobalt
1U. Copper
11. Iron
12. Lead
Wavelength
(nir.)
Model Number Furnace AA Nuober
1DL
(ug/L)
Element
13. Mapnesiun
JA. Manganese
Wavelength
(nc)
15. Mercury
16. Nickel
17. Potassiuc
Ib. Seleniuc
J9. Silver
20. Sodium.
21. Thslliuc
22. Vanadiur.
23. Zinc
IUL
(up/L)
Footnotes: • Indicate the instrument for which the 1DL applies with a "f" (for ICF
an "A" (for Flame AA), or an "F" (for furnace AA) behind the IUL valu
• Indicate elements commonly run with background correction (AA) with
a "b" behind the analytical wavelength.
• If more than one ICP/Klane or Furnace AA is used, submit separate
Korms X1-X111 for each instrument.
CUMMLKTb:
Lab Manager
ONE - 29
Revision 0
Date September 1986
-------
ICP Interelement Correction Factors
LABORATORY
DATE
ICP Model Nucber
Analyte
1. Ant loon v
2. Arsenic
3. Bariuc
4. Bervlliur
5. Cadciur
6. Chroriur
7. Cobalt
6. Copper
9. Lead
10. Manganese
11. Mercurv
12. Nickel
13. Potassiur
14. Seleniuc
15. Silver
16. Sodium
17. Thalliur,
16. Vanadiuir.
J>. Zinc
Analyte
Wavelength
(n=)'
Interelemen: Correction Joctor'
for
Al
Ca
Fe
«Ł
I
i
1
i
i
COMMENTS:
Lab Manager
ONE - 30
Revision 0
Date September 1986
-------
Fore XII
1CP Interelement Correction Factors
LABORATOKY_
DATE
ICP Model Nucber
Analyte
1. Antimony
2. Arsenic
3. Bariur.
4. Berylliuc
5. Cadciur
6. Chroma UT.
7. Cobalt
fc. Copper
9. Lead
10. Manganese
11. Mercury
12. Nickel
13. Potassium
14. Selenium
15. Silver
16. Sodium
17. Thallium
18. Vanadium
IV. Zinc
Analyte
Wavelength
(nr.)
Intereleoent Correction Factors
for
1
COMMENTS:
Lab Manager
ONE - 31
Revision 0
Date September 1986
-------
LAB NAM!
DATE
Forts XIII
1CP Linear Ranges
1C? Model Nuraber
Analyte
1. Aluninu?.
2. Antioonv
3. Arsenic
t>. Bariur.
5. Berylliuc
•
6. Cadoiuc
7. Calciur
8. Chrociur
9. Cobalt
10. Copper
11. Iron
12. Lead |
Integration
Tir.e
(Seconds )
Concen-
tration
(UE/L)
Analyte
13. Kagnesiur
14. Manganese
1
15. Mercurv
16. Nickel
17. Potassiur
16. Seleniu-
19. Silver
20. Sodiur.
21. Thalliur
22. Vanadiur
23. Zinc
Integration
Time
(Seconds)
Concen-
tration
(ug/L)
1
Footnotes:
• Indicate elements not analyzed by 1CP with the notation **NA".
COMMENTS:
Lab Manager
ONE - 32
Revision 0
Date September 1986
-------
Organics Analysis Data Sheet
(Pagel)
Sample Number
Laboratory Name.
Lab Sample ID i\;
Sample Matrix
Case No.
QC Report No:
Data Release Authorized B\
Date Sample Received:
Volatile Compounds
Date Extracted/Prepared:
Date Analyzed:
Conc/Dit Factor:
-PH.
Percent Moisture: (Not Decanted).
CAS ug/lorug/Kg.
Number (Circle One)
74-87-3
74.63-9
75-01-4
75-00-3
75-09 2
67-64-1
75-15-0
75-35-4
75-34-3
156-60-5
67-66-3
107-06-2
78-933
71-55-6
56-23-5
108-05-4
75-27-4
Cniorometusie
BroTtometheie
Vinyl Cnio'ide
Cnloroethane
Metnylene Cnlonde
Acetone '
Carbon Disuldde
1. 1-DicWoroethene
1. 1-Dichloroeihene
Trans-1. 2-Dtchloroethene
Chlorotorrr.
1. 2-Dichloroethane
2-Butanone
1.1. 1-Trichloroethene
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
CAS 09 /I or ue 'Kg
Number (Circle One!
78-67-5
10061-02-6
79-01-6
124-46-1
79-00-5
71-43-2
10061-01-5
110-75-8
75-25-2
106-10-1
591-78-6
127-18-4
79-34-5
108-86-3
108-90-7
100-41-4
100-42-5
1. 2-Dichlorop'Opene
Trans- 1, 3-Dichloropropene
Trichloroethene
Oibromochloromethane
1.1. 2 -Trichloroethene
Benzene
cis-1. 3-Dichloropropeie
2-Chloroethylvinylethe'
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1. 1.2. 2-Tetrachloroeth»ne
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Tota' Xylenes
0*u Reporting Qualifiers
for reporting muhl to EPA. the following mulit qualifier! iri intC
Additional Hags 0' footnotes eiplammg results »'• encouraged However, the
definition of each flag mult b* aiplici:
Value
M the rttult a • value greater inen or equ*i 10 lie detection limn.
repo'i txe «*iuc
Indictitt compound w*i antlynd lor bu< noi detected Deport tht
minimum detection limit lor the Mmpl* with ine U (e g .' OUI batefl
en neceiMry concentration-dilution tenon (Tnn u not necetM'iiv
the m$trumeni detection limit I Toe (ootnott thoulO re«e U-
Compound wat anaiyred lor but not detected The number » the
minimum attainable detection limit lor the (ample
Indicate! an estimated value Tnn llac a uted timer when
•tlimating a concentration lor tentatively identified compounds
wnert a 1 I rnponae is (Uumefl or when the mats apecirti OKI
indicated the pretence o< a compound inat meets ine idennlicmor.
oneria but the result u less than the rpecilwd detection limn Out
fteatar than tero le g . 10JI H limn o< detection is 10 vg 'I ane a
concentration of 3 ng 'I is calculated repoM at 3J
Other
This li»e applies to pesticide parameters wnere uw idennlicaiion net
been conlirmed by GC'MS kmgit component pesiicides2tC
ng -ul in ine final attract should be conlirmed by CC • MS
This flag is used when the anaiyte is lound m the blank as wen as *
(ampit it mdicates possible probtbit 6Un» coma mine non and
warns the data user to lake appropriate action
Other specific Hags and loot notes may be required to properly define
the results H used, they must be luiiy described and such description
•nached to the data summary rapon
Form I
ONE - 33
Revision 0
Date September 1986
-------
Laboratory Name
Case No
Sample Number
Date Extracted/Prepared
Date Analyzed.
Conc/Dil Factor:
Organics Analysis Data Sheet
(Page 2)
Semivolatile Compounds
GPC Cleanup DYes DNo
Separatory Funnel Extraction DYes
Continuous Liquid • Liquid Extraction DYes
Percent Moisture (Decanted).
CAS ug/lorug/Kg
Number (Circle One)
108-95-2
111-44-4
95-57.6
541-73-1
106-46-7
100-51-6
95-50-1
95-467
39636-32-9
106-44-5
621-64-7
67-72-1
98-95-3
78-59-1
8675-5
105-67-9
65-85-0
111-91-1
120-83-2
120-82-1
91-203
106-47-8
87-68-3
59-50-7
91-57-6
77-47-4
88-06-2
95-95-4
91-58-7
68-74-4
131-11-3
208-96-8
99-09-2
Pnenol
bis(-2-Chloroethyl)Ether
2-Cnlorophenoi
1. 3-Dichlorobenzene
1. 4-Dichlorobenzene
Benzyl Alcoho'
1. 2-Dichlorobenzene
2-Methylpheno!
bis(2-chloroisopropyl)Ethe.'
4-rVlethylpheno!
N-Niiroso-Di-n-Propylamme
Hexachloroethane
Nitrobenzene
Isophorone
2-Nurophenol
2. 4-Dimethylphenol
Benzole Acid
bis(-2-Chloroethoxy)Methane
2. 4-Dichlorophenol
1. 2. 4-Trichlorobenzene
Naphthalene
4-Chloroanilme
Hexachlorobutadtene
4-Chloro-3-Methylpheno!
2-Methylnaphthalene
Hexachlorocyclopentadiene
2. 4. 6-Trichlorophenol
2. 4. 5-Trichloropheno!
2-Chloronaphthalene
2-Nitroaniline
Dimethyl Pnthalate
Acenaphthylene
3-Nitroanilme
CAS ug/lorug/Kg
Number (Circle One!
83-32-9
51-28-5
100-02-7
132-64-9
121-14-2
606-20-2
84-66-2
7005-72-3
86-73-7
100-01-6
534-52-1
86-30-6
101-55-3
118-74-1
87-86-5
85-01-8
120-12-7
84-74-2
206-44-0
129-00-0
85-68-7
91-94-1
56-55-3
117-81-7
218-01-9
117-84-0
205-99-2
207-08-9
50-32-8
193-39-5
53-70-3
191-24-2
Acenaphthene
2, 4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
2, 4-Dinitrotoluene
2. 6-Dinitrotoluene
Oiethylphthalate
4-Chlorophenyl-phenyle:her
Fluorene
4-Nitroaniline
4. 6-Dmitro-2-Methylpheno
N-Nitrosodiphenylamlne (1)
4-Bromophenyl-phenylethe
Hexachlorobenzene
Pentachlorophenol
Pnenanthrene
Anthracene
Di-n-Butyiphthalaie
Fluoranthene
Pyrene
Butylbenzylphthalaie
3, 3'-Oichlorobenzidme
Benzo(a)Anthracene
bic(2-Ethylhexyl)Pnthalate
Chrysene
Oi-n-Octyl Phihalate
Benzo(b)Fluoranthene
Benzo{k)Fluoranthene
Benzo(a)Pyrene
Indenod. 2, 3-cd)Pyrene
9ibenz(a h)Anthracene
Benzole h. i)Perylene
(1 )-Cannot b« Mpamt*d from diphenylimine
Form I
ONE - 34
Revision 0
Date September 1986
-------
Laboratory Name
Case No
Sample Number
Date Extracted/Prepared
Date Analyzed:
Conc/Dil Factor:
Percent Moisture (decanted).
Organics Analysis Data Sheet
(Page 3)
Pesticide/PCBs
GPC Cleanup DYes DNc
Separatory Funnel Extraction DYes
Continuous Liquid • Liquid Extraction DYes
CAS ug/lorug/Kg
Number (Circle One)
319-84-6
319-85;?
319-86-8
58-89-9
76-44- 6
309-00-2
1024-57-3
959-96-8
60-57-1
72-55-9
72-20-E
33213-65-9
72-54-8
1031-07-8
50-29-3
72-43-5
53494-70-5
57-74-9
8001-35-2
12674-11-2
11104-26-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
Alpha-BHC
Bete-BHC
Oelia-BHC
Gemme-BHC (Lindane)
Heptachio'
Aid-in
Hepiachlor Epoxide
Endosulfen 1
Dielbnn
4.4'-DDE
End'ir.
Endosulfa-i I.1
4. 4--DOO
EndosuHan SuHaie
4. 4'- DDT
MethOKychlor
Endrin Ketone
Chlordane
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1246
Aroclor-1254
Aroclor-1260
V( = Volume of extract injected (ul)
V$ = Volume of water extracted (ml)
W( = Weight of sample extracted (g)
V( e Volume of total extract (ul)
orW.
Form 1
ONE - 35
Revision 0
Date September 1986
-------
LBDoratory Name:
Case No
Organics Analysis Data Sheet
Sample Number
CAS
Number
v
2
a
A
B '
*
7
ft
«»
10
11
15
13
14
IK
Ifi
17
If)
19
3n
31
2?
33
94
3R
3fi
37
3ft
3B
Compound Name
Friction
RT or Scan
Number
Estimated
Concentration
(ug/lorug/kg)
Form 1, Pan B
ONE - 36
Revision 0
Date September 1986
-------
Case No..
WATER SURROGATE PERCENT RECOVERY SUMMARY
Laboratory Name .
o
Q>
r+
n
CO
O>
a
r*
n>
CT
a>
-j
t— •
«0
oo
o
3
O
•MWlf
NO.
VALUES
WAI ft If H r
t«.UCI«-««
•r»
(M-IK)
u owMLona-
tTM*Mf-D<
»-n«>
t-rioono-
•imturL
l«3- 1I«)
TtKFMtll't-
01*
(jj-nn
EMI-VOLATIL
MtMl-M
UO-»«>
t-riuora-
PMtBOl.
(tl-100)
».«.« KUBfMO
PMCMCH.
I1IV-IJ3I
•PESTICIOE--
01»UT»l-
CMIO*CM**TC
«t«-l»«>
ARE OUTSIDE OF REQUIRED OC LIMITS Volatiles: out of ; outside of OC limits
Semi-Volatiles: out of ; outsida of OC limits
Pesticides: out of ; outside of OC limits
ta:
- •__ __^ _^
FORM II
-------
Case No..
SOIL SURROGATE PERCENT RECOVERY SUMMARY
Laboratory Name _____—
ONE - 38
Revision 0
Date September 1986
MMPLC
NO.
T7
wt
CTM*Nt-0«
l»«-tf«t
-
_ _ ________—_———— S
•m--
•ti/mc-BS
-------
Case No.
WATER MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Laboratory Name •
CO
to
FRACTION
VOA
SAMPLE NO.
B/N
SAMPLE NO.
Adn
SAMPLE NO
COMPOUND
1 .1 -DieMoroettwne
Triehloroethene
Ch'orobenren*
Toluene
Benrene
1 .2.4.TrieHlorobcn?rnp
AcenaDhth.?ni»
2.4 Oinijfotolupne
Di-n-Butylphlhalate
PV'*"*
N-Nitro$o-Di-fi-PropYl<«m'f"
1 ,4-Dichlorob<»nzrnc
Pentachlorophenol
Phenol
2-CMorophenol
4.Chloro-3 Methylphrnol
4-Nitroohenol
Lindane
Heptachlor
Aldrin
Dieldrin
Endrin
4 4'-DOT
CONC. SPIKE
ADDED (uq/L)
SAMPLE
RESULT
CONC.
MS
%
RCC
CONC.
MSO
%
REC
Don
o
nro
14
14
13
13
11
28
31
38
40
31
38
28
50
42
40
42
50
15
20
22
18
21
27
" UM.ITS
HtcovERV
61-145
75-130
76-125 ^.
76-177
39-98
46-118
24-96 __
11-117
26 127
41-116
36 97
9 103
12 89
27 12.1
2397
10 80
56 123
40 131
40 120
52 126
56 121
18-127
O 73
01 n
rf <
n -fc
CO
loo o
m> 3
|«-f
m>i
vo
oo
ADVISORY LIMITS
RPD: VOA»
R/N
AC'O
PFST
OtfMMnant^*
f>nf
-------
SOIL MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Case No..
Laboratory Name.
O 73
Ot O>
r* <
n -*
FRACTION
VOA
SAMPLE NO.
B/N
SAMPLE NO.
Af*in
CAMPt E NO
PEST
SAMPLE NO.
rowpoi nun
1 .1 -Dichotorethen*
TrichkHoethene
Chloroben/ene
Toluene
Benzene
1 ,2,4-Trichlorohen7rne
Acenaphthene
2.4 Dinitrotoluene
Di-n-Butylphthalate
Pyrene
N-Nitrosodi-n-Propvlan'i'w
1 .4-Dichlorobenj>enp
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chtoro-3-Methvlph(«nol
4-Nitrophenol
Lindane
Heptachlor
AWrin
OieMrin
Endrin
4.4'-ODT
CONC. SPIKE
ADDF.O (ixi/Kql
SAMPLE
RRSULT
CONC.
MS
%
RHC
CONC,
MSD
%
REC
°1
npo
22
24
21
21
21
23
19
47
47
36
38
27
47
35
50
33
50
50
31
43
38
45
50
? UIM'TF
RECOVERY
59-172
87-137
80-133
59139
66-142
38107
31-137
78-89
29-135
35-142
41 126
28-104
J7-109
2690
25102
26103
11 114
46127
35130
34-132
31 134
42139
23-134
ADVISORY LIMITS
n
a
O
ro
oo
O
=»
RPO:
Comn
VOAs out of ; outside OC limit*
RIN .,.., Wft o' _ • nift*irti> OP limit*
ACIf ... Orr limit*
PFST _ Otlt Of ' OlItsM'* OC lifnit*
w>nt OC limit*
FORM Ml
-------
METHOD BLANK SUMMARY
i
m
1
030
tu n
rt <
n -fc
to o
rt) 3
o
r*
A
CT
fD
-J O
VO
CO
0»
r«.Ł»
(UTCor
ANALYSIS
r.ACT.9.
y.rm,
CONC.
Lf.vr.t
MST. tO
CHS NUttflCK
COMPaiwn (MSL.TIC on UNKNOONI
-
CONC.
OMITS
com.
Comments: ;
FORM IV
-------
GC/MS TUNING AND MASS CALIBRATION
Bromofluorobcnzcne (BFB)
Case No..
Instrument ID
Laboratory Name.
Date
Time.
m/e
Data Release Authorized By:
ION ABUNDANCE CRITERIA ^RELATIVE ABUNDANCE
60
75
95
66
173
174
175
176
177
15.0 • 40.0% of the base peak
30.0 • 60.0% of the base peak
Bait peak, 100% relative abundance
6.0 • 9.0% of the base peak
Less than 1.0% o' the base peek
Greater than 50.0% of the base peak
5.0 • 0.0% of mass 17<
Greater than 95.0%. but less than 101.0% of mass 174
5.0 • 9.0% of mass 176
C )'
c )'
( )2
THIS PERFORMANCE TUNE APPLIES TO THE FOLLOWING
SAMPLES. BLANKS AND STANDARDS.
Value in parenthesis is % mast 174.
Value in parentheiis is \ mass 17Ł.
SAMPLE ID
LAB ID
DATE OF ANALYSIS TIME OF ANALYSIS
FORM V
ONE - 42
Revision 0
Date September 1986
-------
Case No..
GC/MS TUNING AND MASS CALIBRATION
Decafluorotriphenylphosphine (DFTPP)
Laboratory Name _____
Instrument ID
Date
Time
m/e
Data Release Authorized By:
ION ABUNDANCE CRITERIA ^RELATIVE ABUNDANCE
61
68
69 .
70
127
187
196
169
275
36S
441
442
443
30.0 • 60.0% of mass 19E
teis than 2.0\ o< n»s 6S
miss 69 relative abundance
less thtn 2.0% of miss 69
40.0 • 60.0% of mass 196
less than 1.0V of mass 19E
bate peak. 100W relative abundance
5.0-9.0^of mass 19E
10.0 -30.0% of mass 19E
greater thirv 1.00% of mass 19E
present, but less than mass 443
greater than 40.0°* of mass 19E
17.0 • 23.0% of mass 442
( ')'
( )'
( )2
THIS PERFORMANCE TUNE APPLIES TO THE FOLLOWING 'Value in parenthesis is % mass 6Ł.
SAMPLES. BLANKS AND STANDARDS. 2vaiue in pa-emhesis is * mass 4«
SAMPLE ID
LAB ID
DATE OF ANALYSIS
TIME OF ANALYSIS
FORM V
ONE - 43
Revision 0
Date September 1986
-------
Case No:
Laboratory Name
Initial Calibration Data
Volatile HSL Compounds
Instrument I D. .
Calibration Date:
Minimum I?F for SPCC is 0.300
(0.25 for Bromoform)
Maximum % RSD for CCC is 30c/c
Laboratory ID
Compound
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disuldde
1. 1-Bichloroethene
1. 1-Dichloroe:hant
Trans-1. 2-Dichloroethene
Chloroform
1. 2-Oichloroethane
2-Butenone
1,1. l-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1. 2-DiChloropropane
Trans-1, 3-Dichloropropene
Trichloroethene
Dibromochloromethane
1,1. 2-Trichloroethane
Benzene
cis-1. 3-Dichloropropene
2-Chloroethylvinylether
Bromolorm
4-Methyl-2-Pentanone
2-Hexanone
Tetrachlorvethene
1.1.2. 2-Tetrachloroethanc
Toluene
Chlorobenzene
Ethytbenzene
Styrene
Total Xylenes
RF20
RFeo
RF100
'
BFlSO
RF200
RTE
V. RSD
ccc«
SPCC««
• •
•
•
» •
•
•
» •
• •
•
• •
•
RF -Response Factor (subscript is the amount of ug/U
RT -Average Response Factor
KRSD -Percent Relative Standard Deviation
CCC -Calibration Check Compounds (•)
SPCC -System Performance Check Compounds (••)
Form VI
ONE - 44
Revision p
Date September 1986
-------
Initial Calibration Data
Volatile HSL Compounds
Case No:
Laboratory Name.
Instrument I D: .
Calibration Date:
Minimum EF for SPCC is 0.300 Maximum % RSD for CCC is 30%
(0.25 for Bromoform)
Laboratory ID
Compound
RF100
RF200
CCC*
SPCC"
RF -Response Factor (subscript is the amount of ug/LI
HF -Avtrgpe Response Factor
KRSD -Ptrcant Ralative Standard Deviation
CCC -Calibration Cheek Compounds (•)
SPCC -System Performance Check Compounds (••)
Form VI
ONE - 45
Revision 0
Date September 1986
-------
Case No:
Laboratory Name.
Initial Calibration Data
Semivolatile HSL Compounds
(Pagel)
Instrument ID: _
Calibration Date:
Minimum RF for SPCC is 0.050 Maximum % RSD for CCC is 30%
Laboratory ID
Compound
Phenol
bis(-2-Chloroethyl)Ether
2-Chlorophenol
1. 3-Dichlorobenzene
1 . 4-DiChlorobenzene
Benzyl Alcohol
1. 2-DiChlorobenzene
2-Methylphenol
bi$(2-chloroisopropyl)Ethef
4-Methylphenol
N-Nitroso-Di-n-Propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nurophenol
2. 4-Dimethylpheno!
Benzoic Acid
bis(-2-Chloroethoxy)Metiane
2. 4-Dichlorophenoi
1 . 2. 4-Tnchlorobenzene
Naphthalene
4-Chloroanilme
Heiachlorobuiadiene
4-Chloro-3-Methylpheno!
2 -Methylnaphtha le ne
HexBChlorocyclopemadiene
2. 4. 6-Trichloropheno!
2. 4. 5-Trichlorophenol
2 -Chloronaphtha le ne
2-Nitroaniline
Dimethyl Phjhalaie
Acenaphthylene
3-Nitroanilme
Accnaphthene
2, 4-Dinitrophenol
4-Nitrophenol
Dibenzofuren
RF20-
t
1
T
T
' •
' '
«PBO
"PSO
'
*
'
«F120
R^ieo
RF
%R$0
CCC*
8PCC»«
•
•
• •
•
•
•
•
• •
•
•
• •
• •
Response Factor (subscript is the amount of nanograms)
fi? -Averaoe Response Factor
%RSO -Percent Relative Standard Deviation
CCC -Calibration Check Compounds (•)
SPCC -System Performance Check Compounds (••)
t -Not detectable at 20 ng
Form VI
ONE - 46
Revision 0
Date September 1986
-------
Case No:
Laboratory Name
Initial Calibration Data
Semivolatile HSL Compounds
(Page 2)
Instrument ID: _
Calibration Date:
Minimum RF for SPCC is 0.050 Maximum % RSD for CCC is 30%
Laboratory ID
Compound
2.4-Dinitrotoluene
2. 6-Diniuotoluene
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroanilme
4. 6-Dmiuo-2-Me!hylpheno'
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachloropheno!
Phenanthrene
Anthracene
Di-N-Butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3. 3'-Diehlorobentidme
BeniofatAnthracene
bit(2-Ethylhexyl)Phthalaie
Chrysene
Di-n-Octyl Phthalate
Benxo(b)Ftuoranihene
BenzofklFiuoranthene
Benio(8)Pyrene
lr»deno(1.2. 3-cd|Pyrene
Dibtrufa. hJAnthracene
Bcnzofg. h. i)Parylene
RF20
1
1
t
"FBO
"FBO
RF120
RF160
KF
VRSD
CCC-
SPCC««
•
•
•
•
•
ftMponte Factor (»ubteript is the amount of nanograms)
H? -Avarage Rasponse Factor
%RSD -Pvrcant Ralative Standard Deviation
CCC •Calibration Chaek Compounds (•)
SPCC -System Performance Check Compounds (••)
t-Noi detectable at 20 ng
(1) -Cannot be aeparated from diphenylamine
Form VI
ONE - 47
Revision 0
Date September 198fi
-------
Case No
Laboratory Name.
Initial Calibration Data
Semivolatile HSL Compounds
(Page 1)
Instrument ID _
Calibration Date
Minimum RF for SPCC is 0.050 Maximum % RSD for CCC is 30c/c
Laboratory ID
Compound
^20
F80
RF
SRSD
CCC-
8PCC»
Response Factor (subscript is the amount of nanofl'ams'
R? -Average Response Factor
-------
Continuing Calibration Check
Volatile HSL Compounds
Case No:
Laboratory Name.
Contract No:
Instrument ID:
Calibration Date:
Time:
Laboratory ID:
Initial Calibration Date:
Minimum RF for SPCC is 0.300
(0.25 for Bromoform)
Maximum %D for CCC is 25%
Compound
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1. 1-Dichloroethene
1, 1-Dichloroethane
Trans-1. 2-Dichloroetnene
Chloroform
1. 2-Dichloroe'.nene
2-Butanone
1,1. 1-Trichloroeihane
Carbon Teuachloride
Vinyl Acetate
Bromodiehloromethane
1. 2-Dichloropropane
Trans- 1. 3-DiChloropropene
Trichloroethene
Dibromochlorornethane
1,1. 2-Trichloroethane
Benzene
cis-1. 3-Oichloropropene
2-Chloroethylvinylether
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1.1.2. 2-T«tr«ehloroethsne
Toluene
Chloroberuene
Ethylberoene
Styrene
Total Xylenes
R?
RF60
VD
CCC
*
•
•
•
•
•
SPCC
• •
• •
• •
• •
• •
RFgg -Response Factor from daily standard file at SO ug 'I
RF -Average Response Factor from initial calibration Form VI
%D -Percent Difference
CCC -Calibration Check Compounds (•)
SPCC -System Performance Check Compounds (••)
Form VI!
ONE - 49
Revision 0
Date September 1986
-------
Case No
Laboratory Name
Contract No
Continuing Calibration Check
Volatile HSL Compounds
Calibration Date
Time
Instrument ID
Laboratory ID
Initial Calibration Date
Minimum RF for SPCC is 0.300
(0.25 for Bromoform)
Maximum %D for CCC is 25%
Compound
50
CCC
SPCC
"f 50 'Response Factor from daily standard file at 50 ug I
RF -Average Response Factor from initial calibration Form VI
ctiD -Percent Difference
CCC -Calibration Check Compounds i.)
SPCC -System Performance Cnecu Compounds i..|
Fo-rr. VII
ONE - 50
Revision 0
Date September 1986
-------
Continuing Calibration Check
Semivolatile HSL Compounds
(Pagel)
Case No:
Laboratory Name.
Instrument ID:
Calibration Date:,
Time:
Laboratory ID:
Initial Calibration Date.
Minimum RF for SPCC is 0.050 Maximum %D for CCC is 25%
Compound
Phenol
bis(-2-Chloroethyl)Eiher
2-Chlorophenoi
1. 3-DiChlorobenzene
1 . 4-Dichlorobenzene
Benzyl Alcohol
1. 2-Dichlorobenzenc
2-Methylpheno!
bis(2-chloroisopropyl)Ether
4-Methylpheno!
N-Nitroso-Di-n-Propylamine
Hexachloroetnanc
Nitrobenzene
Isophorone
2-Nnropheno!
2. 4-Dimethylpheno:
Benzoic Acid t
bis(-2-ChioroethoxylMeiharie
2. 4-Dichlorophenol
1. 2. 4-Tnchlorobenzene
Naphthalene
4-Chloroanilme
Henachlorobutadiene
4-Chloro-3-Methylpheno!
2-Meiiiylnaphihalene
Hexachlorocyclopeniadiene
2. 4. 6-Tnchloropheno'
2. 4. 5-Tnchloiopheno! "\
2-Chlorohaphihalene
2-Nitroaoiline t
Dimethyl Pnthalaie
Acenaphthylene
3-Nitroamlme t
Acenaphihene
2. 4-Dihiiropheno!
4-Nitrophenol
Oibenioluran
R?
R^so
% o
CCC
•
•
*
*
•
•
•
•
SPCC
• •
• •
• •
• »
RFgQ •Response Factor from daily siantiaid file ai concentration
tndie*t»d (SO total nanogramt)
RT -Average Response Factor from initial calibration Form VI
f-Dut to tow response, analyze
•t BO total nanograms
SttD -Percent Oillerence
CCC -Calibration Check Compounds (•)
SPCC -System Performance Check Compounds (••)
Form VII
ONE - 51
Revision 0
Date September 1986
-------
Continuing Calibration Check
Semivolatile HSL Compounds
(Page 2)
Case No:
Laboratory Name.
Instrument ID:
: Calibration Date:.
Time.
Laboratory ID. _
Initial Calibration Date:
Minimum RF for SPCC is 0.050 Maximum %D for CCC is 25%
Compound
2, 4-Dinitrotoloene
2, 6-Oinitrotoluene
Diethylphthalaie
4-Chlorophenyl-phenylether
Fluorene
4-Nnroaniline t
4. 6-Dmiuo-2-Methylpheno! j
N-NnroJodiphenyiemme (1)
4-Bromophenyl-phenylet^ie1
Hexachlorobenze ne
Pemachloropheno' f
Phenanthrene
Anthracene
Di-N-Bufylphthalate
Fluoranthene
Pyrene
Butylbenrylphthalate
3. S'-Dichlorobenzidine
Benzo(a)Anthracene
bivi2-Ethylhexyl)Pnthsl8ie
Cnrysene
Oi-n-Octy! Phthalate
Beruo(b)Fluora nihene
BenzotMFluoranthenE
BeruolatPyrene
lndeno(1. 2. 3-cd)Pyrene
Dibenz(a. h)Anthracene
Benzo(g. h. i)Perylene
RT
«F60
!
,
i
1
i
1
fcD
CCC
•
•
•
• »
•
SPCC
RF^O -Reuxmsi; Fiirtor Irom duly sl.niil.iid die > (• I
SPCC -System Pvrlurniiince Ciieck Co'tiuutiml> (..)
(11 Coooul l)o kep.irjli.-d Irum Jiplieii>l.iinnic
ONE - 52
Revision 0
Date September 1986
-------
Case No:
Laboratory Name.
Instrument ID:
Semivolatile HSL Compounds
(Pagel)
Calibration Date:
Time:
Minimum RF for SPCC is 0.050
TP
Laboratory ID:
Initial Calibration Date:
Maximum %D for CCC is 25%
Compound
60
CCC
SPCC
Rf 50 -Ft«kPUHke Factor Iron) daily kl.iiid.inl file ill tonceniMiiun
indicated (50 total nanograms!
RT -Average Response F.itiur Irani mni.il c.ihbirtiion Form VI
^••Out to low rviponsc.
•t BO loul mnograms
%D -Percent Dillereiice
CCC -Calibrrtliun Check Compounds (.)
SPCC Sviie"' Perloniiflnct; Cneck Compounds (••)
Form VI!
ONE - 53
Revision 0
Date September 1986
-------
Pesticide Evaluation Standards Summary
(Page 1)
Case No
Da:e o' Analysis.
Laboratory Name .
GC Column.
Instrument ID..
Evaluation Check for Linearity
Lauorato'v •
ID
Pesticide
Aldrm
Enflnn
66- DDT1'1
Dibutyl
Cniorendate
Calibration
Factor
Evsi. Mix A
Calibration
Facto-
Eval. Mix 6
Calibration
Factor
Eval. Mix C
%RSD
( <10vo)
Evaluation Check for 4.4'- DDT/Endrin Breakdown
(percent breakdown expressed as total degradation)
EvaiM.xB
72 Hojr
Eva: Mix B
Eval Mix E
Eval Mix B
Eval Mix B
Eval Mix B
Eval Mix B
Eval Mix B
Eval Mix B
Eval Mix B
Eval Mix B
Eval Mix B
Laboratory
I.D.
Time o<
Analysis
Endrm
4.4'- DDT
Combmei'''
(1) See Exhibit E, Section 7.5.4
(2) See Exhibit E. Section 7.3.1.2.2.1
Form VIII
RCRA
4/86
ONE - 54
Revision 0
Date September 1986
-------
Pesticide Evaluation Standards Summary
(Page 2)
Evaluation of Retention Time Shift for Dibutyl Chlorendate
Report all standards, blanks and samples
Sample NIC
Lai.
I.D
Tune of
Analysis
Percent
Diff.
SMO
Sample No
Lab
I.D
Time o!
Analyse
Percen:
Diff
RCRA
Form VIII (Continued) 4/86
ONE - 55
Revision 0
Date September 1986
-------
PESTICIDE/PCB STANDARDS SUMMARY
Caae No.,
Laboratory Name.
GC Column _—
OC Instrument ID
^COMPOUND
alpha -BHC
beta -BHC
delta -BHC
.-— DUO
ga"*n*a Drlw
HeptaeMor
AMrin
HeptacMor Epoxide
Endosutfan I
Dieldrin
4,4'-DOE
Endrin
Endosuiran I
4.4'-DDD
Endrin Aldehyde
Endosulfan Solfa te
4.4'-ODT
Methoxychlor
Endrin Ketone
Tech. Chlordahe
alpha-Chlordane
gamma-CMordane
Toxaphene
Aroclor - 1 0 1 6
Aroclor - 1 22 1
Aroclor- 1232
Aroclor- 124.
Aroclor- 1248
Aroclor- 1254
Aroclor - I26O
DATE OF AN/
TIME OF ANA
LABORATORY
RT
ftl VRIft
1 VftIS
nn
RETENTION
TIME
WINDOW
CALIBRATION
FACTOR
CONF.
OR
QUANT.
.
DATE OF AN/
TIME OF ANA
LABORATORY
RT
II YRIS
1 YSIS
f IP
CALIBRATION
FACTOR
CONF.
OR
QUANT.
PERCENT
DIFF.**
** CONr. rr CONFIRMATION (~7!0'v> D'Tr^r'NCD
OMAWT — 01 lANTITATI^-M (-:!'•.'*, fv-rr -r *f-r •»
I
in
o> n
r+ <
n -^
n
o
n
\o
oo
a>
-------
Case No.
P«»«lcld«/PCB Identification
Laboratory Name
I
Ol
030
o> n
v>
co o
n> 3
o
cr
(V
-i
vo
oo
o>
SAMPLE
ID
PRIMARY
COLUMN
PESTICIDE/
PCB
RT OF
TENTATIVE
ID
RT WINDOW
OF APPROPRIATE
STANDARD
CONFIRMATION
COLUMN
RT ON
CONFIRMATORY
COLUMN
RT WINDOW OF
APPROPRIATE
STANDARD
GC/MS
CONflRMED
(Y or N)
FORM X
-------
CHAPTER FIVE
MISCELLANEOUS TEST METHODS
FIVE - 1
Revision
Date September 1986
-------
METHOD 9010
TOTAL AND AMENABLE CYANIDE (COLORIMETRIC, MANUAL)
1.0 SCOPE AND APPLICATION
1.1 Method 9010 is used to determine the concentration of inorganic
cyanide in 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
chlorination. Method 9010 is 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 acid (HCN), is released by refluxing the
sample with strong acid and distillation of the HCN into an absorber-scrubber
containing sodium hydroxide solution. The cyanide ion in the absorbing
solution is then manually determined colorimetrically.
2.2 In the colorimetric measurement, the cyanide is converted to
cyanogen chloride (CNC1) by reaction with chloram1ne-T at a pH less than 8
without hydrolyzing to the cyanate. After the reaction 1s complete, color is
formed on the addition of pyrldine-barbituric acid reagent. The concentration
of NaOH must be the same in the standards, the scrubber solutions, and any
dilutions 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 colorimetric procedures. 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 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 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.
9010 - 1
Revision 0
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Reflux distillation apparatus: Such as shown 1n Figure 1 or 2. The
boiling flasEshould be of 1-liter size with Inlet tube and provision for
condenser. The gas absorber 1s a F1sher-M1ll1gan scrubber (Fisher Catalog
#07-513) or equivalent.
4.2 Spectrophotometer; Suitable for measurements at 578 nm with a
1.0-cm cell or larger.
4.3 Potassium Iodide-starch test paper.
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 1n Type II
water, and dilute to 1 liter with Type II water.
5.3 Bismuth nitrate solution; Dissolve 30.0 grams of B1(N03)3 1n 100 ml
of Type II water. While stirring^ add 250 ml of glacial acetic add. Stir
until dissolved. Dilute to 1 liter with Type II water.
5.4 Sulfurlc add, 1;1: Slowly add 500 ml of concentrated ^Stty to 500
ml of Type II water.
CAUTION: This Is an exothermic reaction.
5.5 Sodium dlhydrogenphosphate, 1 M: Dissolve 138 g of Na^PO^^O- 1n
1 liter of Type II water.
5.6 Stock cyanide solution; Dissolve 2.51 g of KCN and 2 g KOH 1n 900
mL of Type II water.Standardize With 0.0192 N AgN03. Dilute to appropriate
concentration so that 1 ml = 1 mg CN.
5.7 Intermediate standard cyanide solution; Dilute 100.0 ml of stock
cyanide solution(1 ml = 1 mg CN) to1,000 ml with Type II water (1 ml =
100 ug CN).
5.8 Working standard cyanide solution; Prepare fresh dally by diluting
100.0 ml of Intermediate cyanide solution to 1,000 ml with Type II water (1 mL
= 10.0 ug CN). Store 1n a glass-stoppered bottle.
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 hypochlorite solution; Dissolve 5 g of calcium hypo-
chlorlte [Ca(OCl)2] In 100 mL of Type II water.
9010 - 2
Revision 0
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.
9010 - 3
Revision p
Date September 1986
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COOLING WATER
INLET TUBEv
SCREW CLAMP
HEATER-
TO LOW VACUUM
SOURCE
* ABSORBER
~ DISTILLING FLASK
O
Figure 2. Cyanide distillation apparatus.
9010 - 4
Revision 0
Date September 1986
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5.12 Reagents for manual color1metric determination;
5.12.1 Pyr1d1ne-barb1tur1c add 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 add. 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 1.0 g of white, water-
soluble chloram1ne-T 1n 100 mL of Type II water and refrigerate until
ready to use.
5.13 Ascorbic acid; Crystals.
5.14 Phosphate buffer, pH 5.2; Dissolve 13.6 g of potassium dihydrogen
phosphate and 0.28 g of d1sodium 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 (KI)-starch test paper as soon as the sample 1s
collected; a blue color Indicates the need for treatment. Add ascorbic acid a
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 acid 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 chlorination;
7.1.1 Two sample aliquots are required to determine cyanides
amenable to chlorination. To one 500-mL aliquot, or to a volume diluted
9010 - 5
Revision 0
Date September 1986
-------
to 500 ml, add calcium hypochlorlte solution (Paragraph 5.11) dropwlse
while agitating and maintaining the pH between 11 and 12 with sodium
hrdroxide solution (Paragraph 5.2).
CAUTION: The Initial reaction product of alkaline chlorlnatlon 1s
the very toxic gas cyanogen chloride; therefore, 1t 1s
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, 1n
the 1-liter boiling flask. Pipet 50 ml of sodium hydroxide solution
(Paragraph 5.2) Into the absorbing tube. If the apparatus in Figure 1 1s
used, add Type II water until the spiral is covered. Connect the boiling
flask, condenser, absorber, and trap 1n the train (Figure 1 or 2).
7.2.2 Through the air inlet tube start a slow stream of air
entering the boiling flask by adjusting the vacuum source. Approximately
two bubbles of air per second should enter the boiling flask.
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 NC«2, add 50 ml
of sulfamlc add solution (Paragraph 5.10) after the air rate 1s 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.
9010 - 6
Revision 0
Date September 1986
-------
7.2.6 Heat the solution to boiling. Reflux for 1 hr. Turn off
heat and continue the airflow for at least 15 m1n. 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 Manual spectrophotometrlc determination;
7.3.1 Withdraw 50 ml or a measured lesser amount of the solution
from the flask and transfer to a 100-mL volumetric flask. If less than
50 ml 1s taken, dilute to 50 ml with 0.25 N sodium hydroxide solution
(Paragraph 5.2). Add 15.0 ml of sodium dlhydrogenphosphate solution
(Paragraph 5.5) and mix.
7.3.2 Add 2 ml of chloramlne-T (Paragraph 5.12.2) and mix. See
Note Immediately following. After 1 to 2 m1n, add 5 ml of pyrldlne-
barblturlc add solution (Paragraph 5.12.1) and mix. Dilute to mark with
Type II water and mix again. Allow 8 m1n for color development and then
read absorbance at 578 nm 1n a 1-cm cell within 15 mln.
NOTE; Some distillates may contain compounds that have a chlorine
demand. One minute after tjie addition of chloram1ne-T, test
for residual chlorine with Kl-starch paper. If the test 1s
negative, add an additional 0.5 ml chloram1ne-T. Recheck after
1 m1n.
7.4 Standard curve for samples without sulflde;
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:
ml of Working Standard Solution Concentration
(1 ml = 10 ug CN) (ug CN/250 ml)
0 BLANK
1.0 10
2.0 20
5.0 50
10.0 100
15.0 150
20.0 200
7.4.2 It Is 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 Is
reliable. If distilled standards do not agree within +10% of the
undlstilled standards, the analyst should find the cause of th~e apparent
error before proceeding.
9010 - 7
Revision
Date September 1986
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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 sulfide;
7.5.1 All standards must be distilled 1n the same manner as the
samples. A minimum of three standards shall be distilled.
7.5.2 Prepare a standard curve by plotting absorbance of standards
vs. cyanide concentration.
7.6 Calculation; If the colorlmetric procedure 1s used, calculate the
cyanide, 1n ug/L, 1n the original sample as follows:
A X 1,000 50
CN, ug/L = X —
B C
where:
A = ug CN read from standard curve.
B = ml of original sample for distillation.
C = ml taken for colorimetrlc analysis.
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.
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.
9010 - 8
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data for aqueous samples are available 1n
Method 335.2 of Methods for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Annual Book of ASTM Standards, Part 31, "Water," Standard D2036-75,
Method B, p. 505 (1976).
2. Bark, L.S., and H.G. Hlgson, "Investigation of Reagents for the
Color1metr1c Determination of Small Amounts of Cyanide," Talanta, 2, pp. 471-
479 (1964).
3. Casey, J.P., J.W. Bright, and B.D. Helms, "N1trosat1on Interference 1n
Distillation Tests for Cyanide," Gulf Coast Waste Disposal Authority, Houston,
Texas.
4. Egekeze, J.O., and F.W. Oehne, "Direct Potent1ometr1c Determination of
Cyanide 1n Biological Materials," J. Analytical Toxicology, 3, p. 119,
May/June 1979.
5. Elly, C.T., "Recovery of Cyanides by Modified Serfass Distillation,"
Journal Water Pollution Control Federation, 40, pp. 848-856 (1968).
6. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
pp. 367, 370 and 376, Method 413B, D and F (1975).
9010 - 9
Revision
Date September 1986
-------
METHOD 9010
TOTAL AND AMENABLE CYANIDE
7.1.1
0
Have two sample
aliquots
7.1.4
Test for total
cyanide In both
sample allquots
7.1.11 Add
I calcium
hypochlorite
solution to one
sample aliquot
and agitate
7. 1.2
7.2.1
Place
sample
In boiling
flask for
distillation
procedure
Test for
residual
chlorine with
Kl-starch paper
In sample
7.1.3
7.2. 1
Plpet sodium
hydroxide into
absorbing tube
After 1 hour
add ascorbic
acid
7.2.1
I Connect
boiling flask.
condenser.
absorber, and
trap in train
0
©
9010 - 10
Revision o
Date September 1986
-------
METHOD 9010
TOTAL AND AMENABLE CYANIDE
(COLORIMETHIC. MANUAL)
(Continued)
o
7.2.2|
'Enter
slow stream
of air into
boiling flask
o
7.3.6
Cool:
disconnect
absorber.
close off
vacuum source
^r Does sample
contain sulflde?
Does sample
contain NOj
and/or NO27
Add culfamic
acid solution
and mix
sulfurlc acid
rinse tube:
add magnesium
chloride
Heat solution
•nd reflux
7.2.7
Drain
scrubber
solution
into flask
•no dilute
7.3.1
Transfer
•olution to another
flask for manual
•pectophotometrie
determination, add
solium phosphate
solution, mix
7.3.2
Add
Chloramlne-T;
add purldlne
barbituric acid
solution
7.3.2
1 Dilute
• nd nix; allow
8 siin for color
development:
read absorbance
o
9010 - 11
Revision o
Date September 1986
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METHOD 9010
TOTAL AND AMENABLE CYANIDE
(COLORIMETRIC MANUAL)
(Continued)
7.4.1
Prepare
a series of
standards for
standard curve
preparation
7.4.1
Add sodium
hydroxide to
each and dilute
7.4.2
Distill 2
standards
to Insure
distillation
technique is
reliable
7.4.3
Prepare a
standard curve
7.4.41
Check
•fficlency of
•ample
distillation
Prepare a
standard curve
0
7.7 I
Using
colorimeter
and recorder.
analysis
7.8
Compute
concentrations
of samples
f Stop J
9010 - 12
Revision 0
Date September 1986
-------
METHOD 9010
TOTAL" AND ^AMENABLE" CYANIDE ':
1.0 SCOPE AND "APPLICATION
1.1 ^ Method ,9010 ,is"fused It 6' determine"" the ^concentration^ of ^inorganic
cyanide (CAS Registry7Numberl:57rl2-5). jn^wastesiorJ?leachate.>The" method
detects ^inorganic4cyanides"^ithat^"are|present_;as Jjeitherjsoluble'^saltsf or
compl exes.' »• 11 ,i s "'used to^determi ne^val ues ;f or I both^tqtal /cyani de land :cyani de'
:amenable to" chlori nation r^The^ reactive" ..cyanide 'content 'of. a" "waste^';that^is7=
the .cyanide •Tcontent^that^could ''generate ~toxic"-funieVŁwhen ,exposed .'toimild
acidic conditions^js^not-^determined by Method.901p,^(refer.to,Chapter^Seven,"
,Step ^7.3.3.2) .^PMethod -9010 Jis'^not^intended^'to'l'determine^if^a ,waste is
.hazardous by~the characteristic'bf reactivity.': "
1.2 :The _titration procedure using silver nitrate with p-dimethylamino-
benzal-rhodanine -indicator 7-lisTused forJmeasuring "concentrations of cyanide
exceeding 0.1 mg/L (0.025 mg/250 ml of absorbing liquid). -
* i "* '
1.3 The colorimetric procedure is used for concentrations below 1 mg/L of
cyanide and is sensitive to about 0.02 mg/L.
' 2.'0 ^SUMMARY OF'METHOD"
— 2.1 ,t> The ^cyanide,-.as ,hydrocyanic acid (HCN),- is released from samples
containing'cyanide by "mean's 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 (CMC!) 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 reagentr-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.
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.
9010 - 1 Revision 1
December 1987
-------
.,' '••S»*15J'i5" ~> ~ , l 15 V .»••"' '•• T-7"1-'*- a v 'f~ -Ft. "—,*•<•**-v.'-'W ~<.~-"i '•,._•• "r - ,_>-• ^ -
".VV5. 3. 7 ^Chloroform,
---•' /-'- '""-^ ',-1'" "v*r> i- '^-J7^j .,-^1
5.4 Reagents for cyanides amenable to.chlorination .•:
I""J? ~jiur -»~H ^»-C'^- J ""• .~-^,*A-"ifii jTt_ifp .'r'»'V -'Vv-:i *l'^i,--''
^ "• ^ x "• lvt --/•"< -> i^ — t ^ ^ * - ~-\ •>- ' ^ f — -5.^ -^ -^T ? v '^a1* T^ *- - -*~ *»" "^^ " ^' ^r^ ~ ' *• ,
s*. ,^^5.4.1 ^Calcium .hypochlorite ,.solution0(q.35M),\Ca(OCl)2.3Cpmbine 5 g
?of 'calcium" hypochlorite vand 100~mL'of water^Shake before "Jusinc '--—r^'-"-'v •
•- "" r ' - . ~r r . r -~. ^ _»•»».- ^»-. ^1, 5,-vr - f-^-~.S i .>• '
" ^ ' ' __ "• . '&«.-,, -.; J>' - -. ..
; 5.4.2 ,Sodium hydroxide solution (1.25N), NaOHv, Dissolve 50 g of NaOH
yin"l 'liter of water.1" • *; "'^- 'V--i5r^-j-"^---^sV-;-^',-.-^- ^
--,->'V-5.4.3 -Sodium arsenite (O.lN).^See Step, 5.3.1. -
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)3-5H20. Dissolve 30 g
Bi(NO)3-5HeO in 100 ml of water. "While stirring, add 250 ml of glacial
acetic acid, CHaCOOH. Stir until dissolved and dilute to 1 liter with
water.
5.5.3 Sulfamic^ acid (0.4N), HgNSOaH. Dissolve 40 g HzNSOaH in
1 liter of water. v~ ~
5.5.4 Sulfuric acid (18N), ^$04. Slowly and carefully add 500 ml of
concentrated ^$04 to 500 mL of water.
5.5.5 Magnesium chloride solution (2.5M), MgCl2-6H20. Dissolve 510 g
of MgCl2'6H20 in 1 liter of water.
5.6 Reagents for colorimetric determination
5.6.1 Sodium hydroxide solution (0.25N), NaOH. Dissolve 10 g NaOH in
1 liter of water.
9010 - 3 Revision 1
December 1987
\
\
-------
of whitej Jwater( soluble \hloramine-T on ^100 niL-of water^and '/refrigerate \
lintiliready to,use.' '""" ~ " ' ' "
Vs, M^3to«?^W
\''r,^' *»*)Ł*-* H3"'' V**1 *J- - •— -• '- "•- *-**•- > - "f j_*i -,»»^--^*s;. -1 » - , ~" • _F- -,~j»!.> - V
'" . 5.6.4 4>Pyridine-Barbituric ;acid Lreagent,?vC5H5N:C4H4N203.replace-;15 3 '
i s stabl e -:for, approximately "six' months jf Łstored ;"in V^copl S
..
Dissolve; 2:51 fgtof .KCN and '2:g'KOH '1n'"900jmDof >atVr^Standardize .with
0.0192N silyer^"nitrate,'-AgN03. "Dilute Ho\appropriate'concentration ;to
achieve 1 mL'=1000ug 'f_CN.
NOTE: "Detailed procedure for AgNOs standardization "is "described in
/'Standard Methods for the Examination of Water and Wastewater",
J6th Edition,-(1985), Methods=412C ancU07A.
j^.i-'jK 6. 6^g il nt ermed i^tte) standard ^ potassijum^ cyanj de.J so^l ut i on ,"^(1 jnL ^
IQQ ug^CN) ,^'KCN^Dilute~1001inC5"6f "stock 'po'tass1umltcyan1der"so]utio -
5.7-Reagents for titration procedure . ""^J^-.jC "^ c. ^- ,. ^
5.7.1 Rhodanine indicator - Dissolve 20 mg of p-dimethylamino-
benzal:rhodanine, Cj2Hi2N20S2, in 100 mL of acetone.
5.7.2 'Standard silver nitrate solution (0.0192N), AgNOs/ Prepare by
crushing approximately 5 g AgNOs and drying to constant weight at 40°C.
Weigh out 3.2647 g of dried AgNOs. Dissolve in 1 liter of water.
NOTE: Detailed procedure for AgNOs '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.
9010 - 4 Revision 1
December 1987
-------
, ,-<"v>,.j" _ '_" r/_"-T'TY~~.~>":sir,-^rs <^^^^^»^v>er
/\ ^.6.3 j* Oxidizing lagents^such^as v
"*~/^ Q 4* rt y*m l n Q t.»»*x*^l*^»w» ~"^^ ts'*v>J4*»*ns« »*^fA\**^*"*-<** w»/*
'pbta'sYi
; treatment _ _ ^ ^ x ^ _^ ^ ^^
of sample 'produces no'colorrVn^-the^indic^tbr/paper^Add^'an "'a'dditional '5 ml of ,
sodium 'arsenite fsolution^for\ea'ch ^Her^ofCsampleTlAscorbicVacid lean .be 'used
' ' "
.
•J as'uri -al ternati ve ^al though ti t^i s'lribtTastef f ec'ti VetaslTarsenl fe^Add^a ^f ew
-!• , • -. "v- - -.-, 3 "-&^Ł<' . '*• i -, C^. - vjf-j. J-^r -c-Vt -'-JP'^-^', fcx*«»-«-'j""'r't»»?'" '*'• T
crystals of i ascorbic-, acid ^at ragtime ;until; a^drop^ofi'Sample^prpduces^no^color
"on .the^indicator . paper. "t-Then *add7an"f additional S.'6. 06 -g'-df ^ascorbic jacid =for*,
l'l- '•! ~J. -- ~f -'--'- 1 -|."S '*•''* -f— *' ------- '~-' -" - "-1 " --- " -1*1 •-"-- " ""- ^3--— -----s_i- ---- _ .v. ,
;each . %1 '
;;6.6 fWhen i' properly ^preservedj^cyanide^samples^can^^be, stored.-foKup to 14
days^rior-to^analysis.' " " *"" .. ...--. ..-=..—» ,
' T •A^'>:V^^v!'52pwff«l
— % ^ * •*-!• t j. ^^ *^ t —
' " 6.7 Solid-and oily wastes ma/"be extracted prior -to analysis by the
method in Appendix" A. It uses' «fa'-dilute NaOH sblutionV(pH ,X-?12) 'as ^ne
extractant.-vThis yields extractable cyanide.
ii{T«6.8 Mf^fatty acids;\.detergents;jfand 'surfactants "are" •'a problem,\they may
;, '- * .; •» =«•• .-• -»5" -•" • ^-"t-^. • "i 7. 1-1 rvT - so1 •• *-^ — , «• T^V*^. "" . j . F ~-^A. ••'""S.-**- *• T ~'W- •oTu11-' 'j.- ^
. be extracted Busing -the following procedure. -Acidify -the "'sample with acetic
acid (1.6M) to pH 6.0 to 7.0. V " " ' "
- . ? »'-«"':; -.^"-V-^' -"^vtv <^fQ-5 '&$ _ ^ .
CAUTION: "The "initial ^reaction Jpfoduct"of alkaline' chlorinati on is the very
toxic gas cyanogen 'chloride; ^therefore, ^it is necessary that this
'be performed 'i
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. ' - - -
CAUTION: This procedure can produce lethal HCN gas.
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)g]
may decompose under UV light and hence will test positive for cyanide
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
9010 - 5 Revision 1
December 1987
-------
., chl or i ne \'i s a present Łas li ridi cated {by 'KI -starch '• papTr^turni rig"~'bl lie .>Jhe
' -- 1 _ V . . i 1 1 '!._•"_..U,'.._ i"_ J~A_'l_TI-_TJ ! _ I- 1 _ .' • 0. • ' I 'i I. i -tf- i~- _ «.*! •'<*, Ltf^ViiiL-J. .H
I _, necessary-that .this reaction be performed 'in
a. .hood.r"
' r 7.1.3 '"Test ;forVexcess .chlorineTwith jKI-starch,fpaper,tand/'maintain ^
this excess for ;one-hour,with continuous 'agitation?;,A"distinct .blue'icolorjl
on the test7paperjindicates^a "sufficient/chloririeVjevel f|lf Or'"""---•~-"ir--IJ -
V7.1.4 /iAf ter^one^'hour^add
| until KI - starch l paper /tshows^i no
chlorinated and the unchlorinated samples.'-The difference .of,total .'cyanide ^
in the chlorinated 'and^unchlorinated -samoles \is~'the'* cyanide'-amenable toT-
chlorination. -r - ^ ^'{^->
7.2 Distillation Procedure v ,--
••„',• , .7.2.1 'Place 500 ml iof-sample, ^or sample diluted .tol500 mL;in the one \
"liter boiling"fla"sk:-t:Pipet"J50 mL"6f" l".25N Vod ium^hydroxi deli nto'lthe gas 1J
absorber. If the apparatus in Figure 1 is used, add water until the spiral
is covered. Connect the boiling flask, condenser, gasHabsorber.and vacuum ,
trap. * • - " ~ -' - v-^v ••'*•- - -l w ;-a."- .-.••r-Kv.' >• -•<*'-. ^ - - -
-7.2.2 Start~a 'slow'^stfeam 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 Jf samples are known 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.
7.2.4 If samples are known or suspected to contain nitrate or
nitrite, add 50 ml of 0.4N sulfamic acid solution through the, air inlet
tube. Mix for three minutes. ' _
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 absorber.
9010 - 6 Revision 1
December 1987
-------
< ^*t\r * ' j *• <, -/ ^ ' .* VJ .» \
., a, _ ..... c.r x.r ^determination will be
,^ performed ,*Ł proceed /(,t o viStepPs7. 3.1_?%•! f v the >ti trat i on s procedure'^wi 11 be
T/1^ i iv»w»^*-"-*i.'i,iw»*v*-»wv»iiiirfiw ^^,1 «•» rt i wt w\* i *>ij i wviii** -hw / > **^» S***" J wit** ^v»> « • **j,^ • • • • >• ^* • ^; • •>»**^v>^«ri vx-u
f|c6lonmetfic^determirra'tionland Insdisti^lH'io'n^of^a^sValler^Jainple Ms';not
^feasible'^a -rsmal ler^al iquot^may^be^taken'?^If |]ess^thans'i;n^''')i * i <'. tskpni »
^dilute"'to ,50 'mL^iith 0^25NtsVdiurnrshydroxide"fs"blutibn'!s
v-v^'F- «'"• tti^;i^ ^'t^^!^;l ^?^l^^^^,^5^^f'"-l
r'NOTE:^-Temperature Tof/^reagehts^a^nd Lspikirig',solution'_"can 'affect the
^./•,.v1»'ijresponse ^factor^of_.;the \cplorimetric;determination>5The reagents
-S'^jLjiVV-,-stdred in the *"re'frigerator rshould .^be' warmed to'ambient ^temperature
*"'/"8before "use."'-Samples should not'. bV'Oeft' in "a"'warm 'instrument to
, v^-" r \develop color, .but ^instead ^they should be/aliquoted to a cuvette
,-J./x^immediately prior to reading the'absorbance'.^-r" - ' C-,-1 , u ~
^^/?ti^7^3v2^Add.l5^mL-of ;lM^sodjum phosphate,solution^ andjnix.-Add 2 ml of^
>fchloramine-t^ahd Mnix^s6me^distillates~fmaytcontainyfcbmp6unds"^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.M>After one minute recheck'with Kl-starch paper.-Continue to
^add chloramine-T in 0.5 ml increments until an excess is maintained. After
c"l 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.
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 dijute to 250 mL
with water. Prepare^ using the-following table. The sodium hydroxide
concentration will be 0.25N. -
ml of Working Standard Solution Concentration
H ml = 10 ug CM) fuo CN/L)
0 Blank
1.0 40
2.0 80
5.0 200
10.0 400
15.0 600
20.0 800
9010 - 7 Revision 1
December 1987
-------
{vuiumeui i v. ^i i CL:>IS. emu pi ut_eeu .LU oic^ t/ .J . tKoiiujff .0.0 siu^uuta MI :au^ui u.,>-
v"r , %7.4.3 '*It 'is"!; recommended that' aY*1eastj,twVrsTandVrdsTr(a'*high ^and ^~a
•low) , be distilled ;and .compared \to' similar,1 values'/on ^the'-curveftoVensufe
ithat the :|]distillation ^vtechnique".1s^«reliable^Iftclis"tined [^standards 'do :
tr\ot 'agfeeTwi thi n V+^10% .'of |the ?undi sti 1 1 ed jStafftardsH'theTahalystV shoul d :
f. __ | xul"* ^Tll 2"^1ff TL~_*1"_tM ^ *"5"_J. 'c-j'\I _"* "L"'J «-_!*"- "™1-?1 J^T-T J^-?" -'fi'5 J> lS»« JJJ- .~urfi*«'y--< •_ .S.A
/Prepare .-a"! standard Jcurve^by'tpl otting^abslj.^-..^^^ vn
^yersus%the"cyanide^cbn'centratipn7 " ------ - - -----
, "7.4.5 'To"'check 'the -efficiency "of rthe .sample'^distillation,' ;add
cyanide from the"working standard to .500 mLIof sample to'ensure a'Jevel^of
,40 ug/L.- Proceed with the analysis as irTStep^.^.I.^^rl^^^iiffc^*"--3"; -^
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^usingithe^method^f^tanda
distilled by !this method will ^give^a^lineaV^curve^^at '11 off concent rat ions',
but as the concentration increases,—the recovery "decreases. It is
recommended that ateast five standards be -distilled. *iiŁ~A . < ^ ,
* 7.5.2 -.Prepare a-series of-standards*rsimilar-;in -concentration "to
those mentioned in^Step ,7.4.1 and ~analyzevas" in Step*7.2."!.'Prepare a
standard curve by plotting absorbance of standard versus the cyanide
concentration. - *-_""''•"-
r -/
7.6 Calculation - . If the colorimetric procedure is used, calculate
cyanide,^ in ug/L, in the original sample as follows. -
CN (ug/L) = A x B x C ~ '
D x E
where: , • •
A = ug/L CN read from standard curve.
B = mL of original sample for distillation (500 recommended).
C = mL of sample after distillation (250).
D = mL used for colorimetric analysis (50 recommended).
E = mL of sample after preparation of colorimetric analysis (100).
7.7 Titration Procedure
7.7.1 Transfer the gas absorber 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.
9010 - 8 Revision 1
December 1987
-------
r^$4H-;7 - 2'ŁTHfaY_•_!. ;»*'r T« j. J^Jj. ^* »"••*.. LJ. ~^T L.T -v_l, ... Ł ««
Ititratipn^and ,the;ampunt ,of=:indicatorj/toj,belusedvbefore"actually1 titrating '„•
|the7?sanTples>rA=5-mL?tbufet may" be fodnVenientlytus'edltoVobtain ;a precise %<
titration?
ff|||&7;:Ł:OXalcula^
^concentfati6n'3bf /CN ",in"'mg/LHiri''theTofiginal ^s amp! e*"aV" follows:)/
fe-skxaj. " ' " "" ~ •"" ""**- ~
: ;_-;where:;.-"
"A =TmL of AgN03;foF titration of sample\sf;
^B = mL of AgNOs for titration of blank.r-~"
-C ='mL of sample after distillation'(250).\
-D = mL'of original ..sample for distillation'(500 recommended).
^E = mL of sample taken for titration*(250 recommended). '• - •
- .^,,i^aN$^f^^^
- < The above equation assumes'that the'standard silver nitrate concentration
is exactly 0.0192N which is equivalent to one mL of silver nitrate to one
^if-,mg of .cyanide. r =
8.0 DUALITY,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 once 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 10 samples. A replicate sample is
a sample brought through the entire sample preparation process. The CV of the
replicates should be 15% or less. If this criterion is not met, the samples
should be reanalyzed.
8.5 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.
9010 - 9 Revision 1
December 1987
-------
9.0 METHOD ^PERFORMANCE-
0.02 mg/L.'
?>. M;* .i*., j-,s
,:..." 9.2 f EPA Method "335.2: (sampl e di still at i on *'wi tVti trati on) Yeports'TthaV'i n
:range tused .in -these "studies \was ,0.5 >to ^10,., mg/Vf cyanide
detection Ylimit;was tfound to bekO/2 mg/L, f or^both 'total -andjamenable^ cyanide
determinations.^'Jhe'-'precision ~(CV) "was 6:9 rand ^216 ;;fof3total -'cyanide
determinations and 18.6 and 9.1 for amenable cyanide' determinations. 'The mean
recoveries were 94% and 98.9% for , total cyanide, T- and 86.7% and ; 97. 4% -for
amenable cyanide. ' ' •'*- -• > - ' -*'•-. -.-. Ł>-r ^- ??*'•* r:-^- • -. -
.10.0, REFERENCES,,
- -' 'h ^ ^^^^^.
1. 1985 Annual Book of ASTM Standards. Vol. 11.01; "Standard Specification
, , . for Reagent Water!1; ATSM: ^.Philadelphia, , PA, '1985,;,D1193-77.-vUo^-^v/^^
j , , , i- .<- - -~%-.^-ife •»• -r. " t- - - j lt ' V-T-j-i^'i '*• ,.>o-_»^->-~x'ro~-'iŁ * "• - ,*• - "
2. - 1982 Annual J Book ASTM Standards. *Part 49; ^Standard *Test ^Methods .for
' '^Cyanide in Water"; ASTM: Philadelphia,- PAr 1982; "2036-82 .^-^--v' ''
3. Bark, L.S.; Higson, H.G. Talanta 1964, 2, -471-479. ...-- •_ ~
4. Britton, P.; Winter, J.; Kroner, R.C. "EPA Hethod 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. "Nitrosatio'n 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. OL 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.
9010 - 10 Revision 1
December 1987
-------
10' ' Methods'"for-Chemical^Anal vsis "?of ^Water^a'nd ' Wastes;'^U.S;tEnvironmental ;
J & .Protect i on ^Agency .*$•Of f i ce sof ^Research ^.and * Devel opment SlJEnvi ronmental '
,Moriitoring";fand Support^Laboratory^ORD'.PublicationTOffices**ofjCenterlforv
.Environmental ";Research j Information?^-rC
:1986.
''&••> 'i6^'}V'R-
'12 • Stand VrcTMethod s^foTrthe' Exami nation*
' , 3_
Greenberg"r7A. E: ; ;|Trussel 1 ^R.R.';l.Clesceri ^L'.S.^Eds^l! AmerlcantWater,;
Wofks"*!Association,\WaterlPonution"?Cdntfol 1 Federation ^American :Publ ic
..... " "" "' "~'^
13 Umana; "M.^
reportrto -the -U.S. -Environmental 'Protection Agency. "7 Of fice"'of -Solid
Waste." Research Triangle Institute:^ Research Triangle Park,' NC,- 1986.' "- .
/rV*r.-^;v^^r>^T<-^^^^v«y^ .„
14 Umana," 'M.f "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. -
- -—> - •- --~1 " - "
9010 - 11 Revision 1
December 1987
-------
, FIGURE d?_
APPARATUSIFORrCYANIDE'DISTILLATION;
II^SOUIICEJI
,- Jf!& i" ",-*-. o--v^!5f-cC'' --
^ OIST1LLIMG FUSK
9010 - 12
Revision 1
December 1987
-------
APPARATUS"FOR CYANIDE-DISTILLATION
;Ł2*'*c\ro- iv*^ •« ^-wr-**'"'^*-
^Connecting Tubing Ł
— - - - - g~~B8BaB&saa'^
ll
^Condense'
«Ł» * - > . -*j* \. v_ _
"Air Inlet Tube -
One Liter
Bo !>ng Flask
9010 - 13
Revision 1
December 1987
-------
,. ,. METHOD .9010'
ŁTpJAL ŁAND TAMENABLEfCYAN IDE
c
-—r-. — -»-» f-
731 Placi itipli
into faa abaorbar ,"*
tlaak coadanaar,
-, ,„-,.;•.
7 1 3 Add calclBB *
' kypocblorita ,* ;'
•olatloa to o&* ^
1 7 3 6 Cool, clou
7 3 3 All
of air iato boillnf
^i Hal* _- _
"
«llnnot
•«lnt>ia pX at
11-13 »itk 1 3EI
.; I«OH
'diacoiMCt [»•
abaorbtr ^
7 1 3 I.ft tor
•xc*«a calorlaa
vitk II-atarcfc
i • papar add
additional cilcioi
hypockloriti IO!B
Dtcaaiary
.-,'.JU
733 Add 0 083M
„ biiaith aitrata *
aola all tar 3 ,s>
"
714 Aftar 1 aaar
add todloa aratalta
7 3 4 Add 0 41
iliailc acid loin
ail for 3 iliitaa
7 3 S novlj add
111 ailtarle acid
rlxai tiao vitk
watar lix tor 3
aiaatat add 3 SX
(••Ilia calorlda
waak vitk watar
7 1 S Tatt tor
total cyaalda la
botk »apl<
allqtota
791 Traaatar aoli
to aiotkar tlaak
tor maaaal
•pactopkotoaatrle
dotanlaatlaa
9010 - 14
Revision 1
December 1987
-------
[METHOD*901 '^
^Continued)!
7 3 3 Add IX lodlsi'
t- paoaphata aola "Bj
ehlora«lna-t aatil^-
..-, excaaa la ; s f
"aalataiaad add -5.
acid aola »ix T^
•i^fV^irT^I^?^
Ą 1*t 1 "pr«f>ara"» Ł*
aariaa of ataadarda
for ataidard carva '
733 Dilata to v
»olua« vitk vatar
ail allov *
liaataa for color "
davtlopaaat read
abaorbaaca
D -I Cv.^:2*"
> ^>fti.*ji.Ł^ij ^ ^^""v'
1 ""."' "j' " V 'i.»l>1'
/-+'» 741 Plp.t' ^X
appropriate Tola««s
of vorxi&f fttaadard
ICI iola iato /
flaika add 1 Kl
' laQX to aick „
dllnt;« vltk vatir
. to volaa« —
-'. -^"r,4^;" ' -i*\\ •^-Srtr'^-*
- ,. >T' ^ ' - '. -1 'TT. V-D ,,-t^.:
7 E 1 OlatUl all
ataadarda -_,\
743 Pip>t
appropriate volqaa
of aach ataadard
* tola iata fink ,3
obtain abaorbaaei
valuta
773 Titrato vitk
•taadard 0 01521 ;-
' »ilT«r aitrati
tltrat* vat«r blaai
7 B 3 Prtpara a .,
••'•taadard carva »^j.
^ j ^. —T* p^. *-j-\jr_\*.
743 Distill 3
ataadarda coaaara
to alailar valaaa
aa carva
744 Prapart a
ataadar4 carra
7 4 S Cl«cfc
afflclaacr of
•aaplt diatlllatloa
7 7 3 Tl« aaalyit
•hoald b« faaxllar
-vjth titratioa
proctdura b«for*
titr«t:3{ taaplit
7 * For colorliatic
procadara calealat*
eyaalda la V|/U
T 7 4 telcalata
coac of CTaalda
••!•( tltrla.tU
•roca4araa
0
9010 - 15
Revision 1
December 1987
-------
i APPENDIXT9010A
CYAN I DE "EXTRACT ION 'PROCEDURE " FOR "SOL IDS * AND ;QI LSI
...,_,, -.-.., f.-fy1%>&*~j!*i^>i
1.0 'SCOPE AND APPLICATION^
•-^iR,
' ;O?'^^Vu *&*tvr^*""r-lj-^^ . - , r
>!??v^l.l ,; wastes^'The ^method -i s
appl i cable tto^oil risol id.iiand VmultiphaTic^safnples^Thisfmethbd ^is'j'not
. rr,-~ -r-, ,~>1 Ł:T--vV"^' r-- 7 4" '" l"-'.->?;'r«ttt?v«r- ,""L C «Sj» -v-a**~"-j-» «,!-w •«p*S»i i/-a»wtfiie— '^-rf."-j/>-. «h- v •
appl i cablelto^sampl es rcontai ni nali nsol ubl e
2.0,SUMMARY OF^METHOD
» ^-_., ^,T_- ,««^.,-. •.^.^v^v:^i^^Yf^^^qr^'5^^
r-STf>2.1 )Slf,.the waste,samplercontainsi>so .muchtsolid^orrsolidsiof .such a size
w«rr -;. *<*• -~\. ~-*.-~ta. . , i+s. .... ~*-f - i , •>'•*•-*•*<'•>-. »« .'*:*•« «fk ,'c\,H%a-.»«•- . -«•/ .*•••- • . ^.i
as to-interfere with agitation'and ^homogemzationjqfjthe7ssaniple^mixture-in the
distillationjflask,^pr/'so"'much ;-.oil ^or^grea'se/las^toj-interfere^with the
formation;qf^'a;hpmogeneous emulsionKthe^saniple^must^beJextracted^with water
at pH ';iO lor*-greater/Tand _vthe' "extract^analyzed ibyXMethod^90LO.^Samples that
contain free'"water'must be filtered a"nd sseparated^into^an] aqueous 'component
and a combined ]oil and solid componentl^The jioh'aqueous "component may then be
extracted,-'and ,an aliquot-of the jextract-'combined;with Un aliquot of the
filtrate r~*-< * . •aSr,,"' »**'**-sw=tar. i „-. . '*c.^r- -*-•», „ , . . 5S~Jv,«4fir, «iei«-«te^•v-isfA.i'-^-- .«-^i«\ -,..". .
component.^However,*5if>the -"sample^solidsJare^known^to^fcontain ^sufficient
levels of cyanide'(about 50 ug/g) as to be well above the limit of detection,
the extract!on^step may be deleted and the^solids analyzed directly by Method
SOlO.^This'can^be'accomplished^by 'diluting"a'"small "aliquot "of "the"waste solid
-.(1-5 9)--in SOO^mL.water.vin .the distillation-flask^and suspending-the slurry
during distillation with 'a magnetic "stir-bar/^^^^^-^-*"'*^* ^'«-
-------
•4'hi gh purity'Ho^,permit^IitsYuse'ywitho"ut\llessehing^tKe^accii'facy'Hof>ithe*.
i f- j ± ' • rj. • "V-> ••' '.- (•...t.-v VJAWfv- ,"*n-.ij«-j». /ronJ&.rf'vSiAsaM'iii&rfKl *^A"fevJlaio>'*!'!W!;-'.*..M.t*l»SrAji«i'W&d.i'^-**yr,.-tr
;t *&,•*
5.2 ASTM Type' II1,Water (ASTM D1193-77, (1983) j 3$l1 ''referencesVto^water in /
1 .the method refer ^to ASTM Type "H .unless'otherwise^specified.^i'^li^'''""'1'"4"''"""1
•\ ^-:-;>. ^'.-^H^^.^a^^S^^
^-^,5.3 -Sodium hydroxide (50% w/vJ^NapH.^Commerciallyiayail^able^
4."'iW-5 •4 -"'^^ne^'^CgHi^,
considerations^! scussed ii
T *.-Ł * . ^ ,,
Method 9010 for ^additional guidance.']
<„''?, - '" '"— ''.•'-./•„•. " " " " •'-"-'• -v" -;
s 7.0 PROCEDURE;Vl'
'"^v * ""^ 'ir**'^ '^r«* j 'nx.V t
* 1 \ '*l« • ' •-'_"_"•',' ->-"- An ,' ^ "." f1 -J>A T*7^ - 4 -«>.«•»-' '!-> «"'",«-V'3.Ti-'-«,^-J '"SiCjTV'Vf Sv-Tl-fl"" "" - .i" ' *~
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"sovthat the,solids are ,entirely'suspended,^then'the sample may
7\ be analyzed by Method 9010 without an extract!on,step.V"
'u-7-y' •' ^i/r?,t^C»>-t%?'^< ggSRSX'^^^V^^^^f^&^^^m-^f^i
'\-•' -,*,'* 'i..- —T" - " S, lUr-^t -»; j^-ss- -; J-v*t«-^-."jttt-v>-S' «.. >..,.— .- -. „. - -,-..,, •
7.2 Assemble Buchner funnel apparatus._Unroll .glass .filtering fiber and
. fold the .fiber over,itself ^several times tto ,make.a pad ..about 11 ^cm thick when
"' lightly compressed.^Cut"the~pad to'fit the Buchner"funnel r^Weigh the"pad,Hhen~
.. place ,it tJin the^rfunnel. ^Turn ,the aspirator.jOn,and vwet^the ,pad with a known
-' amount'of - water/-i
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. <• f . _"_- • '; >' »",'-•/' •
i -
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.
9010A - 2 Revision 0
December 1987
-------
>7 .'6 -1P1 aceTth'e '/f ol 1 bwi rig^i n "^i-1 i terTwi de"'mouth'ed "'bottl e : >
3&E*%«2*&M,ta ~Ł$* ~ """ "~"^~" ' "**"*" ------ "~ ------ ^ ~"
r
:500 mb water N:^.
[5 ml 50%'w/v NaOH
I „., / «
weigh
^representative 'aliqubVof'25.'g-and addVitHo the bottle;'otherwise
al .1 fof (thejsplidstSCap ,th~e!b6tti e"
saTnples fmay ;
extrac"ti on bottl e" /arid
'extractibh'lstejfjand ^subsequent |f iltration':f-Since''Jsoifne>
a6i d ,%thetpH 3must|belmbni tore'd Vas'tf oil owT?|shake\the7e
af t er>'ne>J/ute $ che~ckj thVVpH .^1 f "ithetpH 4\ s^el ow>12 ^Cadd^.5 W'*NaOH ,'i n J 5 L
i ncrements^'iint i 1 i t Ti s '"at"" 1 east ' 12 .'V Recap t.the^ botfl e'^and repe"at"the*v procedure
bottl eT^in^the^tumbl ef,^making 'sure ""there"' i s
enough .foam insulation to'cushion'the* bottler~Turn the tumbler on and allow
the extraction to run for'about 16 hours^
' ^^^^'^^> T ^ ; ,,.;;' rla/V:
.9 iPrepare a Buchner'funnel 'apparatus* as'in""Step 7.1 with a glass fiber
^ ^
-7.10 Decant the extract to the Buchrier -funnel. Full recovery of the
extract Js not necessary.
t- T —KNj .^-^y <,.^j.-s~ «:->Stir-!-_3( y. '^ »» , i't$
>--;-v-7.11 ^If -,the extract .contains =an toil * phase,^separate -the aqueous-phase
using a *separatory "funnel.^ Neither *the"separation*~nor"the 'filtration Jare
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 analyzed separately and concentrations
given for each phase. This is described by the following equation:
_ ^ " ""
Liquid Sample Aliquot (ml) = Solid Extracted fq) x Total Sample Filtrate (ml)
Extract Aliquot (ml)" -"" "Total Solid (g) ,Total Extraction Fluid (ml)
Where the Total Solids are from Step 7.5, weight of solids and oil phase, dry
weight of filter and tared dish subtracted. , ~ - ,
The Total Sample Filtrate includes volume of all rinses added to the filtrate.
The Total Extraction Fluid is 500 ml water plus volume of NaOH solution. Does
not include hexane, which is subsequently removed.
9010A - 3 Revision 0
December 1987
-------
t •- . *- V"JV. • x-" •* "•^Ki^Vf •i*";^' ^ ; «•" i1'*," t3/l:'»rf'" ^ *"-^."- «/*•'*«*•«'••» • v-j^?i^--gr^*^T-s.--*. M--^V -"'HiOJY***'1 ''^ " *-w"«T" *•'«'*"' ^"*ixi_r- "^
AT ternatively^the sal iquotsAmay?,be»\analyzed!separately^concentrations';for.'i
;.,'->. * \t i * fc«H.!t> •••f' .-' \Tij^*fi •.-/•, *.»,. »*v« **i*. j •»•** . *v. *»»tj*t j>%*^*-^f^-^&jr.*_ v*^•*-* * <**<*•*» *-it«a« ^^_,'jvv • ,v,».«<§,., -*"^
-.each *phase ^reported Tseparatelyr^anditheTamountstof^eachsphase^presenHin ,the;
-' s amp! e "reported teparatel tf^*^^^**********^^
"T^-,>W^V^%5^ """
"8.0 .QUALITY .CONTROL-^
t VJL* iV- ,_ >r -+~L VTN ""•-/»»• *-ft»A.«i-v* t_^
?9.0 METHOD PERFORMANCE I
. DEREFERENCES
•?-r5',~r2^Ł>r^?
> cl" -' *V-*=ti"-"*5'';-*' Tt*f**?*<*'*» •"V
Refer to' Method
9010A - 4 Revision 0
December 1987
-------
59010A-J
gCYA^ID^EXTRACTJON
9010A - 5
Revision 0
December 1987
-------
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
chlori nation. Method 9012 1s not Intended to determine 1f a waste Is
hazardous by the characteristic of reactivity.
2.0 SUMMARY OF METHOD
2.1 The cyanide, as hydrocyanic add (HCN), 1s released by refluxlng the
sample with strong add and distillation of the HCN Into an absorber-scrubber
containing sodium hydroxide solution. The cyanide 1on 1n the absorbing
solution 1s then determined by automated UV colorlmetry.
2.2 In the colorlmetrlc measurement, the cyanide 1s converted to
cyanogen chloride (CNC1) by reaction with Chloramlne-T at a pH less than 8
without hydrolyzlng to the cyanate. After the reaction 1s complete, color 1s
formed on the addition of pyr1d1ne-barb1tur1c acid reagent. The concentration
of NaOH must be the same 1n 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
Paragraphs 7.2.3, 7.2.4, and 7.2.5.
reduced by procedures described In
3.2 Sulfldes adversely affect the colorlmetrlc procedures. Samples that
contain hydrogen sulflde, metal sulfldes, or other compounds that may produce
hydrogen sulflde during the distillation should be treated by addition of
bismuth nitrate prior to distillation as described 1n 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 1n Figure 1 or 2. The
boiling flask should beof"1-litersize with inlet tube and provision for
condenser. The gas absorber is a F1sher-M1ll1gan 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.
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 Na^PCH'^O 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 intermediate cyanide 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
-------
Connecting Tubing
Allihn Condenser
One-Liter
Boiling Flask
Suction
Figure 1. Apparatus for cyanide distillation.
9012 - 3
Revision 0
Date September 1986
-------
COOLING WATER
INLET TUBE*
SCREW CLAMP
I
HEATER*
TO LOW VACUUM
SOURCE
~ ABSORBER
CONDENSER
~" DISTILLING FLASK
O
Figure 2. Cyanide distillation apparatus.
9012 - 4
Revision 0
Date September 1986
-------
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 acid solution; Dissolve 40 g of sulfamlc add 1n Type II
water. Dilute to 1 liter.
5.11 Calcium hypochlorite solution; Dissolve 5 g of calcium hypo-
chlorlte [Ca(OCl)2] In 100 ml of Type II water.
5.12 Reagents for automated color1metric determination;
5.12.1 Pyrid1ne-barb1tur1c add reagent; Place 15 g of barbituric
add In a 250-mL volumetric flask, add just enough Type II water to wash
the sides of the flask, and wet the barbituric add. Add 75 ml of
pyridlne 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 Chloram1ne-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 1n 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 acid; Crystals.
5.14 Phosphate buffer. pH 5.2: Dissolve 13.6 g of potassium dihydrogen
phosphate and 0.28 g of
-------
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 chlorlnatlon. To one 500-mL aliquot, or to a volume diluted
to 500 ml, add calcium hypochlortte 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
fh"e~ very toxic gas cyanogen chloride; therefore, 1t 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 hypochlorite 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, 1n
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
-------
7.2.3 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.
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
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 H2S04.
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 col ori metric 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
baseline 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
-------
VO
O
H-«
ro
I
00
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n -*
OO O
(D 3
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ft
CT
n
y ASTE
1
[ 15
^?=5^,
/fir io
COLORIMETER
S/O NM
15 mm f/C •
199 8073 0
70751 157
TURNS
/r/c
rUmP lUHt
7 O MM ID
6
194 BOO*
WASTE
8089
20 TURNS i
TO SAMPLER WASH
^ RECEPTACLE
f p? TO TOP OF PROBE
|
i/o oioj r11
5 TURNS ' (
PUR ORN
BLK BLK
RED RED
RtD RED
WMT WHT
BLK BLK
GRY GRV
ORN ORN
ORN ORN
cnv GRV
GRY GRV
M1/MIN
3.40 SAMPLE WASH
0.37 AIR
1 0 70 SAMPLE
0 70 DILUTION WATER
0 6O Rf SAMPLE WASTE
O.37 AIR ]
1.00 RE SAMPLE C 3
O.47 BUFFLR
0.10 CHLOROMINE T
1.00 PVRIDIN' BARBITURIC
1.00 FROM F/C
PROPORTIONING
PUMP
Figure 3. Cyanide manifold AA11.
vo
oo
-------
ml of Working Standard Solution Concentration
(1 ml = 10 ug CN) (ug CN/250 ml)
0 BLANK
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
undistilled 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 fh"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 1f
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
-------
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
-------
METHOD 9012
TOTAL AND AMENABLE CYANIDE (COLOHIMETRIC. AUTOMATED UV)
7. 1
Pretreat
to determine
cyanides
amenable to
chlor InatIon
7.S.I Place
I sample
In flask;
plpet sodium
hydroxide Into
absorbing tube
7 .Z.Z
Introduce air
stream Into
boiling flask
7.2.3
Treat
sample by
adding bismuth
nitrate
solution
Are samples
suspected to
contain NO
and/or
NO 7
acid solution
through air
Inlet tube
Add
H SO ;
tube with
rinse
Type II water;
add magnesulm
chloride
solution;
reflux: cool:
close off
vacuum source
Drain solution
from absorber
into flask
Perform
baseline
colorlmetrlc
analysis
9012 - 11
Revision 0
Date September 1986
-------
METHOD 9012
TOTAL AND AMENABLE CYANIDE (COLORIMETHIC. AUTOMATED UV)
(Continued)
7.5.1
Distill
standards In
same manner
as sample
7.5.2
Does sample
contain sulflde?
Prepare a
series of
CN standards
Prepare
standard curve
of absorbances
7 .4.Z
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
eff Iciency
of cample
distillation
( Stop }
9012 - 12
Revision 0
Date September 1986
-------
METHOD 9020
TOTAL ORGANIC HALIDES (TOX)
1.0 SCOPE AND APPLICATION
1.1 Method 9020 determines Total Organic Halldes (TOX) as chloride 1n
drinking water and ground waters. The method uses carbon adsorption with a
mi crocoulometrlc-tltration detector.
1.2 Method 9020 detects all organic halldes 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 1s applicable to samples whose 1norgan1c-hal1de concen-
tration does not exceed the organlc-hallde 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 1s restricted to use by, or under the supervision of,
analysts experienced 1n the operation of a pyrolys1s/m1crocoulometer and 1n
the interpretation of the results.
1.6 This method 1s 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). There are three Instruments that can be
used to carry out this method. They are the TOX-10 available from Cosa
Instruments, and the DX-20 and DX-20A available from Xertex-Dohrmann
Instruments.
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 in the sampling container, and that
is free of undissolved sol Ids, is passed through a column containing 40 mg of
activated carbon. The column is washed to remove any trapped inorganic
halldes and 1s then combusted to convert the adsorbed organohalldes to HX,
which is trapped and titrated electrolytlcally using a ml crocoul ometHc
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.
9020 - 1
Revision 0
Date September 1986
-------
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 1n hot water.
Rinse with tap water and distilled water and drain dry; glassware which
1s not volumetric should, 1n addition, be heated 1n a muffle furnace at
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 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 Cl~/40 mg should be used. The
stock of activated carbon should be stored in its granular form 1n 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 volatlles. 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 1n 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
instrument manufacturer's instructions for method) and Non-Purgeable
Organic Halldes (NPOX, that is, TOX of sample that has been purged of
volatlles) 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 1n Figure 1):
9020 - 2
Revision 0
Date September 1986
-------
N2
Sample
Reservoir
(1of4)
o
ro
o
Nitratr Wash
Reservoir
GAC Column 1
GAC Column 2
O 73
o> n
r* <
ro -*
v>
(D
vo
00
o>
F igure 1. Schematic diagram of adsorption system.
-------
4.1.1 Adsorption module: Pressurized sample and nitrate-wash
reservoirs. (There are three Instruments known to EPA at this time that
can be used to carry out this method. They are the TOX-10, available
from Cosa Instruments, and the DX-20 and DX-20A, available from Xertex-
Dohrmann Instruments.)
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): F1ltrasorb-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 hallde background should be
1,000 ng Cl~ equivalent or less.
4.1.4 Cerafelt (available from Johns-Manvllle) or equivalent: Form
this material Into plugs to fit the adsorption module and to hold 40 mg
of GAC 1n 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 Analytical system;
4.2.1 M1crocoulometr1c-t1trat1on system: Containing the following
components (a flowchart of the analytical system 1s shown 1n Figure 2):
4.2.1.1 Boat sampler: Muffled at 800*C for at least 2-4 m1n
and cleaned of any residue by vacuuming after each run.
4.2.1.2 Pyrolysls furnace.
4.2.1.3 Mlcrocoulometer with Integrator.
4.2.1.4 Tltration cell.
4.2.2 Strip-chart recorder.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities"Interferents should not be observable at the method detection
limit of each parameter of Interest.
5.2 Sodium sulflte (0.1 M): Dissolve 12.6 g ACS reagent grade Na2$03 1n
Type II water and dilute to 1 L.
5.3 Concentrated nitric acid
9020 - 4
Revision
Date September 1986
-------
Sparging
Device
Titration
Cell
Pyrolysis
Furnace
Boat
Inlet
VO
O
ro
o
Microcoulometer
with Integrator
Strip Chart
Recorder
Adsorption
Module
O 73
01 n
Figure 2. Flowchart of analytical system.
(Si O
n 2
a
en
-------
5.4 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-liter volumetric flask and diluting to volume with Type II water.
5.5 Carbon dioxide (C02): Gas, 99.9% purity.
5.6 Oxygen (02): 99.9% purity.
5.7 Nitrogen (N2): Prepurified.
5.8 Acetic acid in water (70%): Dilute 7 volumes of glacial acetic acid
with 3 volumes of Type II water.
5.9 Trichlorophenol solution, stock (1 uL = 10 ug Cl"): Prepare a stock
solution by accurately weighing accurately 1.856 g of trichlorophenol into a
100-mL volumetric flask. Dilute to volume with methanol.
5.10 Trichlorophenol solution, calibration (1 uL = 500 ng Cl~): Dilute
5 ml of the trichlorophenol stock solution to 100 ml with methanol.
5.11 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 uL of the calibration
solution.
5.12 Trichlorophenol standard, adsorption efficiency (100 ug Cl~/liter):
Prepare an adsorption-efficiency standard by injecting 10 uL of stock solution
into 1 liter of Type II water.
5.13 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 This method requires that all samples be run in duplicate.
6.2 All samples must have been collected using a sampling plan that
addresses the considerations discussed in Chapter Nine of this manual.
6.3 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 4°C, and
protected against loss of volatiles by eliminating headspace in the container.
The container must be washed and muffled at 400*C before use, to minimize
contamination.
6.4 All glassware must be dried prior to use according to the method
discussed in Paragraph 3.1.1.
9020 - 6
Revision
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 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 sulflte (5 mg sodium
sulfite crystals per liter of sample). Sulflte 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
may increase on storage of the sample. Samples should be stored at 4°C
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, 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 pyrolysls 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 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 3% of the
calibration-standard value. Repeat analysis of the instrument-
calibration standard after each group of eight pyrolysis determinations
and before resuming sample analysis, and after cleaning or reconditioning
the titration cell or pyrolysls 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/m1n.
NOTE; 100 ml of sample is 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 1001 to 2000 ug/L. If the anticipated TOX is greater
than 2000 ug/L, dilute the sample so that 100 mL will contain
between 1 and 50 ug TOX.
9020 - 7
Revision 0
Date September 1986
-------
7.3.3 Wash the columns-1n-ser1es with 2 ml of the 5,000-mg/L
nitrate solution at a rate of approximately 2 ml_/m1n to displace
Inorganic chloride Ions.
7.4 Pyrolysls 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.
7.4.2 Pyrolysls of the sample 1s accomplished 1n two stages. The
volatile components are pyrolyzed 1n a C02-r1ch atmosphere at a low
temperature to ensure the conversion of bromlnated trlhalomethanes to a
tltratable species. The less volatile components are then pyrolyzed at a
high temperature in an 02-r1ch 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 m1n 1n the 200*C zone of the
pyrolysis tube.
7.4.6 After 2 m1n, advance the boat Into the 800*C zone (center) of
the pyrolysis furnace. This second and final stage of pyrolysis may
require from 6 to 10 m1n to complete.
7.5 Detection; The effluent gases are directly analyzed 1n the mlcro-
coulometric-tltration cell. Carefully follow manual Instructions for
optimizing cell performance.
7.6 Breakthrough; The unpredictable nature of the background bias makes
it especiallydifficult 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, 1n 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 1t 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 1s 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 1s less than 20,000 times the organic chlorine
9020 - 8
Revision 0
Date September 1986
-------
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.
7.7 Calculations; TOX as Cl~ 1s calculated using the following formula:
(C, - C3) + (C2 - C3)
— ^-y — = ug/L Total Organic Hallde
where:
GI = ug Cl~ on the first column In series;
C2 = ug Cl~ on the second column 1n series;
03 = predetermined, dally, average, method-blank value
(nitrate-wash blank for a 40-mg carbon column); and
V = the sample volume 1n liters.
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 Under conditions of duplicate analysis, the reliable limit of
detection is 5 ug/L.
9.2 Analyses of distilled water, uncontamlnated 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 ug/L. Relative standard deviations were generally 20% at
concentrations greater than 25 ug/L. These data are shown in Tables 1 and 2.
9020 - 9
Revision
Date September 1986
-------
10.0 REFERENCES
1. GaskUl, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
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 Halldes (TOX), EPA/600/S4-85/080,. NTIS: PB 86 136538/AS.
9020 - 10
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA3
Spiked
Compound
Bromobenzene
Bromodlchloromethane
Bromoform
Bromoform
Bromoform
Bromoform
Bromoform
Chloroform
Chloroform
Chloroform
Chloroform
Chloroform
D1bromod1chloromethane
D1 bromodl chl oromethane
Tetrachl oroethyl ene
Tetrachl oroethyl ene
Tetrachl oroethyl ene
trans-D1 chl oroethyl ene
trans-D1 chl oroethyl ene
trans-D1 chl oroethyl ene
aResults from Reference 2.
bG.W. = Ground Water.
D.W. = Distilled Water.
Matr1xb
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
(ug/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
9020 - 11
Revision 0
Date September 1986
-------
TABLE 2. METHOD PERFORMANCE DATAa
Ground
Ground
Ground
Ground
Ground
Ground
Sample
Matrix
Water
Water
Water
Water
Water
Water
Unspiked
TOX (ug/L)
68,
5,
5,
54,
17,
11,
69
12
10
37
15
21
Spike
Level
100
100
100
100
100
100
Percent
Recovery
98,
110,
95,
111,
98,
97,
99
110
105
106
89
89
aResults from Reference 3.
9020 - 12
Revision
Date September 1986
-------
METHOD 9020
TOTAL ORGANIC HALIOES (TOX)
f Start J
7.1.1
Take
special
care in
handling sample
to minimize
volatile lose
7.1.3
7.2.2
Analyze nitrate-wash
blanks to establish
repeatability of
method background
each day
Add sulfite to
reduce residual
chlorine
7.1.2
7.2.3
7.3.31 Displace
I inorganic
chloride
ions by washing
columns with
nitrate solut.
Pyrolyze
duplicate
Instrument—
calibration and
blank standards
each day
Store samples
at 4 degrees C
without
headepace
7.2.1
7.4.1
Protect columns
from
contamination
7.3.1
Connect
in series
two columns
containing
activated
carbon
Check
absorption
efficiency for
each batch of
carbon
7.4.2
Pyrolyze
volatile
components
in COi-rich
atmosphere at
low temperature
7.3.2
Fill
sample
reservoir; pass
sample through
activated
carbon columns
7.4.2.
Pyrolyze
less volatile
compounds at
high temp in 0*
rich atmoshpere
9020 - 13
Revision 0
Date September 1986
-------
METHOD 9020
TOTAL ORGANIC HALIOES
(Continued)
(TOX)
Transfer
contents of
each column to
quartz boat
for analysis
7.4.4
Follow
instructions
for gas flow
regulation
7.4.5
Position
•ample
for 2 mln
In 200° C
zone
7.4.6
Advance boat
into BOO' C
zone
7.5
Analyze
effluent
gases in icro-
coulometric—
titration cell
IB 2nd column
measurement > 10X
of 2 column
total?
Reject and
repeat
Is 2nd column
measurement
Disregard
second-column
value
Calculate TOX
as Cl-
9020 - 14
Revision p
Date September 1986
-------
METHOD 9022
TOTAL ORGANIC HALIDES (TOX) BY NEUTRON ACTIVATION ANALYSIS
1.0 SCOPE AND APPLICATION
1.1 Method 9022 determines Total Organic Halides (TOX) 1n aqueous
samples. The method uses a carbon adsorption procedure identical to that of
Method 9020 (TOX analysis using a microcoulometric-titration detector),
irradiation by neutron bombardment, and then detection using a gamma-ray
detector.
1.2 Method 9022 detects all organic halides containing chlorine,
bromine, and iodine that are adsorbed by granular activated carbon under the
conditions of the method. Each halogen can be quantitated independently.
1.3 Method 9022 is restricted to use by, or under the supervision of,
analysts experienced in 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 in addition to TOX.
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
granular activated carbon (GAC). The column is washed to remove any trapped
inorganic halides. The GAC sample is exposed to thermal neutron bombardment,
creating a radioactive isotope. Gamma-ray emission, which is unique to each
halogen, is 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 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
9022 - 1
Revision 0
Date September 1986
-------
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 1n Its granular form 1n 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 1n glass containers with Teflon seals.
4.0 APPARATUS AND MATERIALS
4.1 Adsorption system (a general schematic of the adsorption system 1s
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-mrn I.D.
4.1.3 Granular activated carbon (GAC): Flltrasorb-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 hallde background should be
1000 ng Cl~ equivalent or less.
4.1.4 Cerafelt (available from Johns-Manvllle) 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 1n the adsorption columns.
CAUTION: Do hot 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 lO1^ neutrons/cm2/sec).
4.4 A gamma-ray detector and data-handling system capable of resolving
the halogen peaks from potential Interferences and background.
9022 - 2
Revision 0
Date September 1986
-------
N2
o
ro
ro
I
co
Sample
Reservoir
(1 of 4)
GAC Column 1
L^-CX*-
Nitratr Wash
Reservoir
O 73
at n
rf <
co o
m 3
a
GAG Column 2
vo
oo
en
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 (KNOs) Into
a 1-Hter 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 add (HNOs): 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~/I1ter):
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 1s not
possible, use amber glass, 250-mL, fitted with Teflon-lined caps. Foil may be
substituted for Teflon 1f the sample Is not corrosive. Samples must be
protected against loss of volatlles by eliminating headspace In 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 1n Paragraph 3.1.1.
9022 - 4
Revision
Date September 1986
-------
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 sulflte (1 ml of 0.1 M
sulfHe 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 sol Ids 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 is 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 in the standards are monitored to ensure there is no electronic
drift of the instrument. If drift 1s noted, the system must be recali-
brated.
7.3 Adsorption procedure;
7.3.1 Connect in series two columns, each containing 40 mg of
100/200-mesh activated carbon.
9022 - 5
Revision 0
Date September 1986
-------
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 is 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-in-series with at least 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 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 air-dried 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 is typically for a !5-m1n period at a thermal neutron
irradiation flux of 5 x 10*2 neutrons/cm^/sec. After returning from the
reactor, the rabbit 1s allowed to "cool" for 20 min to allow short-lived
radiolsotopes (primarily Al) present in the GAC to decay.
7.5 Detection;
7.5.1 Analysis 1s performed using a lithium-drifted germanium
[Ge(Li)] 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 it especially difficult to recognize the extent of
breakthrough of organohalides from one column to another. All second-
9022 - 6
Revision 0
Date September 1986
-------
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 Is analyzed using the 442-KeV gamma ray
produced by 25-m1n 128j.
7.6.3 The calculation used for quantltatlon 1s:
ppm halogen =
where:
counting time std.
counting time unk.
uq 1n std.
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 "live" counting time 1n seconds of the
standard.
counting time unk. = the "live" counting time 1n seconds of the
unknown.
9022 - 7
Revision 0
Date September 1986
-------
ug 1n std. = the number of micrograms of the stable element in
question in the standard (25 for Cl, 2.5 for Br and I).
sample vol. = the volume of sample passed through the GAC column, 1n
ml.
e^t = the decay correction to bring all statistics back to
t = 0; X = 0.693/tj/2, where ti/2 = the half-life in
minutes.
t = the time interval in 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 is 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 is, only the radiation
emitted from the sample -- not the sample itself -- should touch the analyzer.
9022 - 8
Revision
Date September 1986
-------
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 Bromine Iodine average
River water
Well water 7 (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
<1
<1
20.4
0.23
55.2
55.4
55.2
539.6
0.18
0.18
0.30
0.61
9.2 The reliable limits of detection are 5 ppb for chlorine and 1 ppb
for Iodine and bromine.
10.0 REFERENCES
None required.
9022 - 9
Revision 0
Date September 1986
-------
METHOD 9O22
TOTAL ORGANIC HALIOES (TOX) BY
NEUTRON ACTIVATION ANALYSIS
7.1.1 Take
I special
care handling
sample to
minimize loss
of volat 1 les
7.1.2
7.2.2
Analyze nitrate-wash
blanks to establish
repeatability of
method background
each day
Add eulflte to
reduce residual
chlorine
7.1.3
7.2.3
Calibrate
Instrument
each day using
radioactive
standards
Centrifuge and
decant samples
with undls-
colved solids
7.3. 1
Connect
In series
two columns
containing
activated
carbon
7.1.3
pH
prior
SI
Adjust
of sample
to adding
imple to
reservoir
7.3.2
Fill
sample
reservior: pass
sample through
activated
carbon columns
7.2.1
ac
ef f ic
each
c
Check
tsorpt Ion
:iency for
batch of
.arbon
7.3.3
Chic
t
CO]
nltrt
Displace
Inorganic
iride ions
>y washing
umnc with
ite «olut.
7.4. i
Remove GAC
quartz
collection tube
7.4.1
Extrude
GAC and
cerafelt
pads into e
prewashed
plastic vial
7 .4.2
Introduce
samples
and standards
into reactor
for neutron
IrradlatIon
7.S. 1
Anaylze using
Ge (Li) gamma
ray detector
7.5.2
To
analyze.
count standard
•nd samples
for a suitable
tine period
9022 - 10
Revision 0
Date September 1986
-------
TOTAL ORGANIC HALIDES
METHOD 9OZ2
(TOX) BY NEUTRON ACTIVATION ANALYSIS
(Continued)
IE 2nd column
measurement > 1OX
of 2 column
total?
Disregard
second—column
value
7.6
Analyze and
calculate
f Stop J
9022 - 11
Revision 0
Date September 1986
-------
METHOD 9030
SULFIDES
1.0 SCOPE AND APPLICATION
1.1 Method 9030 1s used to measure the concentration of total and
dissolved sulfldes 1n drinking, surface, and saline waters. The method does
not measure acid-Insoluble sulfldes. (Copper sulflde 1s the only common acid-
Insoluble sulflde.)
1.2 Method 9030 1s suitable for measuring sulflde 1n concentrations
above 1 mg/L.
2.0 SUMMARY OF METHOD
2.1 Excess Iodine is added to a sample which has been treated with zinc
acetate to produce zinc sulfide. The iodine oxidizes the sulflde to sulfur
under acidic conditions. The excess iodine is back-titrated with sodium
thiosulfate or phenylarsine oxide.
3.0 INTERFERENCES
3.1 The lodometric method suffers Interference from reducing substances
that react with iodine, Including thiosulfate, sulfHe, and various organic
compounds, both solid and dissolved.
3.2 Samples must be taken with a minimum of aeration 1n order to avoid
volatilization of sulfldes and reaction with oxygen, which may convert sulfide
to unmeasurable forms.
3.3 If the sample is not preserved with zinc acetate, analysis must
start immediately.
4.0 APPARATUS AND MATERIALS
4.1 Ordinary laboratory glassware.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Zinc acetate, 2 N: Dissolve 220 g Zn(C2H302)2-2H20 in 870 mL
Type II water and adjust volume to 1 L with Type II water.
9030 - 1
Revision
Date September 1986
-------
5.3 Sodium hydroxide solution, NaOH, 6 N.
5.4 Hydrochloric acid, HC1, 6 N.
5.5 Potassium Iodide; KI crystals.
5.6 Amylose Indicator.
5.7 Starch solution; Use either an aqueous solution or soluble starch
powder mixtures. Prepare an aqueous solution as follows:
5.7.1 Dissolve 2 g laboratory-grade soluble starch and 2.0 g
salicylic add, as a preservative, 1n 100 ml hot Type II water.
5.8 Tltrant; Choice of two:
5.8.1 Standard sodium thlosulfate solution, 0.0250 N: Dissolve
6.205 g Na2S203-5H20 in distilled water. Add 1.5 ml 6 N NaOH or 0.4 g
solid NaOH and dilute to 1,000 ml. Use starch solution as Indicator
during titration.
5.8.2 Standard phenylarslne oxide solution (PAD), 0.0250 N:
Commercially available (CAUTION: Toxic). Use amylose solution as
indicator during titration.
5.9 Standard iodine solution, 0.0250 N: Dissolve 20 to 25 g KI in a
little water in a litervolumetric flask and add 3.2 g iodine. Allow to
dissolve. Dilute to 1 liter with Type II water and standardize against
0.0250 N sodium thlosulfate or phenylarslne oxide using a starch indicator, as
follows.
5.9.1 Dissolve approximately 2 g (+1 g) KI crystals in 100 to
150 ml Type II water.
5.9.2 Add 20 ml of the Iodine solution to be standardized and
dilute to 300 ml with Type II water.
5.9.3 Titrate with 0.0250 N phenylarslne oxide (PAO) until a pale
straw color occurs.
5.9.4 Add a small amount of amylose Indicator and wait until a
homogeneous blue color develops.
5.9.5 Continue titration, drop by drop, until the color disappears.
5.9.6 Run in duplicate.
5.9.7 Calculate normality by the following equation:
N _ ml PAO x 0.0250
"1 ~ 20
9030 - 2
Revision
Date September 1986
-------
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 must be preserved with zinc acetate. Use 4 drops of 2 N
zinc acetate soution per 100 mL sample. Fill the bottle completely and
stopper with a minimum of aeration. The treated sample 1s relatively stable
and can be held for several days. If high concentrations of sulfide are
expected to be 1n the sample, continue adding zinc acetate until all the
sulfide has precipitated out.
7.0 PROCEDURE
7.1 Pretreatment to remove Interfering substances;
7.1.1 This procedure will eliminate Interferences due to sulflte,
thlosulfate, Iodide, and many other soluble substances (but not
ferrocyanlde) by producing a precipitate that may Include ZnS.
7.1.2 Put about 0.75 mL (15 drops) 2 N zinc acetate solution Into a
500-mL glass bottle, fill with preserved sample (see Paragraph 6.2), and
add enough NaOH to produce a pH above 9.
7.1.3 Vary the volume of reagents added according to the sample so
that the resulting precipitate Is not excessively bulky and settles
rapidly.
7.1.4 Stopper with no air bubbles under the stopper and mix by
rotating back and forth vigorously about a transverse axis.
7.1.5 Let the precipitate settle for 30 m1n. The treated sample 1s
relatively stable and can be held for several hours. However, 1f much
Iron 1s present, oxidation may be fairly rapid.
7.1.6 Filter the precipitate through glass fiber filter paper and
continue at once with titratlon.
7.2 Titratlon of the supernatant;
7.2.1 Measure from a buret Into a 500-mL flask an amount of Iodine
solution estimated to be 1n excess over the amount of sulfide present.
7.2.2 Add Type II water to bring the volume to about 20 mL.
7.2.3 Add 2-mL 6 N HC1.
9030 - 3
Revision 0
Date September 1986
-------
7.2.4 P1pet 200 ml of the sample Into the flask, discharging the
sample under the solution surface. If the Iodine color disappears, add
more Iodine so that the color remains. Record the total amount of Iodine
solution used.
7.2.5 Back-titrate with ^$203 solution or PAD, adding a few drops
of starch solution as the end point Is approached, and continue until the
blue color disappears. Record the total amount of tltrant used.
7.3 Titratlon of precipitated solids;
7.3.1 If sulfide was precipitated and filtered out (Paragraph 7.1),
return the filter and precipitate to the original bottle and add about
100 ml distilled water.
7.3.2 Add Iodine solution and HC1 , and titrate as 1n Paragraph 7.2.
7.4 Calculations;
7.4.1 1 ml of 0.0250 N Iodine solution reacts with 0.4 mg of
sulfide present 1n the tltratlon vessel. Thus, the following equation
should be used to calculate sulfide concentration;
• r(fl x B) ~AW x 16-000
where:
A = ml Iodine solution;
B = normality of Iodine solution;
C = ml tltrant; and
D = normality of tltrant.
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. The three standards should be sulfide solutions
at concentrations above, below, and at the expected/found concentration of the
sample.
8.3 Dilute samples if they are more concentrated than the highest
standard or if they fall on the plateau of a calibration curve.
9030 - 4
Revision
Date September 1986
-------
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 The precision of the end point varies with the sample. In clean
waters, 1t should be determined within 1 drop, which 1s equivalent to 0.1 mg/L
1n a 200-mL sample.
10.0 REFERENCES
1. Greenberg, A.E., Conners, J.J. and Jenkins, D. eds., Standard Methods for
the Examination of Water and Wastewater, 15th ed. (1980), American Public
Health Association, Washington, D.C., Methods 427, 427A, 427B, and 427D.
9030 - 5
Revision
Date September 1986
-------
METHOD 9030
SULFIOES
7.1
Eliminate
Interferences by
precipitating with
zinc acetate and NaOH
7.2.1
Measure Iodine
solution Into
flask
7.2.2
Add Type II
water
7.2.3
Add HC1
0
O
7.2.4
Titrate
I cample
with Iodine
solution;
record amount
of Iodine used
7.2.S
Back-titrate with
Na S O solution or
PAD; record amount of
tltrant used
7.3
Titrate
precipitated
solids
7.4
Calculate
sulfIde
concentration
f Stop J
9030 - 6
Revision 0
Date September 1986
-------
METHOD 9035
SULFATE (COLORIMETRIC. AUTOMATED. CHLORANILATE)
1.0 SCOPE AND APPLICATION
1.1 This automated method is 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 chloranilate is added to a solution containing
sulfate, barium sulfate 1s precipitated, releasing the highly colored acid
chloranilate 1on. The color intensity in the resulting chloranilic acid
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 chloranilate. These Ions are removed by passage through an ion-
exchange column.
3.2 Samples should be centrifuged 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
Impurities.
(ASTM D1193): Water should be monitored for
5.2 Barium chloranllate; Add 9 g of barium chloranilate (BaCfiC^O/i) 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 acid 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
This solution 1s also used to clean out the
water and dilute to 1 liter.
manifold system at end of sampling run:
5.5 Ion exchange resin; Dowex-50 W-X8, Ionic 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)
1.0
2.0
4.0
6.0
8.0
10.0
15.0
20.0
30.0
40.0
Concentration (mg/L)
10
20
40
60
80
100
150
200
300
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 0
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 chloranilate 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 mln. 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 in alternate openings in sampler and
set sample timing at 2.0 min.
7.4 Place working standards in sampler in 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 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 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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FIGURE 1 - SULFATE 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. Bertolacini, R.J., and J.E. Barney, II, ColoHmetric 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 Colorimetric Analysis, Analyst, 93, 97 (1968).
9035 - 5
Revision
Date September 1986
-------
METHOD 9035
SULFATE (COLORIMETRIC. AUTOMATED. CHLORANIUATE)
7.1
Set up manifold
7.2
7 .a
Place
working
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
sampler
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 S04~2/11ter 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 equimolar 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 (GRY. GRY.)
O
CO
0X1
o> o>
VI
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r+
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ION EXCHANGE
COLUMN 116 GOO6 01
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WASTES SLEEVING
L. 157-B095
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IIT TURNS
TO SAMPLER
WASH RECEPTACLE
170 0103 01
5 TURNS I
kNDARD
•
157 0370
f
22 \_ 116 04B9
1
116-04B9-OI
•
01
COLORIMETER f
TO F/C PUMP WASTP m
TUBE
460 NM
5 mm F/C "2.0 mm 10
TO ANALYZE SAMPLES IN THE
RANGE 0 30 mq/l CHANGE THE WATER
GRN. GRN.
BLK. BLK.
GRN. GRN.
ORN. GRN.
GRY. GRY.
BLK. BLK.
RED RED
ORN. ORN.
GRN. GRN.
PROPORTION!
PUMP
MVMIN.
2.0
0.32 AIR
2.00 DILU1
0.10 SAM
7.00 WAST
0.32 AIR
0.70 METH
0.42 ••SODIl
2.00 FROW
• *
MG
SAMPL1N
•O.O34 P
AND SAMPLE TUBES TO GRY/GRY (I.OOt
FIGURE 1 SULFATE MANIFOLD AA11
••SILICONF RUBBER
o>
10
00
en
-------
4.1.6 Filters: Of specified transmlttance.
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) 1n 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) in 25 ml of barium chloride solution (Paragraph 5.2). Add
4 ml of 1.0 N hydrochloric acid, 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 in a brown
plastic bottle in 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 is
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 SO/f2: 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/p2) 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-in. long, 2.0-mm I.D., and 3.6-mm O.D. This
is conveniently done by using a pipet 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 is used.
9036 - 4
Revision
Date September 1986
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7.3 Allow the colorimeter, recorder, and printer to warm up for 30 m1n.
Pump all reagents until a stable baseline Is 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 Is 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 is done by placing the
methyl thymol blue line and the sodium hydroxide line in water for a few
minutes and then in the buffered EDTA solution for 10 min. Wash the system
with water for 15 min 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
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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
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METHOD 9O36
SULFATE (COLORIHETRIC. AUTOMATED. METHYLTHYMOL BLUE. AA II)
7. J
Set up manifold
7.2
Prepare ion
exchange column
7.3
Harm up
colorimeter.
recorder and
printer. Get
stable baseline
o
7 .A
Develop
a standard
Curve: check
calibration
every hour
7 .5
Wash system
down at end of
day
7.6
Compute
concentration
of samples
Stop
9036 - 7
Revision Q
Date September 1986
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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 $04*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 1s 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 SI11ca In concentrations over 500 mg/L will Interfere.
4.0 APPARATUS AND MATERIALS
4.1 Magnetic stlrrer; Variable speed so that It can be held constant
just below splashing.Dse 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 stirrer is not equipped with an accurate
timer.
9038 - 1
Revision
Date September 1986
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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 1n solution In
a container. Add 50 ml glycerol anti 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 Na2C03 at 250*Cfor 4 hr and cool 1n a desiccator. Weigh
2.5 + 0.2 g (to the nearest mg), transfer to a 1-Hter 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 ^$04:
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 potent1ometr1cally to a pH of about
5. Lift electrodes and rinse Into beaker. Boll gently for 3 to 5
min 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 H2S04 using:
A x B
53.00 x C
where:
A = g N32C03 weighed Into 1 liter flask (Paragraph 5.4);
B = ml Na2C03 solution used 1n the standardization;
C = ml acid used in tltratlon;
5.6.1.2 Standard acid, 0.02 N: Dilute appropriate amount of
standard acid, 0.1 N (Paragraph 5.6.1.1) to 1 liter (use 200.00 ml
standard acid if 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
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5.6.1.3 Place 10 ml standard sulfuric add, 0.02 N (Paragraph
5.6.1.2) 1n 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
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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"^ from linear calibration curve:
2 mg SO^ x 1,000
mg S04~ /L = 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 1f they are more concentrated than the highest
standard or if 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 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
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Increment as
Sul fate
(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
(%)
-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 NaHCOs),
was analyzed In 19 laboratories by the turb1d1metr1c method, with a relative
standard deviation of 9.1% 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
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METHOD 9036
SULFATE (TURBIDIMETHIC)
7.1.1
o
Place
sample
In flask for
formation of
barium sulfate
turbidity
7.1.2
7 .Z.Z
Measure
turbidity:
record max.
reading
Add
conditioning
reagent and mix
7.1.4
7.3
Prepare
calibration
curve
Add BoCli
crystals: stir
for 1 minute
7.E.
7.4
Correct for
sample color
and turbidity
Pour solution
into absorbance
cell
7.5
Calculate SO,
-2
0
f Stop J
9038 - 6
Revision 0
Date September 1986
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METHOD 9060
TOTAL ORGANIC CARBON
1.0 SCOPE AND APPLICATION
1.1 Method 9060 Is 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 1n a
sample 1s directly proportional to the concentration of carbonaceous material
in 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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Date September 1986
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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 reproduclbly by means of a microllter-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
War1ng-type blender 1s 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 Is recommended as superior. If the
technique of chemical oxidation 1s used, the laboratory must be certain
that the Instrument 1s capable of achieving good carbon recoveries 1n
samples containing particulates.
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 C02.
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 Is preferable.
Sampling and storage 1n plastic bottles such as conventional polyethylene and
cubltalners 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 cubltalners 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 Ł 2) with HC1 or ^04.
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 is 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 if
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 in 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 (1976).
2. Standard Methods for the Examination of Water and Wastewater, 14th ed.,
p. 532, Method 505 (1975).
9060 - 4
Revision
Date September 1986
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METHOD 9060
TOTAL ORGANIC CARBON
f Start J
o
7. 1
Homogenize
the sample in
a blender
7.2
7.4
Follow manufacturer's
Instructions for
calibration.
procedure, end
calculations using
carbonaceous analyzer
Lower the
sample pH
7.3
7.S
Use series of
standards for
calibration
Purge the
sample with
nitrogen
7.6
Quadruplicate
analysis
O
f Stop J
9060
Revision 0
Date September 1986
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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 Is extracted and concentrated 1n a solvent
phase using phenol as a standard.
1.3 The method Is capable of measuring phenolic materials that contain
more than 50 ug/L In 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 ferricyanide 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-amlnoantlpyrlne 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 in 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 in the presence of potassium iodide, are removed
immediately after sampling by the addition of an excess of ferrous ammonium
sulfate. If chlorine is not removed, the phenolic compounds may be partially
oxidized and the results may be low.
9065 - 1
Revision 0
Date September 1986
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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 Spectrophotometert For use at 460 or 510 nm;
4.4 Funnels.
4.5 Filter paper.
4.6 Membrane filters.
4.7 Separatory funnels; 500- or il,000-mL.
4.8 Messier tubes; Short or long form.
5.0 REAGENTS ;
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Sulfuric add solution, ^$04; Concentrated.
5.3 Buffer solution; Dissolve 16.9 g NftyCl In 143 mi. concentrated NH/jOH
and dilute to 250 ml with Type II water. Two ml of buffer should adjust
100 ml of distillate to pH 10.
5.4 Amlnoantlpyrlne solution; Dissolve 2 g of 4-am1noant1pyr1ne (4-AAP)
In Type II water and dilute to 100 ml.
5.5 Potassium ferrlcyanide solution; Dissolve 8 g of K3Fe(CN)6 1n Type
II water and dilute to 100 ml.T~
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 mg phenol).
NOTE; This solution 1s 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).
I
5.9 Chloroform.
9065 -r 2
Revision
Date September 1986
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5.10 Ferrous ammonium sulfate: Dissolve 1.1 g 1n 500 ml Type II water
containing 1 ml concentrated ^$04 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 ^$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 H2S04 (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 amlnoantipyrlne solution (5.3) and mix.
7.2.4 Add 2.0 mL potassium ferricyanide solution (5.4) and mix.
7.2.5 After 15 min read absorbance at 510 nm.
9065 - 3
Revision 0
Date September 1986
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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 (ug/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 1n
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 ferrlcyanlde solution (5.4) and mix.
7.3.6 After 3 m1n, extract with 25 ml of chloroform (5.9). Shake
the separatory funnel at least 10 times, let CHCls 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
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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 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 9O65
PHENOLICS (SPECTROPHOTOMETHIC. MANUAL 4-AAP WITH DISTILLATION)
C
7.1.1
Measure
sample
Into beaker;
lower pH with
concentrated
7.1.2
Distill sample
Yes
Prepare
standards
using working
solution A
7.1.3
Filter
o
0
7.8.2
Add buffer
solution; mix
7.2.3
Add
amlnoantpyrtne
solution
7.2.4
Add potassium
ferricyanide
solution; mix
7.2.5
Read absorbance
7.3.1
Prepare
standards
using working
solution B
0
9065 - 6
Revision 0
Date September 1986
-------
METHOD 9065
PHENOLICS (SPECTROPWOTOMETRIC. MANUAL 4-AAP WITH DISTILLATION)
(Continued)
o
7.3.Z
1 Place
distillate or
diluted aliquot
In separator/
funnel
7.3.3|
Add
buffer solution
to cample and
standards: mix
7.3.4
Add
amlnoantipyrlne
solution: mix
7.3.51
Add potassium
ferricyanlde
solution: mix
0
O.
7.3.6
Extract with
chloroform
7.3.7
Filter
chloroform
extracts
7.3.e|
Read absorbance
7.4
Calculate
concentration
value of sample
( Stop J
9065 - 7
Revision 0
Date September 1986
-------
METHOD 9066
PHENOLICS (COLORIMETRIC. AUTOMATED 4-AAP WITH DISTILLATION)
1.0 SCOPE AND APPLICATION
1.1 This method is applicable to the analysis of ground water and of
drinking, surface, and saline waters.
1.2 The method is capable of measuring phenolic materials from 2 to
500 ug/L in the aqueous phase using phenol as a standard.
2.0 SUMMARY OF METHOD
2.1 This automated method is based on the distillation of phenol and
subsequent reaction of the distillate with alkaline ferricyanide (K3Fe(CN)s)
and 4-amino-antipyrine (4-AAP) to form a red complex which is 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 in the presence of potassium iodide, are removed
immediately after sampling by the addition of an excess of ferrous ammonium
sulfate (5.5). If chlorine is 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
is 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 ferricyanlde; Dissolve 2.0 g potassium
ferrlcyanide, 3.1 g boric add, and 3.75 g potassium chloride In 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 Br1j-35 (available from Technlcon).
(Br1j-35 1s a wetting agent and 1s a proprietary Technicon 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-Am1noantipyrine; Dissolve 0.65 g of 4-am1noantipyr1ne in 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
1n 500 ml Type II water containing 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 in 500 ml of Type II water and
dilute to 1,000 ml. Add 0.5 ml concentrated H2S04 as preservative (1.0 ml =
1.0 mg phenol). ,
CAUTION: This solution is tbxic.
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
in 100-mL volumetric flasks. Each standard should be preserved by adding 2
drops of concentrated ^04 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 Is Inhibited by the acidification to a pH <4
with H2S04. The sample should be kept at 4*C and analyzed within 28 days of
collection.
7.0 PROCEDURE f
7.1 Set up the manifold as shown 1n 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 mln. Run a
baseline with all reagents, feeding Type II water through the sample line.
Use polyethylene tubing for sample line. When new tubing 1s 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
-------
10
o
en
en
O 73
a* CD
r+ <
a> ->•
CO O
a
rt-
a>
To Waste * » »
lf?l S
s'
r T RESAMPLE
^soS[\ nnnn - * 1
vS^/
ATING BATH W
5TILLATION 0
1
5(
S.M. ^ ^
ITH ^
OIL ^
-^
157-8089 .. .
QPJIP i
A t
r 1
li
3 mm Tubular f/c "^
BLACK ^. BLACK
G - G
0-0
0 ^ 0
GRAY ^ GRAY
BLACK ^ BLACK
Y T; Y
0 < W
0 ^ W
GRAY ^. GRAY
Ml /min
0 32 AIR
2.OO SAMPLE
0.42 DISTILLING SOL.
0.42 WASTE FROM
STILL
1.0 RESAMPLE WASTE
0 32 AIR
1.2 RESAMPLE
0.23 4 AAP
SAM
m
i '
A-2
0 23 BUFFERED POTASSIUM
FERRI CYANIDE
J .0 WASTE FROM F/ C
PROPORTIONING
PUMP
SAMPLE RATE 20/hr. 1:2
*« 100 ACIOFLEX
• «» 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 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 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, 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. Technicon AutoAnalyzer II Methodology, Industrial Method No.l27-71W,
AA II.
9066 - 6
Revision
Date September 1986
-------
METHOD 9066
PHENOLICS CCOLORIMETHIC. AUTOMATED 4-AAP WITH DISTILLATION)
7.1
Set up manifold
7.2
Fill wash
receptac le
7.3
Warm up
colorimeter and
recorder
7.3
Run a baseline
0
o
7.4
Load phenol
standards and
unknown samp las
Have samples been
preserved?
(6.2)
7.S
Switch sample
to sampler;
analyze
7.6
Compute
concentration
of samples
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 Q,
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 is capable of measuring phenolic materials at the 2 ug/L
level when the colored end product is extracted and concentrated in a solvent
phase using phenol as a standard.
1.3 The method is capable of measuring phenolic materials that contain
from 50 to 1,000 ug/L in 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 oxidant. The coupling takes place
in the p-position; 1f this position is occupied, the MBTH reagent will react
at a free o-pos1tion. 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 Is required to remove
interfering materials.
3.2 Color response of phenolic materials with MBTH is not the same for
all compounds. Because phenolic-type wastes usually contain a variety of
phenols, it is 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 ^04 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-
thlazollnone hydrazone hydrochlorlde 1n 200 ml of Type II water.
5.4 Cerlc ammonium sulfate solution: Add 2.0 g of Ce($04)2*2^4)2504-
2H90 and 2.0 ml of concentrated H2S04 to 150 ml of Type II water. After the
solid has dissolved, dilute to 200 ml with Type II water.
5.5 Buffer solution; Dissolve, 1n the following order: 8 g of sodium
hydroxide, 2 g EDTA (d1 sodium 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 = 0.001 mg phenol).
5.11 Ferrous ammonium sulfate: Dissolve 1.1 g ferrous ammonium sulfate
in 500 ml Type II water containing 1 ml concentrated ^$04 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 in Chapter Nine of this manual.
6.2 Biological degradation is inhibited by acidification to a pH of <4
with H2S04. 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 sulfuric acid 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, filter through a prewashed
membrane filter.
7.2 Concentration above 50 ug/L:
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 Wait another 5 min and add 7 mL of working buffer solution
(5.6).
7.2.4 After 15 min, read the absorbance at 520 nm against a reagent
blank. The color is 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 mln, 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 mln, 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 analysts.
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 1f
contamination has occurred.
i '
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. Frlestad, H.O., E.E. Ott, and F.A. Gunther, "Automated Colorometric Micro
Determination of Phenol by Ox1dat1ve Coupling with 3-Methyl-benzoth1azol1none
Hydrazone," Technlcon International Congress, 1969.
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. HBTH WITH DISTILLATION]
c
Start
7.1.1
coppc
SI
to i
ad
7.1.2
Add
:r sulfate
tlutlon
sample to
ust pH
Distill sample
9067 - 6
Revision Q
Date September 1986
-------
METHOD 9067
PHENOLICS (SPECTPOPHOTOMETRIC. MBTH WITH DISTILLATION)
(Continued)
7.2.1
Add MBTH
solution
to distillate
or diluted
al Iquot
7.3.1
7.2.2
Add
cerlc ammonium
sulfate
solution
7.2.3
Add working
Duffer solution
7.2.4
Read absorbance
7.4
Calculate
concentration
value of sample
f Stop J
Add MBTH
solution
to distillate
in separator/
funnel
7.3.2
Add cerlc
ammonia sulfate
solution
7.3.3
Add working
buffer solution
7.3.4
Add
chloroform:
shake: filter
chloroform
layer
7.3.5
Read abeorbanca
9067 - 7
Revision 0
Date September 1986
-------
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 is
applicable to the determination of relatively nonvolatile hydrocarbons,
vegetable oils, animal fats, waxes, soaps, greases, and related matter.
1.2 The method is 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 in 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 1n sludge samples,
Method 9071 1s to be employed.
2.0 SUMMARY OF METHOD
2.1 The 1-Hter 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; Claisen or equivalent.
9070 - 1
Revision
Date September 1986
-------
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 (I,l,2-tr1chloro-l,2,2-tr1fluoroethane): Boiling
point, 48*C.
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 Is
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 1n 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-sens1t1ve paper to the cap to ensure that the pH 1s 2 or lower.
Add more add 1f necessary. ;
7.2 Pour the sample Into a separatory funnel.
7.3 Tare a boiling flask (pre-dr1ed 1n an oven at 103° and stored 1n a
desiccator). Use gloves when handling flask to avoid adding fingerprints.
9070 - 2
Revision
Date September 1986
-------
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 1n the
flask.
7.7 Connect the boiling flask to the distilling head and evaporate the
solvent by immersing the lower half of the flask in water at 70*C. Collect
the solvent for reuse. A solvent blank should accompany each set of samples.
7.8 When the temperature in 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 1s 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 in a desiccator for 30 min and weigh.
7.10 Calculation:
R R
mg/L total oil and grease = v
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 0
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 If 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
-------
METHOD 9O7O
TOTAL RECOVERABLE OIL AND GREASE
(Gravimetric. Separatory Funnel Extraction)
was
cample acidified?
7.2
Pour cample
into eeparatory
funnel
o
7.3
Tare boiling
flask
7.5
Combine solvent
in boiling
flask
0
7.7
Evaporate
.solvent:
collect for
reuse
7.4
f lot
113:
f lite
]
7.5
Repc
add!
EC
Add
irocarbon-
Extract:
•r solvent
ayer
•at twice
ng fresh
>lvent
7.8
Remove solvent
vapor
7.9
Cool flask ana
weigh
9.O
Calculate total
amount of
grease and oil
(
--
9070 - 5
Revision 0
Date September 1986
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METHOD 9071
OIL AND GREASE EXTRACTION METHOD FOR SLUDGE SAMPLES
1.0 SCOPE AND APPLICATION
1.1 Method 9071 1s used to recover low levels of oil and grease
(10 mg/L) by chemically drying a wet sludge sample and then extracting via the
Soxhlet apparatus.
1.2 Method 9071 Is used when relatively polar, heavy petroleum fractions
are present, or when the levels of nonvolatile greases challenge the solu-
bility limit of the solvent.
1.3 Specifically, Method 9071 is suitable for biological Hpids, mineral
hydrocarbons, and some industrial wastewaters.
1.4 Method 9071 1s not recommended for measurement of Iow-bo1l1ng
fractions that volatilize at temperatures below 70*C.
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 1n forming MgS04«7H20 and is used to dry the acidified sludge
sample.
2.3 After drying, the oil and grease are extracted with trlchlorotrl-
fluoroethane (Fluorocarbon 113) using the Soxhlet apparatus.
3.0 INTERFERENCES
3.1 The method 1s 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 1n 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.
9071 - 1
Revision
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Extraction apparatus: Soxhlet.
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 70°C.
4.12 Desiccator.
5.0 REAGENTS
5.1 Concentrated hydrochloric acid (HC1).
5.2 Magnesium sulfate monohydrate; Prepare MgSO^^O by spreading a
thin layer in a dish and drying in an oven at 150°C overnight.
5.3 Tri chlorotrif1uproethane (l,l,2-trichloro-l,2,2,-trifluoroethane):
Boiling point, 47'C.THesolvent should leave no measurable residue on
evaporation; distill if necessary.
5.4 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
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, semi sol id, 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.
9071 - 2
Revision
Date September 1986
-------
6.3 Any turbidity or suspended sol Ids 1n the extraction flask should be
removed by filtering through grease-free cotton or glass wool.
7.0 PROCEDURE
7.1 Weigh out 20 + 0.5 g of wet sludge with a known dry-solid content.
Place in a 150-mL beaker.
7.2 Acidify to a pH of 2 with approximately 0.3 ml concentrated HC1.
7.3 Add 25 g prepared Nk^SO/p^O and stir to a smooth paste.
7.4 Spread paste on sides of beaker to facilitate evaporation. Let
stand about 15-30 min or until substance is solidified.
7.5 Remove solids and grind to fine powder in a mortar.
7.6 Add the powder to the paper extraction thimble.
7.7 Wipe beaker and mortar with pieces of filter paper moistened with
solvent and add to thimble.
7.8 Fill thimble with glass wool (or glass beads).
7.9 Extract in Soxhlet apparatus using trichlorotrifluoroethane at a
rate of 20 cycles/hr for 4 hr.
7.10 Using grease-free cotton, filter the extract into a pre-weighed
250-mL boiling flask. Use gloves to avoid adding fingerprints to the flask.
7.11 Rinse flask and cotton with solvent.
7.12 Connect the boiling flask to the distilling head and evaporate the
solvent by immersing the lower half of the flask in water at 70°C. Collect
the solvent for reuse. A solvent blank should accompany each set of samples.
7.13 When the temperature in 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 1s connected
to a vacuum source. Immediately remove the flask from the heat source and
wipe the outside to remove excess moisture and fingerprints.
7.14 Cool the boiling flask in a desiccator for 30 min and weigh.
7.15 Calculate oil and grease as a percentage of the total dry solids.
Generally:
v nf nit anH nvaaca _ gain in weight of flask, g x 100
% or oil ana grease = wt> Qf wet sol1dSr g x dry Sol1ds fract1on
9071 - 3
Revision
Date September 1986
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8.0 QUALITY CONTROL
8.1 Before processing any samples, the analyst should demonstrate
through the analysis of a Type II water method blank that all glassware 1s
free of organic contamination; If there 1s a change 1n reagents, a method
blank should be processed as a safeguard against reagent contamination. The
blank sample should be carried through all stages of the sample preparation
and measurement.
8.2 Standard quality assurance practices should be used with this
method. Laboratory replicates should be analyzed to validate the precision of
the analysis. Fortified samples should be carried through all stages of
sample preparation and measurement; they should be analyzed to validate the
sensitivity and accuracy of the analysis.
8.3 Comprehensive quality control procedures are specified for each
target compound 1n the referring analytical method.
8.4 All quality control data should be maintained and available for easy
reference or Inspection.
8.5 Employ a minimum of one blank per sample batch to determine 1f
contamination has occurred.
8.6 Verify calibration with an Independently prepared check standard
every 15 samples.
8.7 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 No data provided.
10.0 REFERENCES
1. Blum, K.A. and M.J. Taras, "Determination of Emulsifying Oil 1n
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).
9071 - 4
Revision 0
Date September 1986
-------
METHOD 9071
OIL AND GREASE EXTRACTION METHOD FOR SLUDGE SAMPLES
CEED O
7. 1
weigh
and place In
beaker sample
of wet sludge
7.2
Acidify to
PH Z.O
7.3
Add and stir
7.4
Let substance
solidify
7.S
Remove and
grind solids to
a fine powder
O
7.6
Add
powder to paper
extraction
thimble
7.7
Wipe beaker and
mortar; add to
thimble
7.B
Fill thimble
with glass wool
7.9 j
Extract in
Soxhlet
apparatus
7.10
Filter
•xtract into
boiling flask
O
0
7.11
Rinse flask
with solvent
7. 12
Evaporate and
collect solvent
for reuse
7.13
Remove solvent
vapor
7. 14
Cool and weigh
boiling flask
7.151
Calculate X of
oil and grease
9071 - 5
Revision 0
Date September 1986
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METHOD 9131
TOTAL COLIFORM; MULTIPLE TUBE FERMENTATION TECHNIQUE
1.0 SCOPE AND APPLICATION
1.1 This method 1s 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
in 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 1n any amount
within 48 + 3 hr 1s 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 pos1tive~conf1rmed 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 col 1 form 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 in Microbiological
Methods for Monitoring the Environment (see References, Section 10.0).
3.0 INTERFERENCES
3.1 The distribution of bacteria in .water 1s irregular. Thus, a
five-tube test 1s required In 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
thiosulfate 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. Chelating agents such as ethylenediamlnetetraacetic add
(EDTA) should be added only when heavy metals are suspected of being present.
3.4 It 1s important to keep in mind that MPN tables are probability
calculations and inherently have poor precision. They Include a 23% positive
bias that generally results 1n 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 1n all areas, that 1s, they must not vary more than +0.5'C
in 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 in 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 in
liquid (glycerine, water, or mineral oil) on each shelf in use within the
incubator and record daily temperature readings (preferably morning and
afternoon). It is desirable, in 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 in the water bath sufficient to immerse
tubes to upper level of media.
4.2 Hot-air 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 is located properly on
the exhaust line so as to register minimum temperature within the
sterilizing chambers (temperature-recording instrument is 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 min.
4.3.2 Use of a vertical autoclave or pressure cooker is not
recommended because of difficulty in adjusting and maintaining
sterilization temperature and the potential hazard. If a pressure cooker
is used in 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 electrometric 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
Is clean and free of residues, dried agar, or other foreign materials that may
contaminate media.
4.8 Plpets and graduated cylinders;
4.8.1 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 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.
V ;
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 bacterlostatlc 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 Petrl dishes; Use glass or plastic Petrl 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 tlght-Hd 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
-------
4.12 Fermentation tubes and vials; Use only 10-mm 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 in diameter and at least 2.5 cm longer than the fermentation
tube; sterilize by dry heat and store in glass or other nontoxic 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 dlhydrogen phosphate (KHpPO^ 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 in amounts that will provide 99 + 2.0 ml or 9 + 0.2 ml after
autoclaving for 15 min.
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 autoclaving for 15 min.
5.2.5 Do not suspend bacteria in any dilution water for more than
30 min at room temperature because death or multiplication may occur,
depending on the species.
9131 - 5
Revision 0
Date September 1986
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5.3 Lauryl tryptose broth;
5.3.1 Components of the broth are:
Tryptose 20.0 g
Lactose 5.0 g
Diphosphate 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 is also available in 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 in accordance
with Table 1.
TABLE 1. PREPARATION OF LAURYL TRYPTOSE BROTH
Inoculum
(mL)
1
10
10
100
100
100
Amount of
Medium in Tube
(mL)
10 or more
10
20
50
35
20
Volume of
Medium +
Inoculum
(mL)
11 or more
20
30
150
135
120
Dehydrated Lauryl
Tryptose Broth
Requi red
(g/liter)
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 min. 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%dyecontent)In20ml95%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 1n a mortar. Add Type II water, a few m1llH1ters 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 Counterstaln; 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 1n 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 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.
6.2.2 Sterilize sample bottles not made of plastic as above, or 1n
an autoclave at 121°C for 15 mln. Perform a sterility check on one
bottle per batch.
9131 - 7
Revision
Date September 1986
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6.2.3 If water containing residual chlorine and other halogens 1s
to be collected, add sufficient ^28203 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 Na2S203 (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 in heavy metals in sample bottles containing a chelating
agent that will reduce metal toxicity. This is particularly significant
when such samples are in transit for 4 hr or more. Use 372 mg/L of the
tetrasodium 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 it with the ^$203 solution before addition.
6.3 When the sample is collected, leave ample air space in 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 it is 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 in the mixture of medium and added sample conforms
to the requirements given in Paragraph 5.3. Use a sterile pi pet for
Initial and subsequent transfers from each sample container. If the
pi pet becomes contaminated before transfers are completed, replace with a
sterile pi pet. Use a separate sterile plpet for transfers from each
different dilution. Do not prepare dilutions in direct sunlight. Use
caution when removing sterile plpets from the container; to avoid
contamination, do not drag pipet tip across exposed ends of plpets or
across lips and necks of dilution bottles. When removing sample, do not
insert pipets more than 2.5 cm below the surface of sample or dilution.
When discharging sample portions, hold pi pet 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
in size and number with the character of the water under examination, but
9131 - 8
Revision 0
Date September 1986
-------
in 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 in
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 1n any amount in 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 conform bacteria and provide
quality control data for 20% of all samples analyzed.
9131 - 9
Revision
Date September 1986
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Delivery
volume
Culture dishes
Actual volume
of sample in
dish
1 ml
0.1 ml
10'2 ml 10'3 ml
Figure 1. Preparation of dilutions.
9131 - 10
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Date September 1986
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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 coliform 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 in 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, if 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;
if gas is 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 1n 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. Air-dry or fix by
passing the slide through a flame and stain for 1 min with the ammonium
oxalate-crystal violet solution. Rinse the slide in tap water; apply
Lugol's solution for 1 min. (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 safranin (Paragraph 5.7) for 15 sec, then rinse with tap water, blot
dry with bibulous paper, and examine microscopically.
9131 - 11
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Date September 1986
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7.4.3 Cells that decolorize and accept the safranin stain are pink
and defined as gram-negative in 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 coliform bacteria in 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
0
0.1
0.5
1.6
3.3
8.0
Upper
6.0
12.6
19.2
29.4
52.9
Infinite
7.5.2 Three dilutions are necessary for the determination of the
MPN index. For example (see Table 3), if 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 is 4-2-0 and the MPN index is 22 per
100 mL. ^
7.5.3 In cases when the serial decimal dilution is other than 10,
1, and 0.1 mL, or when more than three sample volumes are used in the
series, refer to the sources cited in 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
Date September 1986
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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
Limits
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
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
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Date September 1986
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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
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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 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 1n deionlzed 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 1f 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 9131
TOTAL COLIFORM: MULTIPLE TUBE FERMENTATION TECHNIQUE
C
Presumpt1vc
Stage
7.1.1
Inoculate a series of
fermentation tubes
with graduated
Quantities of sample
7.
Incubate
inoculated
fermentatIon
tubes
^X^ 7.1.2 x
Has gas
formed after
. hours?
\ /
-^NC
2« ^ »
7.1.2
Reincubate and
reexamlne at
end of 4B hours
Con fIrmed
Stage
7 .2.1 I
Submit tubes
for which gas
'has formed, to
Confirmed Test
7.2.8 Shake
1 tube:
place culture
in tube with
green lactose
bile broth
7.2.3
Incubate bile
oroth tube for
48 hours
9131 - 17
Revision 0
Date September 1986
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Method 9131
TOTAL COHFORM: MULTIPLE TUBE FERMENTATION TECHNIQUE
(Continued)
Comoleted
Test
7.3.1
of bacterial
growth from
agar slant for
gram-staIn
Submit
tuoes for
which gas has
formeo to
Completed Test
7.3.3
7.4. 1
Alr-ary or fix
Streak eosln
metnylene blue Dlates
from each tube of
bile broth
snowing gas
7.3.3
Helncubate:
examine again
at 6 hours
stained prep-
arations from
slant cultures
(see 7.4)
Decolorize.
counterstaIn
with se f ran In;
examine
Incubate
Inverted plates
7.3.4
7.4.3
Gram
negative cells
are pink; gram
positive cells
are deep blue
Pick typical
colonies: transfer
growth to
fermentation tube
•no agar alant
7.5
'Calculate
density of
coll form
bacteria from
MPN table
7.3.5
Incubate
secondary
broth tubes
for Ł4 hours
( Stop J
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 is used to determine the presence of a member of a
coliform group 1n wastewater and ground water.
1.2 The coliform group analyzed in 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 is filtered through a membrane
filter which retains the bacteria found in 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 35°C + 0.5'C. Sheen colonies are
then counted under magnification and reported per 100 ml of original sample.
2.3 A more detailed treatment of this method is presented in Standard
Methods for the Examination of Water and Wastewater and in 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 in 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.
9132 - 1
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Date September 1986
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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 boroslH-
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 pi pets or pi pets conforming to the APHA standards given in 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 presterilized 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 1f sterilized by dry heat, or 1n suitable paper
substitute when autoclaved. If glass Petrl 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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Date September 1986
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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 In 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 mln. Do not Ignite plastic parts.
4.5.3 For filtration, mount receptacle of filter-holding assembly
in 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 is complete retention of col 1 form 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 in number of confluent colonies or
spreaders. Preferably, use membranes grid-marked in such a manner that
bacterial growth is neither Inhibited nor stimulated along the grid
lines. Store membrane filters held in stock in an environment without
extremes of temperature and humidity. Obtain no more than a year's
supply at any one time.
4.6.2 If presterillzed membrane filters are to be used, use those
for which the manufacturer has certified that the sterilization technique
has neither induced toxicity 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 in 10-cm Petri dishes or wrap in
heavy wrapping paper. Autoclave for 10 min 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 sulfltes or other
substances that could Inhibit bacterial growth. Use pads approximately
48 mm In diameter and of sufficient thickness to absorb 1.8 to 2.2 ml of
medium. PresteriUzed absorbent pads or pads subsequently sterilized 1n
the laboratory should release less than 1 mg total acidity (calculated as
CaC03) when titrated to the phenolphthaleln end point, pH 8.3, using
0.02 N NaOH. Where there Is evidence of absorbent pad toxlclty, presoak
pads 1n Type II water at 121*C (in an autoclave) for 15 m1n, decant the
water, and repackage pads 1n a large Petrl dish for sterilization and
subsequent use. Sterilize pads simultaneously with membrane filters
available 1n 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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Date September 1986
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5.2 M-Endo medium;
5.2.1 Components of the medium are:
Tryptose or polypeptone 10.0 g
Thiopeptone or thlotone 5.0 g
Casltone or tryptlcase 5.0 g
Yeast extract 1.5 g
Lactose 12.5 g
Sodium chloride, NaCl 5.0 g
D1potassium hydrogen
phosphate, K2HP04 4.375 g
Potassium d1hydrogen
phosphate, KH2P04 1.375 g
Sodium lauryl sulfate 0.050 g
Sodium desoxycholate 0.10 g
Sodium sulfHe, N32S03 2.10 g
Basic fuchsln 1.05 g
Distilled (Type II) water 1 liter
5.2.2 Rehydrate In 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 in the dark at 2 to 10*C 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 1n 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 In 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
Na2S203 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^C^ (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 in heavy metals in :sample bottles containing a chelating
agent that will reduce metal toxicity. This 1s particularly significant
when such samples are in transit for 4 hr or more. Use 372 mg/L of the
tetrasodium salt of ethylenediaminetetraacetic acid (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 N32S203 solution before addition.
6.3 When the sample is collected, leave ample air space in 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 it is 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 it 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
in delivery of samples longer than 6 hr, make field examinations using field
laboratory facilities located at the site of collection or use delayed-
incubation 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 1n 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 1n 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 1n 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 is 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 is 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 + o.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 is used, prepare final
culture by removing enrichment culture from Incubator and separating the
dish halves. Place a fresh sterile pad in 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 noncoliform) on Endo-type medium has no relation to the
total number of bacteria present in the original sample and, so far as Is
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) coliforms/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 col 1 form
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 col 1 forms." If the total number of bacterial
9132 - 8
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Date September 1986
-------
colonies, conforms plus noncollforms, 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 col 1 form 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 coliform 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, 1f 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 1n
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 1s greater
than that of the MPN procedure, membrane counts really are not absolute
numbers. Table 1 illustrates some 95% confidence limits.
9132 - 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
Number of Coll form
Colonies Counted
95% Confidence Limits
Lower
Upper
1
2
3
4
5
0.05
0.35
0.81
1.4
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
containers should be discarded after 6 mo.
than 2 yr. Opened media
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
Discard and remake if 1t is not.
stated value.
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 autoclaving, 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
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Date September 1986
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METHOD 9132
TOTAL COLIFORM: MEMBRANE FILTER TECHNIQUE
7. 1
Select
sample size on
basis expected
bacterial
density
7.2
Filter sample with
sterile aparatus;
rinse funnel: remove
fllate and place on
sterile pad or agar
9132 - 12
Revision 0
Date September 1986
-------
METHOD 913S
TOTAL COLIFORM: MEMBRANE FILTER TECHNIQUE
(Cont Inued)
7.4. 1
Roll
filter onto
• gar surface:
incubate
7.3.2.
Remove
from Incubator;
roll filter
onto agar
surface
culture dish:
saturate with
M-Enoc medium
7.4.2
Place
filter on pad:
Invert dish;
Incubate
7
.3.2 Remove
1 from
Incubator:
saturate fresh
pad: transfer
filter to pad
7
.3.2
Invert dish
. and Incubate
7
.5. 1
Count sheen
colonies
7.6
Calculate
collform
density
{ Stop J
9132 - 13
Revision o
Date September 1986
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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 is 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 ion with
brucine sulfate in 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 Brucine-
sulfanllic acid reagent. This also applies to natural color, not due to
dissolved organics, that is present.
3.2 If the sample is colored or 1f 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 brudne-
sulfanilic add 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 is 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 1n concentrations less than 1 mg/L these are
negligible.
9200 - 1
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Date September 1986
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3.5 Uneven heating of the samples and standards during the reaction time
will result 1n 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 1n temperature when the tubes are Immersed.
4.5 Water bath suitable for use at 10-15*C.
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 Sulfurlc add 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 Bruclne-sulfam'Hc acid reagent; Dissolve 1 g brucine sulfate --
(C23H26N2°4)2-H2S04-7H20 — and 0.1 g 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 1s
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) 1n 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 = O.OOPmg N03-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
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Date September 1986
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5.7 Acetic acid (1+3): Dilute 1 volume glacial acetic acid (COCOON)
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/I concentrated ^504) 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 1t 1s 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 1n 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
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Date September 1986
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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 If 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
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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 Brudne Method for the Determination of
Nitrate 1n Ocean, Estuarine, 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 0
Date September 1986
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METHOD 9800
NITRATE
7. 1
Adjust
of camples
7: filter
pH
to
If
necessary
7.2
Set up cample
tubes in rack
Correct for
color, dissolved
organic
natter?
Run
duplicate
sulfanlllc
acid reagent
to each tube
samples with
bruclne
sulfanilic odd
Bathe
rack of tubes
In 100 *C water
for 25 mln
9200 - 6
Revision 0
Date September 1986
-------
METHOD 9300
NITRATE
(Continued)
o
Pipette
standards and
samples Into
sample tubes
7.a
Read absorbance
against reagent
blank 41O nm
Yes
7.6
Pipette
sulfurlc acid
solution Into
each tube: mix
7.5
Add 30X sodium
chloride
solution; mix
7.9.1 C
abe
Cl
cc
mg
)btaln a
itandard
.orbonce
jrve and
ilculate
NOj-N/1
f Stop J
7.7
I Immerse
tubes in cold
water; allow to
reach thermal
equl1ibrlum
9200 - 7
Revision 0
Date September 1986
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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 ion, the liberated SCN forms highly colored ferric
thiocyanate 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 Type IIwater. Add 355 mL of concentrated HN03 and
dilute to 1 liter with Type II water. Filter.
9250 - 1
Revision 0
Date September 1986
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5.3 Saturated mercuric thiocyanate: Dissolve 5 g of Hg(SCN)2 1n 1 liter
of Type II water.DecantantJfiltera 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 in 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 is required. Set up manifold, as
shown in Figure 1. For water samples known to be consistently low in chloride
content, it is 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
-------
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-------
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 1n sampler 1n 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 if 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 I
9.1 Precision and accuracy data are available in 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 9250
CHLORIDE (COLORIMETRIC. AUTOMATED FERRICYANIOE AAI)
7.1
Set up manifold
as shown In
Figure 1
7.2
Place
working
standards and
unknown samples
In sampler tray
Warm up
colorimeter
and recorder:
obtain a stable
baseline
7.3
7.5
Switch sample
line to
sampler;analyze
Place
water wash
tubes In
sampler:
set timing
7.6.1
Prepare
standard
curve: compute
concentration
of samples
f Stop J
9250 - 5
Revision Q
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 In 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-rnm 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 Hg(SCN)? 1n 500
mL methanoTDilute 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 ^03)3* 91^0 in
500 ml of Type II water. 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 CT).
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 (mq/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 in 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 When particulate matter is present, the sample must be filtered
prior to the determination. The sample may be centrifuged in place of
filtration. Set up the manifold, as shown in Figure 1.
9251 - 2
Revision 0
Date September 1986
-------
, WASTE
ro
en
I
CO
O 73
ft) CO
(V — '•
CO
CO O
O> 3
-
rr>
10
oo
DILUTION
LOOP
WASTE
i
d
V
'//
&
TO SAMPLER
170
5
146-0152-02
onaoooo , .'
TURNS t
j
14 TURNS f
•" TO F/C
COLORIMETER PUMP TUBE
480 NM
15mm F/C
TO WHT/WHT
^ WASTE TUBE
1/0-0103 1
oogooo o *
5 TURNS f
WA0iTF «
PUR. ORG.
BLK. BLK.
PUR. PUR.
ORG. CRN.
BLK. BLK.
BLK. BLK.
GRY. GRY.
ORG. CRN.
GRY. GRY.
WHT. WHT.
GRY. GRY.
PROPOR
PI i
M1/MIN
3.40 OIL. WATER
0.32 AIR
2.50 OIL. WATER
0.10 SAMPLE
0.32 AIR
0.32 AIR
1.00 RE-SAMPLE
0.10 OIL. WATER
1.00 COLOR REAGENT
0.60 SAMPLE WASTE
1.00 FROM F/C
TIONING
MP
A4
Figure 1. Chloride Manifold A AH 0-200 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.
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 if 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 9251
CHLORIDE (COLOHIMETRIC. AUTOMATED FERRICYANIOE AA II)
Yes
Imeter and
-ecorder; run a
baseline with
all reagents
7. l
Filter
7.3
star
unknot
In son
Place
work Ing
Sards and
in camples
ipler tray
7.4
Obtain stable
baseline: start
sampler
7.5.1
curv
cone
01
Prepare
standard
re: compute
rentretlon
samples
( Stop j
9251 - 5
Revision p
Date September 1986
-------
METHOD 9252
CHLORIDE (TITRIMETRIC. MERCURIC NITRATE)
1.0 SCOPE AND APPLICATION
1.1 This method 1s 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 tltratlon volume, a sample aliquot
containing not more than 10 to 20 mg Cl per 50 ml 1s used.
1.3 Automated tHration may be used.
2.0 SUMMARY OF METHOD
2.1 An acidified sample 1s titrated with mercuric nitrate 1n the
presence of mixed diphenylcarbazone-bromophenol blue indicator. The end point
of the titration 1s the formation of the blue-violet mercury diphenylcarbazone
complex.
3.0 INTERFERENCES
3.1 Anlons and cations at concentrations normally found in surface
waters do not interfere. However, at the higher concentration often found 1n
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.
4.0 APPARATUS AND MATERIALS
4.1 Standard laboratory titri metric equipment, including 1-mL or 5-mL
nricroburet with 0.01-mL gradations.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Standard sodium chloride solution. 0.025 N: Dissolve 1.4613 g +
0.0002 g of sodium chloride (dried at 600'C for 1 hr) in chloride-free water
in a 1-liter volumetric flask and dilute to the mark.
5.3 Nitric acid (HNOs) solution; Add 3.0 mL concentrated nitric acid to
997 mL of Type II water ("3 + 997" solution).
9252 - 1
Revision 0
Date September 1986
-------
5.4 Sodium hydroxide (NaOH) solution (10 g/L): Dissolve approximately
10 g of NaOH in Type II water and dilute to 1 L.
5.5 Hydrogen peroxide (^02): 30%.
5.6 Hydroquinone solution (10 g/L): Dissolve 1 g of purified
hydroqulnone in water in a 100-mL volumetric flask and dilute to the mark.
5.7 Mercuric nitrate titrant (0.141 N): Dissolve 24.2 g Hg(N03)2*H?0 in
900 ml of Type II water acidified with 5.0 ml concentrated HN03 in a 1-11ter
volumetric flask and dilute to the mark with Type II water. Filter, 1f
necessary. Standardize against standard sodium chloride solution (Paragraph
5.2) using the procedures outlined in Section 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.
5.8 Mercuric nitrate titrant (0.025 N): Dissolve 4.2830 g Hg(N03)2-H20
in 50 ml ofType IIwateracidified with 0.05 ml of concentrated HN03
(sp. gr. 1.42) in a 1-liter volumetric flask and dilute tb the mark with Type
II water. Filter, if necessary. Standardize against standard sodium chloride
solution (Paragraph 5.2) using the procedures outlined in Section 7.0. Adjust
to exactly 0.025 N and check. Store in a dark bottle.
i
5.9 Mercuric nitrate titrant (0.0141 N): Dissolve 2.4200 g Hg
(N03)2'H20 in 25 ml of Typenwater acidified with 0.25 ml of concentrated
HN03 {sp. gr. 1.42) 1n a 1-liter volumetric flask and dilute to the mark with
Type II water. Filter, if necessary. Standardize against standard sodium
chloride solution (Paragraph 5.2) using the procedures outlined 1n Section
7.0. Adjust to exactly 0.0141 N and check. Store 1n a dark bottle. A 1-mL
aliquot is equivalent to 500 ug of chloride.
5.10 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
volumetric flask and dilute to the mark with 95% ethanol. Store In brown
bottle and discard after 6 mo.
5.11 Alphazurine indicator solution; Dissolve 0.005 g of alphazurlne
blue-green dye in 95% ethanolorisopropanol in 100-mL 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.
9252 - 2
Revision 0
Date September 1986
-------
7.0 PROCEDURE
7.1 Place 50 ml of sample in a vessel for tHratlon. If the
concentration 1s greater than 20 mg/L chloride, use 0.141 N mercuric nitrate
tHrant (Paragraph 5.7) 1n Step 7.6, or dilute sample with Type II water. If
the concentration 1s less than 2.5 mg/L of chloride, use 0.0141 N mercuric
nitrate titrant (Paragraph 5.9) in step 7.6. Using a 1-mL or 5-mL mlcroburet,
determine an Indicator blank on 50 ml chloride-free water using step 7.6. If
the concentration 1s 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 (Paragraph 5.10); shake
or swirl solution.
7.3 If a blue-violet or red color appears, add HN03 solution (Paragraph
5.3) dropwlse until the color changes to yellow.
7.4 If a yellow or orange color forms Immediately on addition of the
mixed indicator, add NaOH solution (5.3) dropwlse until the color changes to
blue-violet; then add HN03 solution (5.2) dropwlse until the color changes to
yellow.
7.5 Add 1 mL excess HN03 solution (5.2).
7.6 Titrate with 0.025 N mercuric nitrate titrant (5.8) until a blue-
violet color persists throughout the solution. If volume of titrant exceeds
10 mL or 1s less than 1 mL, use the 0.141 N or 0.0141 N mercuric nitrate
solutions, respectively. If necessary, take a small sample aliquot.
Alphazurlne Indicator solution (Paragraph 5.11) may be added with the
indicator to sharpen the end point. This will change color shades. Practice
runs should be made.
7.6.1 If chromate is present at <100 mg/L and Iron is not present,
add 5-10 drops of alphazurine Indicator solution (Paragraph 5.11) 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 1s not present,
add 2 mL of fresh hydroquinone solution (Paragraph 5.6).
7.6.3 If ferric iron 1s present use a volume containing no more
than 2.5 mg of ferric Ion or ferric 1on plus chromate ion. Add 2 mL
fresh hydroquinone solution (Paragraph 5.6).
7.6.4 If sulflte ion 1s present, add 0.5 mL of »2Q2 solution (5.5)
to 50-mL sample and mix for 1 min.
9252 - 3
Revision 0
Date September 1986
-------
7.7 Calculation;
rag cMorlde/mer .
where:
A = ml tltrant for sample;
B = ml titrant for blank; and
j
N = normality of mercuric nitrate tltrant.
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 has occurred.
8.3 Analyze check standards after approximately every 15 samples.
8.4 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample preparation and analytical
process.
8.5 Spiked samples or standard reference materials shall be periodically
employed to ensure that correct procedures are being followed and that all
equipment is operating properly.
9.0 METHOD PERFORMANCE
9.1 Forty-two analysts in eighteen laboratories analyzed synthetic water
samples containing exact Increments of chloride, with the following results:
Increment as
Chloride
(mg/L)
17
18
91
97
382
398
Precision as
Standard Deviation
(mg/L)
1.54
1.32
2.92
3.16
11.70
11.80
Accuracy as
Bias
(%)
+2.16
+3.50
+0.11
-0.51
-0.61
-1.19
Bias
(mg/L)
+0.4
+0.6
+0.1
-0.5
-2.3
-4.7
9252 - 4
Revision
Date September 1986
-------
9.2 In a single laboratory, using surface water samples at an average
concentration of 34 mg Cl/L, the standard deviation was +1.0.
9.3 A 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
NaHCOs) In Type II water was analyzed 1n 10 laboratories by the mercurlmetric
method, with a relative standard deviation of 3.3% and a relative error of
2.9%.
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.
9252 - 5
Revision
Date September 1986
-------
METHOD 9252
CHLORIDE (TITRIMETRIC. MERCURIC NITRATE)
Place sample In
vessel for
tltration
What is the
concentration of
chloride?
UGC
mercuric
nitrate titrant
Ł mlcroburet:
determine
indicator blank
nitrate titrant
In step 7.6
or dilute
<0.l ma/liter
Concentrate
volume to SO ml
Add
mixed indicator
reagent: shake
solution
Yellow or
orange
Blue-violet
or red
Which color
appears?
Add NaOH until
blue-violet
Add HNOj
solution until
yellow
Add HNO,
solution until
9252 - 6
Revision 0
Date September 1986
-------
METHOD 9253
CHLORIDE tTITRIMETRIC. MERCURIC NITRATE)
(Continued)
7.6
Titrate
1 with
mercuric
nitrate until
blue—violet
color persists
16 chromate
present at <1OO
m/llter and
no Iron?
olphezurine
Indicator
solution:
acidify .
Chromate at
> 100 mg/llter
7.6.3
Adjust
volume: add
fresh
Add HtOV
solution: mix
Add fresh
hydroquInone
solution
hydroquinone
solution
Calculate mg
chloride/liter
9252 - 7
Revision 0
Date September 1986
-------
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 radium-226 on the same sample. If the
level of rad1um-226 1s above 3 pC1/L, the sample must also be measured for
radium-228.
1.2 This technique 1s devised so that the beta activity from actinlum-
228, which 1s produced by decay of rad1um-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
actinlum-228 (avg. beta energy of 0.404 keV) 1s 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 1s collected by coprec1p1tat1on with
barium and lead sulfate and purified by reprec1p1tat1on from EDTA solution.
Both rad1um-226 and rad1um-228 are collected 1n this manner. After a 36-hr
Ingrowth of act1n1um-228 from radium-228, the act1n1um-228 1s 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 stront1um-90 in the water sample gives a positive bias to the radium-228
activity measured. However, stront1um-90 is not likely to be found 1n ground
water, except possibly in monitoring wells around a radioactive burial site.
3.2 Excess barium 1n 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
-------
4.3 Centrifuge.
4.4 Membrane filters; Matrlcel 47-mm.
4.5 Drying Tamp.
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 C^COOH (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 (Nfy) 20204^0 1n Type II water
and dilute to 100 ml.
5.5 Ammonium sulfate, 200 mg/mL: Dissolve 20 g (NH/^SCty in Type II
water and dilute to 100 ml.
5.6 Ammonium sulflde. 2%: Dilute 10 ml (NH4)2S (20-24%), to 100 ml with
Type II water.
5.7 Barium carrier, 16 mg/mL, standardized: Dissolve 2.846 g BaCl2'2H20
in Type II water, add 0.5 ml 16 N HNOs, and dilute to 100 ml with Type II
water.
5.8 Citric acid. 1 M: Dissolve 19.2 g CeHgO/'^O 1n Type II water and
dilute to 100 ml.
5.9 EDTA reagent, basic (0.25 M) ; Dissolve 20 g NaOH in 750 mL Type II
water, heat, and slowly add 93 g disodlum ethyl enedinitriloacetate dihydrate
(Na2CioHi408N2-2H20) 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 in Type II
water, add 0.5 mL 16 N HN03, and dilute to 100 mL with Type IT 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
act1nium-228 or strontium-89 (tj/2 =51 d). Strontium-89 has an average
beta energy of 0.589 KeV, while the average beta energy for act1n1uni-228
1s 0.404 KeV. A standard strontium-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 CffioPj '^2® • anŁl a ^ew drops of
methyl orange indicator. The solution should be red.
NOTE: At the time of sample collection add 2 mL 16 N HNOa 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 NH4OH until a definite yellow color is
obtained; then add a few drops excess. Heat to incipient boiling and maintain
at this temperature for 30 m1n.
7.4 Precipitate lead and barium sul fates by adding 18 N H2SOA 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 matrlcel
membrane filter (GA6,0.45-micron 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 in the bottom of a 250-mL
beaker. Add about 10 mL 16 N HN03 and heat gently unti'1 the filter completely
9320 - 3
Revision
Date September 1986
-------
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 HN03, 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 If 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 1f any precipitate forms.
7.10 Add 1 ml (NH/^SOA (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 act1n1um-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 dropwlse with
vigorous stirring until lead sulfide precipitates; then add 10. drops excess.
Stir Intermittently for about 10 m1n. Centrifuge and decant supernatant Into
a clean tube.
7.14 Add 1 mL lead carrier (1.5 mg/mL), 0.1 mL (NH/^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 act1n1um-228 Ingrowth time and
beginning of act1m'um-228 decay time.)
7.16 Dissolve the precipitate In 2 mL 6 N HN03. Heat and stir 1n a hot
water bath about 5 m1n. Add 5 mL water and repreclpltate yttrium hydroxide
with 3 mL 10 N NaOH. Heat and stir 1n a hot water bath until precipitate
coagulates. Centrifuge and add this supernate to the supernate produced 1n
step 7.15 1n order to determine barium yield.
7.17 Dissolve precipitate with 1 mL 1 N HN03 and heat 1n hot-water bath
a few minutes. Dilute to 5 mL and add 2 mL 5% ^4^204 ^0. 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 HNOs and 6 drops 5%
Heat and stir in 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 HMOs and 2 mL
>2S04 (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 in 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 (NH4)2S04 (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 radium-228 concentration, D, in picocuries per
liter as follows:
\t *
D Ł x —i3r- x ^- x *
2.22 x EVR (1_e-Xt2} -t3 ^ -t>
_2 is a factor to correct the average count rate to the count
-Xt9 rate at the beginning of counting time.
9320 - 5
Revision 0
Date September 1986
-------
where:
C = Average net count rate, cpm;
E = Counter efficiency, for actinium-228, or comparable beta
energy nuclide;
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
picocuries;
X = The decay constant for actinium-228 (0.001884 min~J);
ti = The time interval (in min) between the first yttrium
hydroxide precipitation in Step 7.15 and the start of
the counting time;
tŁ = The time interval of counting in min; and
t3 = The Ingrowth time of actinium-228 1n min measured from
the last barium sulfate precipitation in Step 7.11 to
the first yttrium hydroxide precipitation in 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 is 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
-------
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 0
Date September 1986
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METHOD 9320
RADIUM-226
I Start J
7.1.1
Calibrate
beta counter
with Ac-226
or Si—89
7.5 \
Cool slightly:
filter
7.2
Add
C.H.O,' HtO and
methyl orange
Indicator to
water
7.3
7.6 [
Put filter end
precipitate in
beaker;
add HNO<:
heat: centrifuge:
discard
cupernate
Add
lead, strontium.
barium, and
yttrium
carriers; stir
7.3
7.7
Wash
precipitate:
centerfuge:
discard
supernate
Add NH«OH until
yellow color
obtained: heat
7.4
7.7
Repeat once
Add H.SO
to
precipitate
lead and barium
•ulfates; add
stir
7.8
Add basic EOTA
reagent: neat:
stir
Does
precipitate
readily
dissolve?
Add NaOH to
dissolve
strontium
yttrium mixed
carrier: add
NaOH
7. 10
Add
(NH.,), SCU: add
CH COOH; digest:
centrifuge:
discard supern.
Add basic EOTA
reagent: heat:
stir
Repeat sections
7.9 and 7.1O
9320 - 8
Revision 0
Date September 1986
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METHOD 9330
PADIUM-286
(Continued)
Dissolve
precIpltate
in EOTA; add
yttrium and
lead carriers
7.14
Centrifuge and
filter
-------
METHOD 9320
RAOXUM-228
(Contlnuea)
Old
precipitate
readily
dissolve?
Add (NH<)jSO^: stir;
add CHjCOOH; digest:
centrifuge: discard
super-note
7.23
Hash
prec ipltate:
centrifuge:
discard
supernate
7.24
prec
plane
Ml
bar]
Transfer
ipitete to
:het: dry;
:igh for
I urn yield
7.25
r
cone
uslr
Calculate
•adlum-228
rentratlon
-------
CHAPTER SIX
PROPERTIES
Methods appropriate for measuring properties are Included on the
following pages.
SIX - 1
Revision
Date September 1986
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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 acid;nitric 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
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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 in 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 if
contamination or any memory effects are occurring.
8.3 All quality control measures suggested in 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 1320
MULTIPLE EXTRACTION PROCEDURE
C st-rt ) O
7.1
Run extraction
procedure test
(Method 1310)
7.2
7.5
0
Combine
K agitate
solid phase
sample and acid
rain fluid:
record pH
Analyze metals
according to
Table 1
7.6
7.7
Repeat
separetIon
procedure
(Method 1310)
Agitate
mixture for 24
hre; record pH
at end.
7.3 I
Prepare
synthetic acid
rain extraction
fluid
7.4
7.8
Analyze
extract for
constituents
of concern
O
7.9 |
Repeat 8 times
Weigh
solid phase
of sample:
measure acid
rain extraction
O
Is concentr. of
9th extraction >
the 7th and
8th?
7.11
Report
initial
•nd final
extraction
pH and concetr.
of constituents
7.10|
' Continue
extracting
until concentr.
ceases to
increase
f Stop J
1320 - 4
Revision 0
Date September 1986
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METHOD 1330
EXTRACTION PROCEDURE FOR OILY WASTES
1.0 SCOPE AND APPLICATION
1.1 Method 1330 1s used to determine the mobile metal concentration
(MMC) In oily wastes.
1.2 Method 1330 1s 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 1s placed 1n a Soxhlet extractor, charged with
tetrahydrofuran, and extracted. The THF Is removed, the extractor Is then
charged with toluene, and the sample 1s re-extracted.
2.3 The EP method (Method 1310) 1s 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.
1330 - 1
Revision
Date September 1986
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4.7 Muslin cloth disks.
4.8 Evaporative flask; 250-mL.
4.9 Analytical Balance; Capable of weighing to +0.5 mg.
5.0 REAGENTS
5.1 Tetrahydrofuran; ACS Reagent grade.
5.2 Toluene; ACS Reagent grade.
6.0 SAMPLING
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 using the filtration Steps 7.1-7.6 in Method 1310.
7.2 Determine the quantity of liquid (ml) and the concentration of the
species of concern in the liquid phase (mg/L) using appropriate analytical
methods.
7.3 Place the solid phase into a Soxhlet extractor, charge the
concentration flask with 300 ml tetrahydrofuran, and extract for 3 hr.
7.4 Remove the flask containing tetrahydrofuran and replace it with one
containing 300 ml toluene.
7.5 Extract the solid for a second time, for 3 hr, with the toluene.
7.6 Combine the tetrahydrofuran and toluene extracts.
7.7 Determine the quantity of liquid (ml) and the concentration of the
species of concern in the combined extracts (mg/L).
7.8 Take the solid material remaining in the Soxhlet thimble and dry it
at 100'C for 30 min.
1330 - 2
Revision
Date September 1986
-------
7.9 Run the EP (Method 1310) on the dried solid.
7.10 Calculate the mobile metal concentration (MMC) in mg/L using the
following formula:
(Qi + Q, + Q,)
MMC = 1,000 x —^-
L2)
where:
Ql = amount of metal in Initial liquid phase of sample (amt. of
liquid x cone, of metal) (mg).
Q2 = amount of metal in combined organic extracts of sample (mg).
Q3 = amount of metal in EP Extract of solid (amt. of extract x cone.
of metal) (mg).
LI = amount of initial liquid (ml).
12 = amount of liquid in EP (mL) = 20 x [weight of dried solid from
Step 9 (mg)].
8.0 QUALITY CONTROL
8.1 Standard quality assurance practices should be used with this
method. Laboratory replicates should be analyzed to validate the precision of
the analysis. Fortified samples should be carried through all stages of
sample preparation and measurement; they should be analyzed to validate the
sensitivity and accuracy of the analysis.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
1330 - 3
Revision
Date September 1986
-------
METHOD 1330
EXTRACTION PROCEDURE TOR OILY HASTE
7. 1
Separate
sample Into
solid Ł liquid
components
(Method 1310)
7.2
Determine quantity
of liquid end
concetr. of metals In
liquid phase (Method
3040. or 3050)
7.3
Place solid phase in
extractor, charge
with tetrahydrofuran;
extract for 3 hours
7.4
Replace
tetrahydrofuren
flask with
toluene flask
7.5
Extract solid
for 3 houre
0
7.6
Combine the 2
extracts
7.7
Determine
quantity
of liquid end
concentr. of
metals
(Method 3040)
7.8
Dry remaining
solid material
for 30 mlns .
7.9
Run EP on
dried solid
(Method 131O)
7.101
Calculate mob 11
metal
concentration
o
f Stop J
1330 - 4
Revision 0
Date September 1986
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METHOD 9040
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.
2.0 SUMMARY
2.1 The pH of the sample 1s determined electrometrlcally using either a
glass electrode 1n combination with a reference potential or a combination
electrode. The measuring device 1s calibrated using a series of standard
solutions of known pH.
3.0 INTERFERENCES
3.1 The glass electrode, 1n general, 1s not subject to solution
Interferences from color, turbidity, colloidal matter, oxldants, reductants,
or high 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 (1:9) 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 can 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.
9040 - 1
Revision 0
Date September 1986
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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 Magnetic stirrer and Teflon-coated stirring bar.
4.5 Thermometer or temperature sensor for automatic compensation.
5.0 REAGENTS
5.1 Primary standard buffer salts are available from the National Bureau
of Standards (Special Publication 260) 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.
5.2 Secondary standard buffers may be prepared from NBS salts or
purchased as solutions from commercial vendors. These commercially available
solutions have been validated by comparison with NBS 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. Various instrument designs
may involve use of a dial to "balance" or "standardize" or a slope
adjustment, as outlined in the manufacturer's instructions. Repeat
9040 - 2
Revision 0
Date September 1986
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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
1 pH).
7.3 If the sample temperature differs by more than 2*C 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 volumes of sample until values differ by <0.1 pH units. Two or
three volume changes are usually sufficient.
8.0 QUALITY CONTROL
8.1 Duplicate samples and check standards should be analyzed routinely.
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:
pH Units
3.5
3.5
7.1
7.2
8.0
8.0
Standard Deviation
pH Units
0.10
0.11
0.20
0.18
0.13
0.12
Accuracy as
Bias
-0.29
-0.00
+1.01
-0.03
-0.12
+0.16
Bias
pH Units
-0.01
+0.07
-0.002
-0.01
+0.01
10.0 REFERENCES
1. National Bureau of Standards,
87, Special Publication 260.
Standard Reference Material Catalog 1986-
9040 - 3
Revision 0
Date September 1986
-------
METHOD 9040
pH MEASUREMENT
I Start J
7. J
Calibrate
pH meter
7.2
Place sample or
buffer solution
in glass beaker
Immerse
electrodes and
measure pH of
sample
7.4
recc
ten
repi
Note and
>rd pH and
nperature:
;at 2 or 3
tines
f Stop J
9040 - 4
Revision p
Date September 1986
-------
METHOD 9041
pH PAPER METHOD
1.0 SCOPE AND APPLICATION
1.1 Method 9041 may be used to measure pH as an alternative to Method
9040 or in cases where pH measurements by Method 9040 are not, possible. This
method may be used to define a waste as corrosive or noncorrosive under
certain conditions (see Paragraph 1.3).
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 can be used to define a waste as corrosive or noncorrosive (see RCRA
regulations 261.22 (a)(1) only if the measured values differ from either
threshold limit (pH 2 or 12.5) by a full pH unit. If readings within the
ranges of either pH 1-3 or pH 11.5-13.5 are obtained with Method 9041, then
Method 9040 should be used if possible to determine whether or not the waste
is corrosive.
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 buffer.
9041 - 1
Revision 0
Date September 1986
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4.3 pH Meter (optional).
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 1n 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 1s chosen and the pH of a
second aliquot of the waste 1s 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 add dropwlse until a pH change 1s 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
add 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.
7.4 pH Measurements taken with Method 9041 can be used to define a waste
as corrosive or noncorroslve only if the measured values differ from either
threshold limit (pH 2 or 12.5) by a full pH unit. If readings in the ranges
of either pH 1-3 or pH 11.5-13.5 are obtained with Method 9041, then the pH of
the solution must be determined electrometrically (Method 9040).
9041 - 2
Revision
Date September 1986
-------
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.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
9041 - 3
Revision
Date September 1986
-------
METHOD 90<41
pH PAPER METHOD
7. 1 [
Determine
approximate pH
with wide-range
pH paper
7.S
1 Select
narrow—range pH
paper;determine
twice the pH of
2nd aliquot
Does pH differs.
from threshold
limits by
full pH
unit?
7.3.1 Using 3rd
I aliquot.
add acid to
waste until pH
changes: note
color change
7.3.2
Add base to 4th
aliquot: note
color change
7.4
Define waste as
corrosive or
noncorroslve
( Stop J
9041 - 4
Revision p
Date September 1986
-------
METHOD 9045
SOIL pH
1.0 SCOPE AND APPLICATION
1.1 Method 9045 is an electrometric procedure which has been approved
for measuring pH in calcareous and noncalcareous soils.
2.0 SUMMARY OF METHOD
2.1 The soil sample is mixed either with Type II water or with a calcium
chloride solution (see Section 5.0), depending on whether the soil is
considered calcareous or noncalcareous. The pH of the solution is then
measured with a pH meter.
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 either (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.
4.0 APPARATUS AND MATERIALS
4.1 pH Meter with means for temperature compensation.
4.2 Electrodes;
4.2.1 Calomel electrode.
4.2.2 Glass electrode.
4.2.3 A combination electrode can be employed instead of calomel or
glass.
4.5 Beaker: 50-mL.
9045 - 1
Revision 0
Date September 1986
-------
4.6 Volumetric flask; 2-Liter.
4.7 Volumetric flask: l-L1ter.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Primary standard buffer salts are available from the National Bureau
of Standards (NBS) and should beused 1n situations where extreme accuracy 1s
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 NBS salts or
purchased as solutions from commercial vendors. These commercially available
solutions, which have been validated by comparison with NBS standards, are
recommended for routine use.
5.4 Stock calcium chloride solution (CaCl2), 3.6 M: Dissolve 1059 g of
H20 in Type II water 1n a 2-liter volumetric flask. Cool the solution,
dilute 1t to volume with Type II water, and mix it well. Dilute 20 ml of this
solution to 1 liter with Type II water in a volumetric flask and standardize
it by titrating a 25-mL aliquot of the diluted solution with standard 0.1 N
AgN03, using 1 ml of 5% K2Cr04 as the Indicator.
5.5 Calcium chloride (CaCl2), 0.01 M: Dilute 50 ml of stock 3.6 M CaCl2
to 18 liters with Type II water. If the pH of this solution is not between 5
and 6.5, adjust the pH by adding a little Ca(OH)2 or HC1. As a check on the
preparation of this solution, measure its electrical conductivity. The speci-
fic conductivity should be 2.32 + 0.08 iranho per 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 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 1s recommended.
9045 - 2
Revision 0
Date September 1986
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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 noncalcareous soils;
7.2.1 To 20 g of soil 1n a 50-mL beaker, add 20 ml of Type II water
and stir the suspension several times during the next 30 m1n.
7.2.2 Let the soil suspension stand for about 1 hr to allow most of
the suspended clay to settle out from the suspension.
7.2.3 Adjust the electrodes 1n 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 1n this manner. For combination electrodes, Immerse just below
the suspension.
7.2.4 If the sample temperature differs by more than 2*C from the
buffer solution, the measured pH values must be corrected.
7.2.5 Report the results as "soil pH measured 1n water."
7.3 Sample preparation and pH measurement of calcareous soils;
7.3.1 To 10 g of soil 1n a 50-mL beaker, add 20 mL of 0.01 M CaCl2
(Step 5.5) solution and stir the suspension several times during the next
30 m1n.
7.3.2 Let the soil suspension stand for about 30 m1n to allow most
of the suspended clay to settle out from the suspension.
7.3.3 Adjust the electrodes 1n the clamps of the electrode holder
so that, upon lowering the electrodes Into the beaker, the glass
electrode will be Immersed well Into the partly settled suspension and
the calomel 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 electrode
Into the sample solution in this manner.
7.3.4 If the sample temperature differs by more than 2°C from the
buffer solution, the measured pH values must be corrected.
7.3.5 Report the results as "soil pH measured in 0.01 M CaCl2".
9045 - 3
Revision 0
Date September 1986
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8.0 QUALITY CONTROL
8.1 Duplicate samples and check standards should be analyzed routinely.
8.2 Electrodes must be thoroughly rinsed between samples.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
9045 - 4
Revision
Date September 1986
-------
METHOD 9045
SOIL PH
( Stert )
7.
1 Calibrate
each
instrument/
electrode
system
Add
CaClisolution
to soil: stir
Calcareous
7.2
Non-
calcareous
Is soil samplers.
noncalcareous or
calcareous?
7 .2. 1
Add Type II
water to soil:
stir
7.3.3
Let
soil suspension
stand for
30 mln
7.2. Z
Let soil
suspension
stand for 1 hr
9045 - 5
Revision 0
Date September 1986
-------
METHOD 9CM5
SOIL pH
(Cont Inued)
7.3.3
Insert
electrooc :nto
sample solution
7.2.3
Insert
electrodes Into
sample solution
7.3.4
Correct
measured pH
values
7.3.5
Heport results
9045 - 6
Revision 0
Date September 1986
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METHOD 9050
SPECIFIC CONDUCTANCE
1.0 SCOPE AND APPLICATION
1.1 Method 9050 is used to measure the specific conductance of drinking,
ground, surface, and saline waters and domestic and industrial aqueous wastes.
Method 9050 is not applicable to solid samples.
2.0 SUMMARY OF METHOD
2.1 The specific conductance of a sample is 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 replatinized.
3.2 The specific conductance cell can become coated with oil and other
materials. It is essential that the cell be thoroughly rinsed and, if
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 it. The latter has the advantage
of a linear reading of conductivity. Choose an instrument capable of
measuring conductivity with an error not exceeding 1% or 1 umho/cm, whichever
is greater.
4.2 Platinum-electrode or non-platinum-electrode specific conductance
cell.
4.3 Water bath.
4.4 Thermometer; capable of being read to the nearest 0.1'C and
covering the range 23* to 27*C. An electrical thermometer having a small
thermistor sensing element is convenient because of its rapid response.
9050 - 1
Revision 0
Date September 1986
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5.0 REAGENTS
5.1 Conductivity water; Pass distilled water through a mixed-bed
deionizer and discard first 1,000 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 N KC1 solution. 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)(RKCI) 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 temperature of a 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 the same as that of standard KC1 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 1s measured, conductivity at 25°C 1s:
(1.000.OOP)(C)
K =
Rm 1 + 0.0191(t - 25)
where:
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:
(yd,ooo,ooo) (c)
K ~
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
in 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
umhos/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 9O5O
SPECIFIC CONDUCTANCE
f Start J
7. 1
r
and tc
EOlUt
eel
Measure
-esistance
:mp of KC1
on; calc.
L constant
7.2
Measure
1 sample
resistance OP
conductivity
and note
temperature
7.3
Calculate
sample
conductivity
at Z5 "C
( Stop \
9050 - 5
Revision p
Date September 1986
-------
METHOD 9080
CATION-EXCHANGE CAPACITY OF SOILS (AMMONIUM ACETATE)
1.0 SCOPE AND APPLICATION
1.1 Method 9080 is used to determine the cation-exchange capacity of
soils. The method is not applicable to soils containing appreciable amounts
of vermiculite clays, kaolin, halloysite, or other l:l-type clay minerals.
They should be analyzed by the sodium acetate method (Method 9081). That
method (9081) is 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 is mixed with an excess of 1 N ammonium acetate solution.
This results in an exchange of the ammonium cations for exchangeable cations
present in the soil. The excess ammonium is removed, and the amount of
exchangeable ammonium is determined.
3.0 INTERFERENCES
3.1 Soils containing appreciable vermiculite clays, kaolin, halloysite,
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% N82CO3
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/10H2SO4
in 100ml
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 (NfyOAc), 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 (NfyOH) and add water to obtain a volume of
about 1,980 ml. Check the pH of the resulting solution, add more NH/^OH, 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 (NH4C1), 1 N: Dissolve 53.49 g of NH4C1 in Type
II water, adjust the pH to 7.0 with NH40H, and dilute to 1 L.
5.4 Ammonium chloride (NffyCl), 0.25 N: Dissolve 13.37 g of NfyCl in
Type II water, adjust the pH to 7.0 with NfyOH, and dilute to 1 L.
5.5 Ammonium oxalate ((NH^^O/p^O) , 10%: Add 90 ml of Type II water
to 10 g of ammonium oxalate ((NH4)2C2°4'H2°) and mix well.
5.6 Dilute ammonium hydroxide (NfyOH) : Add 1 volume of concentrated
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 (^COs), 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 add (^$04), 0.1 N standard: Add 2.8 ml
concentrated ^$04 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
in Type II water and dilute to 1 L. Standardize against an acid 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),
II water and dilute to 1 L.
1 N: Dissolve 40 g of NaOH 1n Type
5.9.3 Boric add (H3B03), 2% solution:
ml Type II water and mix well.
Dissolve 20 g H3B03 in 980
5.9.4 Standard sulfurlc acid (H2S04), 0.1 N: See Step 5.8.3.
5.9.5 Bromocresol green-methyl
ml
0.1 g of bromocresol green with 2
add 95% ethyl alcohol to obtain a total
0.1 g of methyl red with a few ml of
mortar. Add 3 ml of 0.1 N NaOH
100 ml with 95% ethyl alcohol.
solution with 25 ml of the methyl
200 ml with 95% ethyl alcohol.
red mixed Indicator: Triturate
0.1 N NaOH in an agate mortar and
volume of 100 ml. Triturate
95% ethyl alcohol in an agate
and dilute the solution to a volume of
Mix 75 ml of the bromocresol green
red solution and dilute the mixture to
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 NH/^OAc 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
0.25 N NH4C1.
neutral 1 N NH4C1 and once with
9080 - 4
Revision 0
Date September 1986
-------
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 h^SCty 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 1n 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 Na2C03 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 1n 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 ^$04. 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 1f
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 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).
9080 - 6
Revision
Date September 1986
-------
METHOD 9OBO
CATION-EXCHANGE CAPACITY (AMMONIUM ACETATE)
7.1
Sieve a
sample of soil
through 2—mm
screen; dry
7. 1
Place
soil In
flask; add
NH OAC: let
stand overnight
Filter soil
with light
suction
7.3.
Leach soil with
neutral NH^OAc
7.3
Test for
calcium
Yes
7.3
Calcium
detected?
7.4
Leach soil
with NH^Cl
9080 - 7
Revision 0
Date September 1986
-------
METHOD 9O8O
CATION-EXCHANGE CAPACITY (AMMONIUM ACETATE)
(Continued)
7.S
ele
allc
< Wash
out the
sctrolyte;
iw soil to
drain
Aeration method ^Xwhich method Is'X^Acld-NaCl method
* used to determine
adooroea NH47
7.7.1
Place HtSO4 in
aeration apparatus
flask; add methyl
red Indicator and
distilled water
7.7.2
7.6.1
Leach soil from
Step 7.S with
acidified NaCl
Attach
flask to
apparatus;
transfer soil
sample (7.S) to
KJeldahl flask
7.8.2
Transfer
leachate
to KJeldahl
flask: add
NaOH; distill
into HjBOj sol.
9080 - 8
Revision 0
Date September 1986
-------
METHOD 9080
CATION-EXCHANGE CAPACITY (AMMONIUM ACETATE)
(Continued)
Add
7.7.31
solution and
paraffin oil:
attach flask
to apparatus
7.7.4
Titrate HjBO.
solution with
H,S04
Aerate for 17
hours
7.8.3
Run
blanks; correct
tltratlon
figure for
blanks;
7.7.S|
Shut off
suction: remove
flask: titrate
residual acid
7.8.3
Calculate
ammonium
in soil
7.7.5
Calculate
content of
absorbed
ammonium
f Stop J
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 1s 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
acid soils.
2.0 SUMMARY OF METHOD
2.1 The soil sample 1s mixed with an excess of sodium acetate solution,
resulting in an exchange of the added sodium cations for the matrix cations.
Subsequently, the sample 1s 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 NaC^H^^O in
water and dilute it 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/jOAc), 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
-------
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 1n 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 it in a
mechanical shaker for 5 min, and centrifuge it 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 min, and centrifuge it until the supernatant liquid is
clear.
7.5 Repeat the procedure described in Paragraph 7.4 two more times.
7.6 Add 33 mL of NfyOAc solution, stopper the tube, shake it 1n a
mechanical shaker for 5 min, and centrifuge it until the supernatant liquid 1s
clear. Decant the washing into a 100-mL volumetric flask.
7.7 Repeat the procedure described in 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 if
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 Is based on Chapman, H.D., "Cation-exchange Capacity,"
pp. 891-900, in 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
-------
METHOD 9O61
CATION-EXCHANGE CAPACITY OF SOILS (SODIUM ACETATE)
( Start J
7. 1
Weigh
out sample.
transfer to
centrifuge tube
7.2
Add
NaOAc solution:
shake;
centrifuge
7.3
Decant liquid:
repeat 3 more
times
7.A
Add isopropyl
alcohol: shake:
centrifuge
7.5
Repeat 2 more
times
o
Add
7.6
solution; shake:
centrifuge:
Decant washing
into flask
7.7
Repeat
procedure
2 times
7.6
Dilute
combined
washing
with ammonium
acetate
solution
7.8
Determine
sodium
concentration
f Stop J
O
9081 - 4
Revision 0
Date September 1986
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METHOD 9090
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
1s Immersed 1n the chemical environment for minimum periods of 120 days at
room temperature (23 + 2*C) and at 50 + 2'C. 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 50*C. 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 1n 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 1t 1s 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 + 2* C) and 50 +
2°C and for preventing evaporation of the solution (e.g., use a cover equippecf
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
9090 - 1
Revision 0
Date September 1986
-------
waste In actual use and (2) 1s not designed to withstand exposure to the
chemical environment, then such a Uner may be treated with only the barrier
surface exposed.
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 + 2*C.
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 compostlon and the
type of liner material. For example, certain organic waste
constituents, if present in the representative waste fluid, can be
absorbed by the Uner 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 1n
order to maintain representative conditions 1n 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.
9090 — 2
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Obtain a representative sample of the waste fluid. If a waste
sample 1s received 1n more than one container, blend thoroughly. Note any
signs of stratification. If stratification exists, Uner samples must be
placed 1n each of the phases. In cases where the waste fluid 1s expected to
stratify and the phases cannot be separated, the number of Immersed samples
per exposure period can be Increased (e.g., 1f 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 1n the
land disposal unit 1s 1n solid form, generate a synthetic leachate (See Step
7.9.1).
7.2 Perform the following tests on unexposed samples of the polymeric
membrane Uner material at 23 + 2*C and 50 + 2*C (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 1n Table 1. See Figure 1 for cutting patterns for
nonre,1nforced liners, Figure 2 for cutting patterns for reinforced liners, and
Figure 3 for cutting patterns for semicrystal line liners. (Table 2, at the end
of this method, gives characteristics of various polymeric Uner materials.)
1. Tear resistance, machine and transverse directions, three specimens
each direction for nonrelnforced Uner 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 1n 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
nonrelnforced Uner samples.
4. Hardness, three specimens, Duro A (Duro D 1f Duro A reading 1s
greater than 80), ASTM D2240. The hardness specimen thickness for
Duro A 1s 1/4 In., and for Duro D 1t 1s 1/8 In. The specimen
dimensions are 1 1n. by 1 in.
5. Elongation at break. This test 1s 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 crystal line Uner materials only,
ASTM D882 modified Method A (see Table 1).
7. Volatlles content, SW 870, Appendix III-D.
8. Extractables content, SW 870, Appendix III-E.
9090 - 3
Revision 0
Date September 1986
-------
Table 1. Physical testing of exposed membranes 1n liner-waste llqjld compatibility test
Type of coopound and
construction
Number of specimens
Speed of test
Values to be reported
CrosslInked or vulcanized
Thermoplastic
Semicrystal line
Fabric-reinforced8
Tensile properties method
Type of specimen
ASTMD412
Dunbbellb
ASTM D638
Dumbbell0
ASTM D638
Dumbbell0
ASTM D751, MethodB
l-1n. wide strip and 2-1n.
Jaw
3 1n each direction
20 1pm
Tensile strength, ps1
Elongation at break, %
Tensile set after break.
Stress at 100 and 200%
elongation, ps1
3 1n each direction
20 1pm
Tensile strength, psl
Elongation at break, %
Tensile set after break, %
Stress at 100 and 200%
elongation, psl
3 1n each direction
2 1pm
Tensile strength at yield, psl
Elongation at yield, %
Tensile set at break, psl
Elongation at break, psl
Tensile set after break, %
Stress at 100 and 200%
elongation, psl
separation
3 1n each direction
12 1pm
Tensile at fabric break, pp1
Elongation at fabric break, %
Tensile at ultimate break, ppl
Elongation at ultimate break, pp1
Tensile set after break, %
Stress at 100 and 200%
elongation, psl
o
10
o
I
-P>
Modulus of elasticity method
Type of specimen
Number of specimens
Speed of test
Values reported
Tear resistance method
ASTMD624
ASTM 1004
ASTM D882, Method A
Strip: 0.5 In. wide and 6. 1n long
at a 2 In. Jaw separation
2 1n each direction
0.2 1pm
Greatest slope of Initial stress -
strain curve, psl
ASTM D1004
O 70
Ol CD
tt>
CO O
tt> =3
a
rt
a>|
a>
-s
CO
cn
Type of specimen
Number of specimens
Speed of test
Values reported.
Puncture resistance method
OleC
3 In each direction
20 1pm
Stress, pp1
RMS 101C, Method 2065
3 1n each direction
20 1pm
Stress, pp1
FTMS 101C, Method 2065
2 1n each direction
2 1pm
Maximum stress, pp1
FTMS 101C, Method 2065
jJCan be thermoplastic, crosslInked, or vulcanized meibrane.
"See Figure 4.
•jNot performed on this material.
°Ho tear resistance test Is reuiimemfad for fabric-reinforced sheetings 1n the 1nmers1on study.
e5ame as ASTM D624, Die C.
FTMS 101C. Method 2065
Type of specimen
Number of specimens
Speed of test
Values reported
2 1n. square
2
20 1pm
Gage. mil.
Stress, lb
Elongation, 1n.
2 1n. square
2
20 1pm
Gage, mil
Stress, 1°
Elongation, In.
2 1n. square
2
20 1pm
Gage, mil.
Stress, lb
Elongation, 1n.
2 In. square
2
20 1pm
Gage, mil
Stress, lb
Elongation, In.
-------
A
10"
Puncture test specimens
test specimens
Volatiles test specimen
Tensile test specimens
Not to scale
Figure 1 . Suggested pattern for cutting test specimens from
nonreInforeed crosslinked or thermoplastic Immersed
liner samples.
9090 - 5
Revision 0
Date September 1986
-------
VoTatlles test specimen
Puncture test specimens
Ply adhesion test specimens
m^m^^m^m^^^m^^.^m
a^^^-.^lf****.*.--.^^.,^:^^*;:- . •• -.^v*. ... •+*r^ ''^'3~f .
jjjjjji Tensile test specimensp|:|ffivv
Not to scale
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.
9090 - 6
Revision 0
Date September 1986
-------
Modulus of elasticity
test specimens
Tensile test specimens
Volatile* test specimen
Puncture test specimens
test specimens
Not to scale
Figure 3 . Suggested pattern for cutting test specimens from
semi crystalline Immersed Uner samples. Note: To
avoid edge effects, cut specimens 1/8 * 1/4 Inch
1n from edge of Immersed sample.
9090 - 7
Revision 0
Date September 1986
-------
t
1
wo
1
i
N
./
1
*
w
t
1
D. ,.
LO
X
V
W - Width of narrow section
L • Length of narrow section
WO - Width overall
LO - Length overall
G • Gage length .
D - Distance between grips
0.25 inches
1.25 inches
0.625 inches
3.50 inches
1.00 inches
2.00 inches
Figure 4. Die for tensile dumbbell (nonreinforced liners) having the following
dimensions.
9090 - 8
Revision Q
Date September 1986
-------
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
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 Uner samples into the test specimen shapes shown
in Figure 1, 2, or 3 at this time. Test specimens will be cut as
specified 1n 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 plastidzed membranes
are being tested. Expose the Uner 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 1n 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 1n 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 1n no case later than 24 hr after
removal.
9090 - 9
Revision 0
Date September 1986
-------
7.6 To test the Immersed sample, wipe off any remaining waste and rinse
with delonlzed water. Blot sample dry and measure the following as 1n Step
7.3:
1. Gauge thickness, 1n.
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 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 1n.
5. Elongation at break. This test 1s 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 crystal line liner materials only, ASTM D882
modified Method A (see Table 1).
7. Volatlles content, SW 870, Appendix III-D.
8. Extractables content, SW 870, Appendix III-E.
9090 - 10
Revision
Date September 1986
-------
9. Ply adhesion, machine and transverse directions, two specimens each
direction for fabric reinforced Hner 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.
3. Percent change 1n 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 1n pounds-force per
square Inch.
7. Percent volatiles of unexposed and exposed Hner material.
8. Percent extractables of unexposed and exposed Hner material.
9. The adhesion value, determined in accordance with ASTM D413,
Section 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 Toxlcity Characteristic Leaching Procedure (TCLP)
that was proposed in the Federal Register on June 13, 1986, Vol. 51, No.
114, p. 21685.
7.9.2 For semi crystal line membrane liners, the Agency suggests the
determination of the potential for environmental stress cracking. The
9090 - 11
Revision
Date September 1986
-------
test that can be used to make this determination is either ASTM D1693 or
the National Bureau of Standards 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 min. 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.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
9090 - 12
Revision 0
Date September 1986
-------
TABLE 2. POLYMERS USED IN FLEXIBLE MEMBRANE LINERS
Thermoplastic Materials (TP)
CPE (Chlorinated polyethylene)*
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)a
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)a
A blend of EVA and polyvinyl chloride resulting in a thermoplastic
elastomer.
PVC (Polyvinyl chloride)3
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)3
A blend of polyvinyl chloride and chlorinated polyethylene.
TN-PVC (Thermoplastic nitrile-polyvinyl choloride)3
An alloy of thermoplastic unvulcanized nitrile rubber and polyvinyl
chloride.
Vulcanized Materials (XL)
Butyl rubber3
A synthetic rubber based on isobutylene and a small amount of isoprene to
provide sites for vulcanization.
3Also supplied reinforced with fabric.
9090 - 13
Revision 0
Date September 1986
-------
TABLE 2. (Continued)
EPDM (Ethylene propylene diene monomer)a'b
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)3
Synthetic rubber, Including two eplchlorohydrln-based elastomers that are
saturated, h1gh-molecular-we1ght aliphatic polyethers with chloromethyl
side chains. The two types Include homopolymer (CO) and a copolymer of
eplchlorohydrln and ethylene oxide (ECO).
CR (Polychloroprene)a
Generic name for a synthetic rubber based primarily on chlorobutadlene.
Polychloroprene 1s also known as heoprene.
Semi crystalline 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 adds and long-chain
glycols and short-chain ester units derived from dicarboxylic adds and
low-molecular-weight diols.
aAlso supplied reinforced with fabric.
"Also supplied as a thermoplastic.
9090 - 14
Revision
Date September 1986
-------
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 dlene monomer blend resulting 1n a thermoplastic
elastomer.
9090 - 15
Revision
Date September 1986
-------
METHOD 9O90
COMPATIBILITY TEST FOR WASTES AND MEMBRANE LINERS
_Ld
Obtain cample .
of waste fluid
O
7.5
I Determine
I membrane
physical
properties at
30 day
Intervals
7.2
Perform
tests on
unexposed
camples of
liner material
7.6
To test
exposed
specimens.
measure gauge
thickness, mass.
length, width
7.3
I Cut
pieces of
lining material
for each test
condition
7.7
Perform tests
on exposed
samples
7.4
Label
test specimens
and expose
to waste fluid
7.6
Report and
evaluate data
O
f Stop J
9090 - 16
Revision o
Date September 1986
-------
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 is placed in a paint filter. If
any portion of the material passes through and drops from the filter within
the 5-min 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 1s 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 is to be fluted or have a
large open mouth in 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
Date September 1986
-------
KING 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
7.1
Assemble test
apparatus
7.2
Place sample
filter
In
7.3
Allow
sample to drain
into graduated
cylinder
Old any test
material collect
in graduated
cylinder?
7.4
Material
is deemed
to contain free
liquids; cee 4O
CFR 264.314 or
365.314
f Stop J
9095 - 4
Revision 0
Date September 1986
-------
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 hydrogeologist
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
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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)/Sect1on
264.221(a),(b)
Soil liner 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
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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)(i)/
Section 264.251(a)(1)
Soil liner leachate Guidance section D(2)(b)(ii) 2.11
conductivity and D(2)(c)(ii)
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
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TABLE A (continued)
Landfills
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.
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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//>g,
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:
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K = f ; (2)
where:
K is the fluid conductivity, LI""1;
k is the intrinsic permeability, a property of the porous medium
alone, l_2; and
u is the dynamic viscosity of the fluid at the prevailing
temperature, ML"1 T"1. ;
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'1,
Q is the volumetric fluid flux, I.3T-1,
A is the cross-sectional area, L2, and
I is the fluid potential gradient, L°.
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 Transmlsslvlty, 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
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property of the aquifer, the term also includes the saturated thickness
of the aquifer and the properties of the fluid. It is 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 is defined by:
Kt u
K
f u
f uf ft
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, 1t 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:
\, - M
k - * '
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
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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 is some characteristic dimension of the system, often represented
by the median grain size diameter, DSQ, (Bouwer, 1978), and
q is the fluid flux per unit area, LT~1.
For most field situations, the Reynolds number is less than one, and Darcy's
law is valid. However, for laboratory tests it 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 in
Equation (6) and using an upper limit of 10 for Re:
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 in 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 1t is possible to reconstruct relatively accurately the desired
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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 microcracks 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 in 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 is made of fieldconditionsat a disposal site, a site
investigation plan should be developed to direct sampling and analysis. This
plan generally requires$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~App1ication (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 Uner.
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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
in 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~*;
L = length of sample, L;
A = cross-sectional ,area of sample, L^;
Q = outflow rate, L3T-1; and
' h = fluid head difference across the sample, L.
Constant-head methpds 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 1s shown in Figure 2. The head of inflow fluid decreases
from hi to \\2 as a function of time (t) in a standpipe directly connected to
the specimen. The fluid head at the outflow is 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:
K '
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WATER SUPPLY
OVERFLOW
I
AIN ^r
T HEAD
f
L
1
• CR
J
-•=-- •=•
• *«••*• .1
^— t-A ' »
^v;-K;;
E E H~r
(
t
1
^IBM
4
OHAOUATID
CYLINDER
Figure 1.—Principle of the constant head method
9100 - 11
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STANOPIPE
OVE RF LOW
" ~
-
*
••«_«••••
I
«*— d
'••'•'D • '•
:••'•'
1
I
HO
^=H '
|
1
L
OVERFLOW 1
&
' \
ho
"B— r r=
7
V
:'o'.'
— —
(8)
(b)
<4-»2
Figure 2.—Principle of the falling head method
using a small (a) and large (b) standpipe.
9100 - 12
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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 t\ 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-aired. Air 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 dimensionally correct; that 1s, 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 is recommended for disturbed
coarse-grained soils. If this method is 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
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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 Is shown schematically 1n 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 1t 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 1n 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
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Constant A
Haad Tank 8
hi hj
-
•
_
-
-
•arfo
=•
—
5
—
5
Sc
-
-
™
-
-
V I°I
[p
T .
H |
JL {I f lltar
BlBBBMaBBB*l
raan
ratad .
O lie A Scraan
^7 | M tl
W
/i* •* A" ' ^ '
p'Q'T
^.^.^iji
•-
k_|
•=•
C raduatad
Cyllndar
v.uv
, 1
]}
•
V alva
Ah
^*" Watar Supply
Sttndplpa
T"
F
hi
In O
T *
-
_
-
_
a >•
i
«.
.^^
—
1
^^
-
.
-
"
n
II Tharm o-
F lltar II m atar
M tl « [j
Scraan.
V alva
H B
I^Hl
-f;-.-'i /.•'..*.
- • 4- ***' •"*
:;:fv-.':V
-b ' 1 1 - I^TI - %d
1 l_l_ll ' I 1
O lieharga
^r*V Laval
Watta
T
L
J_
_ Parforatad
(a)
constant head
Watta
(b)
falling head
Figure 3.— Apparatus setup for the constant head (a)
and falling head (b) methods.
9100 - 15
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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 in. 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 in 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.
i
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.
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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 plezometric heads (hi and \\2) and the water temperature 1n
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 1n
Equation (8) 1s the difference between hj and h2-
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 is 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 1n 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 in 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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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, hj, 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 rectannular coordinate paper, or use semi-log paper. The
slope of the linear part of the curve is used to determine
Iogjo(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
Revision
Date September 1986
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cA?
Y//?,
TO REGULATED PRESSURE SOURCE AND
PRESSURE GAGE OR MANOMETER USED TO
MEASURE H .
PRESSURE RELEASE VALVE
TOP PLATE
.•'
,-i
MI
$
S
/N
X
X
/
FLUID CHAMBER
. • SOIL CHAMBER V-
RUBBER "O1 RING SEALS
BASE PLATE
'— 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.
i i
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
Revision
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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ASUHHC start*
Figure 5.—
Schematic diagram of typical triaxial compression
apparatus for hydraulic conductivity tests with
back pressure.
Source: U.S. Army Corps of Engineers, 1970
9100 - 22
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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
back pressure 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 1n
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 1s
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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.-LCVCLINC «ULI
CHAOUATCO
noTt:cow»*cs3ce AIM usco rot
HlCxrH LATCHAL PMSSUNtS
M PLACt OF LCVfLINC 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 is 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 in 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 numerouspotentialsourcesoferrorin 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 1n Table C, the measurement
should be repeated after checking the source of error in Table B.
9100 - 26
Revision
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
(01 sen and Daniel, 1981).
3. Use of distilled water as a
permeant (Fireman, 1944; and
Wilkinson, 1969).
4. A1r 1n 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 1n-s1tu 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
From Sample Description
Degree of Sorting
Poor Moderate Well
Silt Content
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
U) Reduce by 10 percent if grains are subangular.
Source: Lappala (1978).
(continued)
9100 - 28
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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 Gravel
Very coarse sand
Very coarse sand to fine gravel
Very coarse sand to medium 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
(1) 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 1 eachates 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 1n EPA
Publication SW870 (EPA 1980).
2.11.2 Leachate used: A supply of leachate must be obtained that
1s 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 in
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
1eachates 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 triax1al-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 1s the same for
leachate conductivity tests as for hydraulic conductivity tests.
However, if 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 1n 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 1n 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-construction considerations; The purpose of using properly
constructed wells for hydraulic conductivity 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. Air 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-
grained 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 is placed on top of
the material surrounding the screen, and cement grout 1s placed 1n
the borehole to the next higher screened interval (1n 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 1s
that wells to be tested by pumping, bailing, or Injection 1n 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 inwellsthatare 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
strati graphic 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
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Date September 1986
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pumping can be very similar. Consequently, it is 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 anisotropy. 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 in coarse materials, the tests are generally
limited to zones with a transmisslvity 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 unconfined 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 1n
all radial directions from the test well. Figure 7 illustrates the
test geometry for this method.
9100 - 35
Revision 0
Date September 1986
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WELL CASING
! i
WELL SCREEN
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 is 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 In 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 in 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 is usually used because essentially full recovery may occur
in 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 formoderately permeable formations under confined
conditions can be made using the following procedure:
1. Determine the transmissivity 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
in 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 is moved horizontally until the data fits one of
the type curves. A value of time on the data plot corresponding
to a dlmensionless time (/O on the type curve plot is chosen,
and the transmissivity is computed from the following:
(10)
where:
rc is the radius of the casing (Lohman, p. 29 (1972)).
9100 - 37
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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 "Thels Curves" which
are used for pumping tests 1n 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,B) on the arithmetic
scale and dimenslonless 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 ofinterest 1s open to the well
screen or boreholes and that flow 1s principally radial. If this is
not the case, the computed hydraulic conductivity may be too high.
If the well 1s not properly developed, the computed conductivity
will be too low.
Measurement errors; Determining or recording the fluid level 1n 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 1n 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 to one of 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 1n determining the thickness of the zone tested,
this 1s 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) and modified by Neuzil (1982) is conducted by
suddenly pressurizing a packed-off zone in a portion of a borehole
or well. The test is 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 1n Appendix
A as described in Section 3.4.1.3. The values of time (t) and
dimensionless time (/?) 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:
T =
where:
VN 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
Date September 1986
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sure Gage f/f
System Filled
with Water ^
-"—Well Point
J 1
jl
s.
\ i
1 '
i »
it
!
V
Valve
~!# .,„.,'..,_„:*- Pump
Pressure Gagef/
Initial Head
? ? -in Tested ? * -
^Casing Interval
Interval to —
be Tested *— :
~_i • — ~
rt
TC~ _
I-;
Jf
1
•si
^i^BB
Valve
T
i'i.ia* ^- P
System Filled
with Water
*^
Open Hole
""Packer-
Interval to--
be Tested - —
Pump
(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
Revision p
Date September 1986
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If the compresslve storage is 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 = VAP (n^
(Neuzil, 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 unconfined
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 1n fluid potential 1n 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 is
calculated using the following equation from Bouwer and Rice (1976),
in the notation of this report:
r* In R/r Y
K = 2Let I" r <12>
9100 - 41
Revision
Date September 1986
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WELL CASING
WELL SEAL
; I
I;-; KH*
••: I fei-
^ i I-:-
(•:
I'-
GRAVEL PACK
Lw
Lw
STATIC WATER
LEVEL
IMPENETRABLE STRATUM '
(•) 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 in 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):
1.1 + A * B 1n[(H0-g/rw] ,| -1
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:
1.1 ^ C
(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 1n 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 in 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 pumping tests in which water is continuously withdrawn or
injected using one well, and the water-level response is measured over time in
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 in pumping
contaminated fluids, and the expense of conducting such tests generally
9100 - 43
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Date September 1986
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14
A
ond
C
12
10
2 -
10
SO 100
500 1000
.i.l UP
5OOO
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 groundwaterflowsystemsto 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, 1967Jthecoefficient of consolidation (Cv) of a saturated,
compressible, porous medium is related to the hydraulic conductivity by:
(15)
• /*»>»
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'l-T2.
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 0
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 1t
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,
it 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 1n
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, L.E., Effect of Microorganisms on Permeability of Soil under
Prolonged Submergence, Soil Science, 63, pp. 439-450 (1947).
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, Ijn Proceedings of Solid Waste Symposium, U.S.
EPA, p. 119-130, 1981.
5. Bear, J., Dynamics of Fluids in Porous Media, American Elsevler, 764 p.,
1972.
6. Bouwer, H., and R. C. Rice, A Slug Test for Determining Hydraulic
Conductivity of Unconfined 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, HI Permeability and Ground Water Contaminant Transport, ed. T. F.
Zimmie and C. 0. Riggs, ASTM Special Technical Publication 746, p. 101-120,
1981.
14. Hillel, D., Soil and Water, Academic Press, 288 p., 1971.
i
15. Hvorslev, M. J., Time Lag and ,Soil Permeability in 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 'Slug' 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, ^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, Iji Permeability and Ground Water Transport, ed. T. F. Z1mm1e 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 In 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 COONOUCTIVITY OF SOIL SAMPLES:
CONSTANT-HEAD TEST KITH CONVENTIONAL PEHNEAMETER
2.5.3
Oven-dry and
weigh sample
2.5.3
Admit de-aired
water to
permeameter
2.5.3
Place
•peclmen
in permeameter.
taking care to
avoid
segregat ion
2.5.31
Obtain
weight and
dimensions
of specimen
2.5.41 Adjust
I height
of tank to
obtain desired
hydraulic
gradient
O
0
2.5.41 Open
' valve A;
stabilize flo«:
obtain initial
piezometer
readings
2.5.4
Allow flow to
reacn
eguillbrulm
2.5.4
Record
quantity of flow.
plezomotrlc readings.
and water temperature
over an interval
of time
2.5.5
Plot
outflow
ve time:
obtain slope of
linear portion
of curve
2.5.51
Calculate
conductivity
using
Equation (8)
( 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 PERMEAMETER
GED Q
2.5.3
Oven-dry and
weigh sample
2.5.3
2.6.4
Q
Slowly
bring water
up to discharge
level of
percneemeter
Admit
de-aired water
to permeameter
2.6.4
2.6.4
Record water
temperature
Raise head of water
in stardpipe above
discharge level of
permeameter
2.5.3
Place
specimen
in permeameter.
taking care
to avoid
segregation
2.6.4
2.6.5
Plot
head vs time;
obtain slope of
linear portion
of curve
Open Valve B; Record
height of water In
stardpipe above
discharge level at
times t, arid tŁ
2.5.3
Obtain weight
and dimensions
of specimen
2.6.5
Calculate
conductivity
using
Equation (9)
o
Q
9100 - 51
Revision 0
Date September 1986
-------
METHOD 9100
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
MODIFIED COMPACTION PARAMETER METHOD
0
a.7.3
Air dry
' sample:
mix with water
for desired
moisture
content
2.7.3
2.7 .
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 ve 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 (6)
0
f Stop J
9100 - 52
Revision 0
Date September 1986
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METHOD 91OO
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
TRIAXIAL CELL METHOD WITH BACK PRESSURE
o
Trim sample
to diameter
of top cap of
triaxial cell
o
2.8.4
Saturate specimen
by applying chamber
pressure and back
pressure in small
increments
Does
pore
Tsressure Incr.
Immediately -
chamber
pressure
incr.
res
.No
2.8.4 Maintain
min imum
head lose
consistent with
a measureable
flow rate
2.8.4
Open valves 0 and F;
record burette
readings and
temperature as a
function of time
2.6.4 Measure
[dimension
and weigh
of sample:
place specimen
on base
2.8.4
2.8.4
Increase chamber
pressure to attain
desired effective
ancolidation pressure
Secure membrane
over specimen
2.8.4
2.8.4
3.8.4
Determine flow
rate from slope
of curves
Open valves E and F;
record and plot dial
indicator and burette
readings as a
function of time
Assemble trlaxlal
chamber and fill with
fluid: insert filter
paper disks
2.8.5
Calculate
conductivity
using
Equation (8)
O
o
9100 - 53
Revision 0
Date September 1986
-------
METHOD 91OO
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
PRESSURE-CHAMBER PARAMETER METHOD
o
Trim sample
to diameter
of top cap of
triaxlal cell
0
2.9.4 Apply
confining
pressure by
adjusting
leveling held
or compress elr
2. 9.
2.94.
Record
head drop
In standplpe
as function
of time
Allow sample to
consolidate
2.8.4) Measure
'dimension
and weigh
of sample;
place specimen
on base
2.B.4
2.9.4
Flush
sample
with water
until no air
bubbles are
observed
Secure membrane
over specimen
2.8.4
2.9.4
Adjust
head of
water to
attain desired
hydraulic
gradient
Assemble triaxlal
chamber and fill with
fluid: insert filter
paper disks
2.9.4
Calculate
conductivity
us Ing
Equation (9)
( Stop j
0
O
9100 - 54
Revision 0
Date September 1986
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METHOD 9100
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
FIELD METHODS FOR EXTREMELY TIGHT FORMATIONS UNDER CONFINED CONDITIONS
f Start J
3.4.Z.2
0
Fill
borehole
with water to
prevailing
water level
3.4.2.2
Add a
known
volume of
water with a
hlQh—pressure
pump
3.4.8.2
Shut valve
and monitor
pressure decay
Has pressure
reached BSX of
Initial
value?
3.4.2.3
transm
of test
uslr
curv«
3.4.2.2
for
In v<
pat
c
3.4.2.3
condi
transm
by thlc*
testc
Deter-
mine
tsslvlty
:ed zone
10 type
: method
Correct
changes
ilume of
:ked-of f
:avlty
Deter-
mine
jctlvlty
tsslvlty
cness of
•d rone
f Stop J
9100 - 55
Revision 0
Date September 1986
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METHOD 9100
HYRAULIC CONDUCTIVITY OF SOIL SAMPLES
FIELD METHODS FOR MODERATELY PERMEABLE MATERIALS UNDER UNCONFINEO CONDITIONS
( Start 1
3.4.3.Z
Rapidly
remove a volume
of water from
the well bore
3.4.3.3
Record
watei — level
changes over
time
3.4.3.3
condi
using <
Bouwer t
(•
Calcu-
late
JCtlvlty
Equation
ind Rice
1976)
f Stop J
9100 - 56
Revision Q
Date September 1986
-------
METHOD 9100
HYDRAULIC CONDUCTIVITY OF SOIL SAMPLES:
FIELD METHOD FOR MODERATELY PERMEABLE FORMATIONS UNDER CONFINED CONDITIONS
Start
D
3.4.1.2
Rapidly
remove a volume
of water from
the well bore
3.4.1.2
Record
water-leve 1
changes -over
time
transmlsElvity
of tested zone
using tyoe
curve method
3.4.1
Determine
conductlv Ity' by
dividing
tran«mlsslvIty by
thickness of
tested zone
f Stop J
9100 - 57
Revision 0
Date September 1986
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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 is 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 is that size aliquot which gives a solids density thickness of
5 mg/cm^ in the counting planchet. For a 2-in. diameter counting planchet
(20 cm^), 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 is 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 Radlonuclides 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
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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 radloiodine) 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 pCi/L in a sample shall be analyzed for
stront1um-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 pCi/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 1s dried to constant weight, reweighed
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
1t obstructs counting and self-absorption characteristics. If a sample is
counted 1n an internal proportional counter, static charge on the sample
residue can cause erratic counting, thereby preventing an accurate count.
3.2 Nonun1form1ty 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/cm^ for gross alpha and not more than 20 mg/cm^ for gross beta.
9310 - 2
Revision
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 being1 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 25'C.
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
radium-226 radlonuclldes but 1s close to the energy of the alpha
particles emitted by naturally occurring thorium-228 arid rad1um-224.
Standards should be prepared In the geometry and weight ranges to be
encountered In these gross analyses. It 1s, therefore, the prescribed
radlonucllde for gross alpha calibration. NBS or. NBS-traceable
amer1cium-24l 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 Strontium-90 and cesium-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. Strontium-90 in equilibrium with its daughter yttr1um-90 1s
the prescribed radionuclide 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 1s varied
between 0 and 100 mg (for a 2-1n. 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 1t 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 1n 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 1f 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 sol Ids. 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 1n a desiccator, weigh, and count. Store the sample residue In a
desiccator until ready for counting.
7.4 Some types of water-dissolved sol Ids, 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 1s 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 1s to be recounted for reverlflcation, store It 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 1n 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 1s
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 (pC1/liter) = 2 ^Vc^V
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 solids 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 ino significant alpha counts when the
sample is counted at the alpha voltage plateau, the beta activity
can be determined from the following equation:
Beta (pd /liter) =
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 cm^ of
planchet area, (cpm/dpm).
V = volume of sample aliquot (ml).
2.22 = conversion factor from dpm/pCi .
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 0
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 is 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 (pCi/liter) = •%=
where:
B = as defined above.
D = as defined above.
A = as defined above.
E = alpha amplification factor, read from the graph of the
ratio of alpha counted at the beta voltage/alpha counted
at the alpha voltage vs. sample density thickness.
V = volume of sample aliquot (ml).
2.22 = conversion factor from dpm/pCi.
7.7 Errors associated with the results of the analysis should also be
reported.
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 is occurring.
8.3 Run one duplicate sample for every 10 samples. A duplicate sample
is a sample brought through the whole sample-preparation and analytical
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 is operating properly.
9310 - 7
Revision
Date September 1986
-------
9.0 METHOD PERFORMANCE
9.1 In a collaborative study of two sets of paired water samples
containing known additions of radlonuclides, 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
alpha activity: Sr-go
or Cs-137 for gross
beta activity
7.1.3
Prepare
separate
alpha and
beta particle
self-absorption
graphs
7.1.4
Does Mater
•ample contain
Chloride
•alts?
o
7.6. 1
Calculate alpha
radioactivity
swirl:
each aliquot to
tard planchet:
avaporate
Acidify
tap water
allquots with
HNOt: evaporate:
transfer to
planchet
7.3
7.6.2
Calculate beta
radioactivity
Dry sample
residue: weigh
and count
f Stop J
7. 1.41 Evaporate
I and dry:
count alpha.
beta residue
for reference
standard
7.3
Transfer
aliquot of
water sample
to baaker;
avaporate
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 pCi/L, then the radium-
226 analysis is required. If the level of radium-226 exceeds 3 pCi/L, the
sample must also be measured for radium-228 (Method 9320).
1.3 Because this method provides for the separation of radium from other
water-dissolved solids 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 in the surface water or ground water sample is collected
by coprecipitation with barium and lead sulfate and purified by reprecipi-
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, is alpha counted to determine the total disintegration rate of the radium
isotopes.
2.2 The radium activities are counted in 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 in the sample. Because some daughter ingrowth can
occur before the separated radium is counted, it is 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.
3.0 INTERFERENCES
3.1 Inasmuch as the radiochemical yield of the radium activity is based
on the chemical yield of the BaS04 precipitate, the presence of significant
natural barium in the sample will result in 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 «1 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 add. 17.4 N: glacial CH3COOH (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 H2S04 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 in
desiccator, and weigh as BaS04.
5.5 Citric acid. 1 M: Dissolve 19.2 g C^Qj-^O 1n water and dilute to
100 ml.
9315 - 2
Revision
Date September 1986
-------
5.6 EDTA reagent, basic (0.25 M): Dissolve 20 g NaOH In 750 mL water,
heat and slowly add 93 g d1sodium ethylened1n1tr1loacetate dlhydrate
(Na2CioHi408N2'2H20). 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 in 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 in 80 mL water and dilute
to 100 ml.
5.9 Sulfuric acid, 18 N: Cautiously mix 1 volume 36 N H2S04 (concen-
trated) with 1 volume of water.
5.10 Sulfuric acid. 0.1 N: Mix 1 volume 18 N H2S04 with 179 volumes
of water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected in 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 in 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 BaS04 (same
carrier amount used in samples). This 1s done with spiked distilled
water samples, and the procedure for regular samples is followed. Note
the time of the Ra-BaS04 precipitation.
7.1.2 The radium alpha counting efficiency, E, is calculated as
follows:
E (cpm/dpm) = j^-j
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where:
C = sample net cpm (gross counts minus background divided
by the counting time 1n minutes).
A = dpm of rad1um-226 added to sample.
I = Ingrowth factor for the elapsed time from Ra-BaSC^,
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 ^504. 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 (NfyJeSC^ (200 mg/mL) and stir thoroughly. Add 17.4 N
CH3COOH dropwise until precipitation begins and then add 2 mL extra. Digest 5
to 10 ml n.
7.8 Centrifuge, discard the supernate, and record time.
NOTE: At this point, the separation of the BaS04 is complete, and the
ingrowth of radon (and daughters) commences.
7.9 Wash the BaSCty 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 hot 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.
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7.13 Calculation;
7.13.1 Calculate the rad1um-226 concentration, D (which would
Include any rad1um-224 and radlum-223 that Is present), 1n plcocurles per
liter as follows:
D =
2.22 xExVxRxI
where:
C = net count rate, cpm.
E = counter efficiency, for radlum-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/pd.
7.14 It 1s not always possible to count the BaS04 precipitate
immediately after separation; therefore, corrections must be made for the
ingrowth of the radium-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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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
is 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 is operating properly.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
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METHOD 9315
ALPHA-EMITTING RADIUM ISOTOPES
7.1.1
Calibrate
detectors for
radium alpha
measurement
Dissolve
precipitate
in EOTA; heat:
add NaOH
7.2
Add C«H.O,'HtO. lead
and barium carriers
to water sample;
heat to boiling
7.3
7.7
Add
stir;
CHjCOOH:
ado
Digest
Add HjSO* while
• tirring: digest:
precipitate:
discard cupernate
7.4
7.6
Cool, weigh.
and store in
desiccator
Use counter to
determine alpha
activity
Centrifuge:
discard
•upernate:
record time
Centrifuge;
discard
•upernate
7.9
Calculate
rsaium-236
concentration
Mash
BaSCM
precipitate;
centrifuge;
diachard wash
7.5 I
Mash
precipitate:
centrifuge:
discard washes
7.
Correct
for ingrowth
of radlum-226
daughters
7.10
Transfer
precipitate
to planchet:
dry
( Start J
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PART II CHARACTERISTICS
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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 verbatim from the RCRA
regulations (40 CFR 261.21).
Characteristics Of Ignitability Regulation
A solid waste exhibits the characteristic of ignitability if a
representative sample of the waste has any of the following properties:
1. —-It-1s a liquid, other than an aqueous solution, containing <24%
alcohol by volume, and it has a flash point <60°C (140*F), as
determined by a Pensky-Martens Closed Cup Tester, using the test
method specified in ASTM Standard D-93-79 or D-93-80, or a Setaflash
Closed Cup Tester, using the test method specified in ASTM standard
D-3278-78, or as determined by an equivalent test method approved by
the Administrator under the procedures set forth in Sections 260.20
and 260.21. (ASTM standards are available from ASTM, 1916 Race
Street, Philadelphia, PA 19103.)
2. It is not a liquid and is capable, under standard temperature and
pressure, of causing fire through friction, absorption of moisture,
or spontaneous chemical changes and, when ignited, burns so
vigorously and persistently that it creates a hazard.
3. It 1s 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 oxldizer, as defined 1n^49 CFR 173.151.
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Ign1table Compressed Gas
For the purpose of this regulation the following terminology 1s defined:
1. Compressed gas. The term "compressed gas" shall designate any
material or mixture having in the container an absolute pressure
exceeding 40 ps1 at 21'C (70°F) or, regardless of the pressure at
21*C (70°F), having an absolute pressure exceeding 104 ps1 at 54°C
(130°F), or any liquid flammable material having a vapor pressure
exceeding 40 psi absolute at 38*C (100*F), as determined by ASTM
Test D-323.
2. Ignitable compressed gas. Any compressed gas, as defined in
Paragraph 1, above,shall be classed as an "ignitable compressed
gas" 1f 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 1n. 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' Closed 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
For the purpose of this regulation, an oxldizer 1s any material that
yields oxygen readily to stimulate the combustion of organic matter (e.g.,
chlorate, permanganate, inorganic peroxide, or a nitrate).
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7.2 CORROSIVITY
7.2.1 Introduction
The corroslvlty characteristic, as defined 1n 40 CFR 261.22, 1s designed
to Identify wastes that might pose a hazard to human health or the environment
due to their ability to:
1. Mobilize toxic metals 1f discharged Into a landfill environment;
2. Corrode handling, storage, transportation, and management equipment;
or
3. Destroy human or animal tissue 1n 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 corroslvlty toward Type SAE 1020 steel.
The following sections present the regulatory background and the
regulation pertaining to the definition of corroslvlty. The procedures for
measuring pH of aqueous wastes are detailed 1n Methods 9040 and 9041, 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 corroslvlty 1f a
representative sample of the waste has either of the following
properties:
a. It 1s aqueous and has a pH Ł2 or >12.5, as determined by a pH
meter using either the test method specified In this manual
(Method 9040) (also described 1n "Methods for Analysis of Water
and Wastes" EPA 600/4-79-020, March 1979), or an equivalent test
method approved by the Administrator under the procedures set
forth 1ri Sections 260.20 and 260.21.
b. It 1s a liquid and corrodes steel (SAE 1020) at rate >6.35 mm
(0.250 1n.) per year at a test temperature of 55*C (130*F), as
determined by the test method specified 1n NACE (National
Association of Corrosion Engineers) Standard TM-01-69, as
standardized in this manual (Method 1110) or an equivalent test
method approved by the Administrator under the procedures set
forth In Sections 260.20 and 260.21.
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7.3 REACTIVITY
7.3.1 Introduction
The regulation 1n 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, 1n 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 wastp management process. The definition is to a large
extent a paraphrase of the narrative definition employed by the National F1re
Protection Association. The Agency chose to rely on a descriptive, prose
definition of reactivity because 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 1s 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, 1t generates toxic gases, vapors, or
fumes in a quantity sufficient to present a danger to human
health or to the environment.
5. It is a cyanide- or sulfide-bearing waste that, when exposed to
pH conditions between 2 and 12.5, can generate toxic gases,
vapors, or fumes 1n a quantity sufficient to present a danger
to human health or to the environment. (Interim Guidance for
Reactive Cyanide and Reactive Sulfide, Sections 7.3.3 and 7.3.4
below, can be used to detect the presence of cyanide and
sulfide 1n wastes.)
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6. It is capable of detonation or explosive reaction if it is
subjected to a strong initiating source or if heated under
confinement.
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.
9. A solid waste that exhibits the characteristic of reactivity,
but is not listed as a hazardous waste in Subpart D, has the
EPA Hazardous Waste Number of D003.
7.3.3 Interim Guidance For Reactive Cyanide
7.3.3.1 The current EPA action 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 the waste is acidified to pH 2 in a closed system.
The gas generated is swept into a scrubber. The analyte is quantified. The
procedure for quantifying the cyanide is Method 9010, Chapter Five, starting
with Step 7.3.5 of that method.
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3.0 SAMPLE HANDLING AND PRESERVATION
3.1 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.
3.2 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 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.
3.3 Testing should be performed in a ventilated hood.
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 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.
4.3 Separatory funnel; With pressure-equalizing tube and 24/40 ground-
glass joint and Teflon sleeve.
4.4 Flexible tubing; For connection from nitrogen supply to apparatus.
4.5 Water-pumped or oil-pumped nitrogen gas; With two-stage regulator.
4.6 Rotometer; For monitoring nitrogen gas flow rate.
5.0 REAGENTS
5.1 Sulfuric acid. 0.005 M: Add 2.8 mL concentrated HpSCty to Type II
water and dilute to 1 L. Withdraw 100 mL of this solution and dilute to 1 L
to make the 0.005 M H2S04.
5.2 Cyanide reference solution; Dissolve approximately 2.5 g of KOH and
2.51 g of KCN in 1literofdistilled water. Cyanide concentration in this
solution is 1 mg/mL.
5.3 NaOH solution, 1.25 N: Dissolve 50 g of NaOH in distilled water and
dilute to 1 liter with distilled water.
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STIRRER
FLOWMETER
REACTION FLASK
* ABSORBER
WASTE SAMPLE
Figure 1. Apparatus to Determine Hydrogen Cyanide Released from Wastes
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Date September 1986
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5.4 NaOH solution. 0.25 N: Dilute 200 ml of sodium hydroxide solution
(5.3) to 1 liter with distilled water.
5.5 Stock cyanide solution, 1 mg/mL: Dissolve 2.51 g of KCN and 2 g of
KOH in 1 liter of distilled water. Standardize with 0.0192 N AgN03. Dilute
to appropriate concentration so that 1 mL = 1 mg CN.
5.6 Intermediate cyanide solution: Dilute 50 ml of stock solution to 1
liter with distilled water.
5.7 Standard cyanide solution, 5 mg/L: Prepare fresh daily by diluting
100 ml of intermediate solution to 1 liter with distilled water, and store in
a glass-stoppered bottle.
5.8 Silver nitrate solution; Prepare by crushing approximately 5 g of
AgN03 crystals and drying to constant weight at 40*C. Weigh 3.3 g of dried
AgN03, dissolve in distilled water, and dilute to 1 liter.
5.9 Rhodanine indicator; Dissolve 20 mg of p-dimethyl aminobenzal-
rhodanine in 100 ml of acetone.
5.10 Methyl red indicator; Prepare by dissolving 0.02 g methyl red in 60
mL of distilled water and 40 ml of acetic acid.
6.0 SYSTEM CHECK
6.1 The operation of the system can be checked and verified using the
cyanide reference solution (Paragraph 5.2). Perform the procedure using the
reference solution as a sample and determine the percent recovery. A recovery
of 50% is adequate to demonstrate proper system operation.
7.0 PROCEDURE
7.1 Add 500 ml of 0.25 N NaOH solution to a calibrated scrubber and
dilute with distilled 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 to the system 10 g of the waste to be tested.
7.4 With the nitrogen flowing, add enough acid to fill the system half
full. While starting the 30-min test period.
7.5 Begin stirring while the acid is entering the round-bottom flask.
7.6 After 30 min, close off the nitrogen and disconnect the scrubber.
Determine the amount of cyanide in the scrubber by Method 9010, Chapter Five,
starting with Paragraph 7.3.5. of the method.
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8.0 CALCULATIONS
8.1 Determine the specific rate of release of HCN, using the following
parameters:
A = Concentration of HCN 1n scrubber (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 = Time N2 stopped - Time
N2 started (sec)
A • L
R = specific rate of release =
W • S
Total available HCN (mg/kg) = R x 1,800.
7.3.4 Interim Guidance For Reactive Sulfide
7.3.4.1 The current EPA action 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 evolved hydrogen sulfide at the
test conditions. It is not intended to measure forms of sulfide other then
those that are evolvable under the test conditions.
2.0 SUMMARY OF METHOD
2.1 An aliquot of the waste is acidified to pH 2 in a closed system.
The gas generated is swept into a scrubber. The analyte is quantified. The
procedure .for quantifying the sulfide is given in Method 9030, Chapter Five.
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3.0 SAMPLE HANDLING AND PRESERVATION
3.1 Samples containing, or suspected of containing, sulflde 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 1n a cool, dark place
until analysis begins.
3.2 It is suggested that samples of sulflde 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.
3.3 Testing should be performed 1n a ventilated hood.
4.0 APPARATUS (See Figure 2)
4.1 Round-bottom flask; 500-mL, three-neck, with 24/40 ground-glass
joints.
4.2 Stirring apparatus; To achieve approximate 30 rpm. This may be
either a rotating magnet and stirring bar combination or an overhead motor-
driven propeller stirrer.
4.3 Separatory funnel; With pressure-equalizing tube and 24/40 ground-
glass joint and Teflon sleeve.
4.4 Flexible tubing; For connection from nitrogen supply to apparatus.
4.5 Water-pumped or oil-pumped nitrogen gas; With two-stage regulator.
4.6 Rotometer; For monitoring nitrogen gas flow rate.
4.7 Detector tube for sulfide; Industrial-hygiene type (100-2,000 ppm
range).
5.0 REAGENTS
5.1 Sulfuric add, 0.005 M: Add 2.8 mL concentrated H?S04 to Type II
water and dilute to 1 L. Withdraw 100 mL of this solution and dilute to
1 L to make the 0.005 M H2S04.
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Date September 1986
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STIRRER
FLOWMETER
REACTION FLASK
WASTE SAMPLE
Figure 2. Apparatus to Determine Hydrogen Sulfide Released from Wastes
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Date September 1986
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5.2 Sulfide reference solution; Dissolve 4.02 g of Na^S-Ql^O 1n 1.0
liter of distilled water. This solution contains 680 ppm hydrogen sulfide.
Dilute this stock solution to cover the analytical range required (100-680
5.3 NaOH solution, 1.25 N: Dissolve 50 g of NaOH in distilled water and
dilute to 1 liter with distilled water.
5.4 NaOH solution, 0.25 N: Dilute 200 ml of sodium hydroxide solution
to 1 liter with distilled water.
6.0 SYSTEM CHECK
6.1 The operation of the system can be checked and verified using the
sulfide reference solution (Paragraph 5.2). Perform the procedure using the
reference solution as a sample and determine the percent recovery. A recovery
of 50% is adequate to demonstrate proper system operation.
7.0 PROCEDURE
The procedure employs a scrubber solution with wet method quantification.
7.1 Add 500 ml of 0.25 N NaOH solution to a calibrated scrubber and
dilute with distilled 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 to the system 10 g of the waste to be tested.
7.4 With the nitrogen flowing, add enough acid to fill the system half
full, while starting the 30-min test period.
7.5 Begin stirring while the acid 1s entering the round-bottom flask.
7.6 After 30 min, close off the nitrogen and disconnect the scrubber.
Determine the amount of sulfide in the scrubber by Method 9030, Chapter 5.
7.7 Substitute the following for 7.2.3 in Method 9030: The trapping
solution must be brought to a pH of 2 before proceeding. Titrate an aliquot
of the trapping solution to a pH 2 end point and calculate the amount of acid
needed for the 200-mL sample for analysis.
8.0 CALCULATIONS
8.1 Determine the specific rate of release of H2S, using the following
parameters:
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Revision
Date September 1986
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A = Concentration of H^S 1n scrubber (mg/L)
(This 1s obtained from Method 9030.)
L = Volume of solution 1n scrubber (L)
W = Weight of waste used (kg)
S = Time of experiment = Time N2 stopped - Time
N2 started (sec)
A • L
R = specific rate of release =
W • S
Total available H2S (mg/kg) = R x 1,800.
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7.4 EXTRACTION PROCEDURE TOXICITY
7.4.1 Introduction
The Extraction Procedure (EP) 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.
It is a laboratory test in which a representative sample of a waste is
extracted with distilled water maintained at a pH of 5, using acetic acid.
The extract obtained from the EP (the "EP Extract") is then analyzed to
determine if any of the thresholds established for the eight elements
(arsenic, barium, cadmium, chromium, lead, mercury, selenium, silver), four
pesticides (Endrin, Lindane, Methoxychlor, Toxaphene), and two herbicides
(2,4,5-trichlorophenoxypropionic acid, 2,4-dichlorophenoxyacetic acid) have
been exceeded. If the EP Extract contains any one of the above substances in
an amount equal to or exceeding the levels specified in 40 CFR 261.24, the
waste possesses the characteristic of Extraction Procedure Toxicity and is a
hazardous waste.
7.4.2 Summary of Procedure
The Extraction Procedure consists of five steps (refer to Figure 3):
1. Separation Procedure
A waste containing unbound liquid is filtered, and, if the solid
phase is <0.5% of the waste, the solid phase is discarded and the
filtrate analyzed for trace elements, pesticides, and herbicides (Step
5). If the waste contains >0.5% solids, the solid phase is extracted and
the liquid phase stored for later use.
2. Structural Integrity Procedure/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 g of waste of 3.1
cm2, or, if it consists of a single piece, be subjected to the Structural
Integrity Procedure. The Structural Integrity Procedure is used to
demonstrate the ability of the waste to remain intact after disposal. If
the waste does not meet one of these conditions, it must be ground to
pass the 9.5-mm sieve.
3. Extraction of Solid Material
The solid material from Step 2 is extracted for 24 hr in an aqueous
medium whose pH is maintained at or below 5 with 0.5 N acetic acid. The
pH is maintained either automatically or manually. (In acidifying to pH
5, no more than 4.0 g of acid solution per g of material being extracted
may be used.)
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Date September 1986
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Wet Waste Sample
Contains < 0.5% ^_
Nonfilterable ^"
Solids
1
Liquid Solid
Separation
Liquid
t Solid
4
Discard
1
> 9.5mm
1
Sample Size
Reduction
Representative
Waste Sample
> 100 Grams
Dry Waste Sample
L_
Particle Size
}.5mm
Wet Waste Sample
Contains > 0.5!c
Nonfilterable
Solids
Solid
Extraction of Solid Waste
Solid
i
iscard
1
Monolithic
i
Structural
Integrity
Procedure
Liquid Solid
Separation
Liquid
Store at 4°C
at pH - 2
I
d Separation
I
uid
L
EP Extract
Analysis Methods
Figure 3. Extraction Procedure Flowchart.
SEVEN - 15
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Date September 1986
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4. Final Separation of the Extraction from the Remaining Solid
After extraction, the 11 quid:sol Id ratio Is adjusted to 20:1, and the
mixed solid and extraction liquid are separated by filtration. The solid
1s discarded and the liquid combined with any filtrate obtained 1n Step
1. This Is the EP Extract that 1s analyzed and compared with the
threshold listed 1n Table 1 of 40 CFR 261.24.
5. Testing (Analysis) of EP Extract
Inorganic and organic species are identified and quantified using the
appropriate methods in the 7000 and 8000 series of methods 1n this
manual.
7.4.3 Regulatory Definition
A solid waste exhibits the characteristic of EP toxldty if, using the
appropriate test methods described 1n this manual or equivalent methods
approved by the Administrator under the procedures set forth in 40 CFR 260.20
and 260.21, the extract from a representative sample 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.
SEVEN - 16
Revision
Date September 1986
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TABLE 7-1.
MAXIMUM CONCENTRATION OF CONTAMINANTS
FOR CHARACTERISTIC OF EP TOXICITY
Contaminant
Arsenic
Ban' urn
Cadmi urn
Total Chromium
Lead
Mercury
Selenium
Silver
Endrin (1,2,3,4,10,10-Hexachloro-l
7-epoxy-l,4,4a,5,6,7,8,8a-octahydro-l
4-endo , endo-5 , 8-di methanonaph-
thalene)
Lindane (1,2,3,4,5,6-
Hexachlorocyclohexane, gamma isomer)
Methoxychlor (l,l,l-Trichloro-2,2-b1s
(p-methoxypheny 1 ) ethane)
Toxaphene (CjoHioClSi Technical
chlorinated camphene, 67-69%
chlorine)
2,4-D (2,4-Dichlorophenoxyacetic acid)
2,4,5-TP (Silvex) (2,4,5-
Trichlorophenoxypropionic acid)
SEVEN -
Maximum
concentration
(mg/L)
5.0
100.0
1.0
5.0
5.0
0.2
1.0
5.0
0.02
0.4
10.0
0.5
10.0
1.0
17
Analytical
Method
7060, 7061
7080
7130, 7131
7190, 7191
7420, 7421
7470
7740, 7741
7760
8080
8080
8080
8080
8150
8150
Revision 0
Date September 1986
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CHAPTER EIGHT
METHODS FOR DETERMINING CHARACTERISTICS
Methods for determining the characteristics of Ignitability for liquids,
Corrosivity for liquids, and Extraction Procedure Toxicity are included.
Interim guidance for determining Toxic Gas Generation is found in Chapter
Seven, Sections 7.3.3 and 7.3.4.
EIGHT - 1
Revision
Date September 1986
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8.1 IGNITABILITY
EIGHT - 2
Revision
Date September 1986
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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 sol Ids
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 1s 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 1n *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
b75/25 v/v analyzed by four laboratories.
a!2 determinations over five-day period.
1010 - 1
Revision
Date September 1986
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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.( Salmons, C., 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 1020
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 0* and 110'C (32*
and 230°F) and viscosities lower than 150 stokes at 25'C (77°F).
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 the 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 3'C (5°F) below the expected flash point.
2.2 As a flash/no-flash test, the expected flash-point temperature may
be a specification (e.g., 60*C). 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 min, 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 measurement, the temperature is sequentially
increased through the anticipated range, the test flame being applied at 5°C
(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
0.5*C (1'F) intervals.
For further information on how to conduct a test with this method, see
Reference 1 below.
3.0 METHOD PERFORMANCE
See Method 1010.
1020 - 1
Revision 0
Date September 1986
-------
4.0 REFERENCES
1. D 3828-81, Test Method for Flash Point by Setaflash Closed Tester,
American Society for Testing and Materials, 1613 Race Street, Philadelphia, PA
19103, 05.03. 1986.
2. Umana, M., Gutknecht, W., Salmons, C., et al., Evaluation of Ignitabllity
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.
1020 - 2
Revision
Date September 1986
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8.2 CORROSIVITY
EIGHT - 3
Revision
Date September 1986
-------
METHOD 1110
CORROSIVITY TOWARD STEEL
1.0 SCOPE AND APPLICATION
1.1 Method 1110 is used to measure
aqueous and nonaqueous liquid wastes.
the corrosivity 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 corrosivity of the waste.
3.0 INTERFERENCES
3.1 In laboratory tests, such as
coupons is usually reproducible to within
corrosion rates may occasionally occur
surfaces become passivated. Therefore,
corrosion rate should be made.
this one, corrosion of duplicate
10%. However, large differences in
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 in 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
-------
J]
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 = thermowel1, 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 in.)
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.)-diameter 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) +
where:
t = thickness.
D = diameter of the specimen.
d = diameter of the mounting hole.
If the hole is completely covered by the
the equation, (t) (3.14) (d), is omitted.
mounting support, the last term in
4.5.1 All coupons should be
calculation of the exposed areas.
usually adequate.
measured carefully to permit accurate
An area calculation accurate to +1% is
4.5.2 More uniform results may be expected if a substantial layer
of metal is removed from the coupons prior to testing the corrosivity 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
coupon to be used 1n this test is 40 ml/cm2.
to area of the metal
5.0 REAGENTS
5.1 Sodium hydroxide (NaOH), (20%): Dissolves 200 g NaOH in 800 ml Type
II water and mix well .
5.2 Zinc dust.
5.3 Hydrochloric acid (HC1); Concentrated.
5.4 Stannous chloride (SnCl2).
5.5 Antimony chloride
1110 - 3
Revision 0
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 addresses
the considerations discussed in Chapter Nine of this manual.
7.0 PROCEDURE
7.1 Assemble the test apparatus as described in 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 is not required; only a determination
as to whether the rate of corrosion 1s less than or greater than 6.35 mm 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 is the most popular of these methods. The others are used 1n
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 m1n Boiling
or
Cone. HC1 + 50 g/L SnCl2 + 20 g/L SbCl3 Until clean Cold
1110 - 4
Revision
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 H2S04
Anode: Carbon or lead
Cathode: Steel coupon
Cathode current density: 20 amp/cm2 (129 amp/in.2)
Inhibitor: 2 cc organic inhibitor/liter
Temperature: 74°C (165*F)
Exposure Period: 3 min.
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
diorthotolyl thiourea or quinolin ethiodide can be used.
7.7 Whatever treatment is employed to clean the coupons, its effect in
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
reweighed. The weight loss is 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 (.py) .
where: weight loss 1s in milligrams,
area in square centimeters,
time 1n hours, and
corrosion rate in 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 1110
CORROS1VITY TOWARD STEEL
Assemble test
apparatus
7.2
Fill container
with waste
7.3
Agitate
7.4
Heat
0
7.6
Clean
coupons
by mechanical.
chemical and/or
electrolytic
methods
7.7
Check
effect
of cleaning
treatment on
removing sound
metal
7.8
Determine
corrosion rate
f stop J
O
1110 - 7
Revision 0
Date September 1986
-------
8.3 REACTIVITY
Refer to guidance given in Chapter Seven, especially Sections 7.3.3 and
7.3.4.
EIGHT - 4
Revision 0
Date September 1986
-------
8.4 TOXICITY
EIGHT - 5
Revision 0
Date September 1986
-------
METHOD 1310
EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
AND STRUCTURAL INTEGRITY TEST
1.0 SCOPE AND APPLICATION
1.1 This method is employed to determine whether a waste exhibits the
characteristic of Extraction Procedure Toxldty.
1.2 The procedure may also be used to simulate the leaching which a
waste will undergo if disposed of in a sanitary landfill. Method 1310 1s
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 1s maintained at a pH of 5 + 0.2, with acetic add.
Wastes that contain <0.5% solids are not subjecteH to extraction but are
directly analyzed. Monolithic wastes which can be formed Into a cylinder
3.3 cm (d1a) 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 1n the individual analytical methods.
4.0 APPARATUS AND MATERIALS
4.1 Extractor: For purposes of this test, an acceptable extractor 1s
one that wTTlimpart 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.
1310 - 1
Revision 0
Date September 1986
-------
Non-Clogging Support Bushing
1 Inch Blade at 30° to Horizontal
Figure 1. Extractor.
1310 - 2
Revision 0
Date September 1986
-------
?-Liter Plastic or Glass Bottles
CO
I—»
o
I
CO
0X3
01 m
r* <
m -*
1/15—Horsepower Electric Motor
29RPM t-f
Screws for Holding Bottles
-------
CO
I—'
o
I
O 70
O> CD
rt- <
(T>
a
CD I
3 I
IVO
oo
cnl
1-Gallon Pintle
or Glass Bottle
Foam Bonded to Cover
Totally Enclosed
Fan Cooled Motor
40 mm, 1/8 HP
3 Position Toggle Switch
Box Assembly
Plywood Construction
Foam Inner Liner
Figure 3. EPRI extractor.
-------
4.3 Filter holder; Capable of supporting a 0.45-um 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.
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 hr
(I.e., curls, dissolves, shrinks, or swells) is unsuitable for use.
TABLE 1. EPA-APPROVED FILTER HOLDERS
Manufacturer Size Model No. Comments
Vacuum Filters
Nalgene 500 mL 44-0045 Disposable plastic unit,
including prefilter, filter
pads, and reservoir; can be
used when solution is to
be analyzed for inorganic
constituents.
Nuclepore 47 mm 410400
Millipore 47 mm XX10 047 00
Pressure Filters
Nuclepore 142 mm 425900
Micro Filtration 142 mm 302300
Systems
Millipore 142 mm YT30 142 HW
1310 - 5
Revision
Date September 1986
-------
TABLE 2. ERA-APPROVED FILTRATION MEDIA
Supplier
Filter to be used
for aqueous systems
Filter to be used
for organic systems
Coarse prefliter
Gel man
Nuclepore
Millipore
61631, 61635
210907, 211707
AP25 035 00,
AP25 127 50
61631, 61635
210907, 211707
AP25 035 00,
AP25 127 50
Medium prefilters
Nuclepore
Millipore
210905, 211705
AP20 035 00,
AP20 124 50
210905, 211705
AP20 035 00,
AP20 124 50
Fine prefilters
Gel man
Nuclepore
Millipore
64798, 64803
210903, 211703
APIS 035 00,
APIS 124 50
64798, 64803
210903, 211703
APIS 035 00,
AP15 124 50
Fine filters (0.45 urn)
Gelman
60173, 60177
60540 or 66149,
60544 or 66151
Pall
Nuclepore
Millipore
Selas
NX04750, NX14225
142218
HAWP 047 00,
HAWP 142 50
83485-02,
83486-02
142218s
FHUP 047 00,
FHLP 142 50
83485-02,
83486-02
aSusceptible to decomposition by certain polar organic solvents.
1310 - 6
Revision 0
Date September 1986
-------
4.4.2 To test for absorbtlon 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 Acetic acid (0.5 N): This can be made by diluting concentrated
glacial acetic acid (17.5 N) by adding 57 ml glacial acetic acid to 1,000 ml
of water and diluting to 2 liters. The glacial acetic acid should be of high
purity and monitored for impurities.
5.2 Analytical standards should be prepared according to the applicable
analytical 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 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 +0.01 g. Handle membrane and prefilters with blunt
curved-tip forceps or vacuum tweezers, or by applying suction with a pi pet.
1310 - 7
Revision 0
Date September 1986
-------
'15.25cm {
(6")
Combined
• Weight
.33 kg (.73 Ib)
(3.15cm)
(1.25")
Sample
Elastomeric
Sample Holder'
T //
V .
•^ I 3.3 cm l^-
^^ M t"\ I ^
7.1 cm
(2.8")
I
* Elutomeric sample holder fabricated of material firm enough to support the sample.
Figure A. Compaction tester.
1310 - 8
Revision o
Date September 1986
-------
7.2 Assemble filter holder, membranes, and prefilters following the
manufacturer's instructions. Place the 0.45-um 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:
7.7.1 Dry the filter and residue at 80*C until two successive
weighings yield the same value.
7.7.2 Calculate the percent solids, using the following equation:
weight of filtered solid and filters - tared weight of filters 1nn v -,. .
initial weight of waste material x 1UU = * sonas
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 80*C. A new sample will have to be used for extraction
if a percent solids determination is performed.
1310 - 9
Revision
Date September 1986
-------
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 should 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 should proceed to Step 7.11.
If the surface area is smaller or the particle size larger than specified
above, the solid material is 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 Section 7.6) to calculate the amount of liquid and
acid to employ for extraction by using the following equation:
W = Wf - Wt
where :
W = wet weight in g of solid to be charged to extractor;
Wf = wet weight in g of filtered solids and filter media; and
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 of Type II water.
7.13 After the solid material and Type II water are placed in the
extractor, the operator should 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 + 0.2 by adding 0.5 N acetic acid. If the pH is <[ 5.0, no
1310 - 10
Revision 0
Date September 1986
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acetic add should be added. The pH of the solution should be monitored, as
described below, during the course of the extraction, and, 1f the pH rises
above 5.2, 0.5 N acetic acid should be added to bring the pH down to 5.0 +
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 hr and maintained at 20-40'C (68-104'F) 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 0.5 N acetic acid. If such a system is
not available, the following manual procedure shall be employed.
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 + 0.2. The pH of the solution should be adjusted at 15-,
. 30-, and 60-min 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
hr.
7.13.4 If, at the end of the 24-hr extraction period, the pH of the
solution is not below 5.2 and the maximum amount of acid (4 ml per g of
sol Ids) has not been added, the pH should be adjusted to 5.0 + 0.2 and
the extraction continued for an additional 4 hr, during which the pH
should be adjusted at 1-hr intervals.
7.14 At the end of the extraction period, Type II water should be added
to the extractor in an amount determined by the following equation:
V = (20) (W) - 16 (W) - A
where:
V = ml Type II water to be added;
W = weight in g of solid charged to extractor; and
A = ml of 0.5 N acetic acid added during extraction.
7.15 The material in the extractor should be separated into its
component liquid and solid phases in the following manner:
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).
1310 - 11
Revision 0
Date September 1986
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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 and should be analyzed for the presence of any of the
contaminants specified in 40 CFR Part 261.24 using the analytical procedures
as designated in Step 7.17.
7.17 The extract is then prepared and analyzed using the appropriate
analytical methods described in Chapters 3 and 4 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)(contaminant cone, in oil) + (1.000)(contaminant cone, of aqueous phase)
1050
7.18 The extract concentrations are compared with the maximum
contamination limits listed in 40 CFR Part 261.24. If the extract
concentrations are greater than or equal to the respective values, the waste
then is considered to exhibit the characteristic of Extraction Procedure
Toxicity.
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 Chapter 1 and in the
referenced analytical methods should be followed.
9.0 METHOD PERFORMANCE
9.1 The data tabulated below were obtained from records of state and
contractor laboratories and are intended to show the precision of the entire
method (1310 plus analysis method).
1310 - 12
Revision
Date September 1986
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TABLE 3. PRECISIONS OF EXTRACTION-ANALYSIS
PROCEDURES FOR SEVERAL ELEMENTS
El ement
Arsenic
Barium
Cadml urn
Chromium
Mercury
Lead
Sample Matrix
1. Auto fluff
2. Barrel sludge
3. Lumber treatment
company sediment
1. Lead smelting emission
control dust
2. Auto fluff
3. Barrel sludge
1. Lead smelting emission
control dust
2. Wastewater treatment
sludge from
electroplating
3. Auto fluff
4. Barrel sludge
5. Oil refinery
tertiary pond sludge
1. Wastewater treatment
sludge from
electroplating
2. Paint primer
3. Paint primer filter
4. Lumber treatment
company sediment
5. Oil refinery
tertiary pond sludge
1. Barrel sludge
2. Wastewater treatment
sludge from
electroplating
3. Lead smelting emission
control dust
1. Lead smelting emission
control dust
2. Auto fluff
3. Incinerator ash
4. Barrel sludge
5. Oil refinery
tertiary pond sludge
(Continued)
1310 - 13
Analysis
Method
7060
7060
7060
6010
7081
7081
3010/7130
3010/7130
7131
7131
7131
3010/7190
7191
7191
7191
7191
7470
7470
7470
3010/7420
7421
7421
7421
7421
Laboratory
Replicates
1.8, 1.5 ug/L
0.9, 2.6 ug/L
28, 42 mg/L
0.12, 0.12 mg/L
791, 780 ug/L
422, 380 ug/L
120, 120 mg/L
360, 290 mg/L
470, 610 ug/L
1100, 890 ug/L
3.2, 1.9 ug/L
1.1, 1.2 mg/L
61, 43 ug/L
—
0.81, 0.89 mg/L
—
0.15, 0.09 ug/L
1.4, 0.4 ug/L
0.4, 0.4 ug/L
940, 920 mg/L
1540, 1490 ug/L
1000, 974 ug/L
2550, 2800 ug/L
31, 29 ug/L
Revision 0
Date September 1986
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Chromium(VI)
TABLE 3 (Continued)
Element
Nickel
Sample Matrix
1.
2.
Sludge
Wastewater treatment
sludge from
electroplating
Analysis
Method
7521
3010/7520
Laboratory
Replicates
2260,
130,
1720 ug/L
140 mg/L
1. Wastewater treatment
sludge from
electroplating
7196
18, 19 ug/L
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.
1310 - 14
Revision 0
Date September 1986
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Method 1310
EXTRACTION PROCEDURE
-------
METHOD 13tO
EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
ANO STRUCTURAL INTEGRITY TEST
(Cont InueQ)
7.8
Discard Solid
Area > 3.1 cm2/gm
or passes through
Area < 3.1 cm2/gn
or particle size
w MOBBED v«» uuyii .^—: *v wl M<" v*w.*e »*
9.5 mm sieves ^Xwhat Is surface^s.> 9.5mm sieve
f area or particle ^
size of the
material?
Material Is In
single piece
7.10. 1
Cut or
cast
cylinder from
waste material
for Structural
Integrity Proc.
7.10.2
7.9
Preoere
material
for extraction
by crushing.
cutting or
grind ing
Assemble
tester: oroo
hammer IS times
7.10.3
Remove
• olid materiel;
weigh; transfer
to Extractor
1310 - 16
Revision 0
Date September 1986
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METHOD 1310
EXTRACTION PROCEDURE (EP) TOXICITY TEST METHOD
AND STRUCTURAL INTEGRITY TEST
(Continued)
res
7. 11
Calculate
•mount of
llgulo ana ocla
to use for
extract Ion
7. 12
Place
material Into
extractor;add
delonlzea water
7.13
7.15
Allow
slurries
to stand:
set uo filter
apparatus:
filter
7.111
Use lOOg
of material
for extraction
procedure
7. 16
Combine
' liquids
from section
7.5 end 7.15
to analyze for
contaminants
Agitate
for ZA hours
and monitor pH
of solution
7. 13
0
7. 17
Obtain
analytical
method from
Table 1
Calibrate and
adjust pH meter
7. IB
Compare extract
concentration to max
contamination limits
in Table 1. to
determine EP toxlclty
7. 1<|
At and of
••traction
period add
delonizad water
( Stop }
1310 - 17
Revision 0
Date September 1986
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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
Vineland, NJ 08360
(609) 692-3333
Aldrlch 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
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
Fairfleld, 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
Mil ford, MA 01757
(617) 478-2000
(800) 252-4752
Whatman Laboratory Products, Inc.
Clifton, NJ 07015
(201) 773-5800
COMPANIES - 3
Revision
Date September 1986
ir U. S. GOVERNMENT PRINTING OFFICE : 1986 0 - 169-934
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