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 IA: Laboratory Manual
Physical/Chemical Methods
-------
VOLUME ONE,
SECTION A
Revision 0
Date September 1986
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For sale by the Superintendent of Documents, tl.S. Government Printing Office, Washington. D.C. 20402
-------
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,
corroslvlty, 1gn1tab1l1ty, and composition of the waste and the mobility of
toxic species present 1n 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 AMALYTES
3.1 Sampling Considerations
3.2 Sample Preparation Methods
Method 3005: Add Digestion of Waters for Total Recoverable
or Dissolved Metals for Analysis by Flame
Atomic Absorption Spectroscopy or
Inductively Coupled Plasma Spectroscopy
Add Digestion of Aqueous Samples and Extracts
for Total Metals for Analysis by Flame
Atomic Absorption Spectroscopy or
Inductively Coupled Plasma Spectroscopy
Add Digestion of Aqueous Samples and Extracts
for Total Metals for Analysis by Furnace
Atomic Absorption Spectroscopy
Dissolution Procedure for 011s, Greases, or
Waxes
3050: Add Digestion of Sediments, Sludges, and Soils
Method 3010:
Method 3020:
Method
Method
3040:
3.3 Methods for Determination of Metals
Method 6010:
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
Method
7000:
7020:
7040:
7041:
7060:
7061:
7080:
7090:
7091:
7130:
7131:
7140:
7190:
7191:
7195:
7196:
7197:
7198?
7200:
7201:
7210:
7380:
7420:
7421:
7450:
7460:
Inductively Coupled Plasma Atomic Emission
Spectroscopy
Atomic Absorption Methods
Aluminum (AA, Direct Aspiration)
Direct Aspiration)
Furnace Technique)
Furnace Technique)
Arsenic (AA, Gaseous Hydride)
Antimony (AA
Antimony (AA
Arsenic (AA,
Barium (AA, Direct Aspiration)
Beryllium (AA, Direct Aspiration)
(AA, Furnace Technique)
Beryl 11 urn
Cadmium (AA,
Cadmium
Calcium
Chromium
Chromium
Chromlurn
Chromium
Chromium
Chromium,
Direct Aspiration)
AA, Furnace Technique)
AA, Direct Aspiration)
AA, Direct Aspiration)
AA, Furnace Technique)
Hexavalent Coprec1p1tat1on)
Hexavalent Colorlmetrlc)
Hexavalent Chelat1on/Extract1on)
(Differential Pulse
Hexavalent
Polarography)
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: Son1cation 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: Florlsll 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 Chromatographlc Methods
Method 8000: Gas Chromatography
Method 8010: Halogenated Volatile Organlcs
Method 8015: Nonhalogenated Volatile Organlcs
Method 8020: Aromatic Volatile Organlcs
Method 8030: Acroleln, Acrylonltrlle, Aceton1tr1le
Method 8040: Phenols
Method 8060: Phthai ate Esters
Method 8080: Organochlorlne Pesticides and PCBs
Method 8090: NHroaromatlcs 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 Organlcs
Method 8250: Gas Chromatography/Mass Spectrometry for
Semi volatile Organlcs: Packed Column
Technique
Method 8270: Gas Chromatography/Mass Spectrometry for
Semi volatile Organlcs: Capillary Column
Technique
Method 8280: The Analysis of Polychlorlnated D1benzo-P-
D1ox1ns and Polychlorlnated Dlbenzofurans
Appendix A: Signal-to-No1se Determination Methods
Appendix B: Recommended Safety and Handling Procedures
for PCDD's/PCDF's
4.3.3 High Performance Liquid Chromatographlc Methods
Method 8310: Polynuclear Aromatic Hydrocarbons
4.4 Miscellaneous Screening Methods
Method 3810: Headspace
Method 3820: Hexadecane Extraction and Screening of Purgeable
Organlcs
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 (Color1metric,
Manual)
Total and Amenable Cyanide (Color1metr1c,
Automated UV)
Total Organic Halldes (TOX)
Total Organic Halldes (TOX) by Neutron
Activation Analysis
Sulfides
Sulfate (Color1metr1c, Automated, Chloranllate)
Sulfate (Color1metric, Automated, Methyl thymol
Blue, AA II)
Sulfate (Turbldlmetrlc)
Total Organic Carbon
Phenol 1cs (SpectrophotometHc, Manual 4-AAP with
Distillation)
Phenol1cs (Color1metr1c, Automated 4-AAP with
Distillation)
PhenolIcs (Spectrophotometrlc, MBTH with
Distillation)
Total Recoverable 011 & Grease (Gravimetric,
Separatory Funnel Extraction)
011 & 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 Collform: Multiple Tube Fermentation
Technique
Total Conform: Membrane Filter Technique
Nitrate
Chloride (Color1metric, Automated Ferricyanide
AAI)
Chloride (Colorimetric, Automated Ferricyanide
AAII)
Chloride (T1tr1metr1c, Mercuric Nitrate)
Rad1um-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 01ly Wastes
pH Electrometrlc 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 Ign1tab1l1ty
7.2 Corros1t1v1ty
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 Sulflde
Released from Wastes
7.4 Extraction Procedure Tox1c1ty
CONTENTS - 7
Revision 0
Date September 1986
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CHAPTER EIGHT METHODS FOR DETERMINING CHARACTERISTICS
8.1 Ign1lability
Method 1010: Pensky-Martens Closed-Cup Method for Determining
Ign1tab1l1ty
Method 1020: Setaflash Closed-Cup Method for Determining
Ign1tab1l1ty
8.2 Corros1v1ty
Method 1110: Corros1v1ty Toward Steel
8.3 Reactivity
8.4 Toxldty
Method 1310: Extraction Procedure (EP) Toxldty Test Method
and Structural Integrity Test
APPENDIX COMPANY REFERENCES
CONTENTS - 8
Revision 0
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 IVMONITORING
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 (4.2.1)
Four
Four
Four
Four
Four
4.2.1)
4.2.1)
4.2.1)
4.2.1)
4.2.1)
Four (4.2.2
Four (4.2.2
Four (
Four i
Four i
,4.2.2
,4.2.2
[4.2.2
Four (4.2.2)
Four
Four
Four
Four
Four
Four
Three
Three
Three
4.2.2)
4.2.2]
4.4)
4.4)
[4.2.1]
(4.2.1)
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
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
Three
7040
7041
7060
7061
7080
7090
7091
7130
7131
7140
7190
7191
7195
7196
7197
7198
7200
7201
7210
7380
7420
7421
7450
7460
7470
7471
7480
7481
7520
7550
7610
7740
7741
7760
7770
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
0
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 |
Four I
Four 1
Four 1
Four 1
Four I
Four
Four
Four
Four
Four
Four
Four
Four
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
4.3
Four (4.3
Four (4.3
Four
Four
Five
Five
Five
Five
Five
Five
Five
Six
Six
Six
Six
4.3
4.3
-1
.1)
Al
.1)
-1!
.1)
.1)
Al
.1)
.1
.1
.1
.1
.2
.2)
.2]
2i
.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
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 1n SW-846 Include
quality control, sampling plan development and Implementation, analysis of
Inorganic and organic constituents, the estimation of Intrinsic physical
properties, and the appraisal of waste characteristics.
The procedures described 1n this manual are meant to be comprehensive and
detailed, coupled with the realization that the problems encountered 1n
sampling and analytical situations require a certain amount of flexibility.
The solutions to these problems will depend, In part, on the skill, training,
and experience of the analyst. For some situations, 1t 1s possible to use
this manual 1n rote fashion. In other situations, It will require a
combination of technical abilities, using the manual as guidance rather than
1n a step-by-step, word-by-word fashion. Although this puts an extra burden
on the user, 1t 1s unavoidable because of the variety of sampling and
analytical conditions found with hazardous wastes.
ORGANIZATION AND FORMAT
This manual 1s divided Into two volumes. Volume I focuses on laboratory
activities and 1s divided for convenience Into three sections. Volume IA
deals with quality control, selection of appropriate test methods, and
analytical methods for metallic species. Volume IB consists of methods for
organic analytes. Volume 1C Includes a variety of test methods for
miscellaneous analytes and properties for use 1n evaluating the waste
characteristics. Volume II deals with sample acquisition and Includes quality
control, sampling plan design and Implementation, and field sampling methods.
Included for the convenience of sampling personnel are dlscussslons of the
ground water, land treatment, and Incineration monitoring regulations.
Volume I begins with an overview of the quality control procedures to be
Imposed upon the sampling and analytical methods. The quality control chapter
(Chapter One) and the methods chapters are Interdependent. The analytical
procedures cannot be used without a thorough understanding of the quality
control requirements and the means to Implement them. This understanding can
be achieved only be reviewing Chapter One and the analytical methods together.
It Is expected that Individual laboratories, using SW-846 as the reference
PREFACE - 1
Revision 0
Date September 1986
-------
source, will select appropriate methods and develop a standard operating
procedure (SOP) to be followed by the laboratory. The SOP should Incorporate
the pertinent Information from this manual adopted to the specific needs and
circumstances of the Individual laboratory as well as to the materials to be
evaluated.
The method selection chapter (Chapter Two) presents a comprehensive
discussion of the application of these methods to various matrices 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 matr1x/analyte/concentrat1on combination of Interests.
The section discusses the objective of the testing program and Us
relationship to the choice of an analytical method. Flow charts are presented
along with tables to guide 1n the selection of the correct analytical
procedures to form the appropriate method.
The analytical methods are separated Into distinct procedures describing
specific, Independent analytical operations. These Include extraction,
digestion, cleanup, and determination. This format allows Unking of the
various steps 1n the analysis according to: the type of sample (e.g., water,
soil, sludge, still bottom); analytes(s) of Interest; needed sensitivity; and
available analytical Instrumentation. The chapters describing Miscellaneous
Test Methods and Properties, however, give complete methods which are not
amenable to such segmentation to form discrete procedures.
The Introductory material at the beginning of each section containing
analytical procedures presents Information on sample handling and
preservation, safety, and sample preparation.
Part II of Volume I (Chapters Seven and Eight) describes the
characteristics of a waste. Sections following the regulatory descriptions
contain the methods used to determine 1f 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 1s also given 1n this volume. These Include ground
water monitoring, land treatment, and incineration. The purpose of this
guidance 1s to orient the user to the objective of the analysis, and to assist
in developing data quality objectives, sampling plans, and laboratory SOP's.
Significant Interferences, or other problems, may be encountered with
certain samples. In these situations, the analyst 1s advised to contact the
Chief, Methods Section (WH-562B) Technical Assessment Branch, Office of Solid
Waste, US EPA, Washington, DC 20460 (202-382-4761) for assistance. The
manual 1s Intended to serve all those with a need to evaluate solid waste.
Your comments, corrections, suggestions, and questions concerning any material
contained 1n, 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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ACKNOWLEDGEMENTS
The Office of Solid Waste thanks the following Individuals and groups for
their efforts, assistance and advice 1n the preparation of this manual:
Dr. William Loy, Chemist, Analytical Support Branch, EPA Region IV;
Mr. Theodore Martin, Research Chemist, EMSL-CI;
Dr. Nancy Rothman, Assistant Director, ERCO/A Division of ENSECO;
Ms. Ann Soule, Technical Editor, ERCO/A Division of ENSECO;
Ms. Dorothy Bell, Technical Editor, ERCO/A Division of ENSECO;
Ms. Margaret Layne, Technical Program Manager, Research Triangle
Institute;
Mr. Alvla Gasklll, Senior Environmental Scientist, Research Triangle
Institute;
Mr. Ronald Ramsey, Technical Program Manager, Dynamac Corp.;
Mr. Gene E. Fax, Managing Director, The Cadmus Group, Inc.;
Mr. Robert Hlrsch, New Jersey Department of Environmental
Protection;
Mr. Henry Hoffman, New Jersey Department of Environmental
Protection;
Mr. David Bennett, Hazardous Substance Branch, EPA;
The EPA SW-846 Work Group.
ACKNOWLEDGEMENTS - 1
Revision
Date September 1986
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PART I METHODS FOR ANALYTES AND PROPERTIES
Revision 0
Date September 1986
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CHAPTER ONE
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 in 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
is an overview of such a program.
The following sections discuss some minimum standards for QA/QC programs.
The chapter is 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 simllarily evaluate their QA/QC
programs.
Most of the laboratories who will use this manual also carry out testing
other than that called for in 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 in 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 1s not directly
Involved 1n 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 Its preparation are described 1n 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 1n 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 1n 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 1s 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 1s 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 1n
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 1s 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, chain-
of-custody records, packing lists) 1s correct and transmitting that
Information, along with the samples, to the analytical laboratory.
The analysis monitor Is responsible for laboratory activities. These
Include:
Training and qualifying personnel in 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 11st or cha1n-of-custody sheet; and
Verifying that laboratory QC and analytical procedures are being followed
as specified 1n 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 1s 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, 1f 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 1s 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 1n the organizational or
management plan. The final report for each project should also Include a
separate QA section which summarizes data quality Information contained 1n the
periodic reports.
Other guidance on quality assurance management and organizations 1s
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 1n 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:
Accuracy means the nearness of a result or the mean (X) of
a set of results to the true value. Accuracy 1s assessed
by means of reference samples and percent recoveries.
ANALYTICAL BATCH: The basic unit for analytical quality control 1s the
analytical batch. The analytical batch 1s 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 1n continuous sequential time periods. Samples
1n each batch should be of similar composition.
BLANK:
A blank 1s an artificial sample designed to monitor the
Introduction of artifacts Into the process. For aqueous
samples, reagent water 1s used as a blank matrix; however,
a universal blank matrix does not exist for solid samples,
and therefore, no matrix 1s used. The blank 1s taken
through the appropriate steps of the process.
A reagent blank 1s an aliquot of analyte-free water or
solvent analyzed with the analytical batch. Field blanks
are allquots of analyte-free water or solvents brought to
the field 1n 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 1n the field. They are a check
on sample contamination originating from sample transport,
shipping and from site conditions. Equipment blanks are
opened 1n the field and the contents are poured
appropriately over or through the sample collection device,
collected 1n 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, 1s done by analyzing for
appropriate solvent. Calibration
from a stock solution which 1s
analyte standards In 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 limit.
shall be phase matched with the
characterized: for an example,
appropriate for an aqueous sample.
The matrix used
samples and well
reagent grade water 1s
ENVIRONMENTAL
SAMPLE:
An environmental sample or field sample 1s a representative
sample of any material (aqueous, nonaqueous, or multimedia)
collected from any source for which determination of
composition or contamination 1s 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
sol Ids, contaminated soils, and Industrial liquid and solid
wastes.
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MATRIX/SPIKE-
DUPLICATE
ANALYSIS:
MQL:
PRECISION:
PQL:
RCRA:
REAGENT GRADE:
REPLICATE SAMPLE:
STANDARD CURVE:
SURROGATE:
In matrix/spike duplicate analysis, predetermined quantl-
tles 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 1s 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
themselves without assumption of
the true result. Precision 1s
replicate results among
any prior information as to
assessed by means of duplicate/replicate sample analysis.
The practical quantitatlon 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, and
reagent grade are synonomous terms for reagents which
conform to the current specifications of the Committee on
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.
A standard curve 1s a
known analyte standard
the analyte.
curve which plots concentrations of
versus the Instrument response to
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 1aboratory pure water means
distilled or delonlzed water or Type II reagent water which
1s free of contaminants that may Interfere with the
analytical test 1n question.
1.2 QUALITY CONTROL
The procedures Indicated below are to be performed for all analyses.
Specific Instructions relevant to particular analyses are given 1n 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 1n the
sampling plan;
Procedures for documenting and justifying any field actions contrary to
the QAPP;
Documentation of all pre-f1eld 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 1n 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 1s only useful 1f 1t 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 spilt/spiked field sample shall be analyzed with every analytical batch
or once Intwentysamples, whichever 1s 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 1n
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 (1n 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 in 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 1n the matrix of the check sample. In particular, check
samples for metallic analytes shall be matched to field samples 1n phase and
1n generaT~matr1x 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 (Florlsll, alumina, silica gel, etc.) prepared for use shall be
checked for analyte recovery by running the elutlon pattern with standards as
a column check. The elutlon pattern shall be optimized for maximum recovery
of analytes and maximum rejection of contaminants.
1.2.2.2.1 Column Check Sample
The elutlon 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 elutlon fraction. Recovery as
specified 1n the methods 1s considered an acceptable column check. A result
lower than specified Indicates that the procedure 1s 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 1n 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 1n 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 1s 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. I? the results of the second verification are not
within +10% of the original standard curve, a reference standard should be
employed" to determine 1f 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 1n 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
in the methods.
The tune of each GC/MS system used for the determination of organic
analytes shall be checked with 4-bromof1uorobenzene (BFB) for determinations
of volatlles and with decafluorotrlphenylphosphlne (DFTPP) for determinations
of semi-volatlles. The required 1on 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 dally 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 in 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 is tentative.
For gas chromatographic 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 1n 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 1n 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 is
specified 1n 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 dlgestate 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 quantltatlon 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 11st 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 organlcs (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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Date September 1986
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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.
ONE - 17
Revision
Date September 1986
-------
Lab Name
Date
COVER PAGE
1KORCAK1C ANALYSES 1MTA PACKAGE
Case l.o.
Q.C. Report No.
EPA No.
Comments:
Sample Numbers
.Lab ID No. EPA No.
Lab ID No.
ONE - 18
Revision 0
Date September 1986
-------
Form I
Sample
No.
Date
LAB NAME
INORGANIC ANALYSIS DATA SHLET
CASE NO.
LAb SAMPLE 1L>. NO.
Lab Receipt Date
QC REPORT NO.
Elements Identified and Measured
Matrix: Water
Soil
Sludge
Other
ug/L or rat/kg dry weight (Circle One)
1. Aluminum 13. Magnesium
2. Antimonv
3. Arsenic
A. Barium
5. Beryllium
6. Cadmium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
14.
15.
16.
17.
Ib.
19.
2o.
21.
22.
23.
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thallium
Vanadium
Zinc
Precent Solids (;O
Cyanide
Commonts:
Lab Manager
ONE - 19
Revision 0
Date September 1986
-------
LAB NAME
Form II
Q. C. Report No.
INITIAL AND CONTINUING CALIBRATION VERIFICATION
CASE NO.
DATE
Compound
Metals:
1 . Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
t>. Cadmium
7. Calcium
b. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
Ib. Nickel
17. Potassium
Its. Selenium
IV. Silver
UNITS: . ug/L
Initial Calib.1 Continuing^ Calibration2
True Value
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide 1
Found
%R
True Value
Found
j£
Found
%k
Met hod 4
Initial Calibration Source
Continuinx Calibration Source
Indicate Analytical Method Used: P - 1CP; A - Flame AA; F - Furnace AA
ONE - 20
Revision 0
Date September 1986
-------
LAB NAME
DATE
Form III
Q. C. Report No.
BLANKS
CASE NO.
UNITS
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
A. Barium
5. Beryllium
b. Cadmium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
lb. Selenium
19. Silver
2U. Sodium
^1. Thallium
22. Vanadium
2J. Zinc
Other:
Cyanide
Initial
Cali bration
Blank Value
Continuing Calibration
1
Blank Value
2 3
4
Preparation Blank
Matrix: Matrix:
1 2
Reporting Units: aqueous,
; solid rag/kg
ONE - 21
Revision 0
Date September 1986
-------
Form IV
Q« C. Report No.
LAB NAME
ICP INTERFERENCE. CHECK SAMPLE
CASE NO.
DATE
Check Sample l.D. _
Check Sample Source
Units: ug/L
Compound
Metals:
1 . Aluminum
2. Antimony
3. Arsenic
4. Barium
5. beryllium
6. Cadmium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
IB. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
2J. Zinc
Other:
Control Limits1
Mean
Std. Dev.
True^
Initial
Observed
7.R
Final
Observed
%R
Mean value based on n =
True value of EPA ICP Interference Check Sample or contractor standard.
ONE - 22
Revision 0
Date September 1986
-------
Form V
Q« C. Report No.
SPIKE SAMPLE RECOVERY
LAB NAME
DATE
CASE NO.
Sample No.
Lab Sample ID No.
Units
Matrix
Compound
Metals:
1. Aluminum
2. Antimonv
3. Arsenic
4. Barium
5. Beryllium
6. Cadmium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
Ib. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide
Control Limit
ZR
Spiked Sample
Result (SSR)
Sample
Result (SR)
Spiked
Added (SA)
ZR1
1 ZR « |(SSR - SK)/SA] x 100
"N"- out of control
NR - Not required
Comments:
ONE - 23
Revision 0
Date September 1986
-------
LAB NAME
DATE
Form 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. Barium
5. Beryllium
6. Cadmium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
IB. Selenium
ly. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide
Control Limit1
Sample(S)
Duplicate(D)
RPD2
* Out of Control
1 To be added at a later date. 2 RPD = (|S - D|/((S + D)/2)] x 100
NC - Non calculable KPU due to value(s) less than CRDL
ONE - 24
Revision 0
Date September 1986
-------
LAB NAME
Form VII
Q.C. Report No.
INSTRUMENT DETECTION LIMITS AND
LABORATORY CONTROL SAMPLE
CASE NO.
DATC
LCS NO.
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
6. Cadmium
7. Calcium
b. Chromium
9. Cobalt
10. Copper
11. Iron
12. Lead
13. Magnesium
1A. ilanganese
15. Mercury
16. Nickel
17. Potassium
18. Selenium
1*. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Other:
Cyanide
Required Detection
Limits (CRDL)-uj
-------
Form VIII
O..C. Report No.
STANDARD ADDITION RESULTS
LAB NAME
UATt
tPA
Sample it
CASE NO.
tleroent
Matrix
0 ADD
ABS.
1
CON.
ABSZ
UMTS .' ug/L
2 ADD
CON.
ABS.Z
3 ADD1
CON.
ABS.^
FINAL
CON.3
r*
* CON is the concentration added, ABS. is the instrument readout in absorbance or
concentration.
* Concentration as_ determined by MSA
*"r" is the correlation coofticient.
+ - correlation coefficient is outsidt- ol control window of O.yy5.
ONE - 26
Revision 0
Date September 1986
-------
LAB NAME
DATE
Form IX
Q« C. Report No.
1CP SERIAL DILUTIONS
CASE NO.
Sample No.
Lab Sample ID M0.
Units'. ug/L
Matrix
Compound
Metals:
1. Aluminum
2. Antimony
3. Arsenic
A. Barium
i. Berylliun
6. Cadmium
7. Calcium
C. Chrotr.ium
y. Cobalt
10. Copper
1 1 . Iron
12. Lead
13. Magnesium
14. Manganese
Ib. Nickel
lt>. Potassium
17. Selenium
lb. Silver
1^. Sodium
2U. Thallium
^1 . Vanadium
22. Zinc
Other:
Initial Sample
Concentration( I)
Serial Dilution
Result(S)
ry
A Difference
1 Diluted sample concentration corrected tor 1:4 dilution (see Exhibit D)
^ Percent Difference = U ~ sl x lUU
1
NK - Not Required, initial sample concentration less than 1U times IUL
NA - Not Applicable, analyte not determined by 1CP
ONE - 27
Revision 0
Date September 1986
-------
Form X
QC Report No.
HOLDING TIMES
LAB NAME
DATE
CASE NO.
LPA
Sample No.
Matrix
Date
Received
Mercury
Prep Date
Mercury
Holding Time1
(Days)
CN Prep
Date
CN
Holding Time1
(Days)
'holding time is defined as number of days between the date received and the
sample preparation date.
ONE - 28
Revision p
Date September 1986
-------
Form XI
INSTRUMENT DETECTION LIMITS
LAb NAME
DATE
ICP/Flame AA (Circle One) Model Number
Furnace AA Number
Element
1 . Aluminum
2. Antimony
3. Arsenic
4. Barium
3. beryllium
b. Cadmium
7. Calcium
ti. Chromium
9. Cobalt
1U. Copper
11. Iron
12. Lead
Wavelength
(nm)
IDL
(ug/L)
1
1
Element
13. Magnesium
14. Manganese
15. Mercury
1
16. Nickel
17. Potassium
18. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Wavelength
(no)
IDL
(up/L)
Footnotes: Indicate the instrument for which the IDL applies with a "P" (for ICP
an "A" (for Flame AA), or an "F" (for Furnace AA) behind the IDL valu
Indicate elements commonly run with background correction (AA) with
a "b" behind the analytical wavelength.
If more than one ICP/Flame or Furnace AA is used, submit separate
Forms XI-X111 for each instrument.
COMMENTS:
Lab Manager
ONE - 29
Revision 0
Date September 1986
-------
Form XII
ICP Interelement Correction Factors
LABORATORY_
DATE
ICP Model Number
Anal yte
1. Antimonv
2. Arsenic
3. BariuE
4. Bervlliun;
5. Cadmium
6. Chrottiuc
7. Cobalt
8. Copper
9. Lead
10. Manganese
11. Mercurv
12. Nickel
13. Potass iuc:
14. Selenium
15. Silver
16. Sodium
17. Thallium
Itt. Vanadium
i*. /inc
Analyte
Wavelength
(nc)
Interelement Correction Factors
for
Al
Ca
Fe
Mg
1
1
|
1
COMMENTS:
Lab Manager
ONE - 30
Revision p
Date September 1986
-------
Form XII
1CP Interelement Correction Factors
LABORATORY^
DATE
ICP Model Number
Analyte
1. Antimony
2. Arsenic
3. Barium
4. beryllium
5. Cadmium
6. Chromium
7. Cobalt
8. 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
(no)
Interelement Correction Factors
for
COMMENTS:
Lab Manager
ONE - 31
Revision 0
Date September 1986
-------
Form XIII
ICP Linear Ranges
LAB NAME
DATE
ICP Model Number
Analyte
1. Aluminum
2. Antimony
3. Arsenic
4. Barium
5. Beryllium
6. Cadmium
7. Calcium
8. Chromium
9. Cobalt
10. Copper
1 1 . Iron
12. Lead
Integration
Time
(Seconds )
Concen-
tration
(ug/L)
Analyte
13. Magnesium
14. Manganese
15. Mercury
16. Nickel
17. Potassium
18. Selenium
19. Silver
20. Sodium
21. Thallium
22. Vanadium
23. Zinc
Integration
Time
(Seconds)
Concen-
tration
(ug/L)
i
Footnotes:
COMMENTS:
Indicate elements not analyzed by ICP with the notation "NA"
Lab Manager
ONE - 32
Revision 0
Date September 1986
-------
Organics Analysis Data Sheet
(Page!)
Sample Number
Laboratory Name:
Lab Sample ID No
Sample Matrix:
Case No:
QC Report No:
Data Release Authorized By:
Date Sample Received:
Voiatile Compounds
Date Extracted/Prepared:
Date Analyzed:
Conc/Dil Factor:
-pH.
Percent Moisture: (Not Decanted).
CAS ug/lorug/Kg
Number (Circle One)
74-87-3
74-83-9
75-01-4
75-00-3
75-09-2
67-64-1
75-15-0
75-35-4
75-34-3
156-60-5
67-66-3
107-06-2
78-93-3
71-55-6
56-23-5
108-05-4
75-27-4
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone "
Carbon Disulfide
1, 1-Dichloroethehe
1, 1-Dichloroeihane
Trans-1. 2-Diehloroeihene
Chloroform
1. 2-Dichloroethane
2-Butanone
1,1. 1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
CAS ug/lorug/Kg
Number (Circle One)
78-87-5
10061-02-6
79-01-6
124-48-1
79-00-5
71-43-2
10061-01-5
110-75-8
75-25-2
108-10-1
591-78-6
127-18-4
79-34-5
108-88-3
108-90-7
100-41-4
100-42-5
1, 2-Dichloropropane
Trans-1. 3-Dichloropropene
Trichloroethene
Dibromochloromethane
1.1, 2-Trichloroethane
Benzene
cis-1. 3-Dichloropropene
2-Chloroethylvinylether
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1. 1.2. 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes
Data Reporting Qualifiers
For reporting results to EPA. the following results qualifiers ire used.
Additional flags or footnotes explaining results are encouraged However, the
definition of each flag must be enplicit.
Value
II the result is a value greater than or equal to the detection limn.
report the value
Indicates compound was analyzed for but not detected Report the
minimum detection limit for the sample with the U (e.g.. 10U) based
on necessary concentration 'dilution action (This is not necessarily
the instrument detection limn | The footnote should read U-
Compound was analyied for but not detected. The number is the
minimum attainable detection limn for the sample
Indicates an estimated value This flag is used either when
estimating a concentration for tentatively identified compounds
where all response is assumed or when the mass spectral data
indicated the presence of a compound that meets the identification
criteria but the result is less than the rpecified detection limn but
greater than tero (e.g.. 10J) If limit of detection is to ug'l and a
concentration of 3 vi '< is calculated, report as 3J
Other
This flag applies to pesticide parameters where the idennlicanon has
been confirmed by GC/MS Single component pesncides^IO
no 'ul in the final entract should be confirmed by GC'MS
This flag is used when the analyte is found in the blank as well as a
sample ft indicates possible'probable blank contamination and
warns Ihe data user to take appropriate action
Other specific flags and footnotes may be required to properly define
the results If used, they must be fully described and such description
attached to the data summary report
Form I
ONE - 33
Revision o
Date September 1986
-------
Laboratory Name:
Case No:
Sample Number
Date Extracted/Prepared:
Date Analyzed.
Organics Analysis Data Sheet
(Page 2)
Semivolatile Compounds
GPC Cleanup DYes DNo
Separatory Funnel Extraction DYes
Continuous Liquid Liquid Extraction DYes
Conc/Dil Factor:
Percent Moisture (Decanted).
CAS ug/lorug/Kg
Number (Circle One)
108-95-2
1 1 1 -44-4
95-57-8
541-73-1
106-46-7
100-51-6
95-50-1
95-48-7
3963B.-32-9
106-44-5
621-64-7
67-72-1
98-95-3
78-59-1
88-75-5
105-67-9
65-85-0
111-91-1
120-83-2
120-82-1
91-20-3
106-47-8
87-68-3
59-50-7
91-57-6
77-47-4
88-06-2
95-95-4
91-58-7
88-74-4
131-11-3
208-96-8
99-09-2
Phenol
bis(-2-Chloroethyl)Ether
2-Chlorophenol
1, 3-Dichlorobenzene
1. 4-Dichlorobenzene
Benzyl Alcohol
1, 2-Dichlorobenzene
2-Methylphenol
bis(2-chloroisopropyl)Ether
4-Methylphenol
N-Nitroso-Di-n-Propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2. 4-Dimethylphenol
Benzole Acid
bis(-2-Chloroethoxy)Methane
2, 4-Dichlorophenol
1. 2. 4-Trichlorobenzene
Naphthalene
4-Chloroaniline N
Hexachlorobutadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2, 4, 6-Trichlorophenol
2, 4. 5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Dimethyl Phthalate
Acenaphthylene
3-Nitroaniline
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
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
4. 6-Dinitro-2-Methylphenol
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachlorophenol
Phenanthrene
Anthracene
Di-n-Butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3. 3'-Dichlorobenzidine
Benzo(a)Anthracene
bis(2-Ethylhexyl)Phthalate
Chrysene
Di-n-Octyl Phthalate
Benzo(b)Fluoranthene
BenzofklFluoranthene
Benzo(8)Pyrene
lndeno(1, 2, 3-cd)Pyrene
Dibenz(a. h)Anthracene
3enzo(g. h, i)Perylene
(1)-Cannoi be separated from diphenylamine
Form I
ONE - 34
Revision o
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 DNo
Separatory Funnel Extraction DYes
Continuous Liquid - Liquid Extraction DYes
CAS ug/lorug/Kg
Number (Circle One)
319-84-6
319-85-7
319-86-8
58-89-9
76-44-8
309-00-2
1024-57-3
959-98-8
60-57-1
72-55-9
72-20-8
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
11104-28-2
11141-16-5
53469-21-9
12672-29-6
11097-69-1
11096-82-5
Alpha-BHC
Beta-BHC
Delta-BHC
Gamma-BHC (Linda ne)
Heptachlor
Aldrin
Heptachlor Epoxide
Endosulfan 1
Dieldrin
4. 4'-DDE
Endrin
Endosulfan II
4. 4'- ODD
Endosulfan Sulfate
4, 4--DDT
Methoxychlor
Endrin Ketone
Chlordane
Toxaphene
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroelor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Vj = Volume of extract injected (ul)
Vs = Volume of water extracted (ml)
Ws = Weight of sample extracted (g)
V, = Volume of total extract (ul)
orWc
Form 1
ONE - 35
Revision Q
Date September 1986
-------
Laboratory Name:
Case No:
Organics Analysis Data Sheet
Sample Number
CAS
Number
V
y
a
4
K
6
7
R
s
10
11
13
It
tA
1K
1fi
17
1fi
19
30
31
33
33
3d
3K
3fi
37
3R
3Q
an
Compound Name
Fraction
RT or Scan
Number
Estimated
Concentration
(ug/l or ug/kg)
Form 1, Part 8
ONE - 36
Revision 0
Date September 1986
-------
Case No..
WATER SURROGATE PERCENT RECOVERY SUMMARY
Laboratory Name
MMPIC
NO.
TM.UCNC-M
(1I-110)
eri
(11-119)
U OICHLOOO-
CTHANC-04
<7«-1M)
Nirno-
KHZCNC-09
(39-114)
t-rtuono-
eiPHENTL
(43-1 Id)
tCHPHCmrL-
014
(31-141)
EMI-VOLATIL
mcNOL-M
(lO-*4>
i-ftuo»o-
PHCNOt
(ft- 100)
Z.4.« rniSROKO-
PHtNOt
(in-ill)
-PESTICIOE--
OlOUtTL-
CMLOHCNOITC
(J4-1S4)
I
U>
o
a>
r+
(0
(/> o
n> =)
a-
(0
vo
oo
VALUES ARE OUTSIDE OF REQUIRED OC LIMITS
Comments:
Volatites: . out of ; outside of QC limits
Semi-Volatiles: out of ; outside of QC limits
Pesticides: out of ; outside of QC limits
FORM II
-------
Case No..
SOIL SURROGATE PERCENT RECOVERY SUMMARY
Laboratory Name
CO
00
O 73
fa n
(/) O
0> 3
O
10
00
SAMPU
NO.
TOLUCW-OS
(»1-11T>
«r»
(74- lilt
i.t oicm.o"o-
CTM«NC-0«
(ro-un
IIITHO-
CNZCNt-OS
(M-170)
1-riUOHO-
BI'MENYL
OO-1U)
TtlWMtNTl.-
01*
(i«-iirt
«
VALUES ARE OUTSIDE OF REQUIRED OC LIMITS
Coimnonts:
Vola tiles:
Semi-Vola tiles:
Pesticides:
.out of ; outside of QC limits
out of ; outside of OC limits
out of ; outside of OC limits
FORM II
-------
Case No.
WATER MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Laboratory Name .
CO
vo
FRACTION
VOA
SAMPLE NO.
B/N
SAMPLE NO.
ACID
SAMPLE NO.
PEST
SAMPLE NO.
COMPOUND
1,1-Dichloroethene
Trichloroethene
Chlorobenzene
Toluene
Benzene
1 ,2.4-Trichlorobenzene
Acenaohthenc
2.4 Diniirotoluene
Di-n-Butylphthalate
Pyrene
N-Nitroso-Di-n-Propylamine
1.4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Nitrophenol
Lindane
Heptachlor
Aldrin
Oieldrin
Etxlrin
4.4'-DDT
CONC. SPIKE
ADDED (ug/L)
SAMPLE
RESULT
CONC.
MS
%
REC
CONC.
MSD
%
REC
RPD
Q
RPD
14
14
13
13
11
28
31
38
40
31
38
28
50
42
40
42
50
15
20
22
18
21
27
~ LIMITS
RECOVERY
61-145
71-120
75-130
76-125
76-157
39-98
46-118
24-96
11-117
26-127
41-116
3697
9-103
12-89
27-123
23-97
10-80
56 123
40-131
40 120
52-126
56-121
38-127
O 73
01 n
n
§> o
13
I
Ko
00
M
ADVISORY LIMITS
RPD: VOAs
R/IM
ACID
PEST
O/wnmonta"
eutf nf * Olftsirf^
or
or
QC
QC
limits
limits
limits
limits
RFrOVFRY- VOA« out of
P/N _,. . ,. OU» nf
ACID out of
PEST out of
outside
outside
outside
outside
OC
OC
QC
OC
limits
limits
limits
limits
FORM III
-------
SOIL MATRIX SPIKE/MATRIX SPIKE DUPLICATE RECOVERY
Case No.
Laboratory Name.
-fa-
O
o ?o
O>
r* <
m -.
00
CO O
fD 3
a
FRACTION
VGA
SAMPLE NO.
B/N
SAMPLE NO.
ACID
SAMPLE NO.
PEST
SAMPLE NO.
COMPOUND
1.1 -Dicholorethene
Trichloroethene
Chlorobenzene
Toluene
Benzene
1 ,2,4-Trichlorobenzene
Acenaphthene
2,4 Dinitrotoluene
Di-n-Butylphthalate
Pyrene
N-Nitrosodi-n-Propylamine
1 ,4-Dichlorobenzene
Pentachlorophenol
Phenol
2-Chlorophenol
4-Chloro-3-Methylphenol
4-Nitrophenol
Lindane
Heptachlor
Aldrin
Dieldrin
Endrin
4,4'DDT
CONC. SPIKE
ADDED lug/Kg)
SAMPLE
RESULT
CONC.
MS
'
%
REC
CONC
MSD
%
REC
RPD
Q(
RPD
22
24
21
21
21
23
19
47 ,
47
36
38
27
47
35
50
33
50
50
31
43
38
45
50
? Llftf?
RECOVERY
59-172
62-137
60-133
59-139
66-142
38-107
31-137
28-89
29-135
35-142
41-126
28-104
17-109
2690
25-102
26-103
11-114
46-127
35-130
34-132
31-134
42-139
23-134
ADVISORY LIMITS
RPD:
Comn
VOAt . _ ovt of
R/N out of
AO'O , , f>1lt of
PFST ... , mrt o*
lentil?
outstrip OH limits
outstrip DO limits
nuttiHp DC limits
; Otltsirip OC l^'tS
RECOVERY: VOAs
R/N
ACID
PEST
nut of
out «* ,
out of
out of
; outside QC limits
; outside QC limits
_ ; outsirip OC limits
outside OC limits
FORM III
-------
METHOD BLANK SUMMARY
Case No.
Laboratory Name.
o
m
I
-F*
O 70
fa n
e-t- <
(0 '
CO
oo o'
rt> 3
a
n>
CT
FILE 10
DATE OF
ANALYSIS
FRACTION
MATRIX
CONC.
LCVEL
IHST. ID
CAS NUMBER
COMPOUND (HSL.TIC OR UNKNOWN)
CONC.
UNITS
CROL
Comments:
00
CTi
FORM IV
-------
GC/MS TUNING AND MASS CALIBRATION
Bromofluorobenzene (BFB)
Case No..
Instrument 10
Laboratory Name.
Date
Time.
Data Release Authorized By:
m/e ION ABUNDANCE CRITERIA
KRELATIVE ABUNDANCE
50
75 -
95
96
173
174
175
176
177
15.0 - 40.0% of the base peak
30.0 60.0% of the base peak
Base peak, 100% relative abundance
5.0 9.0% of the base peak
Less than 1 .0% of the base peak
Greater than 50.0% of the base peak
5.0 -9.0% of mass 174
Greater than 95.0%, but less than 101.0% ot mass 174
5.0 9.0% of mass 176
C D1
C ).'
( )2
THIS PERFORMANCE TUNE APPLIES TO THE FOLLOWING
SAMPLES. BLANKS AND STANDARDS.
Value in parenthesis is % mass 174.
'Value in parenthesis is % mass 176.
SAMPLE ID
LAB ID
DATE OF ANALYSIS TIME OF ANALYSIS
FORM V
ONE - 42
Revision 0
Date September 1986
-------
GC/MS TUNING AND MASS CALIBRATION
Decafluorotriphenylphosphine (DFTPP)
Case No Laboratory Name
Instrument ID Date Time
m/e
Data Release Authorized By:
ION ABUNDANCE CRITERIA ^RELATIVE ABUNDANCE
51
68
69
70
127
197
198
199
275
365
441
442
443
30.0 -60.0% of mass 198
less than 2.0% of mass 69
mass 69 relative abundance
less than 2.0% of mass 69
40.0 60.0% of mass 198
less than 1.0% of mass 198
base peak, 100% relative abundance
5.0 -9.0% of mass 198
10.0 30.0% of mass 198
greater than 1.00% of mass 198
present, but less than mass 443
greater than 40.0% of mass 198
17.0 23.0% of mass 442
( )1
C )'
( )2
THIS PERFORMANCE TUNE APPLIES TO THE FOLLOWING 1 Value in parenthesis is % mass 69.
SAMPLES, BLANKS AND STANDARDS. 2Value in parenthesis is % mass 442
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 RF for SPCC is 0.300
(0.25 for Bromoform)
Maximum % RSD for CCC is 30%
Laboratory ID
Compound
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1, 1-Oichloroethene
1, 1-Dichloroethane
Trans-1, 2-Dichloroethene
Chloroform
1. 2-Dichloroethane
2-Butanone
1.1. 1-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
Bromoform
4-Methyl-2-Penianone
2-Hexanone
Tetrachloroethene
1.1.2, 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethyl benzene
Styrene
Total Xylenes
RF20
RF50
RF100
«F1BO
RF200
RT
%RSD
CCC«
SPCC»
* *
*
*
* »
.
»
» *
* *
*
* *
*
RF -Response Factor (subscript is the amount of ug/L)
RT -Average Response Factor
%RSD -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 RF for SPCC is 0.300 Maximum % RSD for CCC is 30%
(0.25 for Bromoform)
Laboratory ID
Compound
RF
20
RF100
RF160
RF200
RT
%RSD
CCC-
SPCC"
RF -Response Factor (subscript is the amount of ug/U
RT -Average Response Factor
%RSD -Percent Relative Standard Deviation
CCC -Calibration Check Compounds ()
SPCC -System Performance Check Compounds ()
Form VI
ONE - 45
Revision p
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-Oichlorobenzene
2-Methylphenol
bis(2-chloroisopropyl)Ether
4-Methylphenbl
N-Nitroso-Di-n-Propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2. 4-Dimethylphenol
Benzoic Acid
bis(-2-Chloroethoxy)Melhane
2. 4-Dichlorophenol
1. 2. 4-Trichlorobenzene
Naphthalene
4-Chloroaniline
Hexachlorobutadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2, 4. 6-Trichloropheno!
2, 4. 5-Trichlorophenol
2-Chloronaphthalene
2-Nitroaniline
Dimethyl Phthalate
Acenaphthylene
3-Nitroaniline
Acenaphthene
2, 4-Dinitrophenol
4-Nitrophenol
Dibenzofuran
RF20
T
T
T
T
t
T
"FBO
RF80
-
RF120
RF160
RF
%RSD
CCC*
SPCC"
*
* *
*
*
*
*
* *
»
*
*
* *
Response Factor (subscript is the amount of nanograms)
RF -Average Response Factor
%RSD -Percent Relative Standard Deviation
CCC -Calibration Check Compounds ()
SPCC -System Performance Check Compounds ()
t -Not detectable at 20 ng
Form VI
ONE - 46
Revision p
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-Oinitrotoluene
2, 6-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenylether
Fluorene
4-Nitroaniline
4. 6-Dinitro-2-Methylphenol
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenylether
Hexachlorobenzene
Pentachloropheno!
Phenanthrene
Anthracene
Di-N-Butylphthalate
Fluoranthene
Pyrene
Butylbenrylphthalate
3. 3'-Dichlorobenzidine
Benzo(a)Anthracene
bis(2-Ethylhexyl)Phthalate
Chrysene
Di-n-Octyl Phthalate
Benzo(b)Fluoranthene
Benzo(k)Fluoranthene
Benzo(a)Pyrene
lndeno(1. 2. 3-cd)Pyrene
Oibenz(a, h)Anthracene
Benzo(g. h, i)Perylene
RF20
t
T
T
Rfso
RF80
RF120
RF160
Iff
KRSD
CCC»
SPCC"
*
*
*
*
Response Factor (subscript is the amount of nanograms)
fi? -Average Response Factor
%RSD Percent Relative Standard Deviation
CCC -Calibration Check Compounds ()
SPCC -System Performance Check Compounds ()
t Not detectable at 20 ng
(1) -Cannot be separated from diphenylamine
Form VI
ONE - 47
Revision p
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
RF
20
RF
50
RF
120
"160
RF
%RSO
CCC«
SPCC*
Response Factor (subscript is the amount of nanograms)
R? -Average Response Factor
%RSD -Percent Relative Standard Deviation
CCC -Calibration Check Compounds ()
SPCC -System Performance Check Compounds ()
t -Not detectable at 20 ng
Form VI
ONE - 48
Revision 0
Date September 1986
-------
Continuing Calibration Check
Volatile HSL Compounds
Case No:
Laboratory Name.
Contract No:
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
Chloromethane
Bromomethane
Vinyl Chloride
Chloroethane
Methylene Chloride
Acetone
Carbon Disulfide
1. 1-Dichloroethene
1, 1-Dichloroethane
Trans- 1. 2-Dichloroethene
Chloroform
1. 2-Dichloroethane
2-Butanone
1.1. 1-Trichloroethane
Carbon Tetrachloride
Vinyl Acetate
Bromodichloromethane
1, 2-Dichloropropane
Trans- 1, 3-Dichloropropene
Trichloroethene
Oibromochloromethane
1,1, 2-Trichloroethane
Benzene
cis-1, 3-Dichloropropene
2-Chloroethylvinylether
Bromoform
4-Methyl-2-Pentanone
2-Hexanone
Tetrachloroethene
1.1,2, 2-Tetrachloroethane
Toluene
Chlorobenzene
Ethylbenzene
Styrene
Total Xylenes
RF
RF50
%D
CCC
*
*
*
»
*
*
SPCC
* *
* *
* »
* *
* *
RFgg -Response Factor from daily standard file at 50 ug/l
RF -Average Response Factor from initial calibration Form VI
%D -Percent Difference
CCC -Calibration Check Compounds ()
SPCC -System Performance Check Compounds ()
Form VII
ONE - 49
Revision 0
Date September 1986
-------
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
RF
RF
50
%D
CCC
SPCC
RFjQ -Response Factor from daily standard file at 50 ug I
RF -Average Response Factor from initial calibration Form VI
%D -Percent Difference
CCC -Calibration Check Compounds ()
SPCC -System Performance Cneck Compounds ()
Form VII
ONE - 50
Revision o
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)Ether
2-Chlorophenol
1, 3-Dichloroberuene
1 . 4-Dichlorobenzene
Benzyl Alcohol
1. 2-Dichlorobenzene
2-Melhylphenol
bis(2 -chloroisopropyOEther
4-Methylphenol
N-Nitroso-Di-n-Propylamine
Hexachloroethane
Nitrobenzene
Isophorone
2-Nitrophenol
2, 4-Dimelhylphenol
Benzole Acid |
bis(-2-Chloroethoxy)Methane
2. 4-Dichlorophenol
1, 2. 4-Tnchlorobenzene
Naphthalene
4-Chloroanilme
Hexachlorobuiadiene
4-Chloro-3-Methylphenol
2-Methylnaphthalene
Hexachlorocyclopentadiene
2. 4. 6-Tnchlorophenol
2. 4. 5-Trichloiophenol f
2-Chloronaphihalene
2-Nitroanilme f
Dimethyl Phthalate
Acenaphthylene
3-Nitroanilme f
Acenaphihene
2. 4-Dmitrophenol
4-Nilrophenol
Dibenzofuran
R?
RF50
%D
*.'
CCC
*
*
*
*
*
*
*
*
SPCC
* *
» »
* *
* *
RFjQ -Response Factor from daily standard die at concentration
indicated (50 total nanograms)
RT -Average Response Factor from initial calibration Form VI
f-Due to low response, analyze
t BO total nanograms
itiD -Percent Difference
CCC -Calibration Check Compounds ()
SPCC -System Performance Check Compounds (.
Form VII
ONE - 51
Revision o
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-Dinitrotoluene
2, 6-Dinitrotoluene
Diethylphthalate
4-Chlorophenyl-phenyleiher
Fluorene
4-Nitroaniline t
4. 6-Dinitro-2-Methylphenol "\
N-Nitrosodiphenylamine (1)
4-Bromophenyl-phenyleiher
Hexachlorobenzene
Pentachlorophenol f
Phenanthrene
Anthracene
Di-N-Butylphthalate
Fluoranthene
Pyrene
Butylbenzylphthalate
3. 3'-Dichlorobenzidine
Benzo(a)Anthracene
bis(2-Ethylhexyl)Phthalate
Chrysene
Di-n-Octyl Phthalate
Benzo(b)Fluoranthene
Benzo(k)Fluoranthene
Benzo(a)Pyrene
lndeno(1. 2, 3-cd)Pyrene
Dibenz(a, h)Anthracene
Benzo(g, h. i)Perylene
RF
R^so
%D
CCC
*
*
*
*
*
SPCC
Rf 50 -Response F.iclur (ruin d.iily si.'iiul.iul die .11 toncenir.ition
indicated (SO total nanograms)
RF -Averiiye Response F.iclur Iniin iinli.il c.ililii.Hiun Form VI
"oD Perceiu Oiffuiuncu
t-Due to low response, analyze
at 80 total nanograms
CCC -C.ilcbr.ition Check Conipuonu sep.ifiilud from Uipheiiydinline
Form VII
ONE - 52
Revision o
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
RF
RF50
%D
CCC
SPCC
RFgQ -Response Faclor (rum daily standard filu ;il concentration
indicated (50 total nanograms)
RT -Average Response Faclor (rom inin.il calibration Form VI
+ «Du« to low response, analyze
t 60 total nanograms
%D -Perceni Dillerence
CCC -Calibration Clieck Compounds (.)
SPCC Sysiem Perlonnanctj Check Compounds ( )
Form VII
ONE - 53
Revision rj
Date September 1986
-------
Pesticide Evaluation Standards Summary
(Pagel)
Case No:
Date of Analysis..
Laboratory Name:.
GC Column:.
Instrument ID..
Evaluation Check for Linearity
Laboratory
ID
Pesticide
Aldrm
Endrin
.4.4'-DDT<'>
Dibutyl
Chlorendate
Calibration
Factor
Eval. Mix A
Calibration
Factor
Eval. Mix B
Calibration
Factor
Eval. Mix C
%RSD
( <10%)
Evaluation Check for 4,4'- DDT/Endrin Breakdown
(percent breakdown expressed as total degradation)
Eval Mix B
72 Hour
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
Eval Mix B
Eval Mix B
Laboratory
I.D.
Time of
Analysis
Endrin
4.4'- DDT
Combined'''
(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 o
Date September 1986
-------
Pesticide Evaluation Standards Summary
(Page 2)
Evaluation of Retention Time Shift for Dibutyl Chlorendate
Report all standards, blanks and samples
Sample No
Lab
I.D.
Time of
Analysis
Percent
Diff.
SMO
Sample No.
Lab
I.D.
Time of
Analysis
Percent
Diff.
>
RCRA
Form VIII (Continued) 4/86
ONE - 55
Revision o
Date September 1986
-------
PESTICIDE/PCS STANDARDS SUMMARY
Case No.,
Laboratory Name.
QC Column
QC Instrument ID
1
COMPOUND
alpha -BHC
beta-BHC
delta -BHC
gamma -BHC
Heptachlor
AWrin
Heptachlor Epoxidc
Endosulfan I .
Dieldrin
4.4'-DOE
Endrin
Endosulfan I
4,4'-DOD
Endrin Aldehyde
Endosulfan Sulfate
4, 4"- DDT
Methoxychlor
Endrin Ketone
Tech. Chlordane
alpha-Chlordane
gamma-Chlordane
Toxaphene
Aroclor - 1 0 1 6
Aroclor - 1 ZZ 1
Aroclor- 1232
Aroclor - 1 24 .
Aroclor - 1 248
Aroclor - 1 254
Aroclor - 1 260
DATE OF AN
TIME OF AN*
LABORATORY
RT
Al YRIft
1 YSIS
tm
RETENTION
TIME
WINDOW
CALIBRATION
FACTOR
CONF.
OR
QUANT.
DATE OF AN;
TIME OF AN/I
LABORATOR'
RT
HI VRIR
1 YRIR
nn
CALIBRATION
FACTOR
CONF.
OR
QUANT.
PERCENT
DIFF.**
I
Ul
O 70
fa n
n- <
n ->
00
GO o
IO
00
** CONF. = CONFIRMATION (<2Q%
OUANT.=OUANTITATION (-=15%
IX
-------
Case No.
Pestlclde/PCB Identification
Laboratory Name.
o
m
I
01
O 77
O> (D
GO O
(T> 3
a
r+
a>
(D
to
oo
CTl
SAMPLE
10
PRIMARY
COLUMN
PESTICIDE/
PCB
RT OP
TENTATIVE
10
RT WINDOW
OF APPROPRIATE
STANDARD
CONFIRMATION
COLUMN
RT ON
CONFIRMATORY
COLUMN
RT WINDOW OF
APPROPRIATE
STANDARD
GC/MS
CONFIRMED
-------
CHAPTER TWO
CHOOSING THE CORRECT PROCEDURE
2.1 PURPOSE
This chapter aids the analyst in choosing the appropriate methods for
samples, based upon sample matrix and the analytes to be determined.
2.2 REQUIRED INFORMATION
In order to choose the correct combination of procedures to form the
appropriate analytical method, some basic information is required.
2.2.1 Physical State(s) of Sample
The phase characteristics of the sample must be known. There are several
general categories of phases 1n which the sample may be categorized:
o Aqueous
o Oil and Organic Liquid
o Sludges
o Solids
o Multiphase Samples
o EP and TCLP Extracts
o Ground Water.
2.2.2 Analytes
Analytes are divided into classes based on the determinative methods
which are used to identify and quantify them. The organic compounds are
divided into different groups as indicated by Tables 2-1 through 2-14. Some
of the analytes appear on more than one table, as they may be determined using
any of several methods.
2.2.3 Detection Limits Required
Regulations may require a specific sensitivity or detection limit for an
analysis, as in the determination of analytes for the Extraction Procedure
(EP) or for delisting petitions. Drinking water detection limits, for those
specific organic and metallic analytes covered by the National Interim Primary
Drinking Water Standards, are desired in the analysis of ground water. Table
2-15 lists those analytes which are determined under the ground water
monitoring guidance. It also includes detection limits for ground water
monitoring and for the EP and TCLP procedures.
TWO - 1
Revision
Date September 1986
-------
2.2.4 Analytical Objective
Knowledge of the analytical objective will be useful 1n the choice of
sub-sampling procedures and 1n the selection of a determinative method. This
is especially true when the sample has more than one phase. Knowledge of the
analytical objective may not be possible or desirable at all management
levels, but that information should be transmitted to the analytical
laboratory management to ensure that the correct techniques are being applied
to the analytical effort.
2.2.5 Detection and Monitoring
The strategy for detection of compounds in environmental or process
samples may be contrasted with the strategy for monitoring samples. Detection
samples define initial conditions. When there 1s little information available
about the composition of the sample source, e.g., a well or process stream,
mass spectral identification of organic analytes leads to fewer false positive
results. Thus, the most practical form of detection for organic analytes,
given the analytical requirements, 1s mass spectral Identification. The
choice of technique for metals is governed by the detection limit requirements
and potential interferents.
Monitoring samples, on the other hand, are analyzed to confirm existing
and on-going conditions, tracking the presence or absence of constituents 1n
an environmental or process matrix. A less compound(s)-speciflc detection
mode may be used because the matrix and the analytical conditions are well
defined and stable.
2.2.6 Sample Containers, Preservations, and Holding Times
Appropriate sample containers, sample preservation techniques, and sample
holding times are listed in Table 2-16, at the end of this chapter.
2.3 IMPLEMENTING THE GUIDANCE
The choice of the appropriate sequence of methods depends on the
information required and on the analyst's experience. Figure 2-1 summarizes
the organic analysis options available. Appropriate selection 1s confirmed by
the quality control results. The use of the recommended procedures, whether
they are approved or mandatory, does not release the analyst from
demonstrating the correct execution of the method.
2.3.1 Determinative Procedures
The determinative methods for organic analytes have been divided into
three categories, shown in Figure 2-2: gas chromatography (GC); gas
chromatography/mass spectrometry (GC/MS); and high pressure liquid
chromatography (HPLC). This division 1s intended to help an analyst choose
which determinative method will apply. Under each analyte column, SW-846
method numbers have been Indicated, if appropriate, for the determination of
the analyte. A blank has been left If no chromatographic determinative method
is available.
TWO - 2
Revision
Date September 1986
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VolMilt
Pnysfcel Characteristic
ol
Sample
Aqueous Liquid I
h
Sample to
be Analyzed lor
Extractabtesor
Volitiloi?
Ex tractable
Sample Prtpmtion:
S030orS040
I Solid. Oil or Sludge
Sempte Preparation:
5030
Sludge
Physical Characteristic
ol
Sempte
Oil
Aqueous Liquid I
Solid
No
Extraction Procedure:
3520. 3540 n
rt- <
n -*
00 O
n 3
a
r*
n
HPLC Analysis Procedure:
Polynuckar Aromatic Hydrocarbons:
GC Analysis Procedures:
8310
Phthalate Esters:
Orojnochlorine Pesticides and PCB's.
Nitroeromatica end Cyclic Ketones:
Polynucteei Aromatic Hydrocartxxis:
Cnlorinated Hydrocarbons:
Orgenopnoiphorous Pesticides:
Chlorinated HerbicidM:
8040
8060
6080
8090
8100
8120
8140
8150
GC/MS
GC/MS Procedures:
Packed Column: 8250
Capillary Column: 8270
VO
CO
Figure 2-1. Organic Analysis Options
-------
O XI
Oi O
rt- <
n ->
CO
(/> o"
^? =3
a
r+
n
OC/MS
Determination
Methods
Specific
Detection
MnleOQS
HPIC
Seat volatile Organic Compounds
PhMMlS
8270
8250
8040
Acids
8270
8250
Withal ate
EsUrs
8270
8250
8060
Nltro-
reMtlcs 4
Cyclic
Ketonet
8270
8250
8090
Polyarauttc
hydrocaftons
8270
8250
8100
8310
Chlorinated
8270
8250
8120
Base/Neutral
8270
8250
Organo-
pnosphorous
P*st1c1d»s
8270*
8140
Org*m-
cblerliw
PMttcldw
t PCBs
8270*
8080
ChtorlnaUd
Hwblcldts
8270*
8150
This Mtftod ts m lUrratlv* conflrMtlen Mthod. It Is not tlw wttod of choice.
Figure 2-2. D«tera1nat1on of Organic Analytes.
-------
o
O 73
01
r+ <
n -
(/>
4*
CO O
n 3
o
GC/MS
Determination
Methods
Specific
Detection
Methods
HPLC
Volatile Organic Compounds
Halogenated
Volatile:
8240
8010
Non-
halogenated
Volatlles
8240
8015
Aromatic
Volatlles
8240
8020
Acroleln
Acrylonltrlle
Acetonltrlle
8240
8030
Volatile
Organlcs
8240
Figure 2-2. Determination of Organic Analytes. (Continued)
-------
Generally, the MS procedures are more specific but less sensitive than
the appropriate gas chromatographlc/speclflc detection method.
Method 8140, for organophosphorous pesticides, and Method 8150, for
chlorinated herbicides, are preferred to GC/MS because of the combination of
selectivity and sensitivity of the fUme photometric and electron capture
detectors.
Methods 8250 and 8270 are both semi volatile GC/MS methods. Method 8250
uses a packed column whereas Method 8270 employs a capillary column. Better
chromatographlc separation of the semi volatile compounds may be obtained by
using Method 8270 rather than 8250. Performance criteria will be based on
Method 8270.
For volatile organic compounds, Method 8240 is the determinative
procedure. Method 5030 has been combined with Method 8240, with which 1t was
used exclusively. A GC with a selective detector is also useful for the
determination of volatile organic compounds in a monitoring scenario,
described in Section 2.2.5.
Method 8000 gives a general description of the method of gas
chromatography. This method should be consulted prior to application of any
of the gas chromatographlc methods.
2.3.2 Cleanup Procedures
Each category in Figure 2-3, Cleanup of Organic Analyte Extracts,
corresponds to one of the possible determinative methods available 1n the
manual. Cleanups employed are determined by the analytes of interest within
the extract. However, the necessity of performing cleanup may also depend
upon the matrix from which the extract was developed. Cleanup of a sample may
be done exactly as instructed in the cleanup method for some of the analytes.
There are some instances when cleanup using one of the methods may only
proceed after the procedure 1s modified to optimize recovery and separation.
Several cleanup techniques may be possible for each analyte category. The
information provided 1s not meant to imply that any or all of these methods
must be used for the analysis to be acceptable. Extracts with components
which Interfere with spectral or chromatographlc determinations are expected
to be subjected to cleanup procedures.
The analyst's discretion must determine the necessity for cleanup
procedures, as there are no clear cut criteria for Indicating their use.
Method 3600 and associated procedures should be consulted for further details
on employing cleanup procedures.
2.3.3 Extraction and Sample Preparation Procedures
Methods for preparing organic analytes are shown 1n Figure 2-4. Method
3500 and associated procedures should be consulted for further details on
preparing the sample for analysis.
TWO - 6
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Date September 1986
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§
I
-J
Pnonois
3630
3640
3650
Acids
3640
3650
Phthalate
Esters
3610
3620
3640
Hltro-
aronatlcs &
Cyclic
Ketones
3620
3640
Polyaromtlc
hydrocarbons
3611
3630
3640
Chlorinated
hydrocarbons
3620
3640
Base/Neutral
3620
3640
3650
3660
Organo-
phosphorous
Pesticides
3620
3640
Organo-
chlorlne
Pesticides
& PCBs
3620
3640
3660
Chlorinated
Herbicides
8150
O 73
o> n
rf <
n ->'
n
a
oo
Cfi
Figure 2-3. Cleanup of Organic Analyte Extracts.
-------
I
CO
o yo
& n
n- <
n -
co o
fl> 3
a
r+
n
Aqueous
PH3
Solids
Aqueous
Emulsions1
Sludges
PH3
Solids
Oils
Phenol s
3510
3520
I2
3540
3550
35802
3520
<2
3650
35802
Adds
3510
3520
I2
3540
3550
35802
3520
<2
3650
35802
Phthalate
Esters
3510
3520
Neutral
3540
3550
35802
3520
Neutral
35802
NHro-
aromatlcs &
Cyclic
Ketones
3510
3520
5-9
3540
3550
35802
» Aqueous Abo\
3520
5-9
»e Solids Abov<
35802
Polyaromatlc
hydrocarbons
3510
3520
Neutral
3540
3550
35802
3520
Neutral
3560
35802
Chlorinated
hydrocarbons
3510
3520
Neutral
3540
3550
35802
3520
Neutral
35802
Base/Neutral
3510
3520
>11
3540
3550
35802
3520
>u
3650
35802
attempts to break up emulsions are unsuccessful, this method may be used.
2Waste dilution, Method 3580, 1s only appropriate 1f the sample Is soluble In the specified solvent.
3pH at which extraction should be performed.
Figure 2-4. Preparation Methods for Organic Analytes.
-------
I
I
vo
O 73
a* n
rt <
n
CO
co o'
rt> =1
Aqueous
pH*
Solids
Aqueous
Emulsions1
Sludges
pH3
Solids
Oils
Organo-
phosphorous
Pesticides
3510
3520
6-8
3540
3550
35802
3520
6-8
35802
Organo-
chlorlne
Pesticides
& PCBs
3510
3520
5-9
3540
3550
35802
3520
5-9
35802
Chlorinated
Herbicides
8150
<2
8150
35802
8150
<2
35802
Halogenated
Vol allies
5030
5030
5030
5030
Non-
halogenated
Vol allies
5030
5030
5030
5030
Aromatic
Vol allies
5030
5030
5030
5030
Acroleln
Acrylonltrlle
Acetonltrlle
5030
5030
5030
5030
Volatile
Organlcs
5030
5030
5030
5030
O)
VO
OO
Figure 2-4. Preparation Methods for Organic Analytes. (Continued)
-------
2.3.3.1 Aqueous Samples
The choice of a preparative method depends on the sample. Methods 3510
and 3520 may be used for extraction of the semi volatile organic compounds.
Method 3510, a separatory funnel extraction, 1s appropriate for samples which
will not form a persistent emulsion interphase between the sample and the
extraction solvent. The formation of an emulsion that can not be broken up by
mechanical techniques will prevent proper extraction of the sample. Method
3520, a liquid-liquid continuous extraction, may be used for any aqueous
sample; this method will minimize emulsion formation.
2.3.3.1.1 Basic or Neutral Extraction of Semivolatiles
The solvent extract obtained by performing either Method 3510 or 3520 at
a neutral or basic pH will contain the compounds of Interest. Refer to Table
1 in the extraction methods (3510 and/or 3520) for guidance on the extraction
pH requirements for analysis.
2.3.3.1.2 Acidic Extraction of Phenols and Acids
The extract obtained by performing either Method 3510 or 3520 at
pH 2 will contain the phenols and add extractables.
2.3.3.2 Solid Samples
Soxhlet (Method 3540) and sonlcatlon (Method 3550) extraction are used
with solid samples. Consolidated samples should be ground finely enough to
pass through a 9.5 mm sieve. In limited applications, waste dilution (Method
3580) may be used if the entire sample is soluble in the specified solvent.
Method 3540 and 3550 are neutral-pH extraction techniques and therefore,
depending on the analysis requirements, acid-base partition cleanup (Method
3650) may be necessary. Method 3650 will only be needed 1f chromatograpMc
interferences are severe enough to prevent detection of the analytes of
interest. This separation will be most important if a GC method is chosen for
analysis of the sample. If GC/MS is used, the 1on selectivity of the
technique may compensate for chromatographic interferences.
2.3.3.3 011s and Organic Liquids
Method 3580, waste dilution, may be used and the resultant sample
analyzed directly by GC or GC/MS. To avoid overloading the analytical
detection system, care must be exercised to ensure that proper dilutions are
made. Method 3580 gives guidance on performing waste dilutions.
To remove Interferences, Method 3611 may be performed on an oil sample
directly, without prior sample preparation.
Method 3650 1s the only other preparative procedure for oils and other
organic liquids. This procedure 1s a back extraction Into an aqueous phase.
It 1s generally Introduced as a cleanup procedure for extracts rather than as
a preparative procedure. Oils generally have a high concentration of
semi volatile compounds and, therefore, preparation by Method 3650 should be
done on a relatively small aliquot of the sample. Generally, extraction of 1
ml of oil will be sufficient to obtain a saturated aqueous phase and avoid
emulsions.
TWO - 10
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Date September 1986
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2.3.3.4 Sludge Samples
There 1s no set ratio of liquid to solid which enables the analyst to
determine which of the three extraction methods cited Is the most appropriate.
If the sludge 1s an organic sludge (solid material and organic liquid, as
opposed to an aqueous sludge), the sample should be handled as a multiphase
sample.
Determining the appropriate methods for analysis of sludges 1s
complicated because of the lack of precise definition of sludges with respect
to the relative percent of liquid and solid components. They may be
classified Into three categories but with appreciable overlap.
2.3.3.4.1 Liquids
Use of Method 3510 or Method 3520 may be applicable to sludges that
behave like and have the consistency of aqueous liquids. Ultrasonlcation
(Method 3550) and soxhlet (Method 3540) procedures will, most likely, be
Ineffective because of the overwhelming presence of the liquid aqueous phase.
2.3.3.4.2 Solids
Soxhlet (Method 3540) and sonlcatlon (Method 3550) will be more effective
when applied to sludge samples that resemble sol Ids. Samples may be dried or
centrlfuged to form solid materials for subsequent determination of
semi volatile compounds.
Using Method 3650, Acid-Base Partition Cleanup, on the extract may be
necessary, depending on whether chromatographlc Interferences prevent
determination of the analytes of Interest.
2.3.3.4.3 Emulsions
Attempts should be made to break up and separate the phases of an
emulsion. Several techniques are effective 1n breaking emulsions or
separating the phases of emulsions.
1. Freezing/thawing: Certain emulsions will separate 1f exposed
to temperatures below 0*C.
2. Salting out: Addition of a salt to make the aqueous phase of
an emulsion too polar to support a less polar phase promotes
separation.
3. Centrlfugatlon: Centrifugal force may separate emulsion
components by density.
4. Addition of water or ethanol: Emulsion polymers maybe
destabilized when a preponderance of the aqueous phase Is
added.
If techniques for breaking emulsions fall, use Method 3520. If the
emulsion can be broken, the different phases (aqueous, solid, or organic
liquid) may then be analyzed separately.
TWO - 11
Revision 0
Date September 1986
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2.3.3.5 Multiphase Samples
Choice of the procedure for sub-sampling multiphase samples 1s very
dependent on the objective of the analysis. With a sample 1n which some of
the phases tend to separate rapidly, the percent weight or volume of each
phase should be calculated and each phase.should be Individually analyzed for
the required analytes. The appropriate sample matrix figure should be
consulted.
An alternate approach Is to obtain a homogeneous sample and attempt a
single analysis on the combination of phases. This approach will give no
information on the abundance of the analytes 1n the Individual phases other
than what can be implied by solubility.
A third alternative 1s to select phases of interest and to analyze only
those selected phases. This tactic must be consistent with the sampling/
analysis objectives or it will yield insufficient information for the time and
resources expended. The phases selected should be compared with Figures 2-1
through 2-4 for further guidance.
2.4 CHARACTERISTICS
Figure 2-5 outlines the testing sequence for determining 1f a waste 1s
hazardous by characteristics.
2.4.1 EP and TCLP extracts
The leachate obtained from using either the EP (Figure 2-6A) or the TCLP
(Figure 2-6B) is an aqueous sample and, therefore, requires further solvent
extraction prior to the analysis of semi volatile compounds. Figure 3 gives
further information on aqueous sample extraction.
The TCLP leachate is solvent extracted with methylene chloride at a
pH >11 by either Method 3510 or 3520. Method 3510 should be used unless the
formation of emulsions between the sample and the solvent prevent proper
extraction. If this problem 1s encountered, Method 3520 should be employed.
The solvent extract obtained by performing either Method 3510 or 3520 at
a basic or neutral pH will contain the base/neutral compounds of Interest.
Refer to the specific determinative method for guidance on the extraction pH
requirements for analysis. When all sem1volat1le analytes are being
determined, the pH 1s then made acidic and the extraction is repeated (Method
3510 or 3520).
Due to the high concentration of acetate 1n the TCLP extract, it is
recommended that purge-and-trap/GC/MS, Method 8240, be used to Introduce the
volatile sample Into the gas chromatograph.
TWO - 12
Revision 0
Date September 1986
-------
Figure 2-5. Schematic of Sequence of Testing to Determine
If a Waste 1s Hazardous by Characteristics.
TWO - 13
Revision 0
Date September 1986
-------
Figure 2-5. (Continued).
TWO - 14
Revision 0
Date September 1986
-------
3010
6010
As
Ba
Cd
Cr
Pb
Ag
Se
Sample
1310
7470
Hg
3510
Neutral
8080
Pesticides
Figure 2-6A. EP.
8150
Herbicides
TWO - 15
Revision 0
Date September 1986
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3010
6010
As
Ba
Cd
Cr
Pb
Ag
Se
7470
Hg
Sample
TCLP
3510
Neutral
8080
Pesticides
3510
(Addle and
Basic)
8270
Semi volatile
Organlcs
8240
Volatile
Organlcs
Figure 2-6B. TCLP.
8150
Herbicides
TWO - 16
Revision 0
Date September 1986
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2.5 GROUND WATER
Appropriate analysis schemes for the determination of analytes 1n ground
water are presented In Figures 2-7A, 2-7B, and 2-7C. Quant1tat1on limits for
the metallic analytes should correspond to the drinking water limits which are
available. These are presented, along with the quantitative limits for
herbicides and anlons, 1n Table 2-15. Nominal detection limits achievable for
volatile organic compounds and the semi-volatile compounds are given, based on
the Indicated methods for ground water monitoring.
2.5.1 Special Techniques for Metal Analytes
All atomic absorption analyses should be performed using Zeeman or Smith-
Hi eftje background correction. These types of background correction will
allow analysis for low level selenium In the presence of high levels of Iron.
They are superior to the deuterium arc background correction technique.
All graphite furnace atomic absorption (GFAA) analyses should be
performed using the Lvov platform technique. This technique reduces matrix
Interferences and should Improve the results for those elements analyzed by
furnace atomic absorption.
Cadmium and antimony should be determined by GFAA. These two elements
are analyzed by GFAA to achieve lower detection limits. Typical GFAA
detection limits for antimony and cadmium are 3 ug/L and 0.1 ug/L, compared to
60 ug/L and 3 ug/L by ICP.
All furnace atomic absorption analysis should be carried out using the
exact matrix modifiers listed below. (See also the appropriate methods.)
Element(s) Modifier
As and Se Nickel Nitrate
Pb Phosphoric Add
Cd Ammonium Phosphate
Sb Ammonium Nitrate
Tl Platinum/Palladium
The ICP calibration standards must match the add composition and
strength of the adds contained 1n the samples. Add strengths 1n the ICP
calibration standards should be stated In the raw data.
2.5.2 Special Techniques for Indicated Analytes and Anlons
If an Auto-Analyzer 1s used to read the cyanide distillates, the
spectrophotometer must be used with a 50-mrn path length cell. If a sample 1s
found to contain cyanide, the sample must be redistilled a second time and
analyzed to confirm the presence of the cyanide. The second distillation must
fall within the 14-day holding time.
TWO - 17
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Date September 1986
-------
VGA
8240
Semivolatile
3510 or 3520
8270
Organic Sample
Pesticides
3510 or 3520
Neutral
3620. 3640
and/or 3660
8080
Herbicides
8150
Dloxlns
8280
^Optional: Cleanup required only If Interferences prevent analysis.
Figure 2-7A. Ground Water Analysis.
TWO - 18
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Date September 1986
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Indicator Analyte
POC
POX
3 Br-
Ion Chromatography
Ion Chromatography
NH3
Ion Chromatography
9060
TOC
9020
TOX
3 Cl-
Ion Chromatography
3 N02/N03
Ion Chromatography
9010
CN-
9066
Phenollcs
Barcelona, 1984 (See Reference 1)
2R1gg1n, 1984 (See Reference 2)
3McKee, 1984 (See Reference 3)
Field Tests
Specific
Conductance
PH
Figure 2-7B. Indicator Analyte.
TWO - 19
Revision 0
Date September 1986
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Sample
3005
3005*
6010 or
FLAA
Ba
Ag 1
Sb
Cr
Co
Mg
Al
Fe
Mn
Zn
Cu
Ni
7131
Cd
7740
Se
7060
As
7041
Sb
7421
Pb
7841
Tl
7470
Hg
*Graphite Furnace Atomic Absorption Is required to achieve detection
limits.
Figure 2-7C. Ground Water.
TWO - 20
Revision 0
Date September 1986
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2.6 REFERENCES
1. Barcelona, M.J., TOC Determinations In Ground Water, Ground Water 22(1).
pp. 18-24 (1984).
2. Riggin, R., et al., Development and Evaluation of Methods for Total
Organic Hallde and Purgeable Organic Hallde 1n Wastewater, Environmental
Monitoring and Support Laboratory, Cincinnati, OH, EPA 600/4-84-008, 1984.
3. McKee, G., et al., Determination of Inorganic Anlons 1n Water by Ion
Chromatography, EPA 600/4-87-017 (Technical addition to Methods for Chemical
Analysis of Water and Wastewater, EPA 600/4-79-020), Environmental Monitoring
and Support Laboratory, Cincinnati, OH, 1984.
TWO- 21
Revision
Date September 1986
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Table 2-1: Phenols and Organic Adds
Benzole acid
Benzyl alcohol
2-sec-Buty1-4,6-d1n1trophenol (DNBP)
4-Chloro-3-methylphenol
2-Chlorophenol
Cresol (methyl phenols)
2-Cyclohexyl-4,6-d1n1trophenol
2,4-Dlchlorophenol
2,6-Dichlorophenol
2,4-Dimethyl phenol
4,6-Di nitro-o-cresol
2,4-D1nitrophenol
2-Methy1-4,6-d1nitrophenol
2-N1trophenol
4-N1trophenol
Pentachlorophenol
Phenol
Tetrachlorophenols
Trlchlorophenols
Table 2-2: Phthalate Esters
Benzyl butyl phthalate
B1s(2-ethy1hexy1)phthalate
D1ethyl phthalate
Dl-n-butyl phthalate
Dimethyl phthalate
D1-n-octyl phthalate
Table 2-3: N1troaromat1cs and Cyclic Ketones
D1nitrobenzene
2,4-D1n1trotoluene
2,6-D1n1trotoluene
Isophorone
Naphthoqulnone
Nitrobenzene
TWO - 22
Revision
Date September 1986
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Table 2-4: Polyaromatic Hydrocarbons
Acenaphthene
Acenaphthylene
Anthracene
Benzo(a)anthracene
Benzo(a)pyrene
Benzo(b)f1uoranthene
Benzo(j)fl uoranthene .
Benzo(k)f1uoranthene
Benzo(g,h,1)perylene
Chrysene
D1benz(a,h)acr1d1ne
D1benz(a,j)acr1d1ne
01benz(a,h)anthracene (D1benzo(a,h)anthracene)
7H-D1benzo(c,g)carbazole
D1benzo(a,e)pyrene
D1benzo(a,h)pyrene
D1benzo(a,1)pyrene
Fluoranthene
Fluorene
Indeno(l,2,3-cd)pyrene
3-Methylcholanthrene
Naphthalene
Phenanthrene
Pyrene
Table 2-5: Chlorinated Hydrocarbons
Benzotr1chlor1de
Benzyl chloride
2-Chloronaphthal ene
Dlchlorobenzenes
D1chloromethy1 benzenes (D1chlorotoluenes)
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclohexane
Hexachlorocyclopentadlene
Hexachloroethane
Pentachlorohexane
Tetrachlorobenzenes
Trlchlorobenzenes
TWO - 23
Revision
Date September 1986
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Table 2-6: Base/Neutral
Acenaphthene
Acenaphthylene
Acetophenone
Aldrln
Aniline
Anthracene
4-Am1nob1phenyl
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
Aroclor-1260
Benz1d1ne
Benzo(a)anthracene
Benzo(b)f1uoranthene
Benzo(k)f1uoranthene
Benzo(g,h,1)pery1ene
Benzo(a)pyrene
a-BHC
0-BHC
5-BHC
7-BHC
B1s(2-chloroethoxy)methane
B1s(2-chloroethy1)ether
81s(2-chlorolsopropyl)ether
B1s(2-ethy1hexy1)phthalate
4-Bromophenyl phenyl ether
Butyl benzyl phthalate
Chlordane
4-Chloroan1l1ne
1-Chloronaphthalene
2-Chloronaphthalene
4-Chlorophenyl phenyl ether
Chrysene
4,4'-DDD
4,4'-DDE
4,4'-DDT
D1benz(a,j)acr1d1ne
D1benz(a,h)anthracene
Dlbenzofuran
D1-n-butyl phthalate
1,3-D1chlorobenzene
1,4-Dlchlorobenzene
1,2-D1ch1orobenzene
3,3'-D1chlorobenz1d1ne
Dleldrln
D1ethyl phthalate
p-D1methyl aminoazobenzene
7,12-D1methy1benz(a)anthracene
a-,a-D1methylphethy1 amine
Dimethyl phthalate
2,4-D1n1trotoluene
2,6-D1n1trotoluene
D1phenylamine
1,2-D1phenylhydrazlne
D1-n-octyl phthalate
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrin
Endrln aldehyde
Endrln ketone
Ethyl methanesulfonate
Fluoranthene
Fluorene
2-Fluorob1phenyl
Heptachlor
Heptachlor epoxlde
Hexachlorobenzene
Hexachlorobutadlene
Hexachlorocyclopentadlene
Hexachloroethane
Indeno(l,2,3-cd)pyrene
Isphorone
Methoxychlor
3-Methylcholanthrene
Methyl methanesulfonate
2-Methy1naphthalene
Naphthalene
l-Naphthylam1ne
2-Naphthylam1ne
2-N1troan1l1ne
3-N1troan1l1ne
4-N1troan1l1ne
Nitrobenzene
N-N1troso-d1-n-buty1 amine
N-N1trosodlmethyl amine
N-N1trosodlphenylamine
N-N1trosodlpropy1 amine
N-N1trosop1per1d1ne
Pentachlorobenzene
Pentachloronltrobenzene
Phenacetln
Phenanthrene
2-P1col1ne
Pronamlde
Pyrene
1,2,4,5-Tetrachlorobenzene
1,2,4-Trlchlorobenzene
Toxaphene
TWO - 24
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Date September 1986
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Table 2-7: Organophosphorous Pesticides
Azlnphos methyl
Bolstar (Sulprofos)
Chlorpyrlfos
Coumaphos
Demeton
Diazinon
Dlchlorvos
Dlmethoate
Dlsulfoton
EPN
Ethoprop
Fensulfothlon
Fenthlon
Malathlon
Merphos
Mevlnphos
Monochrotophos
Naled
Parathlon
Parathion methyl
Phorate
Ronnel
Stlrophos (Tetrachlorvlnphos)
Sulfotepp
TEPP
Tokuthlon (Prothlofos)
Trlchloronate
TWO - 25
Revision
Date September 1986
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Table 2-8: Organochlorlne Pesticides and PCB's
Aldrln
a-BHC
/J-BHC
ff-BHC
7-BHC (Undane)
Chlordane
4,4'-DDD
4,4'-DDE
4,4'-DDT
D1eldr1n
Endosulfan I
Endosulfan II
Endosulfan sulfate
Endrln
Endrln aldehyde
Heptachlor
Heptachlor epoxlde
Kepone
Methoxychlor
Toxaphene
PCB-1016
PCB-1221
PCB-1232
PCB-1242
PCB-1248
PCB-1254
Aroclor-1016
Aroclor-1221
Aroclor-1232
Aroclor-1242
Aroclor-1248
Aroclor-1254
PCB-1260 (Aroclor-1260
Table 2-9: Chlorinated Herbicides
2,4-D
2,4-DB
2,4,5-T
2,4,5-TP (Sllvex)
Dalapon
Dlcamba
Dlchloroprop
Dlnoseb
MCPA
MCPP
TWO - 26
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Date September 1986
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Table 2-10: Halogenated Volatlles
Benzyl chloride
B1s(2-chloroethoxy)methane
B1s(2-chlorolsopropyl)ether
Bromobenzene
Bromodlchloromethane
Brompform
Bromomethane
Carbon tetrachlorlde
Chloracetaldehyde
Chloral
Chlorobenzene
Chloroethane
Chloroform
1-Chlorohexane
2-Chloroethyl vinyl ether
Chloromethane
Chloromethyl methyl ether
Chlorotoluene
Dlbromochloromethane
Dlbromomethane
1,2-01chlorobenzene
1,3-01chlorobenzene
1,4-D1chlorobenzene
01chlorodlf1uoromethane
1,1-01chloroethane
1,2-01chloroethane
1,1-01chloroethylene (Vinyl1dene chloride)
trans-1,2-01chloroethylene
01chloromethane
1,2-01chloropropane
1,3-01chloropropylene
1,1,2,2-Tetrachloroethane
1,1,1,2-Tetrachloroethane
Tetrachloroethylene
1,1,1-Trlchloroethane
1,1,2-Tr1chloroethane
Tr1chloroethylene
Tr1chlorof1uoromethane
Tr1chloropropane
Vinyl chloride
Table 2-11: Non-halogenated Volatlles
Aery1 amide
01 ethyl ether
Ethanol
Methyl ethyl ketone (MEK)
Methyl Isobutyl ketone (MIBK)
Paraldehyde (trlmer of acetaldehyde)
TWO - 27
Revision
Date September 1986
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Table 2-12: Aromatic VolatHes
Benzene
Chlorobenzene
1,2-D1chlorobenzene
1,3-D1chlorobenzene
1,4-D1chlorobenzene
Ethyl benzene
Toluene
Xylenes (Dimethyl benzenes)
Table 2-13: Aceton1tr1le, Acroleln, Acrylonltrlle
Aceton1tr1le
Acroleln (Propenal)
Acrylonltrlle
Table 2-14: Volatlles
Acetone
Acroleln
Acrylonltrlle
Benzene
Bromochloromethane
Bromodlchloromethane
4-Bromof1uorobenzene
Bromoform
Bromomethane
2-Butanone (Methyl ethyl ketone)
Carbon dlsulfide
Carbon tetrachloride
Chlorobenzene
Chlorodlbromomethane
Chloroethane
2-Chloroethyl vinyl ether
Chloroform
Chloromethane
Dlbromomethane
1,4-D1chloro-2-butane
D1chl orodlf1uoromethane
1,1-D1chloroethane
1,2-01chloroethane
1,1-01chloroethene
trans-1,2-01chloroethene
c1s-1,3-01chloropropene
trans-1,3-01chloropropene
1,4-01f 1uorobenzene
Ethanol
Ethyl benzene
Ethyl methacrylate
2-Hexanone
lodomethane
Methylene chloride
4-Methyl-2-pentanone
Styrene
1,1,2,2-Tetrachloroethane
Toluene
1,1,1-Trlchloroethane
1,1,2-Tri chloroethane
Tr1chloroethene
Tr1chlorof1uoromethane
1,2,3-Trlchloropropane
Vinyl acetate
Vinyl chloride
Xylene
TWO - 28
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Date September 1986
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Table 2-15: Ground Water Monitoring Detection Limits
Analyte Class
Specific Analyte
Detection Limit (ug/L
unless otherwise noted)
Volatile Organic Compounds
Semi volatile Base/Neutral
Extractable Compounds
Semi volatile Addle
Extractable Compounds
Metals
Alum1num
Antimony
Arsenic
Ban* urn
Beryl 11 urn
Cadmlurn
Calcium
Chromlurn
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercury
Nickel
Potassium
Selenium
Silver
Sodium
Thai 11 urn
Vanadium
Z1nc
10 ug/L (nominal)
20 ug/L (nominal)
20 ug/L (nominal)
200
60
10
200
5
2
5,000
10
50
25
100
5
5,000
15
0.
40
5,000
5
10
5,000
10
50
20
(continued on next page)
TWO - 29
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Date September 1986
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Table 2-15: Ground Water Monitoring Detection Limits (Continued)
Analyte Class
Specific Analyte
Detection Limit (ug/L
unless otherwise noted)
Herbicides, by Method 8150 (capillary column optional)
Chiorobenzllate
2,4-D
2,4,5-TP
2,4-DB
2,4,5-T
Sulfurous add, 2-
chloroethyl 2-[4-
(I,l-d1methyl)-
phenoxy]-1-methyl-
ethyl ester
D1ox1ns and Dlbenzofurans, by Method 8280
60
80
60
1.0
200
60
Anlons and Indicator Analyses
Bromide
Chloride
Cyanide
Fluoride
NH3
N1trate-N
N1tr1te-N
Phenol1cs
POC
POX
Sulfate
Sulflde
TOC
TOX
10 ppt per congener
1000
1000
10
1000
300
300
300
50
10
5
1000
1000
1000
5
TWO - 30
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Date September 1986
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TABLE 2-16. REQUIRED CONTAINERS, PRESERVATION TECHNIQUES, AND HOLDING TIMES
Name
Container
Preservation
Maximum holding time
Bacterial Tests;
Ooliforra, fecal and total P, G
Fecal streptococci P, G
Inorganic Tests;
Acidity P, G
Alkalinity P, G
Anmonia P, G
Biochemical oxygen demand P, G
Bromide P, G
Biochemical oxygen demand, P, G
carbonaceous
Chemical oxygen demand P, G
Chloride P, G
Chlorine, total residual P, G
Color P, G
Cyanide, total and amenable P, G
to chlorination
Fluoride P
Hardness P, G
Hydrogen ion (pH) P, G
Kjeldahl and organic P, G
nitrogen
Metals:
Chromium VI P, G
Marcury P, G
Matals, except chromium VI P, G
and mercury
Nitrate P, G
Nitrate-nitrite P, G
Nitrite P, G
Oil and grease G
Organic carbon P, G
Orthophosphate
Oxygen, Dissolved Probe
Winkler
Phenols
Phosphorus (elemental)
Phosphorus, total
Residue, total
Residue, Filterable
Residue, Nonfilterable (TSS) P, G
Residue, Settleable P, G
Residue, volatile P, G
Silica P
Specific conductance P, G
P, G
G Bottle and top
do
G only
G
P, G
P, G
P, G
Cool, 4°C, 0.008% NEL
Cool, 4°C, 0.008T "-
Cool, 4°C
Cool, 4°C
Cool, 4°C, 1LSO, to pH<2
Cool, 4°C L *
None required
Cool, 4°C
Cool, 4°C, 1LS04 to pH<2
None requirea
None required
Cool, 4°C
Cool, 4°C, NaOH to pH>12,
0.6g ascorbic acid
None required
HNQj to ptK2, H2S04 to pH<2
None required
Cool, 4°C, H2S04 to ptK2
Cool, 4°C
HNCL to pH<2
HNO: to pH<2
Cool, 4°C
Cool, 4°C, 1LSO, to pH<2
Cool, 4°C
Cool, 4°C, H,SO to pH<2
Cool, 4°C, m or ILSO, to
pH<2 L *
Filter immediately, cool, 4°C
None required
Fix on site and store in dark
Cool, 4°C, H,SO, to pH<2
Cool, 4°C i
Cool, 4°C, H-SO, to pHCZ
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
Cool, 4°C
6 hours
6 hours
14 days
14 days
28 days
48 hours
28 days
48 hours
28 days
28 days
Analyze Immediately
48 hours
14 days
28 days
6 months
Analyze immediately
28 days
24 hours
28 days
6 months
48 hours
28 days
48 hours
28 days
28 days
48 hours
Analyze immediately
8 hours
28 days
48 hours
28 days
7 days
7 days
7 days
48 hours
7 days
28 days
28 days
TWO - 31
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Date September 1986
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TABLE 2-16. REQUIRED CONTAINERS, PRESERVATION TECHNIQUES, AND HIDING TMS (CONTINUED)
Name
Container
Preservation
Maximo holding tine
Sulfate
Sulfide
Sulfite
Surfactants
Temperature
Turbidity
Organic Tests;
Purgeable Halocarbons
Purgeable aromatic
hydrocarbons
Acrolein and acrylonitrile
Phenols
Benzidines
Phthalate esters
Nitrosamines
PCBs, acrylonitrile
Nitroaromatics and
isophorone
Polynuclear aromatic
hydrocarbons
Haloethers
Chlorinated hydrocarbons
TCDD
Total organic halogens
Pesticides Tests;
Pesticides
Radiological Tests;
Alpha, beta and radium
P, G
P, G
P, G
P, G
P, G
P, G
G, Teflon-lined
septum
G, Teflon-lined
septum
G, Teflon-lined
septum
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
G, Teflon-lined cap
Cool, 4°C 28 days
Cool, 4°C, add zinc acetate 7 days.
plus sodium hydroxide to ptt>9
None required Analyze immediately
Cool, 4°C 48 hours
None required Analyze
Cool, 4°C 48 hours
Cool, 4°C, 0.008%
Cool, 4"C, 0.008% Na_S_0_,
HC1 to pH2
Cool, 4°C, 0.008% NauS 0 ,
Adjust pH to 4-5
Cool, 4°C, 0.008%
Cool, 4°C, 0.008% NauS 0
Cool, 4°C , .-.
Cool, 4°C, store in dark,
0.008%
Cool, 4°C
Cool, 4°C, 0.008%
store in dark
Cool, 4°C, 0.008% NcuS203
store in dark
Cool, 4°C, 0.008% Na S 0
Cool, 4°C ^ J
Cool, 4°C, 0.008% Na S 0
Cool, 4°C, HS0 to pTT<2
G, Teflon-lined cap Cool, 4°C, pH 5-9
P, G
to pHC2
14-days
14 days
14 days
7 days until extraction,
40 days after extraction
7 days until extraction
7 days until extraction
40 days after extraction
40 days after extraction
40 days after extraction
40 days after extraction
40 days after extraction
40 days after extraction
40 days after extraction
40 days after extraction
7 days
40 days after extraction
6 months
Polyethylene (P) or Glass (G)
TWO - 32
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CHAPTER THREE
METALLIC ANALYTES
3.1 SAMPLING CONSIDERATIONS
3.1.1 Introduction
This manual contains procedures for the analysis of metals 1n a variety
of matrices. These methods are written as specific steps 1n the overall
analysis scheme sample handling and preservation, sample digestion or
preparation, and sample analysis for specific metal components. From these
methods, the analyst must assemble a total analytical protocol which 1s
appropriate for the sample to be analyzed and for the Information required.
This Introduction discusses the options available in general terms, provides
background Information on the analytical techniques, and highlights some of
the considerations to be made when selecting a total analysis protocol.
3.1.2 Definition of Terms
Optimum concentration range; A range, defined by limits expressed 1n
concentration, below which scale expansion must be used and above which curve
correction should be considered. This range will vary with the sensitivity of
the instrument and the operating conditions employed.
Sensitivity; a) Atomic Absorption: The concentration 1n milligrams of
metal per liter that produces an absorption of 1%; b) ICP; The slope of the
analytical curve, I.e., the functional relationship between emission intensity
and concentration.
Method detection limit (MDL); The minimum concentration of a substance
that can Be measured and reported with 99% confidence that the analyte
concentration is greater than zero. The MDL 1s determined from analysis of a
sample 1n a given matrix containing analyte which has been processed through
the preparative procedure.
Total recoverable metals; The concentration of metals in an unflltered
sample following treatment with hot dilute mineral acid (Method 3005).
Dissolved metals; The concentration of metals determined in sample after
the sample is filtered through a 0.45-um filter (Method 3005).
e»
Suspended metals; The concentration of metals determined 1n the
portion of a sample that 1s retained by a 0.45-um filter (Method 3005).
Total metals; The concentration of metals determined 1n a sample
following digestion by Methods 3010, 3020, or 3050.
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Instrument detection limit; The concentration equivalent to a signal due
to the analyte whichIsequal to three times the standard deviation of a
series of 7 replicate measurements of a reagent blank's signal at the same
wavelength.
Interference check sample (ICP): A solution containing both Interfering
and analyteelementsoTKnown concentration that can be used to verify
background and Interelement correction factors.
Initial calibration verification standard; A certified (EPA or other) or
Independently prepared solution usedto verify the accuracy of the Initial
calibration. For ICP analysis, 1t must be run at each wavelength used 1n the
analysis.
Cont1nu1ng cal1bratlon verlf1 cat1on; Used to assure calibration accuracy
during each analysis run.It mustBerun for each analyte at a frequency of
10% or every 2 hrs during the run, whichever 1s more frequent. It must also
be analyzed at the beginning of the run and after the last analytical sample.
Its concentration must be at or near the mid-range levels of the calibration
curve.
Calibration standards; A series of known standard solutions used by the
analyst for calibration of the Instrument (I.e., preparation of the analytical
curve).
Linear dynamic range; The concentration range over which the analytical
curve remains linear.
Preparation blank; A volume of Type II water processed through each
sample preparation procedure.
Calibration blank; A volume of Type II water acidified with the same
amounts of adds as were the standards and samples.
Laboratory control standard; A volume of Type II water spiked with known
concentrations of analytes andcarried through the preparation and analysis
procedure as a sample. It 1s used to monitor loss/recovery values.
Method of standard addition; The standard-addition technique Involves
the use of the unknown and the unknown plus a known amount of standard. See
Method 7000, Section 8.7 for detailed Instructions.
Sample holding time; The storage time allowed between sample collection
and sample analysis when the designated preservation and storage techniques
are employed.
3.1.3 Sample Handling and Preservation
Sample holding times, digestion procedure and suggested collection
volumes are listed 1n Table 1. The sample volumes required depend upon the
number of different digestion procedures necessary for analysis. This may be TABLE 1.
THREE - 2
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AND RECOMMENDED COLLECTION VOLUMES FOR METAL DETERMINATIONS
Digestion
Vol. Req.a
Measurement (mL)
Collection
Volume (mL)D Preservative
Holding
Time
Metals (except hexavalent chromium and mercury):
Total recoverable
Dissolved
Suspended
Total
Chromium VI:
Mercury;
Total
Dissolved
100
100
100
100
100
100
100
600
600
600
600
400
400
400
HN03 to pH <2
Filter on site;
HNOa to pH <2
Filter on site
HN03 to pH <2
Cool , 4'C
HNOa to pH <2
Filter; HN03 to
PH<2
6 mo
6 mo
6 mo
6 mo
24 hr
28 days
28 days
aSo!1d samples must be at least 200 g and usually require no preservation
other than storing at 4*C until analyzed.
''Either plastic or glass containers may be used.
determined by the application of graphite-furnace atomic absorption
spectrometry (GFAA), flame atomic absorption spectrometry (FLAA), Inductively
coupled argon plasma emission spectrometry (ICP), hydride-generation atomic
absorption spectrometry (HGAA), or cold-vapor atomic absorption spectrometry
(CVAA) techniques, each of which may require different digestion procedures.
The Indicated volumes 1n Table 1 refer to that required for the Individual
digestion procedures and recommended sample collection volumes.
In the determination of trace metals, containers can Introduce either
positive or negative errors 1n the measurement of trace metals by (a)
contributing contaminants through leaching or surface desorptlon, and (b)
depleting concentrations through adsorption. Thus the collection and
treatment of the sample prior to analysis require particular attention. The
THREE - 3
Revision
Date September 1986
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following cleaning treatment sequence has been determined to be adequate to
minimize contamination 1n the sample bottle, whether borosHlcate glass,
linear polyethylene, polypropylene, or Teflon: detergent, tap water, 1:1
nitric acid, tap water, 1:1 hydrochloric add, tap water, and Type II water.
NOTE: Chromic acid should not be used to clean glassware, especially 1f
chromium 1s to be Included 1n the analytical scheme. Commercial,
non-chromate products (e.g., Nochromlx) may be used 1n place of
chromic add 1f adequate cleaning 1s documented by an analytical
quality control program. (Chromic add should also not be used
with plastic bottles.)
3.1.4 Safety
The toxldty or cardnogenlcity of each reagent used In this method has
not been precisely defined. However, each chemical compound should be treated
as a potential health hazard. From this viewpoint, exposure to these
chemicals must be reduced to the lowest possible level by whatever means
available. The laboratory 1s responsible for maintaining a current awareness
file of OSHA regulations regarding the safe handling of the chemicals
specified 1n this method. A reference file of material data-handling sheets
should also be made available to all personnel Involved 1n the chemical
analysis. Additional references to laboratory safety are available. They
are:
1. "Carcinogens - Working with Carcinogens," Department of Health,
Education, and Welfare, Public Health Service, Center for Disease
Control, National Institute for Occupational Safety and Health,
Publication No. 77-206, August 1977.
2. "OSHA Safety and Health Standards, General Industry" (29 CFR 1910),
Occupational Safety and Health Administration, OSHA 2206, revised
January 1976.
3. "Proposed OSHA Safety and Health Standards, Laboratories," Occupational
Safety and Health Administration, Federal Register, July 24, 1986, p. 26660.
4. "Safety 1n Academic Chemistry Laboratories," American Chemical Society
Publication, Committee on Chemical Safety, 3rd edition, 1979.
THREE - 4
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3.2 SAMPLE PREPARATION METHODS
The methods 1n SW-846 for sample digestion or preparation are as follows:
Method 3005 prepares ground water and surface water samples for total
recoverable and dissolved metals determination by FLAA or ICP. The unflltered
or filtered sample 1s heated with dilute HC1 and HN03 prior to metal determi-
nation.
Method 3010 prepares waste samples for total metal determination by FLAA
and ICP^ The samples are vigorously digested with nitric add followed by
dilution with hydrochloric add. The method 1s applicable to aqueous samples,
EP and mobility-procedure extracts.
Method 3020 prepares waste samples for total metals determination by
furnace GFAA. The samples are vigorously digested with nitric add followed
by dilution with nitric add. The method 1s applicable to aqueous samples, EP
and mobility-procedure extracts.
Method 3040 prepares oily waste samples for soluble metals determination
by AA and ICPmethods. The samples are dissolved and diluted 1n organic
solvent prior to analysis. The method 1s applicable to the organic extract In
the oily waste EP procedure and other samples high 1n oil, grease, or wax
content.
Method 3050 prepares waste samples for total metals determination by AA
and ICT^TResamples are vigorously digested 1n nitric acid and hydrogen
peroxide followed by dilution with either nitric or hydrochloric add. The
method 1s applicable to soils, sludges, and solid waste samples.
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METHOD 3005
ACID DIGESTION OF WATERS FOR TOTAL RECOVERABLE OR
DISSOLVED METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 Method 3005 1s an add digestion procedure used to prepare surface
water and ground water samples for analysis by flame atomic absorption
spectroscopy (FAA) or by Inductively coupled argon plasma spectroscopy (ICP).
Samples prepared by Method 3005 may be analyzed by AAS or ICP for the
following metals:
Aluminum Magnesium
Antimony Manganese
Arsenic* Molybdenum
Barium Nickel
Beryllium Potassium
Cadmium Selenium*
Calcium Silver
Chromium Sodium
Cobalt Thallium
Copper Vanadium
Iron Z1nc
Lead
*ICP only
1.2 For the analysis of total dissolved metals, the sample 1s filtered
at the time of collection, prior to acidification with nitric add.
2.0 SUMMARY OF METHOD
2.1 Total recoverable metals; The entire sample 1s acidified at the
time of collection with nitric add. At the time of analysis the sample 1s
heated with add and substantially reduced 1n volume. The dlgestate 1s
filtered and diluted to volume, and 1s then ready for analysis.
2.2 Dissolved metals; The sample 1s filtered through a 0.5 urn filter at
the time of collection and the liquid phase 1s then acidified at the time of
collection with nitric add. At the time of analysis the sample 1s heated
with add and substantially reduced 1n volume. The dlgestate 1s again
filtered (1f necessary) and diluted to volume and Is then ready for analysis.
3005 - 1
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Date September 1986
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3.0 INTERFERENCES
3.1 The analyst should be cautioned that this digestion procedure may
not be sufficiently vigorous to destroy some metal complexes.
4.0 APPARATUS AND MATERIALS
4.1 Griffin beakers of assorted sizes.
4.2 Watch glasses.
4.3 Qualitative filter paper and filter funnels.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Concentrated n1 trie add, reagent grade (HNOs): Add should be
analyzed to determine level of Impurities. If method blank 1s
-------
7.0 PROCEDURE
7.1 Transfer a 100-mL aliquot of well-mixed sample to a beaker.
7.2 For metals that are to be analyzed by FLAA or ICP, add 2 ml of
concentrated HN03 and 5 ml of concentrated HC1. The sample 1s covered with a
ribbed watch glass and heated on a steam bath or hot plate at 90 to 95*C until
the volume has been reduced to 15-20 ml.
CAUTION: Do not boll. Antimony Is easily lost by volatilization from
hydrochloric acid media.
7.3 Remove the beaker and allow to cool. Wash down the beaker walls
and watch glass with Type II water and, when necessary, filter or centrifuge
the sample to remove silicates and other Insoluble material that could clog
the nebulizer. Filtration should be done only 1f there 1s concern that
Insoluble materials may clog the nebulizer; this additional step 1s liable to
cause sample contamination unless the filter and filtering apparatus are
thoroughly cleaned and prerinsed with dilute HN03.
7.4 Adjust the final volume to 100 ml with Type II water.
8.0 QUALITY CONTROL
8.1 For each analytical batch of samples processed, blanks (Type II
water and reagents) should be carried throughout the entire sample preparation
and analytical process. These blanks will be useful 1n determining 1f samples
are being contaminated.
8.2 Duplicate samples should be processed on a routine basis. A
duplicate sample 1s a sample brought through the whole sample preparation and
analytical process. Duplicate samples will be used to determine precision.
The sample load will dictate the frequency, but 20% 1s recommended.
8.3 Spiked samples or standard reference materials should be employed to
determine accuracy. A spiked sample should be Included with each group of
samples processed and whenever a new sample matrix 1s being analyzed.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
3005 - 3
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METHOD 3005
AGIO DIGESTION OF WATERS FOR TOTAL RECOVERABLE OR
DISSOLVED METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY
7.1 1
Transfer
aliquot of
ample to
beaker
7.Z
»
concen.
metels i
by FLA/
7.2
Add
:oncan.
INOj and
HC1 for
malyzed
k or ICP
Heat sample to
reduce volume
7.3
Cool beaker:
filter If
necessary
7.4 j
Adjust final
volume
( stop J
3005 - 4
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Date September 1986
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METHOD 3010
ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS FOR
TOTAL METALS FOR ANALYSIS BY FLAA OR ICP SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 This digestion procedure is used for the preparation of aqueous
samples, EP and mobility-procedure extracts, and wastes that contain suspended
solids for analysis, by FLAA or ICP, for the metals listed below. The
procedure is used to determine total metals.
1.2 Samples prepared by Method 3010 may be analyzed by FLAA or ICP for
the following:
Aluminum Lead
Arsenic Magnesium
Barium Manganese
Beryl 11 urn Molybdenum
Cadmium Nickel
Calcium Potassium
Chromium Selenium
Cobalt Sodium
Copper Thallium
Iron Vanadium
Zinc
NOTE: See Method 7760 for FLAA preparation for Silver.
1.3 This digestion procedure is not suitable for samples which will be
analyzed by graphite furnace atomic absorption spectroscopy because
hydrochloric acid can cause interferences during furnace atomization.
2.0 SUMMARY OF METHOD
2.1 A mixture of HNOs and the material to be analyzed is refluxed in a
covered Griffin beaker. This step is repeated with additional portions of
HN03 until the digestate is light in color or until its color has stabilized.
After the digestate has been brought to a low volume, it is refluxed with HC1
and brought up to volume. If sample should go to dryness, it must be
discarded and the sample reprepared.
3.0 INTERFERENCES
3.1 Interferences are discussed in the referring analytical method.
3010 - 1
Revision
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Griffin beakers; 150-mL.
4.2 Watch glasses: Ribbed and plain.
4.3 Qualitative filter paper or centrjfugation equipment.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Concentrated nitric add, reagent grade (HN03): Add should be
analyzed to determine levels of Impurities. If method blank 1s
-------
7.2 Continue heating, adding additional add as necessary, until the
digestion 1s complete (generally Indicated when the dlgestate Is light 1n
color or does not change 1n appearance with continued refluxlng). Again,
uncover the beaker or use a ribbed watch glass, and evaporate to a low volume
(3 ml), not allowing any portion of the bottom of the beaker to go dry. Cool
the beaker. Add a small quantity of 1:1 HC1 (10 mL/100 ml of final solution)
and warm the beaker for an additional 15 m1n to dissolve any precipitate or
residue resulting from evaporation.
7.3 Wash down the beaker walls and watch glass with Type II water and,
when necessary, filter or centrifuge the sample to remove silicates and other
Insoluble material that could clog the nebulizer. Filtration should be done
only 1f there 1s concern that Insoluble materials may clog the nebulizer.
This additional step can cause sample contamination unless the filter and
filtering apparatus are thoroughly cleaned and prerlnsed with dilute HN03.
Adjust to the final volume of 100 ml with Type II water. The sample 1s now
ready for analysis.
8.0 QUALITY CONTROL
8.1 For each analytical batch of samples processed, blanks (Type II
water and reagents) should be carried throughout the entire sample-preparation
and analytical process. These blanks will be useful 1n determining If samples
are being contaminated.
8.2 Duplicate samples should be processed on a routine basis. A
duplicate sample 1s a sample brought through the whole sample preparation and
analytical process. Duplicate samples will be used to determine precision.
The sample load will dictate the frequency, but 20% 1s recommended.
8.3 Spiked samples or standard reference materials should be employed to
determine accuracy. A spiked sample should be Included with each group of
samples processed and whenever a new sample matrix Is being analyzed.
8.4 The method of standard addition shall be used for the analysis of
all EP extracts (see Method 7000, Section 8.7).
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
3010 - 3
Revision 0
Date September 1986
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METHOD 3010
AGIO DIGESTION PROCEDURE FOR FLAME ATOMIC ABSORPTION SPECTROSCOPY
7. 1
1 Transfer
aliquot at
sample to
beaker; add
cone. HN03
7. 1
e\
volumi
add cor
7.1
Ir
ten
creeti
ref lu>
7.2 C
until d!
Is cor
avapore
HC1: warn
4eat and
/aporate
tO low
;; cool:
1C . HNOj
Reheat.
icreaae
up . to
! gantla
c action
:ontlnue
icat Ing
oeatlon
iplete;
ite; add
> beaker
7.3 1
Filter If
necesaary and
adjust voluma
3010 - 4
Revision 0
Date September 1986
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METHOD 3020
ACID DIGESTION OF AQUEOUS SAMPLES AND EXTRACTS
FOR TOTAL METALS FOR ANALYSIS BY GFAA SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 This digestion procedure 1s used for the preparation of aqueous
samples, mobility-procedure extracts, and wastes that contain suspended sol Ids
for analysis by furnace atomic absorption spectroscopy (GFAA) for the metals
listed below. The procedure 1s used to determine the total amount of the
metal 1n the sample.
1.2 Samples prepared by Method 3020 may be analyzed by GFAA for the
following metals:
Beryllium Lead
Cadmium Molybdenum
Chromium Thallium
Cobalt Vanadium
NOTE: For the digestion and GFAA analysis of arsenic and selenium, see
Methods 3050, 7060, and 7740. For digestion and GFAA analysis of
silver, see Method 7761.
2.0 SUMMARY OF METHOD
2.1 A mixture of nitric acid and the material to be analyzed 1s refluxed
1n a covered Griffin beaker. This step is repeated with additional portions
of nitric add until the digestate 1s light 1n color or until Its color has
stabilized. After the digestate has been brought to a low volume, 1t 1s
cooled and brought up 1n dilute nitric acid such that the final dilution
contains 3% (v/v) HN03. If the sample contains suspended sol Ids, it must be
centrlfuged, filtered, or allowed to settle.
3.0 INTERFERENCES
3.1 Interferences are discussed 1n the referring analytical method.
4.0 APPARATUS AND MATERIALS
4.1 Griffin beakers; 150-mL.
4.2 Watch glasses.
4.3 Qualitative filter paper or centrifugation equipment.
3020 - 1
Revision
Date September 1986
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5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193) : Water should be monitored for
Impurities.
5.2 Concentrated ni trie add, reagent grade (HNOs) : Add should be
analyzed to determine levels of Impurities. If method blank is
-------
with Injecting the sample Into the graphite atomizer. (This additional step
can cause sample contamination unless the filter and filtering apparatus are
thoroughly cleaned and prerlnsed with dilute HN03.) Adjust to the final
volume of 100 ml with Type II water. The sample 1s now ready for analysis.
8.0 QUALITY CONTROL
8.1 For each group of samples processed, preparation blanks (Type II
water and reagents) should be carried throughout the entire sample preparation
and analytical process. These blanks will be useful in determining If samples
are being contaminated.
8.2 Duplicate samples should be processed on a routine basis. Duplicate
samples will be used to determine precision. The sample load will dictate the
frequency, but 20% is recommended.
8.3 Spiked samples or standard reference materials should be employed to
determine accuracy. A spiked sample should be Included with each group of
samples processed and whenever a new sample matrix 1s being analyzed.
8.4 The concentration of all calibration standards should be verified
against a quality control check sample obtained from an outside source.
8.5 The method of standard addition shall be used for the analysis of
all EP extracts. See Method 7000, Section 8.7, for further Information.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
3020 - 3
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METHOD 3020
AGIO DIGESTION FOR AQUEOUS SAMPLES AND EXTRACTS
PDA TOTAL METALS FOR ANALYSIS BY GFAA SPECTROSCOPY
7.1
Put
al iguot
of sample In
beaker: add cone
HNOj: evaporate
to low volume
7.1
dd cc
hei
gent]
actic
Cool
beaker;
>nc. HNO.:
it until
e reflux
>n occurs
7.Z
(
VI
1C
Heat to
complete
ligestion;
iporate to
>w volume:
cool
7.2
Typi
to dil
preclt
rt
Add
i II; worm
teolve any
(itate or
sldue
7.3 I
Filter
or centrifuge
if neceeeery;
ad)u*t volume
3020 - 4
Revision 0
Date September 1986
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METHOD 3040
DISSOLUTION PROCEDURE FOR OILS. GREASES. OR WAXES
1.0 SCOPE AND APPLICATION
1.1 Method 3040 1s used for the preparation of samples containing oils,
greases, or waxes for analysis by atomic absorption spectroscopy (AAS) or
Inductively coupled argon plasma emission spectroscopy (ICP) for the following
metals:
Antimony Iron
Beryl 11 urn Manganese
Cadmium Nickel
Chromium Vanadium
Copper
1.2 This method is a solvent dissolution procedure, not a digestion
procedure. This procedure can be very useful 1n the analysis of crude oil,
but with spent or used oil high 1n particulate material 1t Is less effective;
most particulate material is not dissolved, and therefore the analysis is not
a "total" metal determination. Because the highest percentage of metals 1s
expected to be contained in the particulate material, oil analysis using
Method 3040 will not provide an adequate estimate of the total metals
concentration.
2.0 SUMMARY OF METHOD
2.1 A representative sample 1s dissolved 1n an appropriate solvent
(e.g., xylene or methyl isobutyl ketone). Organometal11c standards are
prepared using the same solvent, and the samples and standards are analyzed by
AAS or ICP.
3.0 INTERFERENCES
3.1 Diluted samples and diluted organometallic standards are often
unstable. Once standards and samples are diluted, they should be analyzed as
soon as possible.
3.2 Solvent blanks should be used to rinse nebulizers thoroughly
following aspiration of high concentration standards or samples.
3.3 Viscosity differences can result 1n different rates of sample
introduction; therefore, all analyses shall be performed by the method of
standard addition. Peristaltic pumps often prove useful when analysis is
performed by ICP.
3040 - 1
Revision
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Volumetric glassware.
4.2 Balance.
4.3 Atomic absorption spectrometer; With an auxiliary oxldant control
and a mechanism for background correction.
4.4 Inductively coupled argon plasma emission spectrometer system; With
a mechanismfor background correctionandinterelementInterference
correction. A peristaltic pump 1s optional.
5.0 REAGENTS
5.1 Methyl Isobutyl ketone (MIBK).
5.2 Xylene.
5.3 Organometal11c standards (two possible sources are Conostan
Division, Conoco SpecialityProducts, Inc., P.O. Box 1267, Ponca City, OK
74601, and the U.S. Department of Commerce, National Bureau of Standards,
Washington, DC 20234).
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 Samples shall be stored In an undiluted state at room temperature.
6.3 Samples should be processed and analyzed as soon as possible.
7.0 PROCEDURE
7.1 Weigh out a 2-g representative sample of the waste or extract.
Separate and weigh the phases 1f more than one phase 1s present.
7.2 Weigh an aliquot of the organic phase and dilute the aliquot In the
appropriate solvent. Warming facilitates the subsampUng of crude-type oils
and greases and wax-type wastes. Xylene 1s usually the preferred solvent for
longer-chain hydrocarbons and for most analyses performed by ICP. The longer-
chain hydrocarbons usually require a minimum of a 1:10 dilution, and lighter
oils may require only a 1:5 dilution 1f low detection limits are required.
7.3 All metals must be analyzed by the method of standard additions.
Because the method of standard additions can account only for multiplicative
interferences (matrix or physical interferences), the analytical program must
3040 - 2
Revision 0
Date September 1986
-------
account for additive Interference (nonspecific absorption and scattering 1n
AAS and nonspecific emission and Interelement Interference 1n ICP) by
employing background correction.
7.4 Sample preparation for the method of standard additions can be
performed on a weight or volume basis. Sample allquots of viscous wastes
should be weighed. Weigh Identical amounts of the sample Into three wide-
mouth vials. Dilute the first vial such that the final concentration falls on
the lower end of the linear portion of the calibration curve and significantly
above the detection limit. Add sufficient standard to the second aliquot to
Increase the sample concentration by approximately 50*. Adjust the third
sample concentration so that 1t 1s approximately twice that of the first. The
second and third allquots are then diluted to the same final volume as the
first aliquot.
7.5 Set up and calibrate the analytical Instrumentation according to the
manufacturer's directions for nonaqueous samples.
7.6 Report data as the weighted average for all sample phases.
8.0 QUALITY CONTROL
8.1 Preparation blanks (e.g., Conostan base oil or mineral oil plus
reagents) should be carried through the complete sample-preparation and
analytical process on a routine basis. These blanks will be useful In
detecting and determining the magnitude of any sample contamination.
8.2 Duplicate samples should be processed on a routine basis. Duplicate
samples will be used to determine precision. The sample load will dictate the
frequency, but 20% 1s recommended.
8.3 Samples and standards should be diluted as closely as possible to
the time of analysis.
8.4 All analyses must be performed by the method of standard additions.
See Method 7000, Section 8.7, for further Information.
8.5 Data must be corrected for background absorption and emission and
Interelement Interferences.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
3040 - 3
Revision 0
Date September 1986
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METHOD 3040
DISSOLUTION PROCEDURE FOR OILS. GREASE. OR MAXES
Separate and
weigh phases
7.4
Weigh sample
into 3 vials:
dilute 1st vial: add
standard to 2nd vial
to increase cone. by
SOX: adjust 3rd vial
cone, to twice the
cone, of the 1st vial
7.4
Dilute
second and
third aliquota
to sama volume
as first
7.2
I Weigh
J aliquot
of organic
phase: dilute
with appropr.
solvent
7.S |
Set up
and calibrate
analytical
Instrumentation
7.3
i Analyze
netals by
standard
additions
nethod
7.6
Report data as
weighted
average
f stop J
3040 - 4
Revision 0
Date September 1986
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METHOD 3050
ACID DIGESTION OF SEDIMENTS, SLUDGES, AND SOILS
1.0 SCOPE AND APPLICATION
1.1 This method is an acid digestion procedure used to prepare sedi-
ments, sludges, and soil samples for analysis by flame or furnace atomic
absorption spectroscopy (FLAA and GFAA, respectively) or by inductively
coupled argon plasma spectroscopy (ICP). Samples prepared by this method may
be analyzed by ICP for all the listed metals, or by FLAA or GFAA as indicated
below (see also Paragraph 2.1):
Aluminum
Bari urn
Beryllium
Cadmi urn
Calcium
Chromium
Cobalt
Copper
Iron
Lead
FLAA
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Sodi urn
Thallium
Vanadium
Zinc
GFAA
Arsenic
Beryl 1i urn
Cadmi urn
Chromi urn
Cobalt
Iron
Molybdenum
Selenium
Thallium
Vanadium
2.0 SUMMARY OF METHOD
2.1 A representative 1- to 2-g (wet weight) sample is digested in nitric
acid and hydrogen peroxide. The digestate is then refluxed with either nitric
acid or hydrochloric acid. Dilute hydrochloric acid is used as the final
reflux acid for (1) the ICP analysis of As and Se, and (2) the flame AA or ICP
analysis of Al, Ba, Be, Ca, Cd, Cr, Co, Cu, Fe, Mo, Pb, Ni, K, Na, Tl, V, and
Zn. Dilute nitric acid is employed as the final dilution acid for the furnace
AA analysis of As, Be, Cd, Cr, Co, Pb, Mo, Se, Tl, and V. A separate sample
shall be dried for a total solids determination.
3.0 INTERFERENCES
3.1 Sludge samples can contain diverse matrix types, each of which may
present its own analytical challenge. Spiked samples and any relevant
standard reference material should be processed to aid in determining whether
Method 3050 is applicable to a given waste.
3050 - 1
Revision 0
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Conical Phillips beakers; 250-mL.
4.2 Watch glasses.
4.3 Drying ovens; That can be maintained at 30*C.
4.4 Thermometer; That covers range of 0 to 200*C.
4.5 Whatman NbT 41 filter paper (or equivalent).
4.6 Centrifuge and centrifuge tubes.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193); Water should be monitored for
Impurities.
5.2 Concentrated nitric add, reagent grade (HNOs): Add should be
analyzed to determine level of Impurities. If method blank 1s
-------
Using a ribbed watch glass, allow the solution to evaporate to 5 ml without
boiling, while maintaining a covering of solution over the bottom of the
beaker.
7.3 After Step 7.2 has been completed and the sample has cooled, add 2
ml of Type II water and 3 ml of 30% H202. Cover the beaker with a watch glass
and return the covered beaker to the hot plate for warming and to start the
peroxide reaction. Care must be taken to ensure that losses do not occur due
to excessively vigorous effervescence. Heat until effervescence subsides and
cool the beaker.
7.4 Continue to add 30% HgC^ in 1-mL aliquots with warming until the
effervescence is minimal or until the general sample appearance is unchanged.
NOTE: Do not add more than a total of 10 ml 30%
7.5 If the sample is being prepared for (a) the ICP analysis of As and
Se, or (b) the flame AA or ICP analysis of Al, Ba, Be, Ca, Cd, Cr, Co, Cu, Fe,
Pb, Mg, Mn, Mo, Ni, K, Na, Tl , V, and Zn, then add 5 ml of concentrated HC1
and 10 ml of Type II water, return the covered beaker to the hot plate, and
reflux for an additional 15 min without boiling. After cooling, dilute to
100 ml with Type II water. Particulates in the digestate that may clog the
nebulizer should be removed by filtration, by centrifugation, or by allowing
the sample to settle.
7.5.1 Filtration: Filter through Whatman No. 41 filter paper (or
equivalent) and dilute to 100 ml with Type II water.
7.5.2 Centrifugation: Centrifugation at 2,000-3,000 rpm for 10 min
is usually sufficient to clear the supernatant.
7.5.3 The diluted sample has an approximate acid concentration of
5.0% (v/v) HC1 and 5.0% (v/v) HN03. The sample 1s now ready for
analysis.
7.6 If the sample is being prepared for the furnace analysis of As, Be,
Cd, Cr, Co, Pb, Mo, Se, Tl , and V, cover the sample with a ribbed watch glass
and continue heating the acid-peroxide digestate until the volume has been
reduced to approximately 5 ml. After cooling, dilute to 100 ml with Type II
water. Particulates in the digestate should then be removed by filtration, by
centrifugation, or by allowing the sample to settle.
7.6.1 Filtration: Filter through Whatman No. 41 filter paper (or
equivalent) and dilute to 100 ml with Type II water.
7.6.2 Centrifugation: Centrifugation at 2,000-3,000 for 10 min 1s
usually sufficient to clear the supernatant.
7.6.3 The diluted digestate solution contains approximately 5%
(v/v) HN03. For analysis, withdraw aliquots of appropriate volume and
add any required reagent or matrix modifier. The sample is now ready for
analysis.
3050 - 3
Revision 0
Date September 1986
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7.7 Calculations;
7.7.1 The concentrations determined are to be reported on the basis
of the actual weight of the sample. If a dry weight analysis 1s desired,
then the percent solids of the sample must also be provided.
7.7.2 If percent solids Is desired, a separate determination of
percent sol Ids must be performed on a homogeneous aliquot of the sample.
8.0 QUALITY CONTROL
8.1 For each group of samples processed, preparation blanks (Type II
water and reagents) should be carried throughout the entire sample preparation
and analytical process. These blanks will be useful 1n determining 1f samples
are being contaminated.
8.2 Duplicate samples should be processed on a routine basis. Duplicate
samples will be used to determine precision. The sample load will dictate the
frequency, but 20% 1s recommended.
8.3 Spiked samples or standard reference materials must be employed to
determine accuracy. A spiked sample should be Included with each group of
samples processed and whenever a new sample matrix 1s being analyzed.
8.4 The concentration of all calibration standards should be \ser1f1ed
against a quality control check sample obtained from an outside source.
9.0 METHOD PERFORMANCE
9.1 No data provided.
10.0 REFERENCES
10.1 None required.
3050 - 4
Revision
Date September 1986
-------
METHOD 305O
ACID DIGESTION OF SEDIMENTS. SLUDGES. AND SOILS
C -- )
7., |
1 Mix
sample, take
1-2 g portion
for each
digestion
7., |
1 Add HMOs
and reflux:
reflux with
concentrated
HNOj: repeat
7.2
Evaporate
solution to
S ml
7.3
T
water ar
warn
peroxide
Add
rype II
td H^Oj:
» for
react.
_nJ
Add H»0i
nd warm until
f f ervesc«nc«
i* minimal
o
3050 - 5
Revision o
Date September 1986
-------
METHOD 3OSO
ACID DIGESTION OF SEDIMENTS. SLUDGES. AND SOILS
(Continued)
Furnace analysis of
AS. Be. ca. Cr. Co. Pb.
Mo. Se. Tl. ana V
7.6
ICP analysis of As and Se
or flame AA or ICP
analysis of Al. Ba. Be.
Be. Ce. CO. Cr. Cp. Cu.
Fe. PD. Mg. Mn. Mo. Ni.
K. Na. Tl. V. and Zn
Continue
heating to
reduce volume
7.6
7.5
Add
concentrated
HCL and Type II
water; relux
Dilute with
Type II water
7.6
7..5
Cool:
dl lute
with Type II
water: filter
partlculates in
the digestate
Filter
partlculates
in digestate
7.7.1(Determine
I percent
solids on
homogeneous
ample aliquot
for calculation
7.7.2
'Determine
concentrations:
report percent
olidc of
f Stop j
3050 - 6
Revision 0
Date September 1986
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3.3 METHODS FOR DETERMINATION OF METALS
This manual contains six analytical techniques for trace metal
determinations: Inductively coupled argon plasma emission spectrometry (ICP),
direct-aspiration or flame atomic absorption spectrometry (FAA), graphite-
furnace atomic absorption spectrometry (GFAA), hydride-generation atomic
absorption- spectrometry (HGAA), cold-vapor atomic absorption spectrometry
(CVAA), and several procedures for hexavalent chromium analysis. Each of
these 1s briefly discussed below 1n terms of advantages, disadvantages, and
cautions for analysis of wastes.
ICP's primary advantage 1s that 1t allows simultaneous or rapid
sequential determination of many elements 1n a short time. The primary
disadvantage of ICP 1s background radiation from other elements and the plasma
gases. Although all ICP Instruments utilize high-resolution optics and back-
ground correction to minimize these Interferences, analysis for traces of
metals 1n the presence of a large excess of a single metal 1s difficult.
Examples would be traces of metals 1n an alloy or traces of metals 1n a Hmed
(high calcium) waste. ICP and Flame AA have comparable detection limits
(within a factor of 4) except that ICP exhibits greater sensitivity for
refractories (Al, Ba, etc.). Furnace AA, In general, will exhibit lower
detection limits than either ICP or FLAA.
F1ame AAS (FLAA) determinations, as opposed to ICP, are normally
completed as single element analyses and are relatively free of Interelement
spectral Interferences. Either a nitrous-oxide/acetylene or air/acetylene
flame 1s used as an energy source for dissociating the aspirated sample Into
the free atomic state making analyte atoms available for absorption of light.
In the analysis of some elements the temperature or type of flame used 1s
critical. If the proper flame and analytical conditions are not used,
chemical and 1on1zat1on Interferences can occur.
Graphite Furnace AAS (GFAA) replaces the flame with an electrically
heated graphite furnace.The furnace allows for gradual heating of the sample
aliquot 1n several stages. Thus, the processes of desolvatlon, drying,
decomposition of organic and Inorganic molecules and salts, and formation of
atoms which must occur 1n a flame or ICP 1n a few milliseconds may be allowed
to occur over a much longer time period and at controlled temperatures 1n the
furnace. This allows an experienced analyst to remove unwanted matrix
components by using temperature programming and/or matrix modifiers. The
major advantage of this technique 1s that It affords extremely low detection
limits. It 1s the easiest to perform on relatively clean samples. Because
this technique 1s so sensitive, Interferences can be a real problem; finding
the optimum combination of digestion, heating times and temperatures, and
matrix modifiers can be a challenge for complex matrices.
THREE - 6
Revision 0
Date September 1986
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Hydride AA utilizes a chemical reduction to reduce and separate arsenic
or selenium selectively from a sample dlgestate. The technique therefore has
the advantage of being able to Isolate these two elements from complex samples
which may cause Interferences for other analytical procedures. Significant
Interferences have been reported when any of the following Is present: 1)
easily reduced metals (Cu, Ag, Hg); 2) high concentrations of transition
metals (>200 mg/L); 3) oxidizing agents (oxides of nitrogen) remaining
following sample digestion.
Cold-Vapor AA uses a chemical reduction to reduce mercury selectively.
The procedure 1s extremely sensitive but 1s subject to Interferences from some
volatile organlcs, chlorine, and sulfur compounds.
THREE - 7
Revision
Date September 1986
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METHOD 6010
INDUCTIVELY COUPLED PLASMA ATOMIC EMISSION SPECTROSCOPY
1.0 SCOPE AND APPLICATION
1.1 Inductively coupled plasma atomic emission spectroscopy (ICP)
determines elements Including metals 1n solution. The method 1s applicable to
a large number of metals and wastes. All matrices, including ground water,
aqueous samples, EP extracts, Industrial wastes, soils, sludges, sediments,
and other solid wastes, require digestion prior to analysis.
1.2 Elements for which Method 6010 1s applicable are listed in Table 1.
Detection limits, sensitivity, and optimum ranges of the metals will vary with
the matrices and model of spectrometer. The data shown in Table 1 provide
concentration ranges for clean aqueous samples. Use of this method is
restricted to spectroscopists who are knowledgeable 1n the correction of
spectral, chemical, and physical Interferences.
1.3 The method of standard addition (MSA) (Paragraph 8.5.3) shall be
used for the analysis of all EP extracts and sample digests unless either
serial dilution or matrix spike addition demonstrates that it 1s not required.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, samples must be solubllized or digested using
appropriate Sample Preparation Methods (e.g., Methods 3005-3050).
2.2 Method 6010 describes the simultaneous, or sequential, multiele-
mental determination of elements by ICP. The method measures element-emitted
light by optical spectrometry. Samples are nebulized and the resulting
aerosol 1s transported to the plasma torch. Element-specific atomic-line
emission spectra are produced by a radio-frequency inductively coupled plasma.
The spectra are dispersed by a grating spectrometer, and the Intensities of
the lines are monitored by photomultlplier tubes. Background correction is
required for trace element determination. Background must be measured
adjacent to analyte lines on samples during analysis. The position selected
for the background-intensity measurement, on either or both sides of the
analytical line, will be determined by the complexity of the spectrum adjacent
to the analyte line. The position used must be free of spectral Interference
and reflect the same change in background Intensity as occurs at the analyte
wavelength measured. Background correction is not required in cases of line
broadening where a background correction measurement would actually degrade
the analytical result. The possibility of additional interferences named in
Section 3.0 should also be recognized and appropriate corrections made; tests
for their presence are described in Section 8.5.
6010 - 1
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Date September 1986
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TABLE 1. RECOMMENDED WAVELENGTHS AND ESTIMATED INSTRUMENTAL DETECTION LIMITS
Estimated Detection
Element Wavelength3 (nm) L1m1tb (ug/L)
Aluminum
Antimony
Arsenic .
Barium
Beryllium
Boron
Cadml urn
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Molybdenum
Nickel
Potassium
Selenium
Silicon
Silver
Sodium
Thallium
Vanadl urn
Z1nc
308.215
206.833
193.696 '
455.403 "'"
313.042
249.773
226.502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
766.491
196.026
288.158
328.068
588.995
190.864
292.402
213.856
45
32
53
2
0.3
5
4
10
7
7
6
7
42
30
2
8
15
See note c
75
58
7
29
40
8
2
aThe wavelengths listed are recommended because of their sensitivity and
overall acceptance. Other wavelengths may be substituted 1f they can provide
the needed sensitivity and are treated with the same corrective techniques for
spectral Interference (see Paragraph 3.1). In time, other elements may be
added as more information becomes available and as required.
estimated Instrumental detection limits shown are taken from
Reference 1 1n Section 10.0 below. They are given as a guide for an
Instrumental limit. The actual method detection limits are sample dependent
and may vary as the sample matrix varies.
cH1ghly dependent on operating conditions and plasma position.
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3.0 INTERFERENCES
3.1 Spectral Interferences are caused by: (1) overlap of a spectral
line from another element; (2) unresolved overlap of molecular band spectra;
background contribution from continuous or recombination phenomena; and
stray light from the line emission of high-concentration elements.
Spectral overlap can be compensated for by computer-correcting the raw data
after monitoring and measuring the Interfering element. Unresolved overlap
requires selection of an alternate wavelength. Background contribution and
stray light can usually be compensated for by a background correction adjacent
to the analyte line.
Users of simultaneous multielement Instruments must verify the absence of
spectral Interference from an element 1n a sample for which there Is no
Instrument detection channel. Potential spectral Interferences for the
recommended wavelengths are given 1n Table 2. The data 1n Table 2 are
Intended as rudimentary guides for Indicating potential Interferences; for
this purpose, linear relations between concentration and Intensity for the
analytes and the Interferents can be assumed.
3.1.1 The Interference 1s expressed as analyte concentration
equivalents (I.e., false analyte concentrations) arising from 100 mg/L of
the Interference element. For example, assume that As 1s to be
determined (at 193.696 nm) 1n a sample containing approximately 10 mg/L
of Al. According to Table 2, 100 mg/L of Al would yield a false signal
for As equivalent to approximately 1.3 mg/L. Therefore, the presence of
10 mg/L of Al would result 1n a false signal for As equivalent to
approximately 0.13 mg/L. The user 1s cautioned that other Instruments
may exhibit somewhat different levels of Interference than those shown 1n
Table 2. The Interference effects must be evaluated for each Individual
Instrument since the Intensities will vary with operating conditions,
power, viewing height, argon flow rate, etc.
3.1.2 The dashes 1n Table 2 Indicate that no measurable
Interferences were observed even at higher Interferent concentrations.
Generally, Interferences were discernible 1f they produced peaks, or
background shifts, corresponding to 2 to 5% of the peaks generated by the
analyte concentrations.
3.1.3 At present, Information on the listed silver and potassium
wavelengths Is not available, but It has been reported that second-order
energy from the magnesium 383.231-nm wavelength Interferes with the
listed potassium line at 766.491 nm.
3.2 Physical Interferences are effects associated with the sample
nebullzatlon andtransportprocesses. Changes 1n viscosity and surface
tension can cause significant Inaccuracies, especially 1n samples containing
high dissolved solids or high add concentrations. If physical Interferences
are present, they must be reduced by diluting the sample, by using a
peristaltic pump or by using the standard additions method. Another problem
that can occur with high dissolved solids 1s salt buildup at the tip of the
nebulizer, which affects aerosol flow rate and causes Instrumental drift. The
problem can be controlled by wetting the argon prior to nebullzatlon, using a
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TABLE 2. ANALYTE CONCENTRATION EQUIVALENTS ARISING FRCM INTERFERENCE
AT THE 100-rag/L LEVEL
Analyte
Aluminum
Antimony
Arsenic
Barium
Beryllium
Boron
Cadmium
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese .
Molybdenum
Nickel
Selenium
Silicon
Sodium
Thallium
Vanadium
Zinc
Wavelength
(t»0
308.215
206.833
193.6%
455 .403
313.042
249.773
226.502
317.933
267.716
228.616
324.754
259.940
220.353
279.079
257.610
202.030
231.604
196.026
288.158
588.995
190.864
292.402
213.856
Al Ca
0.47
1.3
0.04
0.17
0.02
0.005
0.05
0.23
0.30
Cr Cu
2.9
0.44
0.08
0.03
0.11
0.01
0.07
0.05
0.14
Interferent '
Fe Mg Mn Ni
0.21
0.08
0.32
0.03 0.02
0.01 0.01 0.04
0.003 0.04
OJ305 0.03
0.003
0.12
0.13 0.25
0.002 0.002
0.03 '
0.09
^_ _. -» _»
0.005
0.29
Tl
0.25
0.04
0.03
0.15
0.05
0.07
<
0.08
0.02
V
1.4
0.45
1.1
0.05
0.03
0.04
0.02
0.12
^^
0.01
Dashes indicate that no interference was observed even when interferents
were introduced at the following levels:
Al - 1000 mg/L,
Ca - 1000 mg/L,
Cr - 200 mg/L,
Cu - 200 mg/L
Fe - 1000 mg/L
Mg - 1000 mg/L,
Mn - 200 mg/L,
Tl - 200 mg/L,
V - 200 mg/L
The figures recorded as analyte concentrations are not the actual
observed concentrations; to obtain those figures, add the listed concentration
to the interferent figure.
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tip washer, or diluting the sample. Also, 1t has been reported that better
control of the argon flow rate Improves Instrument performance; this 1s
accomplished with the use of mass flow controllers.
3.3 Chemical Interferences Include molecular compound formation,
1on1zat1on effects, and solute vaporization effects. Normally, these effects
are not significant with the ICP technique. If observed, they can be
minimized by careful selection of operating conditions (incident power,
observation position, and so forth), by buffering of the sample, by matrix
matching, and by standard addition procedures. Chemical interferences are
highly dependent on matrix type and the specific analyte element.
4.0 APPARATUS AND MATERIALS
4.1 Inductively coupled argon plasma emission spectrometer;
4.1.1 Computer-controlled emission spectrometer with background
correction.
4.1.2 Radio frequency generator.
4.1.3 Argon gas supply: Welding grade or better.
4.2 Operating conditions; The analyst should follow the instructions
provided Bythe instrument's manufacturer. For operation with organic
solvents, use of the auxiliary argon Inlet is recommended, as are solvent-
resistant tubing, increased plasma (coolant) argon flow, decreased nebulizer
flow, and increased RF power to obtain stable operation and precise
measurements. Sensitivity, Instrumental detection limit, precision, linear
dynamic range, and interference effects must be established for each
individual analyte line on that particular instrument. All measurements must
be within instrument linear range where coordination factors are valid. The
analyst must (1) verify that the instrument configuration and operating
conditions satisfy the analytical requirements and (2) maintain quality
control data confirming instrument performance and analytical results.
5.0 REAGENTS
5.1 Acids used in the preparation of standards and for sample processing
must be reagent grade or better. Redistilled acids may be, used.
5.1.1 Concentrated hydrochloric acid (HC1).
5.1.2 Hydrochloric acid (1:1): Add 500 ml concentrated HC1 to
400 ml Type II water and dilute to 1 liter.
5.1.3 Concentrated nitric acid
5.1.4 Nitric acid (1:1): Add 500 ml concentrated HNOs to 400 mL
Type II water and dilute to 1 liter.
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5.2 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.3 Standard stock solutions may be purchased or prepared from ultra-
high purity grade chemicals or metals (99.99 to 99.999% pure). All salts must
be dried for 1 hr at 105°C, unless otherwise specified.
(CAUTION: Many metal salts are extremely toxic If Inhaled or swallowed,
Wash hands thoroughly after handling.)
Typical stock solution preparation procedures follow. Concentrations are
calculated based upon the weight of pure metal added, or with the use of the
mole fraction and the weight of the metal salt added.
Metal
Concentration (ppm) =
Metal salts
Concentration (ppm) - e fract1on
5.3.1 Aluminum solution, stock, 1 ml = 100 ug Al : Dissolve 0.10 g
of aluminum metal, weighed accurately to at least four significant
figures, 1n an acid mixture of 4 ml of (1:1) HC1 and 1 ml of concentrated
HN03 1n a beaker. Warm gently to effect solution. When solution is
complete, transfer quantitatively to a liter flask, add an additional
10 ml of (1:1) HC1 and dilute to 1,000 ml with Type II water.
5.3.2 Antimony solution, stock, 1 ml = 100 ug Sb: Dissolve 0.27 g
K(SbO)C4H4(k (mole fraction Sb = 0.3749), weighed accurately to at least
four significant figures, in Type II water, add 10 ml (1:1) HC1 , and
dilute to 1,000 ml with Type II water.
5.3.3 Arsenic solution, stock, 1 ml = 100 ug As: Dissolve 0.13 g
of AspOs (mole fraction As = 0.7574), weighed accurately to at least four
significant figures, in 100 ml of Type II water containing 0.4 g NaOH.
Acidify the solution with 2 ml concentrated HNOs and dilute to 1,000 ml
with Type II water.
5.3.4 Barium solution, stock, 1 ml = 100 ug Ba: Dissolve 0.15 g
BaCl2 (mole fraction Ba = 0.6595), dried at 250°C for 2 hr, weighed
accurately to at least four significant figures, in 10 ml Type II water
with 1 ml (1:1) HC1. Add 10.0 ml (1:1) HC1 and dilute to 1,000 ml with
Type II water.
5.3.5 Beryllium solution, stock, 1 ml = 100 ug Be: Do not dry.
Dissolve 1.97 g BeSOA^^O (mole fraction Be = 0.0509J7 weigned
accurately to at least four significant figures, in Type II water, add
10.0 ml concentrated HN03, and dilute to 1,000 mL with Type II water.
Mole fraction = 0.0509.
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5.3.6 Boron solution, stock 1 ml = 100 ug B: Do not dry. Dissolve
0.57 g anhydrous 1*3803 (mole fraction B = 0.1748), welgfied accurately to
at least four significant figures, 1n Type II water and dilute to 1,000
ml. Use a reagent meeting ACS specifications, keep the bottle tightly
stoppered, and store 1n a desiccator to prevent the entrance of
atmospheric moisture.
5.3.7 Cadmium solution, stock, 1 ml = 100 ug Cd: Dissolve 0.11 g
CdO (mole fraction Cd = 0.8754), weighed accurately to at least four
significant figures, 1n a minimum amount of (1:1) HN03. Heat to Increase
rate of dissolution. Add 10.0 ml concentrated HN03 and dilute to 1,000
ml with Type II water.
5.3.8 Calcium solution, stock, 1 ml = 100 ug Ca: Suspend 0.25 g
CaCC-3 (mole Ca fraction = 0.4005), dried at 180*C for 1 hr before
weighing, weighed accurately to at least four significant figures, in
Type II water and dissolve cautiously with a minimum amount of (1:1)
HN03. Add 10.0 ml concentrated HMOs and dilute to 1,000 ml with Type II
water.
5.3.9 Chromium solution, stock, 1 ml = 100 ug Cr: Dissolve
0.19 g CrC-3 (mole fraction Cr = 0.5200), weighed accurately to at least
four significant figures, in Type II water. When solution is complete,
acidify with 10 ml concentrated HN03 and dilute to 1,000 ml with Type II
water.
5.3.10 Cobalt solution, stock, 1 ml = 100 ug Co: Dissolve 0.1000 g
of cobalt metal, weighed accurately to at least four significant figures,
1n a minimum amount of (1:1) HNOs. Add 10.0 ml (1:1) HC1 and.dilute to
1,000 ml with Type II water.
5.3.11 Copper solution, stock, 1 ml = 100 ug Cu: Dissolve
0.13 g CuO (mole fraction Cu = 0.7989), weighed accurately to at least
four significant figures), 1n a minimum amount of (1:1) HN03. Add 10.0
ml concentrated HN03 and dilute to 1,000 ml with Type II water.
5.3.12 Iron solution, stock, 1 ml = 100 ug Fe: Dissolve 0.14 g
Fe203 (mole fraction Fe = 0.6994), weighed accurately to at least four
significant figures, 1n a warm mixture of 20 ml (1:1) HC1 and 2 ml of
concentrated HN03. Cool, add an additional 5.0 ml of concentrated HN03,
and dilute to 1,000 ml with Type II water.
5.3.13 Lead solution, stock, 1 ml = 100 ug Pb: Dissolve 0.16 g
Pb(N03)2 (mole fraction Pb = 0.6256), weighed accurately to at least four
significant figures, 1n a minimum amount of (1:1) HN03. Add 10 ml (1:1)
HN03 and dilute to 1,000 ml with Type II water.
5.3.14 Magnesium solution, stock, 1 ml = 100 ug Mg: Dissolve
0.17 g MgO (mole fraction Mg = 0.6030), weighed accurately to at least
four significant figures, 1n a minimum amount of (1:1) HN03. Add 10.0 ml
(1:1) concentrated HN03 and dilute to 1,000 ml with Type II water.
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5.3.15 Manganese solution, stock, 1 ml = 100 ug Mn: Dissolve
0.1000 g of manganese metal, weighed accurately to at least four
significant figures, 1n add mixture (10 ml concentrated HC1 and 1 ml
concentrated HNOs) and dilute to 1,000 ml with Type II water.
5.3.16 Molybdenum solution, stock, 1 ml = 100 ug Mo: Dissolve
0.20 g (NH4)6M07024'4H20 (mole fraction Mo = 0.5772), weighed accurately
to at least four significant figures, 1n Type II water and dilute to
1,000 ml with Type II water.
5.3.17 Nickel solution, stock, 1 ml = 100 ug N1 : Dissolve 0.1000 g
of nickel metal, weighed accurately to at least four significant figures,
1n 10.0 ml hot concentrated HN03, cool, and dilute to 1,000 ml with Type
II water. .
5.3.18 Potassium solution, stock, 1 ml = 100 ug K: Dissolve
0.19 g KC1 (mole fraction K = 0.5244) dried at 110'C, weighed accurately
to at least four significant figures, 1n Type II water and dilute to
1,000 ml.
5.3.19 Selenium solution, stock, 1 ml = 100 ug Se: Do not dry.
Dissolve 0.17 g H2Se03 (mole fraction Se = 0.6123), weighed accurately to
at least four significant figures, 1n Type II water and dilute to 1,000
ml.
5.3.20 Silica solution, stock, 1 ml = 100 ug S102t Do not dry.
Dissolve 0.47 g Na2$103'9H20 (mole fraction S1 = 0.09884]", weighed
accurately to at least four significant figures, 1n Type II water. Add
10.0 ml concentrated HN03 and dilute to 1,000 ml with Type II water.
5.3.21 Silver solution, stock, 1 ml = 100 ug Ag: Dissolve 0.16 g
AgN03 (mole fraction Ag = 0.6350), weighed accurately to at least four
significant figures, 1n Type II water and 10 ml concentrated HN03.
Dilute to 1,000 ml with Type II water.
5.3.22 Sodium solution, stock, 1 ml = 100 ug Na: Dissolve 0.25 g
NaCl (mole fraction Na = 0.3934), weighed accurately to at least four
significant figures, 1n Type II water. Add 10.0 ml concentrated HN03 and
dilute to 1,000 ml with Type II water.
5.3.23 Thallium solution, stock, 1 ml = 100 ug Tl : Dissolve
0.13 g T1N03 (mole fraction Tl = 0.7672), weighed accurately to at least
four significant figures, 1n Type II water. Add 10.0 ml concentrated
HN03 and dilute to 1,000 ml with Type II water.
5.3.24 Vanadium solution, stock, 1 ml = 100 ug V: Dissolve
0.23 g NH4V03 (mole fraction V = 0.4356), weighed accurately to at least
four significant figures, 1n a minimum amount of concentrated HN03. Heat
to Increase rate of dissolution. Add 10.0 ml concentrated HN03 and
dilute to 1,000 ml with Type II water.
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5.3.25 Zinc solution, stock, 1 ml = 100 ug Zn: Dissolve 0.12 g ZnO
(mole fraction Zn = 0.8034), weighed accurately to at least four
significant figures, in a minimum amount of dilute HNC»3. Add 10.0 ml
concentrated HN03 and dilute to 1,000 ml with Type II water.
5.4 Mixed calibration standard solutions:
Prepare mixed calibration
volumes of the stock solutions 1n
(1:1) HN03 and 10 ml of (1:1) HC1
Prior to preparing
should be analyzed separately to
the presence of impurities. Care
standard solutions by combining appropriate
volumetric flasks (see Table 3). Add 2 ml
and dilute to 100 ml with Type II water (see NOTE, below).
the mixed standards, each stock solution
determine possible spectral interference or
should be taken when preparing the mixed standards to ensure that the elements
are compatible and stable together. Transfer the mixed standard solutions to
FEP fluorocarbon or previously unused polyethylene or polypropylene bottles
for storage. Fresh mixed standards should be prepared, as needed, with the
realization that concentration can change on aging. Calibration standards
must be Initially verified using a quality control sample (see Paragraph 5.8)
and monitored weekly for stability. Some typical calibration standard
combinations are listed 1n Table 3. All mixtures should then be scanned using
a sequential spectrometer to verify the absence of Interelement spectral
Interference 1n the recommended mixed standard solutions.
NOTE: If the addition of silver to the recommended add combination
results In an Initial precipitation, add 15 ml of Type II water
and warm the flask until the solution clears. Cool and dilute to
100 ml with Type II water. For this add combination, the silver
concentration should be limited to 2 mg/L. Silver under these
conditions is stable in a tap-water matrix for 30 days. Higher
concentrations of silver require additional HC1.
TABLE 3. MIXED STANDARD SOLUTIONS
Solution
Elements
I
II
III
IV
V
Be, Cd, Mn, Pb, Se and Zn
Ba, Co, Cu, Fe, and V
As, Mo, and S1
Al, Ca, Cr, K, Na, and N1
Ag (see Note to Paragraph 5.4),
B, Mg, Sb, and Tl
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5.5 Two types of blanks are required for the analysis. The calibration
blank 1s used 1n establishing the analytical curve, and the reagent blank 1s
used to correct for possible contamination resulting from varying amounts of
the adds used 1n the sample processing.
5.5.1 The calibration blank 1s prepared by diluting 2 ml of (1:1)
HN03 and 10 ml of (1:1) HC1 to 100 ml with Type II water. Prepare a
sufficient quantity to flush the system between standards and samples.
5.5.2 The reagent blank must contain all the reagents and In the
same volumes as used 1n the processing of the samples. The reagent
blank must be carried through the complete procedure and contain the
same add. concentration in the final solution as the sample solution used
for analysis.
5.6 The Instrument check standard is prepared by the analyst by com-
bining compatlBTe~eTenilents at concentrations equivalent to the midpoint of
their respective calibration curves (see Paragraph 8.6.2.1 for use).
5.7 The interference check solution is prepared to contain known
concentrations of Interfering elements that will provide an adequate test of
the correction factors. Spike the sample with the elements of Interest at
approximate concentrations of 10 times the Instrumental detection limits. In
the absence of measurable analyte, overcorrectlon could go undetected because
a negative value could be reported as zero. If the particular instrument will
display overcorrectlon as a negative number, this spiking procedure will not
be necessary.
5.8 The quality control sample should be prepared in the same acid
matrix as the calibrationstandards at 10 times the instrumental detection
limits and 1n accordance with the Instructions provided by the supplier.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the introductory material in Chapter Three, Inorganic Analytes,
Sections 3.1 through 3.3.
7.0 PROCEDURE
7.1 Preliminary treatment of all matrices is always necessary because of
the complexity and variability of sample matrices. SolubiUzation and
digestion procedures are presented 1n Sample Preparation Methods (Methods
3005-3050). The method of standard addition (MSA) (Paragraph 8.5.3) shall be
used for the analysis of all EP extracts and sample digests unless either
serial dilution or matrix spike addition demonstrates that 1t 1s not required.
An internal standard may be substituted for the MSA.
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7.2 Set up the Instrument with proper operating parameters established
In Paragraph 4.2. The Instrument must be allowed to become thermally stable
before beginning (usually requiring at least 30 min of operation prior to
calibration).
7.3 Profile and calibrate the instrument according to the instrument
manufacturer's recommended procedures, using the typical mixed calibration
standard solutions described in Paragraph 5.4. Flush the system with the
calibration blank (5.5.1) between each standard (see NOTE, below). (Use the
average Intensity of multiple exposures for both standardization and sample
analysis to reduce random error.)
NOTE: For boron concentrations greater than 500 ug/L, extended flush
times of 1 or 2 m1n may be required.
7.4 Before beginning the sample run, reanalyze the highest mixed
calibration standard as if it were a sample. Concentration values obtained
should not deviate from the actual values by more than 5% (or the established
control limits, whichever 1s lower). If they do, follow the recommendations
of the Instrument manufacturer to correct for this condition.
7.5 Flush the system with the calibration blank solution for at least
1 min (Paragraph 5.5.1) before the analysis of each sample (see Note to
Paragraph 7.3). Analyze the instrument check standard (5.6) and the
calibration blank (5.5.1) after each 10 samples.
7.6 Calculations; If dilutions were performed, the appropriate factors
must be applied to sample values. All results should be reported 1n ug/L with
up to three significant figures.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Dilute and reanalyze samples that are more concentrated than the
linear calibration limit or use an alternate, less sensitive Hne for which
quality control data is already established.
8.3 Employ a minimum of one laboratory blank per sample batch to
determine 1f contamination or any memory effects are occurring.
8.4 Analyze one duplicate sample for every 20 samples. A duplicate
sample is a sample brought through the whole sample preparation and analytical
process.
8.5 It 1s recommended that whenever a new or unusual sample matrix 1s
encountered, a series of tests be performed prior to reporting concentration
data for analyte elements. These tests, as outlined in 8.5.1 through 8.5.3,
will ensure the analyst that neither positive nor negative Interferences are
operating on any of the analyte elements to distort the accuracy of the
reported values.
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8.5.1 Serial dilution: If the analyte concentration 1s
sufficiently high (minimally, a factor of 10 above the Instrumental
detection limit after dilution), an analysis of a 1:4 dilution should
agree within +10% of the original determination. If not, a chemical or
physical Interference effect should be suspected.
8.5.2 Matrix spike addition: An analyte spike added to a portion
of a prepared sample, or Its dilution, should be recovered to within 75%
to 125% of the known value. The spike addition should produce a minimum
level of 10 times and a maximum of 100 times the Instrumental detection
limit. If the spike 1s not recovered within the specified limits, a
matrix effect should be suspected. The use of a standard-addition
analysis procedure can usually compensate for this effect.
CAUTION: The standard-addition technique does not detect coincident
spectral overlap. If suspected, use of computerized
compensation, an alternate wavelength, or comparison with
an alternate method is recommended.
8.5.3 Standard addition: The standard-addition technique Involves
adding known amounts of standard to one or more aliquots of the processed
sample solution. This technique compensates for a sample constituent
that enhances or depresses the analyte signal, thus producing a different
slope from that of the calibration standards. It will not correct for
additive Interferences which cause a baseline shift. The simplest
version of this technique 1s the single-addition method, in which two
Identical allguots of the sample solution, each of Volume Vx, are taken.
To the first (labeled A) 1s added a small volume Vs of a standard analyte
solution of concentration cs. To the second (labeled B) is added the
same volume Vs of the solvent. The analytical signals of A and B are
measured and corrected for nonanalyte signals. The unknown sample
concentration cx is calculated:
x (S- S ) V
* ^A V Vx
where S/\ and SB are the analytical signals (corrected for the blank) of
solutions A and B, respectively. Vs and cs should be chosen so that S/\
1s roughly twice SB on the average. It is best 1f Vs is made much less
than Vx, and thus cs is much greater than cx, to avoid excess dilution of
the sample matrix. If a separation or concentration step 1s used, the
additions are best made first and carried through the entire procedure.
For the results of this technique to be valid, the following limitations
must be taken Into consideration:
1. The analytical curve must be linear.
2. The chemical form of the analyte added must respond the same
way as the analyte in the sample.
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3. The Interference effect must be constant over the working range of
concern.
4. The signal must be corrected for any additive Interference.
The absorbance of each solution 1s determined and then plotted on the
vertical axis of a graph, with the concentrations of the known standards
plotted on the horizontal axis. When the resulting line 1s extrapolated
back to zero absorbance, the point of Interception of the abscissa 1s the
concentration of the unknown. The abscissa on the left of the ordlnate
1s scaled the same as on the right side, but 1n the opposite direction
from the ordlnate. An example of a plot so obtained 1s shown 1n
Figure 1.
8.6 Check the Instrument standardization by analyzing appropriate
quality control check standards as follows.
8.6.1 Check Instrument calibration using a calibration blank and
two appropriate standards.
8.6.2 Verify calibration every 10 samples and at the end of the
analytical run, using a calibration blank (5.5.1) and a single point
check standard (5.6).
8.6.2.1 The results of the check standard are to agree within
10% of the expected value; 1f not, terminate the analysis, correct
the problem, and recalibrate the Instrument.
8.6.2.2 The results of the calibration blank are to agree
within three standard deviations of the mean blank value. If not,
repeat the analysis two more times and average the results. If the
average 1s not within three standard deviations of the background
mean, terminate the analysis, correct the problem, recalibrate, and
reanalyze the previous 10 samples.
8.6.3 Verify the Interelement and background correction factors at
the beginning and end of an analytical run or twice during every 8-hour
work shift, whichever is more frequent. Do this by analyzing the
Interference check sample (Paragraph 5.7). Results should be within +20%
of the true value obtained 1n 8.6.2.1.
8.6.4 Duplicate spiked samples are to be analyzed at a frequency of
20%.
8.6.4.1 The relative percent difference between duplicate
determinations 1s to be calculated as follows:
Dl - D2
RPD -
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Concentration
Cone, of
Sample
AddnO
No Addn
Addn 1
Addn of 50%
of Expected
Amount
Addn 2 Addn 3
Addn of 100% Addn of 150%
of Expected of Expected
Amount Amount
Figure 1. Standard Addition Plot.
6010 - 14
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where:
RPD = relative percent difference.
DI = first sample value.
D£ = second sample value (duplicate).
(A control limit of +20% for RPD shall be used for sample values
greater than 10 time? the Instrument detection limit.)
8.6.4.2 The duplicate matrix spike sample recovery 1s to be
within +20% of the actual value.
8.6.5 The method of standard addition (Paragraph 8.5.3) shall be
used for the analysis of all EP extracts.
9.0 METHOD PERFORMANCE
9.1 In an EPA round-robin Phase 1 study, seven laboratories applied the
ICP technique to ac1d-d1st1lled water matrices that had been spiked with
various metal concentrates. Table 4 lists the true values, the mean reported
values, and the mean percent relative standard deviations.
9.2 In a single laboratory evaluation, seven wastes were analyzed for 22
elements by this method. The mean percent relative standard deviation from
triplicate analyses for all elements and wastes was 9+2%. The mean percent
recovery of spiked elements for all wastes was 93+6%. Spike levels ranged
from 100 ug/L to 100 mg/L. The wastes Included" sludges and Industrial
wastewaters.
10.0 REFERENCES
1. W1nge, R.K., V.J. Peterson, and V.A. Fassel, Inductively Coupled Plasma-
Atomic Emission Spectroscopy: Prominent Lines, Final Report, March 1977 -
February 1978, Ames Laboratory, Ames, IA, sponsored by Environmental Research
Laboratory, Athens, GA, EPA-600/4-79-017, March 1979.
2. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-05,
December 1982, Method 200.7.
3. Patel, B.K., Raab, 6.A., et al., Report on a Single Laboratory Evaluation
of Inductively Coupled Optical Emission Method 6010, EPA Contract No. 68-03-
3050, December 1984.
6010 - 15
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TABLE 4. ICP PRECISION AND ACCURACY DATAa
Sample No.
Ele-
ment
Be
Mn
V
As
Cr
Cu
Fe
Al
Cd
Co
N1
Pb
Zn
True
Value
(ug/L)
750
350
750
200
150
250
600
700
50
700
250
250
200
40
1
Mean Re-
ported Mean
Value SDb
(ug/L) (%)
733
345
749
208
149
235
594
696
48
512
245
236
201
32
6.2
2.7
1.8
7.5
3.8
5.1
3.0
5.6
12
10
5.8
16
5.6
21.9
Sample No.
Mean Re-
True ported
Value Value
(ug/L) (ug/L)
20
15
70
22
10
11
20
60
2.5
20
30
24
16
6
20
15
69
19
10
11
19
62
2.9
20
28
30
19
8.5
2
Mean
SDb
9.8
6.7
2.9
23
18
40
15
33
16
4.1
11
32
45
42
Sample No.
Mean Re-
True ported
Value Value
(ug/L) (ug/L)
180
100
170
60
50
70
180
160
14
120
60
80
80
10
176
99
169
63
50
67
178
161
13
108
55
80
82
8.5
3
Mean
SDb
/ M \
\ /
5.2
3.3
1.1
17
3.3
7.9
6.0
13
16
21
14
14
9.4
8.3
aNot all elements were analyzed by all laboratories.
bSD = standard deviation.
cResults for Se are from two laboratories.
6010 - 16
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METHOD 6010
INDUCTIVELY COUPLED ATOMIC EMISSION SPECTROSCOPY
7. 1
Prepare
sample
using Method
3O05. 301O. 3O20.
3040. or 3050
as approp.
7.2
o
Set up and
stabilize
Instrument
7.3
7.5
Flush system
and analyze
aamp la
Profile and
calibrate
Instrument
7.4
7.5
Analyze
» check
standard and
calibration
blank after
each 10 samples
Reanalyze
highest mixed
calibration
standard
7.6
Calculate
concentrations
7.4 j
Adjust
instrument per
manufacturer's
reconmandatlona
f Stop J
6010 - 17
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METHOD 7000
ATOMIC ABSORPTION METHODS
1.0 SCOPE AND APPLICATION
1.1 Metals In solution may be readily determined by atomic absorption
spectroscopy. The method Is simple, rapid, and applicable to a large number
of metals In drinking, surface, and saline waters and domestic and Industrial
wastes. While drinking water free of particulate matter may be analyzed
directly, ground water, other aqueous samples, EP extracts, Industrial
wastes, soils, sludges, sediments, and other solid wastes require digestion
prior to analysis.
1.2 Detection limits, sensitivity, and optimum ranges of the metals
will vary with the matrices and models of atomic absorption spectrophoto-
meters. The data shown 1n Table 1 provide some Indication of the detection
limits obtainable by direct aspiration and by furnace techniques. For clean
aqueous samples, the detection limits shown in the table by direct aspiration
may be extended downward with scale expansion and upward by using a less
sensitive wavelength or by rotating the burner head. Detection limits by
direct aspiration may also be extended through concentration of the sample
and/or through solvent extraction techniques. For certain samples, lower
concentrations may also be determined using the furnace techniques. The
detection limits given 1n Table 1 are somewhat dependent on equipment (such
as the type of spectrophotometer and furnace accessory, the energy source,
the degree of electrical expansion of the output signal), and are greatly
dependent on sample matrix. When using furnace techniques, however, the
analyst should be cautioned as to possible chemical reactions occurring at
elevated temperatures which may result in either suppression or enhancement
of the analysis element. To ensure valid data with furnace techniques, the
analyst must examine each matrix for interference effects (see Paragraph
3.2.1) and, 1f detected, treat them accordingly, using either successive
dilution, matrix modification, or method of standard additions (see Paragraph
8.7).
1.3 Where direct-aspiration atomic absorption techniques do not provide
adequate sensitivity, reference is made to specialized procedures (1n addi-
tion to the furnace procedure) such as the gaseous-hydride method for arsenic
and selenium and the cold-vapor technique for mercury.
2.0 SUMMARY OF METHOD
2.1 Although methods have been reported for the analysis of sol Ids by
atomic absorption spectroscopy, the technique generally 1s limited to metals
1n solution or solubillzed through some form of sample processing.
2.2 Preliminary treatment of waste water, ground water, EP extracts,
and Industrial waste is always necessary because of the complexity and
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TABLE 1. ATOMIC ABSORPTION CONCENTRATION RANGES
Metal
Direct Aspiration
Detection Limit Sensitivity
(mg/L) (mg/L)
Furnace Procedure3i
Detection Limit
(ug/L)
Aluminum
Antimony
Arsenic^
Barium(p)
Beryl 1 1 urn
Cadmi urn
Calcium
Chromium
Cobalt
Copper
Iron
Lead
Magnesium
Manganese
Mercuryd
Molybdenum(p)
Nickel (p)
Potassium
Selen1umb
Silver
Sodium
Thallium
Tin
Vanadium(p)
Zinc
0.1
0.2
0.002
0.1
0.005
0.005
0.01
0.05
0.05
0.02
0.03
0.1
0.001
0.01
0.0002
0.1
0.04
0.01
0.002
0.01
0.002
0.1
0.8
0.2
0.005
1
0.5
--
0.4
0.025
0.025
0.08
0.25
0.2
0.1
0.12
0.5
0.007
0.05
0.4
0.15
0.04
__
0.06
0.015
0.5
4
0.8
0.02
__
3
1
0.2
0.1
1
1
1
~~
1
__
2
__
__
1
__
4
--
NOTE: The symbol (p) Indicates the use of pyrolytic graphite with the
furnace procedure.
aFor furnace sensitivity values, consult Instrument operating manual.
^Gaseous hydride method.
cThe listed furnace values are those expected when using a 20-uL
injection and normal gas flow, except in the cases of arsenic and selenium,
where gas interrupt is used.
vapor technique.
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variability of sample matrix. Solids, slurries, and suspended material must
be subjected to a solubilization process before analysis. This process may
vary because of the metals to be determined and the nature of the sample being
analyzed. Solubilization and digestion procedures are presented in Section
3.2 (Sample Preparation Methods).
2.3 In direct-aspiration atomic absorption spectroscopy, a sample 1s
aspirated and atomized in a flame. A light beam from a hollow cathode lamp or
an electrodeless discharge lamp is directed through the flame into a
monochromator, and onto a detector that measures the amount of absorbed light.
Absorption depends upon the presence of free unexcited ground-state atoms in
the flame. Because the wavelength of the light beam is characteristic of only
the metal being determined, the light energy absorbed by the flame is a
measure of the concentration of that metal in the sample. This principle is
the basis of atomic absorption spectroscopy.
2.4 When using the furnace technique in conjunction with an atomic
absorption spectrophotometer, a representative aliquot of a sample is placed
1n the graphite tube in the furnace, evaporated to dryness, charred, and
atomized. As a greater percentage of available analyte atoms is vaporized and
dissociated for absorption in the tube rather than the flame, the use of
smaller sample volumes or detection of lower concentrations of elements is
possible. The principle is essentially the same as with direct aspiration
atomic absorption, except that a furnace, rather than a flame, is used to
atomize the sample. Radiation from a given excited element is passed through
the vapor containing ground-state atoms of that element. The intensity of the
transmitted radiation decreases in proportion to the amount of the ground-
state element 1n the vapor. The metal atoms to be measured are placed 1n the
beam of radiation by increasing the temperature of the furnace, thereby
causing the Injected specimen to be volatilized. A monochromator Isolates the
characteristic radiation from the hollow cathode lamp or electrodeless
discharge lamp, and a photosensitive device measures the attenuated
transmitted radiation.
3.0 INTERFERENCES
3.1 Direct aspiration;
3.1.1 The most troublesome type of interference 1n atomic
absorption spectrophotometry 1s usually termed "chemical" and 1s caused
by lack of absorption of atoms bound in molecular combination in the
flame. This phenomenon can occur when the flame is not sufficiently hot
to dissociate the molecule, as in the case of phosphate interference with
magnesium, or when the dissociated atom is immediately oxidized to a
compound that will not dissociate further at the temperature of the
flame. The addition of lanthanum will overcome phosphate interference in
magnesium, calcium, and barium determinations. Similarly, silica
Interference in the determination of manganese can be eliminated by the
addition of calcium.
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3.1.2 Chemical Interferences may also be eliminated by separating
the metal from the Interfering material. Although complexlng agents are
employed primarily to Increase the sensitivity of the analysis, they may
also be used to eliminate or reduce Interferences.
3.1.3 The presence of high dissolved sol Ids 1n the sample may
result 1n an Interference from nonatomlc absorbance such as light
scattering. If background correction 1s not available, a nonabsorblng
wavelength should be checked. Preferably, samples containing high solids
should be extracted.
3.1.4 lonization interferences occur when the flame temperature is
sufficiently high to generate the removal of an electron from a neutral
atom, giving a positively charged 1on. This type of Interference can
generally be controlled by the addition, to both standard and sample
solutions, of a large excess (1,000 mg/L) of an easily ionized element
such as K, Na, Li or Cs.
3.1.5 Spectral Interference can occur when an absorbing wavelength
of an element present 1n the sample but not being determined falls within
the width of the absorption line of the element of interest. The results
of the determination will then be erroneously high, due to the
contribution of the interfering element to the atomic absorption signal.
Interference can also occur when resonant energy from another element 1n
a multielement lamp, or from a metal impurity 1n the lamp cthode, falls
within the bandpass of the slit setting when that other metal 1s present
in the sample. This type of interference may sometimes be reduced by
narrowing the slit width.
3.1.6 Samples and standards should be monitored for viscosity
differences that may alter the aspiration rate.
3.1.7 All metals are not equally stable in the dlgestate,
especially 1f 1t contains only HNOs, not HN03 and HC1. The dlgestate
should be analyzed as soon as possible, with preference given to Sn, Sb,
Mo, Ba, and Ag.
3.2 Furnace procedure;
3.2.1 Although the problem of oxide formation 1s greatly reduced
with furnace procedures because atomization occurs 1n an inert
atmosphere, the technique 1s still subject to chemical Interferences.
The composition of the sample matrix can have a major effect on the
analysis. It is those effects which must be determined and taken Into
consideration in the analysis of each different matrix encountered. To
help verify the absence of matrix or chemical interference, the serial
dilution technique (see Paragraph 8.6) may be used. Those samples which
Indicate the presence of Interference should be treated 1n one or more of
the following ways:
7000 - 4
Revision
Date September 1986
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1. Successively dilute and reanalyze the samples to eliminate
Interferences.
2. Modify the sample matrix either to remove Interferences or to
stabilize the analyte. Examples are the addition of ammonium
nitrate to remove alkali chlorides and the addition of ammonium
phosphate to retain cadmium. The mixing of hydrogen with the
Inert purge gas has also been used to suppress chemical
Interference. The hydrogen acts as a reducing agent and aids 1n
molecular dissociation.
3. Analyze the sample by method of standard additions while
noticing the precautions and limitations of its use (see
Paragraph 8.7.2).
3.2.2 Gases generated 1n the furnace during atomizatlon may have
molecular absorption bands encompassing the analytical wavelength. When
this occurs, use either background correction or choose an alternate
wavelength. Background correction may also compensate for nonspecific
broad-band absorption interference.
3.2.3 Continuum background correction cannot correct for all types
of background Interference. When the background interference cannot be
compensated for, chemically remove the analyte or use an alternate form
of background correction, e.g., Zeeman background correction.
3.2.4 Interference from a smoke-producing sample matrix can
sometimes be reduced by extending the charring time at a higher
temperature or utilizing an ashing cycle in the presence of air. Care
must be taken, however, to prevent loss of the analyte.
3.2.5 Samples containing large amounts of organic materials should
be oxidized by conventional acid digestion before being placed in the
furnace. In this way, broad-band absorption will be minimized.
3.2.6 Anlon interference studies in the graphite furnace indicate
that, under conditions other than isothermal, the nitrate anlon is
preferred. Therefore, nitric add is preferable for any digestion or
solubilization step. If another acid in addition to HN03 1s required, a
minimum amount should be used. This applies particularly to hydrochloric
and, to a lesser extent, to sulfurlc and phosphoric adds.
3.2.7 Carbide formation resulting from the chemical environment of
the furnace has been observed. Molybdenum may be cited as an example.
When carbides form, the metal is released very slowly from the resulting
metal carbide as atomization continues. Molybdenum may require 30 sec or
more atomizatlon time before the signal returns to baseline levels.
Carbide formation 1s greatly reduced and the sensitivity increased with
the use of pyrolytically coated graphite. Elements that readily form
carbides are noted with the symbol (p) 1n Table 1.
7000 - 5
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3.2.8 For comments on spectral Interference, see Paragraph 3.1.5.
3.2.9 Cross-contamination and contamination of the sample can be
major sources of error because of the extreme sensitivities achieved with
the furnace. The sample preparation work area should be kept
scrupulously clean. All glassware should be cleaned as directed 1n
Paragraph 4.8. P1pet tips are a frequent source of contamination. If
suspected, they should be add soaked with 1:5 HN03 and rinsed thoroughly
with tap and delonlzed (Type II) water. The use of a better grade of
plpet tip can greatly reduce this problem. Special attention should be
given to reagent blanks In both analysis and In the correction of
analytical results. Lastly, pyrolytlc graphite, because of the
production process and handling, can become contaminated. As many as
five to ten high-temperature burns may be required to clean the tube
before use.
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer; Single- or dual-channel,
single- ordouble-beam1nstrumenthaving a grating monochromator,
photomultlpHer detector, adjustable slits, a wavelength range of 190 to
800 nm, and provisions for Interfacing with a strip-chart recorder.
4.2 Burner; The burner recommended by the particular Instrument
manufacturer should be used. For certain elements the nitrous oxide burner 1s
required.
4.3 Hollow cathode lamps; Single-element lamps are preferred but
multielement lamps may beused. Electrodeless discharge lamps may also be
used when available.
4.4 Graphite furnace; Any furnace device capable of reaching the
specified temperatures 1s satisfactory.
4.5 Strip-chart recorder; A recorder 1s recommended for furnace work so
that there will be a permanent record and that any problems with the analysis
such as drift, Incomplete atomlzatlon, losses during charring, changes 1n
sensitivity, peak shape, etc., can be easily recognized.
4.6 Plpets; Mlcrollter, with disposable tips. Sizes can range from 5
to 100 uL as required. Plpet tips should be checked as a possible source of
contamination prior to their use.
4.7 Pressure-reducing valves; The supplies of fuel and oxldant should
be maintainedatpressuressomewhat higher than the controlled operating
pressure of the Instrument by suitable valves.
4.8 Glassware; All glassware, polypropylene, or Teflon containers,
Including samplebottles, should be washed In the following sequence:
detergent, tap water, 1:1 nitric add, tap water, 1:1 hydrochloric add, tap
7000 - 6
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Date September 1986
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water, and Type II water. (Chromic add should not be used as a cleaning
agent for glassware 1f chromium 1s to be Included 1n the analytical scheme.)
If It can be documented through an active analytical quality control program
using spiked samples and reagent blanks that certain steps 1n the cleaning
procedure are not required for routine samples, those steps may be eliminated
from the procedure.
5.0 REAGENTS
5.1 Type II water (ASTM D1193): Use Type II water for the preparation
of all reagents and calibration standards and as dilution water.
5.2 Concentrated nitric acid (HMOs): Use a spectrograde acid certified
for AA use~PrepareaT7IdTlution with Type II water by adding the
concentrated acid to an equal volume of water.
5.3 Hydrochloric acid (HC1, 1:1): Use a spectrograde add certified for
AA use. Prepare a 1:1 dilution with Type II water by adding the concentrated
add to an equal volume of water.
5.4 Fuel and oxidant; Commercial grade acetylene is generally
acceptable"Air mayBesupplied from a compressed air line, a laboratory
compressor, or a cylinder of compressed air. Reagent grade nitrous oxide 1s
also required for certain determinations. Standard, commercially available
argon and nitrogen are required for furnace work.
5.5 Stock standard metal solutions; Stock standard solutions are
prepared fromhighpuritymetals,oxides, or nonhygroscoplc reagent-grade
salts using Type II water and redistilled nitric or hydrochloric acids. (See
individual methods for specific instructions.) Sulfuric or phosphoric adds
should be avoided as they produce an adverse effect on many elements. The
stock solutions are prepared at concentrations of 1,000 mg of the metal per
liter. Commercially available standard solutions may also be used. Where the
sample viscosity, surface tension, and components cannot be accurately matched
with standards, the method of standard addition (MSA) may be used (see
Paragraph 8.7).
5.6 Calibration standards; For those instruments which do not read out
directly 1n concentration, a calibration curve 1s prepared to cover the
appropriate concentration range. Usually, this means the preparation of
standards which produce an absorbance of 0.0 to 0.7. Calibration standards
are prepared by diluting the stock metal solutions at the time of analysis.
For best results, calibration standards should be prepared fresh each time a
batch of samples 1s analyzed. Prepare a blank and at least three calibration
standards 1n graduated amounts 1n the appropriate range of the linear part of
the curve. The calibration standards should be prepared using the same type
of acid or combination of acids and at the same concentration as will result
in the samples following processing. Beginning with the blank and working
7000 - 7
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Date September 1986
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toward the highest standard, aspirate the solutions and record the readings.
Repeat the operation with both the calibration standards and the samples a
sufficient number of times to secure a reliable average reading for each
solution. Calibration standards for furnace procedures should be prepared as
described on the Individual sheets for that metal.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See the Introductory material 1n Chapter Three, Metallic Analytes.
7.0 PROCEDURE .
7.1 Preliminary treatment of waste water, ground water, EP extracts, and
industrial waste 1s always necessary because of the complexity and variability
of sample matrices. Sol Ids, slurries, and suspended material must be
subjected to a solubllization process before analysis. This process may vary
because of the metals to be determined and the nature of the sample being
analyzed. SolubiUzatlon and digestion procedures are presented 1n Chapter
Three, Section 3.2, Sample Preparation Methods.
7.2 Direct aspiration (flame) procedure;
7.2.1 Differences between the various makes and models of
satisfactory atomic absorption spectrophotometers prevent the formulation
of detailed Instructions applicable to every Instrument. The analyst
should follow the manufacturer's operating instructions for a particular
Instrument. In general, after choosing the proper lamp for the analysis,
allow the lamp to warm up for a minimum of 15 m1n, unless operated 1n a
double-beam mode. During this period, align the Instrument, position the
monochromator at the correct wavelength, select the proper monochromator
slit width, and adjust the current according to the manufacturer's
recommendation. Subsequently, light the flame and regulate the flow of
fuel and oxldant. Adjust the burner and nebulizer flow rate for maximum
percent absorption and stability. Balance the photometer. Run a series
of standards of the element under analysis. Construct a calibration
curve by plotting the concentrations of the standards against
absorbances. Set the curve corrector of a direct reading instrument to
read out the proper concentration. Aspirate the samples and determine
the concentrations either directly or from the calibration curve.
Standards must be run each time a sample or series of samples 1s run.
7.3 Furnace procedure;
7.3.1 Furnace devices (fTameless atomizatlon) are a most useful
means of extending detection limits. Because of differences between
various makes and models of satisfactory instruments, no detailed
operating Instructions can be given for each Instrument. Instead, the
analyst should follow the instructions provided by the manufacturer of a
particular Instrument.
7000 - 8
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Date September 1986
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7.3.2 Background correction 1s Important when using flameless
atomizatlon, especially below 350 nm. Certain samples, when atomized,
may absorb or scatter light from the lamp. This can be caused by the
presence of gaseous molecular species, salt particles, or smoke 1n the
sample beam. If no correction 1s made, sample absorbance will be greater
than it should be, and the analytical result will be erroneously high.
Zeeman background correction 1s effective 1n overcoming composition or
structured background Interferences. It 1s particularly useful when
analyzing for As in the presence of Al and when analyzing for Se 1n the
presence of Fe.
7.3.3 Memory effects occur when the analyte 1s not totally
volatilized during atomizatlon. This condition depends on several
factors: volatility of the element and Its chemical form, whether
pyrolytlc graphite is used, the rate of atomizatlon, and furnace design.
This situation 1s detected through blank burns. The tube should be
cleaned by operating the furnace at full power for the required time
period, as needed, at regular intervals during the series of
determinations.
7.3.4 Inject a measured mlcroliter aliquot of sample into the
furnace and atomize. If the concentration found 1s greater than the
highest standard, the sample should be diluted in the same add matrix
and reanalyzed. The use of multiple Injections can Improve accuracy and
help detect furnace pipetting errors.
7.3.5 To verify the absence of interference, follow the serial
dilution procedure given in Paragraph 8.6.
7.3.6 A check standard should be run after approximately every 10
sample Injections. Standards are run in part to monitor the life and
performance of the graphite tube. Lack of reprodudbility or significant
change in the signal for the standard Indicates that the tube should be
replaced. Tube life depends on sample matrix and atomizatlon
temperature. A conservative estimate would be that a tube will last at
least 50 firings. A pyrolytlc coating will extend that estimated life by
a factor of three.
7.4 Calculation;
7.4.1 For determination of metal concentration by direct aspiration
and furnace: Read the metal value 1n ug/L from the calibration curve or
directly from the read-out system of the Instrument.
7.4.2 If dilution of sample was required:
ug/L metal in sample =
7000 - 9
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Date September 1986
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where:
A = ug/L of metal 1n diluted aliquot from calibration curve.
B = Add blank matrix used for dilution, ml.
C = sample aliquot, ml.
7.4.3 For solid samples, report all concentrations as ug/kg based
on wet weight. Hence:
A x V
ug metal/kg sample = Q
where:
A = ug/L of metal 1n processed sample from calibration curve.
V = final volume of the processed sample, ml.
W = weight of sample, grams.
7.4.4 Different Injection volumes must not be used for samples and
standards. Instead, the sample should be diluted and the same size
Injection volume be used for both samples and standards. If dilution of
the sample was required:
(C + B^
ug/L of metal 1n sample = Z * .. '
where:
Z = ug/L of metal read from calibration curve or read-out system.
B = mL of add blank matrix used for dilution.
C = mL of sample aliquot.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 A calibration curve must be prepared each day with a minimum of a
reagent blank and three standards, verified by use of at least a reagent blank
and one standard at or near the mid-range. Checks throughout the day must be
within 20% of original curve.
8.3 If 20 or more samples per day are analyzed, the working standard
curve must be verified by running an additional standard at or near the mid-
range every 10 samples. Checks must be within +20% of true value.
8.4 At least one duplicate and one spike sample should be run every 20
samples, or with each matrix type to verify precision of the method.
7000 - 10
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8.5 Where the sample matrix 1s so complex that viscosity, surface
tension, and components cannot be accurately matched with standards, the
method of standard addition may be used (see Section 8.7 below).
8.6 Serial dilution; Withdraw from the sample two equal allquots. To
one of the allquots add a known amount of analyte and dilute both allquots to
the same predetermined volume. (The dilution volume should be based on the
analysis of the undiluted sample. Preferably, the dilution should be 1:4,
while keeping In mind that the diluted value should be at least 5 times the
Instrument detection limit. Under no circumstances should the dilution be
less than 1:1.) The diluted allquots should then be analyzed, and the
unsplked results, multiplied by the dilution factor, should be compared to the
original determination. Agreement of the results (within 10%) indicates the
absence of interference. Comparison of the actual signal from the spike with
the expected response from the analyte in an aqueous standard should help
confirm the finding from the dilution analysis.
8.7 Method of standard additions;
8.7.1 In the simplest version of this method, equal volumes of
sample are added to a delonlzed distilled (Type II) water blank and to a
standard (refer to Paragraph 8.7.3). If a higher degree of accuracy Is
required, more than one addition should be made. The absorbance of each
solution is determined and then plotted on the vertical axis of a graph,
with the concentrations of the known standards plotted on the horizontal
axis. When the resulting line is extrapolated back to zero absorbance,
the point of Interception of the abscissa 1s the concentration of the
unknown. The abscissa on the left of the ordinate 1s scaled the same as
on the right side, but in the opposite direction from the ordinate. An
example of a plot so obtained is shown in Figure 1.
8.7.2 The method of standard additions can be very useful; however,
for the results to be valid the following limitations must be taken Into
consideration:
a. The absorbance plot of sample and standards must be linear over
the concentration range of concern. For best results, the slope of
the plot should be nearly the same as the slope of the aqueous
standard curve. If the slope is significantly different (more than
20%), caution should be exercised.
b. The effect of the Interference should not vary as the ratio of
analyte concentration to sample matrix changes, and the standard
addition should respond in a similar manner as the analyte.
c. The determination must be free of spectral Interference and
corrected for nonspecific background interference.
7000 - 11
Revision 0
Date September 1986
-------
8.7.3 The simplest version of this technique is the single-addition
method, in which two Identical allquots of the sample solution, each of
Volume Vx, are taken. To the first (labeled A) is added a small volume
Vs of a standard analyte solution of concentration cs. To the second
(labeled B) is added the same volume Vs of the solvent. The analytical
signals of A and B are measured and corrected for nonanalyte signals.
The unknown sample concentration cx is calculated:
seVs
C.. = "i
A - V Vx
where S/\ and SB are the analytical signals (corrected for the blank) of
solutions A and B, respectively. Vs and cs should be chosen so that S/\
is roughly twice SB on the average. It is best if Vs is made much less
than Vx, and thus cs 1s much greater than cx, to avoid excess dilution of
the sample matrix. If a separation or concentration step is used, the
additions are best made first and carried through the entire procedure.
9.0 METHOD PERFORMANCE
9.1 See individual methods.
10.0 REFERENCES
1. U.S. Environmental Protection Agency, Methods for Chemical Analysis of
Water and Wastes, EPA-600/4-79-020 (revised March 1983).
7000 - 12
Revision
Date September 1986
-------
Concentration
Cone, of
Sample
AddnO
No Addn
Addn 1
Addn of 50%
of Expected
Amount
Addn 2 Addn 3
Addn of 100% Addn of 150%
of Expected of Expected
Amount Amount
Figure 1. Standard Addition Plot.
7000 - 13
Revision Q
Date September 1986
-------
METHOD 7000
ATOMIC ABSORPTION METHODS
7. 1
Oo
preliminary
treatment through
solubillzetion and
digestion procedures
(Chapter 3.
Section 3.2)
7.3.1
Choose and
prepare hollow
cathode lamp
7.3.1
Adjust and
align equipment
7.2.1
Light flame
and regulate
7.Z.ll
Run standards
o
7.3.11
1 Follow
operating
instructions
from instrument
manufacturer
7.3.Z
Male* background
correction
Inject and
atomize part
of sample
o
7000 - 14
Revision o
Date September 1986
-------
METHOD 7000
ATOMIC ABSORPTION METHODS
(Continued)
0
7.2.1J
Construct
a calibration
curve and set
curve corrector
7.3.41
Dilute sample
7.2. 1
Aspirate
samples
o
Concentration
greater than
highest
standard?
7.4
Determine
concentration
f Stop . J
7.3.5
Verify
absence
of interference
using serial
dilution
(see 8.8)
7.3.6
Run a check
standard
7000 - 15
Revision 0
Date September 1986
-------
METHOD 7020
ALUMINUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Aluminum may be as much as 15% Ionized 1n a nitrous-oxide/acetylene
flame. Use of an 1on1zat1on suppressor (1,000 ug/mL K as KC1) as In Method
7000, Paragraph 3.1.4, will eliminate this Interference.
3.3 Aluminum 1s a very common contaminant, and great care should be
taken to avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Aluminum hollow cathode lamp.
4.2.2 Wavelength: 324.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of aluminum metal 1n dilute
HC1 with gentle warming. Dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify by
comparison with a second standard.
7020 - 1
Revision
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentration as will result 1n the sample to be analyzed after
processing. Samples and standards should also contain 2 ml KC1/100 ml
solution (Paragraph 3.2 above).
5.3 Potassium chloride solution; Dissolve 95 g potassium chloride (KC1)
in Type II water and dilute to 1 liter.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 202.1 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 5-50 mg/L, with a wavelength of 309.3 nm.
Sensitivity: 1 mg/L.
Detection limit: 0.1 mg/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
Method 202.1, December 1982.
7020 - 2
Revision
Date September 1986
-------
METHOD 7020
ALUMINUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
i
7.1
f
EC
preparat
choc
sect!
7.2
"or
imple
Ion see
ter 3.
on 3.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7020 - 3
Revision 0
Date September 1986
-------
METHOD 7040
ANTIMONY (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 In the presence of lead (1,000 mg/L), a spectral Interference may
occur at the 217.6-nm resonance line. In this case, the 231.1-nm antimony
line should be used.
3.3 Increasing the add concentrations decreases the antimony
absorption. To avoid this effect, the add concentration 1n the samples and
1n the standards should be matched.
3.4 Excess concentrations of copper and nickel (and possibly other
elements), as well as adds, can Interfere with antimony analyses. If the
sample contains these matrix types, either matrices of the standards should be
matched to those of the sample or the sample should be analyzed using a
nitrous oxide/acetylene flame.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Antimony hollow cathode lamp or electrode!ess discharge lamp.
4.2.2 Wavelength: 217.6 nm (primary); 231.1 nm (secondary).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Fuel lean.
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7040 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards:
5.2.1 Stock solution: Carefully weigh 2.7426 g of antimony
potassium tartrate, K(SbO)C^Os'1/2^0 (analytical reagent grade), and
dissolve in Type II water. Dilute to 1 liter with Type II water; 1 ml =
1 mg Sb (1,000 mg/L). Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should contain 0.2% (v/v) HN03 and 1-2% v/v HC1, prepared using the same
types of acid and at the same concentrations as in the sample after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Method 3005.Method 3005, a soft digestion, is presently the
only digestion procedure recommended for Sb. It yields better recoveries than
either Method 3010 or Method 3050. There is no hard digestion for Sb at this
time.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration Procedure.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 1-40 mg/L with a wavelength of 217.6 nm.
Sensitivity: 0.5 mg/L.
Detection limit: 0.2 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 5.0 and 15 mg
Sb/L gave the standard deviations of +0.08 and +0.1, respectively. Recoveries
at these levels were 96% and 97%, respectively.
9.3 For concentrations of antimony below 0.35 mg/L, the furnace
procedure (Method 7041) is recommended.
7040 - 2
Revision 0
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 204.1.
7040 - 3
Revision
Date September 1986
-------
METHOD 7cuo
ANTIMONY (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7.1
prepar
CH
sect!
For
ample
ation-
apter
on 3.1
see
3.
.3
7.2
Analyze ualng
Method 7000.
Section 7.2
f Stop J
7040 - 4
Revision 0
Date September 1986
-------
METHOD 7041
ANTIMONY (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 High lead concentration may cause a measurable spectral interference
on the 217.6-nm line. If this interference is expected, the secondary
wavelength should be employed or Zeeman background correction used.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125*C.
4.2.2 Ashing time and temp: 30 sec at 800*C.
4.2.3 Atomizing time and temp: 10 sec at 2700*C.
4.2.4 Purge gas: Argon or nitrogen.
4.2.5 Wavelength: 217.6 nm (primary); 231.1 nm (alternate).
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
.particular instrument manufacturer.
NOTE: The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20-uL injection,
continuous-flow purge gas, and nonpyrolytic graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomization can be operated using lower atomization temperatures
for shorter time periods than the above-recommended settings.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7041 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Carefully weigh 2.7426 g of antimony
potassium tartrate (analytical reagent grade) and dissolve 1n Type II
water. Dilute to 1 liter with Type II water; 1 ml = 1 mg Sb
(1,000 mg/L). Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should contain 0.2% (v/v) HNOs and 1-2% (v/v) HC1, prepared using the
same types of acid and at the same concentrations as in the sample after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
i
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Method 3005.Method 3005, a soft digestion, 1s presently the
only digestion procedure recommended for Sb. It yields better recoveries than
either Method 3010 or Method 3050. There 1s no hard digestion for Sb at this
time.
NOTE: The addition of HC1 acid to the digestate prevents the furnace
analysis of this digestate for many other metals.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
9.2 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 20-300 ug/L.
Detection limit: 3 ug/L.
7041 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 204.2.
7041 - 3
Revision
Date September 1986
-------
METHOD 7041
ANTIMONY (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
s
.O
Prepare
standards
7. 1
prepar
cf
sec
For
sample
atlon sea
apter -3.
tlon 3.2
7.2
Analyze using
Method 7OOO.
Section 7.3.
calculation 7.4
f StOP J
7041 - 4
Revision 0
Date September 1986
-------
METHOD 7060
ARSENIC (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7060 is an atomic absorption procedure approved for
determining the concentration of arsenic in wastes, mobility procedure
extracts, soils, and ground water. All samples must be subjected to an
appropriate dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7060, samples must be prepared in order
to convert organic forms of arsenic to Inorganic forms, to minimize organic
interferences, and to convert the sample to a suitable solution for analysis.
The sample preparation procedure varies depending on the sample matrix.
Aqueous samples are subjected to the acid digestion procedure described in
this method. Sludge samples are prepared using the procedure described in
Method 3050.
2.2 Following the appropriate dissolution of the sample, a
representative aliquot of the dlgestate 1s spiked with a nickel nitrate
solution and is placed manually or by means of an automatic sampler Into a
graphite tube furnace. The sample aliquot is then slowly evaporated to
dryness, charred (ashed), and atomized. The absorption of hollow cathode or
EDL radiation during atomization will be proportional to the arsenic
concentration.
2.3 The typical detection limit for this method 1s 1 ug/L.
3.0 INTERFERENCES
3.1 Elemental arsenic and many of its compounds are volatile; therefore,
samples may be subject to losses of arsenic during sample preparation. Spike
samples and relevant standard reference materials should be processed to
determine if the chosen dissolution method 1s appropriate.
3.2 Likewise, caution must be employed during the selection of
temperature and times for the dry and char (ash) cycles. A nickel nitrate
solution must be added to all digestates prior to analysis to minimize
volatilization losses during drying and ashing.
3.3 In addition to the normal interferences experienced during graphite
furnace analysis, arsenic analysis can suffer from severe nonspecific
absorption and light scattering caused by matrix components during
atomization. Arsenic analysis 1s particularly susceptible to these problems
because of Its low analytical wavelength (193.7 nm). Simultaneous background
7060 - 1
Revision 0
Date September 1986
-------
correction must be employed to avoid erroneously high results. Aluminum 1s a
severe positive Interferent 1n the analysis of arsenic, especially using D£
arc background correction. Zeeman background correction 1s very useful 1n
this situation.
3.4 If the analyte 1s not completely volatilized and removed from the
furnace during atomlzatlon, memory effects will occur. If this situation 1s
detected by means of blank burns, the tube should be cleaned by operating the
furnace at full power at regular Intervals 1n the analytical scheme.
4.0 APPARATUS AND MATERIALS
4.1 Griffin beaker; 250 ml.
4.2 Volumetric flasks: 10-mL.
4.3 Atomic absorption spectrophotometer; Single or dual channel,
single- ordouble-beam Instrumenthavinga~~ grating monochromator, photo-
multlpHer detector, adjustable si Its, a wavelength range of 190 to 800 nm,
and provisions for simultaneous background correction and Interfacing with a
strip-chart recorder.
4.4 Arsenic hollow cathode lamp, or electrodeless discharge lamp (EDL);
EDLs provide better sensitivity for arsenic analysis.
4.5 Graphite furnace; Any graphite .furnace device with the appropriate
temperature and timing controls.
4.6 Strip-chart recorder; A recorder Is strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis such as drift, Incomplete atomlzatlon, losses during
charring, changes 1n sensitivity, etc., can easily be recognized.
4.7 Plpets; M1crol1ter with disposable tips. Sizes can range from
5 to 1,000 uL, as required.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities. <
5.2 Concentrated nitric acid; Add should be analyzed to determine
levels of Impurities. If a method blank using the add 1s
-------
5.4 Arsenic standard stock solution (1,000 mg/L): Either procure a
certified aqueous standard fromasupplier and verify by comparison with a
second standard, or dissolve 1.320 g of arsenic trloxide (As20^, analytical
reagent grade) or equivalent 1n 100 mL of Type II water containing 4 g NaOH.
Acidify the solution with 20 mL concentrated HNOa and dilute to 1 liter
(1 mL = 1 mg As).
5.5 Nickel nitrate solution (5%); Dissolve 24.780 g of ACS reagent
grade Ni(N03)2*6H20 or equivalent in type II water and dilute to 100 mL.
5.6 Nickel nitrate solution (1%); Dilute 20 mL of the 5% nickel nitrate
to 100 mL with Type II water.
5.7 Arsenic working standards; Prepare dilutions of the stock solution
to be used as calibrationstandards at the time of the analysis. Withdraw
appropriate allquots of the stock solution, add 1 mL of concentrated HN03,
2 mL of 30% H202, and 2 mL of the 5% nickel nitrate solution. Dilute to
100 mL 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 1n Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, adds, and
Type II water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile arsenic compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric add.
6.5 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation; Aqueous samples should be prepared in the
manner described in Paragraphs 7.1.1-7.1.3. Sludge-type samples should be
prepared according to Method 3050. The applicability of a sample-preparation
technique to a new matrix type must be demonstrated by analyzing spiked
samples and/or relevant standard reference materials.
7.1.1 Transfer 100 mL of well-mixed sample to a 250-mL Griff1n
beaker; add 2 mL of 30% H?02 and sufficient concentrated HN03 to result
1n an acid concentration of 1% (v/v). Heat for 1 hr at 95*C or until the
volume is slightly less than 50 mL.
7.1.2 Cool and bring back to 50 mL with Type II water.
7060 - 3
Revision 0
Date September 1986
-------
7.1.3 P1pet 5 ml of this digested solution Into a 10-mL volumetric
flask, add 1 mL of the 1% nickel nitrate solution, and dilute to 10 ml
with Type II water. The sample 1s now ready for Injection Into the
furnace.
7.2 The 193.7-nm wavelength line and a background correction system are
required. Follow the, manufacturer's suggestions for all other spectrophoto-
meter parameters.
7.3 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Because temperature-sensing mechanisms and temperature
controllers can vary between Instruments or with time, the validity of the
furnace parameters must be periodically confirmed by systematically altering
the furnace parameters while analyzing a standard. In this manner, losses of
analyte due to overly high temperature settings or losses 1n sensitivity due
to less than optimum settings can be minimized. Similar verification of
furnace parameters may be required for complex sample matrices.
7.4 Inject a measured mlcroHter aliquot of sample Into the furnace and
atomize. If the concentration found 1s greater than the highest standard, the
sample should be diluted 1n the same add matrix and reanalyzed. The use of
multiple Injections can Improve accuracy and help detect furnace pipetting
errors.
7.5 Analyze all EP extracts, all samples analyzed as part of a dellsting
petition, and all samples that suffer from matrix Interferences by the method
of standard additions.
7.6 Run a check standard after every 10 Injections of samples.
Standards are run 1n part to monitor the life and performance of the graphite
tube. Lack of reproduc1bH1ty or significant change 1n the signal for the
standard Indicates that the tube should be replaced.
7.7 Calculate metal concentrations by (1) the method of standard
additions, or (2) from a calibration curve, or (3) directly from the
Instrument's concentration readout. All dilution or concentration factors
must be taken Into account. Concentrations reported for multlphased samples
must be appropriately qualified (e.g., 5 ug/g aqueous phase).
7.8 Duplicates, spiked samples, and check standards should be routinely
analyzed.
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.
7060 - 4
Revision 0
Date September 1986
-------
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 Employ a minimum of one blank per sample batch to determine if
contamination or any memory effects are occurring.
8.5 Verify calibration with an independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 20 samples. A duplicate
sample is a sample brought through the whole sample preparation and analytical
process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a deli sting petition, and whenever a new sample matrix is being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 206.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The optimal concentration range for this method is 5-100 ug/L.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 206.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7060 - 5
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample
Matrix
Preparation
Method
Laboratory
Replicates
Contaminated soil 3050
01ly soil 3050
NBS SRM 1646 Estuarlne sediment 3050
Emission control dust 3050
2.0, 1.8 ug/g
3.3, 3.8 ug/g
8.1, 8.33 ug/ga
430, 350 ug/g
aB1as of -30 and -28% from expected, respectively.
7060 - 6
Revision 0
Date September 1986
-------
METHOD 7060
ARSENIC (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
Aqueous
samples
Sludge-type
X» \^ ^AWUW«- ^7^
Type of samplers. samples
- for sample
preparation
7.1.1
I Transfer
sample to
beaker: add
H, Oz. and cone.
HNOS: neat
7. 1
Prepare samples
according to
Method 30SO
7.1.21
Cool: increase
volume
7.1.3
1 Pipet
solution
into flask: add
nickel nitrate:
dilute
7060 - 7
Revision 0
Date September 1986
-------
METHOD 7060
ARSENIC (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
(Continued)
Set up
spectrophoto-
meter with
correct
parameters
7.3
7.5
Analyze
by method of
standard
additions
Periodically
verify furnace
parameters
7.4
7.6 I
Run
check standard
after every 10
injections
Inject
aliquot of
sample into
furnace:
atomize
Is
concentration
> highest
standard?
Dilute sample
and reanalyze
7.7
Calculate matal
concentrations
7.8
Analyze
duplicates.
spiked samples
and check
standards
( Stop J
7060 - 8
Revision 0
Date September 1986
-------
METHOD 7061
ARSENIC (ATOMIC ABSORPTION. GASEOUS HYDRIDE)
1.0 SCOPE AND APPLICATION
1.1 Method 7061 is an atomic absorption procedure for determining the
concentration of arsenic in wastes, mobility procedure extracts, soils, and
ground water. Method 7061 is approved only for sample matrices that do not
contain high concentrations of chromium, copper, mercury, nickel, silver,
cobalt, and molybdenum. All samples must be subjected to an appropriate
dissolution step prior to analysis. Spiked samples and relevant standard
reference materials are employed to determine the applicability of the method
to a given waste.
2.0 SUMMARY OF METHOD
2.1 Samples are prepared according to the nitric/sulfuric acid digestion
procedure described in this method (Paragraph 7.1). Next, the arsenic in the
digestate is reduced to the trivalent form with tin chloride. The trivalent
arsenic is then converted to a volatile hydride using hydrogen produced from a
zinc/HCl reaction.
2.2 The volatile hydride is swept into an argon-hydrogen flame located
in the optical path of an atomic absorption spectrophotometer. The resulting
absorption of the lamp radiation is proportional to the arsenic concentration.
2.3 The typical detection limit for this method is 0.002 mg/L.
3.0 INTERFERENCES
3.1 High concentrations of chromium, cobalt, copper, mercury,
molybdenum, nickel, and silver can cause analytical interferences.
3.2 Traces of nitric acid left following the sample work-up can result
in analytical interferences. Nitric acid must be distilled off by heating the
sample until fumes of $03 are observed.
3.3 Elemental arsenic and many of its compounds are volatile; therefore,
certain samples may be subject to losses of arsenic during sample preparation.
4.0 APPARATUS AND MATERIALS
4.1 Beaker: 100-mL.
4.2 Electric hot plate.
7061 - 1
Revision 0
Date September 1986
-------
4.3 A commercially available zinc slurry/hydride generator or a
generator constructed from the following materials (see Figure 1):
4.3.1 Medicine dropper: Capable of fitting Into a size "0" rubber
stopper and delivering 1.5 ml.
4.3.2 Pear-shaped reaction flask: 50-mL, with two 14/20 necks
(Scientific Glass JM-5835).
4.3.3 Gas Inlet-outlet tube: Constructed from a micro cold-finger
condenser (JM-3325) by cutting the portion below the 14/20 ground-glass
joint.
4.3.4 Magnetic stlrrer: To homogenize the zinc slurry.
4.3.5 Polyethylene drying tube: 10-cm, filled with glass to
prevent parti cul ate matter from entering the burner.
4.3.6 Flow meter: Capable of measuring 1 I1ter/m1n.
4.4 Atomic absorption spectrophotometer; Single or dual channel,
single- or double-beam instrument having a" grating monochromator, photo-
multiplier detector, adjustable si Its, a wavelength range of 190 to 800 nm,
and provisions for Interfacing with a strip-chart recorder.
4.5 Burner; Recommended by the particular Instrument manufacturer for
the argon-hydrogen flame.
4.6 Arsenic hollow cathode lamp or arsenic electrode! ess discharge lamp.
4.7 Strip-chart recorder.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid (HNOs) : Add should be analyzed to
determine levels of Impurities. IT" a method blank 1s
-------
Argon
Flow Meter
JM-3325
Medicine
Dropper in
Size "0"
Rubber
Stopper
(Auxiliary Air)
Argon (Nebulizer Air)
Figure 1. Zinc slurry hydride generator apparatus set-up and AAS sample introduction system.
7061 - 3
Revision p
Date September 1986
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5.5 Diluent; Add 100 mL 18 N ^$04 and 400 ml concentrated HC1 to
400 ml Type II water and dilute to a final volume of 1 liter with Type II
water.
5.6 Potassium iodide solution; Dissolve 20 g KI 1n 100 ml Type II
water.
5.7 Stannous chloride solution; Dissolve 100 g SnCl2 1n 100 ml
concentrated HC1.
5.8 Arsenic solutions;
5.8.1 Arsenic standard solution (1,000 mg/L): Either procure a
certified aqueous standard from a supplier and verify by comparison with
a second standard, or dissolve 1.320 g of arsenic trioxide AS203
(analytical reagent grade) or equivalent 1n 100 ml of Type II water
containing 4 g NaOH. Acidify the solution with 20 ml concentrated HN03
and dilute to 1 liter.
5.8.2 Intermediate arsenic solution: Pi pet 1 ml stock arsenic
solution into a 100-mL volumetric flask and bring to volume with Type II
water containing 1.5 ml concentrated HMOs/liter (1 ml = 10 ug As).
5.8.3 Standard arsenic solution: Pi pet 10 ml Intermediate arsenic
solution into a 100-mL volumetric flask and bring to volume with Type II
water containing 1.5 ml concentrated HN03/liter (1 ml = 1 ug As).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, adds, and
Type II water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile arsenic compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric add.
6.5 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Place a 50-mL aliquot of digested sample (or, in the case of
analysis of EP extracts, 50 mL) of the material to be analyzed 1n a 100-mL
beaker. Add 10 mL concentrated HNOs and 12 mL 18 N ^SO/p Evaporate the
7061 - 4
Revision
Date September 1986
-------
sample 1n the hood on an electric hot plate until white $03 fumes are observed
(a volume of about 20 ml). Do not let the sample char. If charring occurs,
immediately turn off the heat, cool, and add an additional 3 ml of HN03.
Continue to add additional HN03 in order to maintain an excess (as evidenced
by the formation of brown fumes). Do not let the solution darken, because
arsenic may be reduced and lost. When the sample remains colorless or straw
yellow during evolution of $03 fumes, the digestion 1s complete. Cool the
sample, add about 25 ml Type II water, and again evaporate until $03 fumes are
produced in order to expel oxides of nitrogen. Cool. Transfer the digested
sample to a 100-mL volumetric flask. Add 40 mL of concentrated HC1 and bring
to volume with Type II water.
7.2 Prepare working standards from the standard arsenic solution.
Transfer 0, 0.5, 1.0, 1.5, 2.0, and 2.5 ml of standard to 100-mL volumetric
flasks and bring to volume with diluent. These concentrations will be 0, 5,
10, 15, 20, and 25 ug As/liter.
7.3 If EP extracts are being analyzed or if a matrix interference is
encountered, take the 15-, 20-, and 25-mg/liter standards and quantitatively
transfer 25 ml of each of these standards Into separate 50-mL volumetric
flasks. Add 10 ml of the prepared sample to each flask. Bring to volume with
Type II water containing 1.5 ml HCl/liter.
7.4 Add 10 ml of prepared sample to a 50-mL volumetric flask. Bring to
volume with Type II water containing 1.5 ml HCl/liter. This is the zero
addition aliquot.
NOTE; The absorbance from the zero addition aliquot will be one-fifth
that produced by the prepared sample. The absorbance from the
spiked samples will be one-half that produced by the standards
plus the contribution from one-fifth of the prepared sample.
Keeping these absorbances 1n mind will assist 1n judging the
correct dilutions to produce optimum absorbance.
7.5 Transfer a 25-mL portion of the digested sample or standard to the
reaction vessel and add 1 ml KI solution. Add 0.5 ml SnCl2 solution. Allow
at least 10 m1n for the metal to be reduced to Its lowest oxidation state.
Attach the reaction vessel to the special gas Inlet-outlet glassware. Fill
the medicine dropper with 1.50 ml zinc slurry that has been kept 1n suspension
with the magnetic stlrrer. Firmly Insert the stopper containing the medicine
dropper into the side neck of the reaction vessel. Squeeze the bulb to
Introduce the zinc slurry into the sample or standard solution. The metal
hydride will produce a peak almost immediately. After the recorder pen begins
to return to the base line, the reaction vessel can be removed.
CAUTION: Arslne 1s very toxic. Precautions must be taken to avoid
Inhaling arslne gas.
7.6 Use the 193.7-nm wavelength and background correction for the
analysis of arsenic.
7061 - 5
Revision 0
Date September 1986
-------
7.7 Follow the manufacturer's Instructions for operating an argon-
hydrogen flame. The argon-hydrogen flame 1s colorless; therefore, 1t may be
useful to aspirate a low concentration of sodium to ensure that Ignition has
occurred.
7.8 If the method of standard additions was employed, plot the
absorbances of spiked samples and blank vs. the concentrations. The
extrapolated value will be one-fifth the concentration of the original sample.
If the plot does not result 1n a straight line, a nonlinear Interference 1s
present. This problem can sometimes be overcome by dilution or addition of
other reagents 1f there 1s some knowledge about the waste. If the method of
standard additions was not required, then the concentration can be part of the
calibration curve.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples 1f they >are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine 1f
contamination or any memory effects are occurring.
8.5 Verify calibration with an Independently prepared check standard
every 15 samples.
8.6 Run one spike duplicate sample for every 20 samples. A duplicate
sample 1s a sample brought through the whole sample preparation and analytical
process.
8.7 The method of standard additions shall be used for the analysis of
all EP extracts, on all analyses submitted as part of a dellstlng petition,
and whenever a new sample matrix 1s being analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 206.3 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods For Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 206.3.
7061 - 6
Revision 0
Date September 1986
-------
METHOD 7O61
ARSENIC (ATOMIC ABSORPTION. GASEOUS HYDRIDE)
7. 1
Place
aliquot of
digested sample
In beaker
7. i
When
digestion
Is complete.
cool sample: add
Type II water:
evaporate: cool
Add cone.
HNO, and H.SO-f:
evaporate
sample
Turn off heat.
cool, and add
7. 1
Transfer
digested sample
to flask; add
cone. HC1:
bring to volume
7.Z
Prepare
working
standards:
transfer to
flasks: bring
to volume
Continue adding
HNOj
7.3
Take standards and
transfer part of each
to separate flasks:
add prepared sample
to each flask:
bring to volume
7061 - 7
Revision o
Date September 1986
-------
METHOD 7061
ARSENIC (ATOMIC ABSORPTION. GASEOUS HYDRIDE)
(Continued)
7.4
1 Ada
prepared sample
to flask: bring
to volume:
use as blank
7.5
7.5
I Introduce
zinc slurry
into sample
or standard
solution
Transfer
portion
of digested
sample or
standard to
reaction vessel
7.5
7.6
Use
193.7-nm
wavelength
end background
correction for
analysis
Add KI
solution; add
SnCl£ solution
7.5
7.7 To
I operate
argon Hydrogen
flame, follow
manufacturer's
Instructions
Reduce metal to
Its lowest
oxidation state
7.5
Attach reaction
vessel to gas
glassware: fill
medicine dropper with
zinc slurry: Insert
Into reaction vessel
o
7.8
1 Plot
ebsorbancas of
spiked samples.
blank vs the
concentrations
Was method of
standard
additions
employed?
concentration
be part of
calibration
curve
7061 - 8
Revision 0
Date September 1986
-------
METHOD 7080
BARIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 High hollow cathode current settings and a narrow spectral band pass
must be used, because both barium and calcium emit strongly at barium's
analytical wavelength.
3.3 Barium undergoes significant 1on1zat1on 1n the nitrous oxide/
acetylene flame, resulting 1n a significant decrease 1n sensitivity. All
samples and standards must contain 2 ml of the KC1 1on1zat1on suppressant
(Section 5.2.3 below) per 100 ml of solution.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Barium hollow cathode lamp.
4.2.2 Wavelength: 553.6 nm.
4.2.3 Fuel: Acetylene.
4.2.4 0x1dant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.7787 g barium chloride
(BaCl2*2H20, analytical reagent grade 1n Type II water and dilute to
7080 - 1
Revision
Date September 1986
-------
1 liter. Alternatively, procure a certified standard from a supplier and
verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result in the sample to be analyzed after
processing. All calibration standards and samples should contain
2 mL/100 ml of the potassium chloride (ionlzation suppressant) solution
described in Section 5.2.3.
5.2.3 Potassium chloride solution: Dissolve 95 g potassium
chloride (KC1) 1n Type II water and dilute to 1 liter.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 'METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 1-20 mg/L with a wavelength of 553.6 nm.
Sensitivity: 0.4 mg/L.
Detection limit: 0.1 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 0.4 and 2 mg
Ba/L gave standard deviations of +0.043 and +0.13, respectively. Recoveries
at these levels were 94% and 113%, respectively.
10.0 REFERENCES
1. .Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 208.1.
7080 - 2
Revision 0
Date September 1986
-------
METHOD 7080
BARIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7.1
prepar
cr
sec
For
aomple
ation sea
apter 3..
tlon 3.2
7.2
Analyze using
Method 7000.
Section 7.2
( Stop J
7080 - 3
Revision 0
Date September 1986
-------
METHOD 7090
BERYLLIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction may be required because nonspecific absorption
and light scattering can be significant at the analytical wavelength.
3.3 Concentrations of aluminum greater than 500 ppm may suppress
beryllium absorbance. The addition of 0.1% fluoride has been found effective
in eliminating this interference. High concentrations of magnesium and
silicon cause similar problems and require the use of the method of standard
additions.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Beryllium hollow cathode lamp.
4.2.2 Wavelength: 234.9 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 11.6586 g beryllium sulfate, BeS04,
in Type II water containing 2 mL nitric acid and dilute to 1 liter.
7090 - 1
Revision
Date September 1986
-------
Beryllium metal can also be dissolved 1n ^$04. Alternatively, procure a
certified standard from a supplier and verify by comparison with a second
standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing (0.5% v/v
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample Preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.05-2 mg/L with a wavelength of 234.9 nm.
Sensitivity: 0.025 mg/L.
Detection limit: 0.005 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial -domestic
waste effluent, digested with Method 3010, at concentrations of 0.01 and 0.25
mg/L gave standard deviations of +0.001 and +0.002, respectively. Recoveries
at these levels were 100% and 97%, "respectively.
9.3 For concentrations of beryllium below 0.02 mg/L, the furnace proce-
dure (Method 7091) 1s recommended.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 210.1.
7090 - 2
Revision
Date September 1986
-------
METHOD 7090
BERYLLIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
s
.0 1
Prepare
standards
7.1
prepar
cr
sec
For
sample
atlon sea
lapter 3.
tion 3.2
7.2
Analyza using
Method 7000.
Section 7.2
f Stop J
7090 - 3
Revision 0
Date September 1986
-------
METHOD 7091
BERYLLIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 The long residence time and high concentrations of the atomized
sample 1n the optical path of the graphite furnace can result 1n severe
physical and chemical Interferences. Furnace parameters must be optimized to
minimize these effects.
3.3 In addition to the normal Interferences experienced during graphite
furnace analysis, beryllium analysis can suffer from severe nonspecific ab-
sorption and light scattering caused by matrix components during atomlzatlon.
Simultaneous background correction 1s required to avoid erroneously high
results.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125*C.
4.2.2 Ashing time and temp: 30 sec at 1000*C.
4.2.3 Atomizing time and temp: 10 sec at 2800*C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 234.9 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular Instrument manufacturer.
NOTE: The above concentration values and Instrument conditions are for a
Perkln-Elmer HGA-2100, based on the use of a 20-uL Injection,
continuous-flow purge gas, and nonpyrolytlc graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomlzatlon can be operated using lower atomlzatlon temperatures
for shorter time periods than the above-recommended settings.
7091 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 11.6586 g beryllium sulfate,
1n Type II water containing 2 ml concentrated nitric acid and dilute to
1 liter. Beryllium metal can also be dissolved in add. Alternatively,
procure a certified standard from a supplier and verify by comparison
with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as cali-
bration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentrations as 1n the sample after processing (0.5% v/v HNOs).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample Preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
9.2 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 1-30 ug/L.
Detection limit: 0.2 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 210.2.
7091 - 2
Revision 0
Date September 1986
-------
METHOD 7O91
BERYLLIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
f Start J
3.0
Prepare
tandards
7.1
1 For'
ample
preparation see
chapter 3.
ection 3.2
7.2
Analyze using
Method 7000.
Section 7.3.
calculation 7.4
( Stop J
7091 - 3
Revision 0
Date September 1986
-------
METHOD 7130
CADMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Nonspecific absorption and light scattering can be significant at
the analytical wavelength. Thus background correction 1s required.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Cadmium hollow cathode lamp.
4.2.2 Wavelength: 228.8 rim.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g cadmium metal (analytical
reagent grade) 1n 20 mL of 1:1 HNOs and dilute to 1 liter with Type II
water. Alternatively, procure a certified standard from a supplier and
verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as cali-
bration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
7130 - 1
Revision
Date September 1986
-------
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.05-2 mg/L with a wavelength of 228.8 nm.
Sensitivity: 0.025 mg/L.
Detection limit: 0.005 mg/L.
9.2 For concentrations of cadmium below 0.02 mg/L, the furnace procedure
(Method 7131) 1s recommended.
9.3 Precision and accuracy data are available 1n Method 213.1 of Methods
for Chemical Analysis of Water and Wastes.
9.4 The data shown 1n Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 213.1.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7130 - 2
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Emission control dust 3050 2,770, 1,590 ug/g
Wastewater treatment sludge 3050 12,000, 13,000 ug/g
7130 - 3
Revision
Date September 1986
-------
METHOD 7130
CADMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.
O
Prepare
standards
7. 1
1 For
sample
preparation, see
chapter 3.
section 3.2
7.2
Analyze using
Method 70OO.
Section 7. a
f Stop J
7130 - 4
Revision Q
Date September 1986
-------
METHOD 7131
CADMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 In addition to the normal interferences experienced during graphite
furnace analysis, cadmium analysis can suffer from severe nonspecific absorp-
tion and light scattering caused by matrix components during atomization.
Simultaneous background correction is required to avoid erroneously high
results.
3.3 Excess chloride may cause premature volatilization of cadmium.
Ammonium phosphate used as a matrix modifier minimizes this loss.
3.4 Many plastic pipet tips (yellow) contain cadmium. Use "cadmium-
free" tips.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125*C.
4.2.2 Ashing time and temp: 30 sec at 500*C.
4.2.3 Atomizing time and temp: 10 sec at 1900*C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 228.8 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular instrument manufacturer.
NOTE: The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20-uL injection,
continuous-flow purge gas, and nonpyrolytic graphite. Smaller sizes
of furnace devices or those employing faster rates of atomization
can be operated using lower atomization temperatures for shorter
time periods than the above-recommended settings.
7131 - 1
Revision 0
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of cadmium metal
(analytical reagent grade) 1n 20 ml of 1:1 HN03 and dilute to 1 liter
with Type II water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock cadmium solution to be used as
calibration standards at the time of analysis. To each 100 ml of
standard and sample alike add 2.0 ml of the ammonium phosphate solution.
The calibration standards should be prepared to contain 0.5% (v/v) HN03.
5.2.3 Ammonium phosphate solution (40%): Dissolve 40 g of ammonium
phosphate, (NH4)2HP04 (analytical reagent grade), 1n Type II water and
dilute to 100 ml.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
1s given 1n Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 213.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.5-10 ug/L.
Detection limit: 0.1 ug/L.
7131 - 2
Revision
Date September 1986
-------
9.3 The data shown 1n Table 1 were obtained from records of state anc
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 213.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7131 - 3
Revision 0
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Lagoon soil 3050 0.10, 0.095 ug/g
NBS SRM 1646 Estuarlne sediment 3050 0.35 ug/ga
Solvent extract of oily waste 3030 1.39, 1.09 ug/L
aB1as of -3% from expected value.
7131 - 4
Revision 0
Date September 1986
-------
METHOD 7131
CAOXUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
5.
O
Prepare
standards
7. 1
1 For
sample
preparation see
chapter 3.
section 3.2
_7.£J
Analyze using
Method 7000.
Section 7.3.
calculation 7.4
f Stop J
7131 - 5
Revision 0
Date September 1986
-------
METHOD 7140
CALCIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000.
3.2 All elements forming stable oxyanlons (P, B, Si, Cr, S, V, T1, Al,
etc.) will complex calcium and Interfere unless lanthanum 1s added. Addition
of lanthanum to prepared samples rarely presents a problem because virtually
all environmental samples contain sufficient calcium to require dilution to be
1n the linear range of the method.
3.3 P04, 504, and Al are Interferents. High concentrations of Mg, Na,
and K Interfere.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Calcium hollow cathode lamp.
4.2.2 Wavelength: 422.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 0x1dant: Nitrous oxide.
4.2.5 Type of flame: Stolchiometrlc.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Suspend 2.500 g of CaC03 (analytical reagent
grade, dried for 1 hr at 180*C) 1n Type II water and dissolve by adding a
7140 - 1
Revision
Date September 1986
-------
minimum of dilute HC1. Dilute to 1 liter with Type II water.
Alternatively, procure a certified standard from a supplier and verify by
comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after
processing, including 1 ml of lanthanum chloride per 10 ml sample or
standard (see Paragraph 5.2.3).
5.2.3 Lanthanum chloride solution: Dissolve 29 g L&2Q3 in 25° mL
concentrated HC1 -
CAUTION: REACTION IS VIOLENT -
and dilute to 500 mL with Type II water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 215.1 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 0.2-7 mg/L with a wavelength of 422.7 nm.
Sensitivity: 0.08 mg/L.
Detection limit: 0.01 mg/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 215.1.
7140 - 2
Revision 0
Date September 1986
-------
METHOD 7 HO
CALCIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
3.0
Prepare
standards
7.1
prepar
cr
sec
For
sample
ation see
apter 3.
tion 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7140 - 3
Revision o
Date September 1986
-------
METHOD 7190
CHROMIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 An iom'zation interference may occur if the samples have a signifi-
cantly higher alkali metal content than the standards. If this interference
is encountered, an ionization suppressant (KC1) should be added to both
samples and standards.
3.3 Background correction may be required because nonspecific absorption
and scattering can be significant at the analytical wavelength. Background
correction with certain instruments may be difficult at this wavelength due to
low-intensity output from hydrogen or deuterium lamps. Consult the specific
instrument manufacturer's literature for details.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Chromium hollow cathode lamp.
4.2.2 Wavelength: 357.9 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7190 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.923 g of chromium tr1 oxide (003,
analytical reagent grade) 1n Type II water, acidify with redistilled
HMOs, and dilute to 1 liter. Alternatively, procure a certified standard
from a supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as cali-
bration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 0.5-10 mg/L with a wavelength of 357.9 nm.
Sensitivity: 0.25 mg/L.
Detection limit: 0.05 mg/L.
9.2 For concentrations of chromium below 0.2 mg/L, the furnace procedure
(Method 7191) 1s recommended.
9.3 Precision and accuracy data are available 1n Method 218.1 of Methods
for Chemical Analysis of Water and Wastes.
9.4 The data shown 1n'Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
7190 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.1.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7190 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Wastewater treatment sludge 3050 6,100, 6,000 ug/g
Emission control dust 3050 2.0, 2.8 ug/g
7190 - 4
Revision
Date September 1986
-------
METHOD 719O
CHROMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standard*
7. t
prepar
cr
sec
For
sampla
atlon sea
tapter 3.
tion 3.2
7.2
Analyiu using
Method 7000.
Section 7.2
( Stop J
7190 - 5
Revision 0
Date September 1986
-------
METHOD 7191
CHROMIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Low concentrations of calcium and/or phosphate may cause
Interferences; at concentrations above 200 mg/L, calcium's effect 1s constant
and eliminates the effect of phosphate. Calcium nitrate 1s therefore added to
ensure a known constant effect.
3.3 Nitrogen should not be used as the purge gas because of a possible
CN band interference.
3.4 Background correction may be required because nonspecific absorption
and scattering can be significant at the analytical wavelength. Background
correction with certain instruments may be difficult at this wavelength due to
low^intensity output from hydrogen or deuterium lamps. Consult the specific
instrument manufacturer's literature for details.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125*C.
4.2.2 Ashing time and temp: 30 sec at 1000'C.
4.2.3 Atomizing time and temp: 10 sec at 2700*C.
4.2.4 Purge gas: Argon (nitrogen should not be used).
4.2.5 Wavelength: 357.9 nm.
4.2.6 Background correction: Not required.
4.2.7 Other operating parameters should be set as specified by the
particular Instrument manufacturer.
NOTE: The above concentration values and instrument conditions are for a
Perkin-Elmer H6A-2100, based on the use of a 20-uL Injection,
7191 - 1
Revision 0
Date September 1986
-------
continuous-flow purge gas, and nonpyrolytlc graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomlzatlon can be operated using lower atomlzatlon temperatures
for shorter time periods than the above-recommended settings.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.923 g of chromium tr1 oxide (003,
analytical reagent grade) 1n Type II water, acidify with redistilled
HN03, and dilute to 1 liter. Alternatively, procure a certified standard
from a supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. These standards should be
prepared to contain 0.5% (v/v) HNOs; 1 ml of 30% ^2 and 1 ml of calcium
nitrate solution, Section 5.2.3, may be added to lessen interferences
(see Section 3.0).
5.2.3 Calcium nitrate solution: Dissolve 11.8 g of calcium
nitrate, Ca(N03)2*4H20 (analytical reagent grade), 1n Type II water and
dilute to 1 liter.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 218.2 of Methods
for Chemical Analysis of Water and Wastes.
7191 - 2
Revision
Date September 1986
-------
9.2 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
9.3 The data shown In Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.2.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7191 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample
Matrix
Paint primer
Contaminated soil
Oily lagoon soil
NBS SRM 1646 Estuarlne sediment
EPA QC Sludge
NBS SRM 1085, Wear Metals 1n
lubricating oil
Preparation
Method
3050
3050
3050
3050
3050
3050
Laboratory
Replicates
2.7, 2.8 mg/g
12.0, 12.3 ug/g
69.6, 70.3 ug/g
42, 47 ug/ga
156 ug/gb
311, 356 ug/gc
aB1as of -45 and -38% from expected, respectively.
^B1as of -24% from expected.
cB1as of +4 and +19% from expected, respectively.
7191 - 4
Revision 0
Date September 1986
-------
METHOD 7191
CHROMIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
5.0
Prepare
tandarda
7.1
prepar
en
ec
For
ample
atlon mem
apter 3,
tlon 3.2
7.2
Analyze using
Method 7000.
Section 7.3.
calculation 7.4
( Stop J
7191 - 5
Revision 0
Date September 1986
-------
METHOD 7195
CHROMIUM. HEXAVALENT (COPRECIPITATION)
1.0 SCOPE AND APPLICATION
1.1 Method 7195 1s to be used to determine the concentration of dis-
solved hexavalent chromium [Cr(VI)] 1n Extraction Procedure (EP) toxldty
characteristic extracts and ground waters. This method may also be applicable
to certain domestic and Industrial wastes, provided that no Interfering
substances are present (see Paragraph 3.1 below).
1.2 Method 7195 may be used to analyze samples containing more than 5 ug
of Cr(VI) per liter. Either flame or furnace atomic absorption spectroscopy
(Methods 7190 and 7191) can be used with coprec1p1tat1on.
2.0 SUMMARY OF METHOD
2.1 Method 7195 1s based on the separation of Cr(VI) from solution by
copredpltatlon of lead chromate with lead sulfate 1n a solution of acetic
acid. After separation, the supernate [containing Cr(III)] 1s drawn off and
the precipitate 1s washed to remove occluded Cr(III). The Cr(VI) 1s then
reduced and resolubiltzed 1n nitric add and quantified as Cr(III) by either
flame or furnace atomic absorption spectroscopy (Methods 7190 and 7191).
3.0 INTERFERENCES
3.1 Extracts containing either sulfate or chloride 1n concentrations
above 1,000 mg/L should be diluted prior to analysis.
4.0 APPARATUS AND MATERIALS
4.1 Filtering flask; Heavy wall, 1-11ter capacity.
4.2 Centrifuge tubes; Heavy duty, conical, graduated, glass-stoppered,
10-mL capacity.
4.3 Pasteur plpets; BoroslHcate glass, 6.8 cm.
4.4 Centrifuge; Any centrifuge capable of reaching 2,000 rpm and
accepting the centrifuge tubes described in Section 4.2 may be used.
4.5 pH meter; A wide variety of instruments are commercially available
and suitable for this work.
4.6 Test tube mixer; Any mixer capable of imparting a thorough vortex
is acceptable.
7195 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Lead nitrate solution; Dissolve 33.1 g of lead nitrate, Pb(N(>3)2
(analytical reagent grade), 1n Type II water and dilute to 100 ml.
5.3 Ammonium sulfate solution: Dissolve 2.7 g of ammonium sulfate,
(analytical reagent grade), 1n Type II water and dilute to 100 ml.
5.4 Calcium nitrate solution; Dissolve 11.8 g of calcium nitrate,
'4H20 (analytical reagent grade), 1n Type II water and dilute to
100 ml (1 ml = 20 mg Ca).
5.5 Nitric add; Concentrated, distilled reagent grade or spectrograde
quality.
5.6 Acetic add, glacial. 10% (v/v): Dilute 10 ml glacial acetic add,
(ACS reagent grade), to 100 ml with Type II water.
5.7 Ammonium hydroxide, 10% (v/v): Dilute 10 ml concentrated ammonium
hydroxide, NfyOH (analytical reagent grade), to 100 ml with Type II water.
5.8 Hydrogen peroxide, 30%: ACS reagent grade.
5.9 Potassium dlchromate standard solution: Dissolve 28.285 g of dried
potassium dlchromate, I^C^O; (analytical reagent grade), In Type II water and
dilute to 1 liter (1 ml = 10 mg Cr).
5.10 Trlvalent chromium working stock solution; To 50 ml of the potas-
sium dlchromate standard solution, add 1 ml of 30% H202 and 1 ml concentrated
HNOs and dilute to 100 ml with Type II water (1 ml = 5.0 mg trlvalent chro-
mium). Prepare fresh monthly, or as needed.
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 Since the stability of Cr(VI) 1n EP extracts Is not completely
understood at this time, the analysis should be carried out as soon as
possible.
6.3 To retard the chemical activity of hexavalent chromium, samples and
extracts should be stored at 4*C until analyzed. The maximum holding time
prior to analysis 1s 24 hr.
7195 - 2
Revision
Date September 1986
-------
7.0 PROCEDURE
7.1 Transfer a 50-mL portion of the sample to a 100-mL Griffin beaker
and adjust to a pH of 3.5 + 0.3 by adding volumes of 10% acetic add dropwlse.
Proceed Immediately to Step 7.2, taking no longer than 15 m1n between these
steps.
NOTE: Care must be exercised not to take the pH below 3. If the pH Is
Inadvertently lowered to <3, 10% NfyOH should be used to readjust
the pH to 3.5 + 0.3.
7.2 PI pet a 10-mL aliquot of the adjusted sample Into a centrifuge tube.
Add 100 uL of the lead nitrate solution, stopper the tube, mix the sample, and
allow to stand for 3 m1n.
7.3 After the formation of lead chromate, to help retain Cr(III) complex
1n solution, add 0.5 ml glacial acetic add, stopper, and mix.
7.4 To provide adequate lead sulfate for copredpltatlon, add 100 uL of
ammonium sulfate solution, stopper, and mix.
7.5 Place the stoppered centrifuge tube In the centrifuge, making sure
that the tube Is properly counterbalanced. Start the centrifuge and slowly
increase the speed to 2,000 rpm 1n small Increments over a period of 5 min.
Hold at 2,000 rpm for 1 m1n.
NOTE: The speed of the centrifuge must be Increased slowly to ensure
complete copredpltatlon.
7.6 After centrlfuglng, remove the tube and withdraw and discard the
supernate using either the apparatus detailed In Figure 1 or careful
decantation. If using the vacuum apparatus, the pasteur pipet 1s lowered Into
the tube and the supernate 1s sucked over Into the filtering flask. With
care, the supernate can be withdrawn to within approximately 0.1 ml above the
precipitate. Wash the precipitate with 5 ml Type II water and repeat steps
7.5 and 7.6; then proceed to 7.7.
7.7 To the remaining precipitate, add 0.5 ml concentrated HN03, 100 uL
30% H202, and 100 uL calcium nitrate solution. Stopper the tube and mix,
using a vortex mixer to disrupt the precipitate and solublUze the lead
chromate. Dilute to 10 ml, mix, and analyze 1n the same manner as the
calibration standard.
7.8 Flame atomic absorption; At the time of analysis, prepare a blank
and a series of at leastfourcalibration standards from the Cr(III) working
stock that will adequately bracket the sample and cover a concentration range
of 1 to 10 mg Cr/L. Add to the blank and each standard, before diluting to
final volume, 1 ml 30% H202, 5 ml concentrated HN03, and 1 ml calcium nitrate
solution for each 100 ml of prepared solution. These calibration standards
should be prepared fresh weekly, or as needed. Refer to Method 7090 for more
detail.
7195 - 3
Revision 0
Date September 1986
-------
7.9 Furnace atomic absorption; At the time of analysis, prepare a blank
and a series of at leastfour calibration standards from the Cr(III) working
stock that will adequately bracket the sample and cover a concentration range
of 5 to 100 ugXr/L. Add to the blank arid each standard, before diluting to
final volume, 1 ml 30% H202, 5 ml concentrated HN03, and 1 ml calcium nitrate
solution for each 100 ml of prepared solution. These calibration standards
should be prepared fresh weekly, or as needed. Refer to Method 7191 for more
detail.
7.10 Verification;
7.10.1 For every sample matrix analyzed, verification 1s required
to ensure that neither a reducing condition nor chemical Interference 1s
affecting precipitation. This must be accomplished by analyzing a second
10-mL aliquot of the pH-adjusted filtrate that has been spiked with
Cr(VI). The amount of spike added should double the concentration found
1n the original aliquot. Under no circumstance should the Increase be
less than 30 ug/L Cr(VI). To verify the absence of an Interference, the
spike recovery must be between 85% and 115%.
7.10.2 If addition of the spike extends the concentration beyond
the calibration curve, the analysis solution should be diluted with blank
solution and the calculated results adjusted accordingly.
7.10.3 If the result of verification indicates a suppressive
Interference, the sample should be diluted and reanalyzed. If necessary,
use furnace atomic absorption to achieve the optimal concentration range.
7.10.4 If the Interference persists after sample dilution, an
alternative method (Method 7197, Chelation/Extraction, or Method 7196,
Colorimetric) should be used.
7.11 Acidic extracts that yield recoveries of less than 85% should be
retested to determine 1f the low spike recovery 1s due to the presence of
residual reducing agent. This determination shall be performed by first
making an aliquot of the extract alkaline (pH 8.0-8.5) using 1 N sodium
hydroxide and then respiking and analyzing. If a spike recovery of 85-115% is
obtained in the alkaline aliquot of an acidic extract that Initially was found
to contain less than 5 mg/L Cr(VI), one can conclude that the analytical
method has been verified.
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.
7195 - 4
Revision 0
Date September 1986
-------
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 or any memory effects are 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 1s a sample brought through the whole sample preparation and analytical
process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a del 1 sting petition, and whenever a new sample matrix 1s being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 218.5 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.5.
7195 - 5
Revision
Date September 1986
-------
METHOD 7195
HEXAVALENT CHROMIUM: COPHECIPITATION METHOD
c
7. 1
Transfer sample
to beaker:
adjust pH
7.6
Remove
tube: discard
supernate: wash
precipitate:
repeat 7.5. 7.6
7.2
Plpet adjusted sample
into centrifuge tube;
add lead nitrate
solution: mix : let
stand
7.7
Add cone
HNO..
30X HjOz and
calcium nitrate
solution: mix;
dilute: analyze
7.3
Add glacial
acetic acid;
nix
7.9
Prepare blank and
series of
standards covering
concentration range
of S to 100 ug
Cr/llter
7.4
Add ammonium
sulfate
solution; mix
7.9
Furnace
Flame
Which type of
atomic absorption
Is used?
7.8
Prepare blank and
series of
standards covering
concentration range
of 1 to 10 mg
Cr/liter
Add 30X
cone HNOi. and
calcium nitrate
solution to
each; analyre
7.6
Add 30X
cone HNO. and
calcium nitrate
solution to
each: analyze
7.5
Place tuba in
centrifuge:
centrifuge
7.10.1
Verify
by analyzing
econd aliquot
of spiked
filtrate
7195 - 6
Revision 0
Date September 1986
-------
METHOD 7195
HEXAVALENT CHROMIUM: COPRECIPITATION METHOD
(Continued)
Dilute bank
solution:
adjust results
Is suppressIveX.
interference
indicated?
Dilute sample
and reanalyze
interference
Use alternative
method
7.12
If no valid
results, and chromium
more than threshold
amount of hexavalent
chromium, sample
exlhlblts EP toxlclty
Analytic
method
verified; waste
not hazardous
v__y
f Stop J
7195 - 7
Revision 0
Date September 1986
-------
METHOD 7196
CHROMIUM. HEXAVALENT (COLORIMETRIC)
1.0 SCOPE AND APPLICATION
1.1 Method 7196 is used to determine the concentration of dissolved
hexavalent chromium [Cr(VI)] in Extraction Procedure (EP) toxicity charac-
teristic extracts and ground waters. This method may also be applicable to
certain domestic and industrial wastes, provided that no interfering
substances are present (see Paragraph 3.1 below).
1.2 Method 7196 may be used to analyze samples containing from 0.5 to
50 mg of Cr(VI) per liter.
2.0 SUMMARY OF METHOD
2.1 Dissolved hexavalent chromium, in the absence of interfering amounts
of substances such as molybdenum, vanadium, and mercury, may be determined
colorimetrically by reaction with diphenylcarbazide in acid solution. A red-
violet color of unknown composition is produced. The reaction is very
sensitive, the absorbancy index per gram atom of chromium being about 40,000
at 540 nm. Addition of an excess of diphenylcarbazide yields the red-violet
product, and its absorbance is measured photometrically at 540 nm.
3.0 INTERFERENCES
3.1 The chromium reaction with diphenylcarbazide is usually free from
interferences. However, certain substances may interfere if the chromium
concentration is relatively low. Hexavalent molybdenum and mercury salts also
react to form color with the reagent; however, the red-violet intensities
produced are much lower than those for chromium at the specified pH.
Concentrations of up to 200 mg/L of molybdenum and mercury can be tolerated.
Vanadium interferes strongly, but concentrations up to 10 times that of
chromium will not cause trouble.
3.2 Iron in concentrations greater than 1 mg/L may produce a yellow
color, but the ferric Iron color is not strong and difficulty 1s not normally
encountered if the absorbance is measured photometrically at the appropriate
wavelength.
4.0 APPARATUS AND MATERIALS
4.1 Colorimetric equipment; One of the following is required: Either a
spectrophotometer, for use at 540 nm, providing a light path of 1 cm or
longer, or a filter photometer, providing a light path of 1 cm or longer and
equipped with a greenish-yellow filter having maximum transmittance near
540 nm.
7196 - 1
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5.0 REAGENTS
5.1 ASTM Type II water (ASTMD1193): Water should be monitored for
Impurities.
5.2 Potassium dlchromate stock solution: Dissolve 141.4 mg of dried
potassium dlchromate, fyCr2Q7 (analytical reagent grade), In Type II water and
dilute to 1 liter (1 mL = 50 ug Cr).
5.3 Potassium dlchromate standard solution; Dilute 10.00 ml potassium
dlchromate stock solution to 100 ml (1 ml = 5 ug Cr).
5.4 Sulfuric add, 10% (v/v): Dilute 10 ml of distilled reagent grade
or spectrograde quality sulfuric add, ^$04, to 100 ml with Type II water.
5.5 Dlphenylcarbazlde solution; Dissolve 250 mg !,5-d1phenylcarbaz1de
1n 50 ml acetone.Store in a brown bottle. Discard when the solution becomes
discolored.
5.6 Acetone (analytical reagent grade); Avoid or redistill material
that comes 1n containers with metal or metal-lined caps.
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 Since the stability of Cr(VI) in EP extracts is not completely
understood at this time, the analysis should be carried out as soon as
possible.
6.3 To retard the chemical activity of hexavalent chromium, the samples
and extracts should be stored at 4*C until analyzed. The maximum holding time
prior to analysis 1s 24 hr.
7.0 PROCEDURE
7.1 Color development and measurement; Transfer 95 mL of the extract to
be tested to a 100-mL volumetric flask. Atfd 2.0 mL dlphenylcarbazide solution
and mix. Add ^$04 solution to give a pH of 2 + 0.5, dilute to 100 mL with
Type II water, and let stand 5 to 10 m1n for full color development. Transfer
an appropriate portion of the solution to a 1-cm absorption cell and measure
its absorbance at 540 nm. Use Type II water as a reference. Correct the
absorbance reading of the sample by subtracting the absorbance of a bla'nk
carried through the method (see Note below). An aliquot of the sample
containing all reagents except diphenyl semlcarbazlde should be prepared and
used to correct the sample for turbidity (I.e., a turbidity blank). From the
7196 - 2
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Date September 1986
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corrected absorbance, determine the mg/L of chromium present by reference to
the calibration curve.
NOTE: If the solution Is turbid after dilution to 100 ml 1n Step 7.1,
above, take an absorbance reading before adding the carbazlde
reagent arid correct the absorbance reading of the final colored
solution by subtracting the absorbance measured previously.
7.2 Preparation of calibration curve;
7.2.1 To compensate for possible slight losses of chromium during
digestion or other operations of the analysis, treat the chromium
standards by the same procedure as the sample. Accordingly, plpet a
chromium standard solution 1n measured volumes into 250-mL beakers or
conical flasks to generate standard concentrations ranging from 0.5 to
5 mg/L Cr(VI) when diluted to the appropriate volume.
7.2.2 Develop the color of the standards as for the samples.
Transfer a suitable portion of each colored solution to a 1-cm absorption
cell and measure the absorbance at 540 nm. As reference, use Type II
water. Correct the absorbance readings of the standards by subtracting
the absorbance of a reagent blank carried through the method. Construct
a calibration curve by plotting corrected absorbance values against mg/L
of Cr(VI).
7.3 Verification;
7.3.1 For every sample matrix analyzed, verification is required to
ensure that neither a reducing condition nor chemical interference 1s
affecting color development. This must be accomplished by analyzing a
second 10-mL aliquot of the pH-adjusted filtrate that has been spiked
with Cr(VI). The amount of spike added should double the concentration
found in the original aliquot. Under no circumstances should the
increase be less than 30 g Cr(VI)/liter. To verify the absence of an
interference, the spike recovery must be between 85% and 115%.
7.3.2 If addition of the spike extends the concentration beyond the
calibration curve, the analysis solution should be diluted with blank
solution and the calculated results adjusted accordingly.
7.3.3 If the result of verification Indicates a suppressive
Interference, the sample should be diluted and reanalyzed.
7.3.4 If the Interference persists after sample dilution, an
alternative method (Method 7195, Coprecipltation, or Method 7197,
Chelation/Extraction) should be used.
7.4 Acidic extracts that yield recoveries of less than 85% should be
retested to determine if the low spike recovery is due to the presence of
residual reducing agent. This determination shall be performed by first
making an aliquot of the extract alkaline (pH 8.0-8.5) using 1 N sodium
hydroxide and then respiking and analyzing. If a spike recovery of 85-115% 1s
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obtained 1n the alkaline aliquot of an acidic extract that Initially was found
to contain less than 5 mg/L Cr(VI), one can conclude that the analytical
method has been verified..
7.5 Analyze all EP extracts, all samples analyzed as part of a dellsting
petition, and all samples that suffer from matrix Interferences by the method
of standard additions (see Method 7000, Section 8.7).
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Dilute samples 1f they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.3 Employ a minimum of one blank per sample batch to determine 1f
contamination or any memory effects are occurring.
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.
8.6 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a del 1 sting petition, and whenever a new sample matrix Is being
analyzed.
9.0 METHOD PERFORMANCE
9.1 The data shown 1n Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Methods 218.4 and 218.5.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7196 - 4
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TABLE 1. METHOD PERFORMANCE DATA
Sample
Matrix
Preparation
Method
Laboratory
Replicates
Wastewater treatment sludge
Sediment from chemical
storage area
Not known
3060
0.096, 0.107 ug/g
115, 117 ug/g
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METHOD 7196
HEXAVALENT CHROMIUM (COLOHIMETRIC)
7. 1
For color development
transfer extract to
flask: add
diphenylcarbazlde
solution: mix
Add
H.SO* solution:
dilute: let
stand-
7. 1
Measure and correct
aosorbance reading:
determine chromium
present
7.2.1
1 Treat
chromium
standards by
same procedure
as sample
7.2.11
1 Plpet
chromium
standard
solution into
beafcera
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METHOD 7196
HEXAVALENT CHROMIUM (COLORIMETRIC)
(Continued)
7.2.2
Develop color of
standards: measure
and correct reading:
construct calibration
curve
7.3.1
Analyze a 2nd
aliquot of pH-
adjusted filtrate
spiked with Cr (VI)
for verification
Does spike
extend concentr.
beyond cali-
bration
curve
Dilute
analysis
solution with
blank solution
Does result
Indicate a
suppresslve
Interfer-
ence?
Dilute sample
and reanalyze
S^ 0088
Interference
persist?
Use alternative
method
7.4 [
Analytical
method verified
-waste is not
hazardous
7.5
Analyze
by method
of standard
additions
(. st°P )
7196 - 7
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METHOD 7197
CHROMIUM. HEXAVALENT (CHELATION/EXTRACTION)
1.0 SCOPE AND APPLICATION
1.1 Method 7197 1s approved for determining the concentration of
dissolved hexavalent chromium [Cr(VI)] 1n Extraction Procedure (EP) toxidty
characteristic extracts and ground waters. This method may also be applicable
to certain domestic and Industrial wastes, provided that no interfering
substances are present (see Paragraph 3.1).
1.2 Method 7197 may be used to analyze samples containing from 1.0 to
25 ug of Cr(VI) per liter.
2.0 SUMMARY OF METHOD
2.1 Method 7197 1s based on the chelatlon of hexavalent chromium with
ammonium pyrrolidlne dlthlocarbamate (APDC) and extraction with methyl
Isobutyl ketone (MIBK). The extract is aspirated into the flame of an atomic
absorption spectrophotometer.
3.0 INTERFERENCES
3.1 High concentrations of other metals may Interfere.
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer; Single or dual channel,
single- ordouble-beaminstrument,having a grating monochromator,
photomultipHer detector, adjustable slits, and provisions for background
correction.
4.2 Chromium hollow cathode lamp.
4.3 Strip-chart recorder (optional).
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Ammonium pyrrol 1dine dithiocarbamate (APDC) solution: Dissolve
1.0 g APDC 1n Type II water and dilute to 100 mL. Prepare fresh dally.
5.3 Bromphenol blue Indicator solution; Dissolve 0.1 g bromphenol blue
1n 100 mL 50% ethanol.
7197 - 1
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5.4 Potassium dichromate standard solution I (1.0 mL = 100 ug Cr):
Dissolve 0.2829 g pure dried potassium dichromate, I^C^O/, in Type II water
and dilute to 1,000 mL.
5.5 Potassium dichromate standard solution II (1.0 mL = 10.0 ug Cr):
Dilute 100 ml chromium standard solution I to 1 liter with Type II water.
5.6 Potassium dichromate standard solution III (1.0 ml = 0.10 ug Cr):
Dilute 10.0 ml chromium standard solution II to 1 liter with Type II water.
5.7 Methyl isobutyl ketone (MIBK), analytical reagent grade: Avoid or
redistill material that comes in contact with metal or metal-lined caps.
5.8 Sodium hydroxide solution, 1 M: Dissolve to 4Q% g sodium hydroxide,
NaOH (ASC reagent grade), in Type II water and dilute to l" liter.
5.9 Sulfuric acid. 0.12 M: Slowly add 6.5 ml distilled reagent grade or
spectrograde-quality sulfuric acid, ^SO/i, to 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 Because the stability of Cr(VI) in EP extracts is not completely
understood at this time, the chelation and extraction should be carried out as
soon as possible.
6.3 To retard the chemical activity of hexavalent chromium, the samples
and extracts should be stored at 4*C until analyzed.
7.0 PROCEDURE
7.1 Pipet a volume of extract containing less than 2.5 ug chromium
(100 mL maximum) into a 200-mL volumetric flask and adjust the volume to
approximately 100 mL.
7.2 Prepare a blank and sufficient standards and adjust the volume of
each to approximately 100 mL.
7.3 Add 2 drops of bromphenol blue indicator solution. (The adjustment
of pH to 2.4, Step 7.4, may be made with a pH meter instead of using an
indicator.)
7.4 Adjust the pH by addition of 1 M NaOH solution dropwise until a blue
color persists. Add 0.12 M H2S04 dropwise until the blue color just disap-
pears in both the standards and sample. Then add 2.0 mL of 0.12 M H2S04 in
excess. The pH at this point should be 2.4.
7197 - 2
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7.5 Add 5.0 ml APDC solution and mix. The pH should then be approxi-
mately 2.8.
7.6 Add 10.0 ml MIBK and shake vigorously for 3 m1n.
7.7 Allow the layers to separate and add Type II water until the ketone
layer 1s completely In' the neck of the flask.
7.8 Aspirate the ketone layer and record the scale reading for each
sample and standard against the blank. Repeat, and average the duplicate
results.
7.9 Determine the mg/Hter of Cr(VI) 1n each sample from a plot of scale
readings of standards. A working curve must be prepared with each set of
samples.
7.10 Verification;
7.10.1 For every sample matrix analyzed, verification 1s required
to ensure that neither a reducing condition nor chemical Interference 1s
affecting chelatlon. This must be accomplished by analyzing a second 10-
ml_ aliquot of the pH-adjusted filtrate that has been spiked with Cr(VI).
The amount of spike added should double the concentration found 1n the
original aliquot. Under no circumstances should the Increase be less
than 30 ug/L Cr(VI). To verify the absence of an Interference, the spike
recovery must be between 85% and 115%.
7.10.2 If addition of the spike extends the concentration beyond
the calibration curve, the analysis solution should be diluted with blank
solution and the calculated results adjusted accordingly.
7.10.3 If the result of verification Indicates a suppresslve
Interference, the sample should be diluted and reanalyzed.
7.10.4 If the Interference persists after sample dilution, an
alternative method (Method 7195, Coprec1p1tat1on, or Method 7196,
Co1or1metr1c) should be used.
7.11 Acidic extracts that yield recoveries of less than 85% should be
retested to determine 1f the low spike recovery 1s due to the presence of
residual reducing agent. This determination shall be performed by first
making an aliquot of the extract alkaline (pH 8.0-8.5) using 1 N sodium
hydroxide and then resplklng and analyzing. If a spike recovery of 85-115% 1s
obtained in the alkaline aliquot of an acidic extract that initially was found
to contain less than 5 mg/L Cr(VI), one can conclude that the analytical
method has been verified.
7197 - 3
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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 or any memory effects are 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 1s a sample brought through the whole sample preparation and analytical
process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a dell sting petition, and whenever a new sample matrix 1s being
analyzed.
9.0 METHOD PERFORMANCE
. 9.1 Precision and accuracy data are available 1n Method 218.4 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.4.
7197 - 4
Revision
Date September 1986
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METHOD 7197
HEXAVAUENT CHROMIUM (CHELATION/EXTFUCTION)
7. 1
Plpet extract
Into flask:
adjust volume
7.5
Add APOC
solution ; mix
7.2
I Prepare
blank and
standards:
adjust volume
of each
7.6
Add MIBK;
shake
7.3
Add bromphenol
blue indicator
solution
7.7
Allow layers to
separate: add
Type II water
7.4
Adjust pH by
adding NaOH:
add
7.8
Aspirate
ketone
layer: record
scale readings:
repeat: average
results
7197 - 5
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Date September 1986
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METHOD 7197
HEXAVALENT CHROMIUM (CHELATION /EXTRACTION)
(Continued)
Determine
Cr (IV) In each
sample: prepare
working curves
jr 7. 10. 4\
Does ^v^
persist? ^S
7. 10. 4J
Use alternative
method
7.10.1 Verify
every
sample matrix
by analyzing
second aliquot
spiked filtrate
Is cone .
Deyond
calibration
curve?
analysis
solution with
blank solution:
adjust results
Is there a
suppresslve
interference?
Dilute sample
and reanalyze
Analytical
method verified
-waste Is not
hazardous
If no valid
results and chromium
concentration over
threshold limits.
sample exhibits
EP toxlclty
( Stop j
7197 - 6
Revision 0
Date September 1986
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METHOD 7198
CHROMIUM. HEXAVALENT (DIFFERENTIAL PULSE POLAROGRAPHY)
1.0 SCOPE AND APPLICATION
1.1 This method 1s used to determine the concentration of hexavalent
chromium [Cr(VI)] 1n natural and waste waters and 1n EP extracts.
1.2 The method can quantltate chromium 1n concentrations of up to
1.0 mg/L to 5.0 mg/L, depending on the mercury drop size. Higher concentra-
tions can be determined by dilution.
1.3 The lower limit of detection for Cr(VI) 1s 10 ug/L for the
Instrumental conditions given 1n this method. The limit of detection could be
easily lowered by changing these conditions.
2.0 SUMMARY OF METHOD
2.1 Method 7198 measures the peak current produced from the reduction of
Cr(VI) to Cr(III) at a dropping mercury electrode during a differential pulse
voltage ramp.
2.2 The method described herein uses 0.125 M NH40H-0.125 M NH4C1 as the
supporting electrolyte. In this electrolyte, Cr(VI) reduction results In peak
current occurring at the peak potential (Ep) of -0.250 V vs. Ag/AgCl.
2.3 Alternative supporting electrolytes, such as those given 1n Table 1,
may be used.
2.4 The technique of standard additions must be used to quantltate the
Cr(VI) content.
3.0 INTERFERENCES
3.1 Copper 1on at concentrations higher than the Cr(VI) concentration 1s
a potential Interference due to peak overlap when using the 0.125 M ammonlacal
electrolyte. Increasing the ammonlacal electrolyte concentration to 0.5 M
shifts the copper peak cathodlcally (Ep = -0.4 V), eliminating the
Interference at a copper-to-chrom1um ratio of 10:1 (Figure 1).
3.2 Reductants such as ferrous Iron, sulflte, and sulflde will reduce
Cr(VI) to Cr(III); thus 1t 1s Imperative to analyze the samples as soon as
possible.
4.0 APPARATUS AND MATERIALS
4.1 Polaroqraphlc Instrumentation; Capable of performing differential
pulse analyses, Including recorder or plotter.
7198 - 1
Revision 0
Date September 1986
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2.0-
1.5-
Current x 10'2'nA
18 Jan 82 No. 1
Sample: DPP
Initial E: -0.100 V
Final E: -0.450 V
Peak 1: -0.292 V
2.047 E2n A
4.0-
3.0-
2.0
Current x 10? nA
18 Jan 82 No. 2
Sample: OPP
Initial E: -0.100V
Final E: -0.450V
Peak 1: -0.256 V
2.680E1 nA
Peak 2: -0.396 V
9.740E1 nA
-0.2 -0.4
A. 20 ppm Cu, 2.5 ppm Cr, 0.1 N buffer.
B. 20 ppm Cu, 2.5 ppm Cr, 0.5 N buffer.
Figure 1. Two polarograms illustrating shift in copper peak at higher ammoniacal
electrolyte concentrations.
7198 - 2
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Date September 1986
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TABLE 1. POLAROGRAPHY OF HEXAVALENT CHROMIUM
Supporting electrolyte
Peak potential (vs. SCE)
1 M NaOH
1 M Pyr1d1ne, 1 M NaOH
1 M NH4OH, 1 M NH4C1
0.1 M NH4OH, 0.1 M (NH4)2 Tartrate
0.2 M KC1, 0.3 M Tr1ethanolam1ne, pH 9
1 M Na2S04
0.1 M NH4OH, 0.1 M NH4C1
-0.85
-1.48
-0.36
-0.244
-0.28
-0.23
-0.25
7198 - 3
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Date September 1986
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4.2 Dropping mercury electrode assembly; Capable of performing
differential pulse analyses.
4.3 Counter electrode; Platinum wire.
4.4 Reference electrode; Ag/AgCl or SCE, with a slow-leakage fritted
tip (unflred Vycor).~
4.5 Nitrogen gas and cell outgassing assembly.
4.6 Mlcroplpets and disposable tips.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Chromium standard solution I, 1.0 ml = 100 ug Cr: Should be made
dally from a 1,000-ppm standard stock solution made with Type II water.
5.3 Chromium standard solution II, 1.0 ml = 10 ug Cr; Should be made
dally from a 1,000-ppm standard stock solution made with Type II water.
5.4 Chromium standard solution III, 1.0 ml = 1 ug Cr: Dilute 10 ml
chromium standard solution II to 100 ml with Type II water.
5.5 Ammoniacal electrolyte, 2.5 N: Dissolve 33.3 g of NfyCl 1n 150 ml
of Type II water, add 42.2 mL of concentrated NfyOH, and dilute to 250 ml.
5.6 Concentrated nitric acid; Add should be analyzed to determine
levels of Impurities.I?Impurities are detected, all analyses should be
blank-corrected.
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 Stability of Cr(VI) 1s not completely understood at this time.
Therefore, the analysis should be carried out as soon as possible.
6.3 If the analysis cannot be performed within 24 hr, take an aliquot of
the sample and add a known amount of Cr(VI) (0.1 mg/L for natural waters,
1 mg/L for wastewaters, and 5 mg/L for EP extracts). Analyze this known
additional sample at the same time the sample 1s analyzed to determine whether
Cr(VI) was reduced during storage.
6.4 To retard the chemical activity of Cr(VI), the sample should be
transported and stored at 4*C until time of analysis.
7198 - 4
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Date September 1986
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7.0 PROCEDURE
7.1 Soak the voltammetric cells overnight 1n 1 + 1 HN03 and/or 1+1
aqua regia.
7.2 Rinse the electrode assembly with Type II water, then with 1 N HN03,
and finally with Type II water prior to and 1n between sample analyses.
7.3 The Instrument should be set using the following Instrumental
parameters.
7.3.1 Mode: Differential pulse.
7.3.2 Scan rate: 2 mV/sec.
7.3.3 Drop time: 1 sec.
7.3.4 Initial potential: -0.05 V + 0.05 V vs. Ag/AgCl.
7.3.5 Final potential: -0.50 V + 0.10 V vs. Ag/AgCl.
7.3.6 Pulse height: 0.05 V.
7.3.7 Deaeratlon time: 240 sec or less Initially, 30 sec between
standard additions.
7.4 Analysis;
7.4.1 P1pet a volume of sample containing less than 10 ug Cr(VI)
Into a voltammetric cell (the maximum volume depends on the voltammetric
cell volume, usually 10 ml).
7.4.2 Add 0.5 ml of the ammonlacal electrolyte and adjust volume to
10 ml with Type II water.
7.4.3 Place the electrode assembly 1n the solution and outgas with
nitrogen for at least 120 sec.
7.4.4 Engage the electrode assembly to the polarographlc analyzer
and displace at least 10 mercury drops before Initiating the voltage ramp
and obtaining the polarogram.
7.4.5 Figure 2 gives typical differential pulse polarograms.
7.5 Prior to the analysis of any samples, and during analysis at a
frequency of at least once every 10 samples, verify that the cell contamina-
tion 1s less than 10 ug/L Cr by analyzing demlnerallzed water and the appro-
priate volume of supporting electrolyte 1n a manner similar to the procedure
described 1n 7.4.3 and 7.4.4.
7.6 Calibration;
7.6.1 After running a differential pulse polarogram on the sample
solution, quantltate the chromium using the technique of standard
addition.
7198 - 5
Revision
Date September 1986
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2.0-
1.5-
Current x 10^ n A
26 Oct 81 No. 1
Standard No. 1 DPP
Initial E: 0.000 V
Final E: -0.350 V
Peak 1:"-0.160 V
1.18lE2nA
250.0 ppb
2.0-
1.5-
Curreht x 10^ nA
260c:81 No. 1
Standard No. 2 DPP
Initial E: 0.000 V
Final E: -0.350V
Peak 1:-0.154V
1.146E3nA
2.500 ppm
-0.1 -0.3
-0.1 -0.3
Figure 2. Typical differential pulse polarogram at 0.25 ppm and 2.5 ppm Cr
in 0.1 N buffer.
7198
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Date September 1986
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7.6.2 Three standard additions should be made to obtain the best
precision and accuracy. The first standard addition should be approxi-
mately one-half the concentration of the sample, the second equal to that
of the sample, and the third about 1.5 times the sample concentration.
The total volume due to standard additions should not exceed the cell
value by more than 10%.
7.6.3 Add an appropriate aliquot of chromium standard solution I,
II, or III to the sample 1n the cell. Deaerate for 30 sec to mix the
solution and remove oxygen added with the known addition.
7.6.4 Repeat the analysis procedure, beginning with Step 7.4.4 for
each standard addition.
7.7 Calculations;
7.7.1 Calculate the concentration of chromium determined by each
standard addition procedure as follows:
£ Ws i_
U"11V1 + (WW Vu
where:
i'l = Current peak height for the sample (nA);
1j = Current peak height for the sample plus standard (nA);
Vu = Volume of sample 1n the cell (ml);
Vi = Volume of standard taken for spiking (ml);
V = Volume 1n cell prior to standard addition;
Cs = Concentration of standard used to spike (mg/L); and
Cu = Concentration of the unknown 1n the sample (mg/L).
7.7.2 Some microprocessor polarographlc systems will perform
these calculations automatically.
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 If necessary, dilute samples so that they fall within the working
range.
7198 - 7
Revision
Date September 1986
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8.3 Quant1tat1on must be performed by the method of standard additions
(see Method 7000, Section 8.7).
8.4 Verify calibration with an Independently prepared check standard
every 15 samples (see Chapter One, Section 1.1.8).
8.5 Standards should be compared to a reference standard on a routine
basis.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data' for this method are summarized 1n
Table 2.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 218.4 and 218.5.
7198 - 8
Revision
Date September 1986
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TABLE 2. PRECISION AND ACCURACY OF THE DPP OF HEXAVALENT CHROMIUM
2a. Precision
Sample type No. of replicates Average value % RSD
Leachatea 3 1.87 0.69
2b. Accuracy (spike recovery data)
Standard
Spike level No. of Average % deviation of
Sample type (mg/L) samples recovery % recovery
EP extracts 5.0 8 92.8 6.4
2c. Methods comparison
Dlff. pulse APDC extrac- Ion chromatography
polarography tlon ICAP-OES coupled to ICAP-OES
Value3 1.87 1.84 1.91
aLeachate sample from a waste disposal site.
7198 - 9
Revision
Date September 1986
-------
METHOD 7i9e
HEXAVALENT CHROMIUM {DIFFERENTIAL PULSE POLAROGRAPH)
C
7.1
i
Soak
voltemmetr ic
cells overnight
assembly.In
solution;
outgas with
nitrogen
7.2
I Rinse
electrode
assembly before
and between
sample analyses
7.3
Set instrument
7.4.1
Plpet
I sample
witn hexavalent
Chromium Into
voltammetric
cell
7.4.e
Add ammoniacal
electrolyte:
adjust volume
7.4.4
Engage electrode
assembly: displace
mercury drops:
initiate voltage
ramp; obtain
polargram
7.S
of
standard
solution:
daaerate
Prior
to ana
during analysis
verify that
cell contamln.
is < 10 ug/1 Cr
7.6.1
7.6.4
Repeat
for eacn
standard
addition
starting with
section 7.4.4
Run
differential
pulse
polarogram on
sample solution
7.7
Calculate
concentration
of chromium
7.6.1]
Quantltate
Chromium using
technique of
standard add.
f Stop J
7198 - 10
Revision p
Date September 1986
-------
METHOD 7200
COBALT (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Excesses of other transition metals may slightly depress the
response of cobalt. Matrix matching or the method of standard additions 1s
recommended.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Cobalt hollow cathode lamp.
4.2.2 Wavelength: 240.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of cobalt metal (analytical
reagent grade) 1n 20 mL of 1:1 HN03 and dilute to 1 liter with Type II
water. Chloride or nitrate salts of cobalt (II) may be used. Although
numerous hydrated forms exist, they are not recommended unless the exact
composition of the compound Is known. Alternatively, procure a certified
standard from a supplier and verify by comparison with a second standard.
7200 - 1
Revision
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.5-5 mg/L with a wavelength of 240.7 nm.
Sensitivity: 0.2 mg/L.
Detection limit: 0.05 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 0.2, 1, and 5
mg/L gave standard deviations of +0.013, +0.01, and +0.05, respectively.
Recoveries at these levels were 98% and 97%, respectively.
9.3 For concentrations of cobalt below 0.1 mg/L, the furnace procedure
(Method 7201) 1s recommended.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 219.1.
7200 - 2
Revision
Date September 1986
-------
METHOD 7200
COBALT (ATOMIC ABSORPTION. DIRECT ASPIRATION)
s.o I
Prepare
standards
7.1
SI
preparat
chat
sectior
or
imp IB
.ion see
)ter 3.
i 3.1.3
7.Z j
Analyze using
Method 7000.
Section 7.2
( StOP J
7200 - 3
Revision 0
Date September 1986
-------
METHOD 7201
COBALT (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Excess chloride may Interfere. It 1s necessary to verify by
standard additions that the Interference is absent.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125*C.
4.2.2 Ashing time and temp: 30 sec at 900*C.
4.2.3 Atomizing time and temp: 10 sec at 2700'C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 240.7 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular Instrument manufacturer.
NOTE: The above concentration values and instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20-uL Injection,
continuous-flow purge gas, and nonpyrolytic graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomization can be operated using lower atomlzation temperatures
for shorter time periods than the above-recommended settings.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7201 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of cobalt metal (analytical
reagent grade) 1n 20 mL of 1:1 HMOs and dilute to 1 liter with Type II
water. Chloride or nitrate salts of cobalt (II) may be used. Although
numerous hydrated forms exist, they are not recommended unless the exact
composition of the compound 1s known. Alternatively, procure a certified
standard from a supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentrations as 1n the sample after processing (0.5% v/v HN03).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000. .
9.0 METHOD PERFORMANCE
. 9.1 Precision and accuracy data are not available at this time.
9.2 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 219.2.
7201 - 2
Revision
Date September 1986
-------
METHOD 7Z01
COBALT (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
_i±J
Prepare
standards
7.1
f
si
preparat
chat
sect!
7.2
'or
imple
.Ion see
)ter 3.
on 3.2
Analyze using
Method 700O.
Section 7.3.
f Stop J
7201 - 3
Revision 0
Date September 1986
-------
METHOD 7210
COPPER (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000.
3.2 Background correction may be required because nonspecific absorption
and scattering can be significant at the analytical wavelength. Background
correction with certain Instruments may be difficult at this wavelength due to
low-Intensity output from hydrogen or deuterium lamps. Consult specific
Instrument manufacturer's literature for details.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Copper hollow cathode lamp.
4.2.2 Wavelength: 324.7 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Recommended, 1f possible.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.00 g of electrolytic copper
(analytical reagent grade) 1n 5 mL of redistilled HN03 and dilute to
1 liter with Type II water. Alternatively, procure a certified standard
from a supplier and verify by comparison with a second standard.
7210 - 1
Revision
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same concentra-
tion as will result 1n the sample to be analyzed after processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
\
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given In Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.2-5 mg/L with a wavelength of 324.7 nm.
Sensitivity: 0.1 mg/L.
Detection limit: 0.02 mg/L.
9.2 Precision and accuracy data are available 1n Method 220.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 220.1.
7210 - 2
Revision
Date September 1986
-------
METHOD 7210
COPPER (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.O |
Prepare
standards
7.1
sample
preparation see
chapter 3.
section 3.2
7.2 |
Analyze using
Method 7000.
Section 7.2
f Stop J
7210 - 3
Revision 0
Date September 1986
-------
METHOD 7380
IRON (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Iron 1s a universal contaminant, and great care should be taken to
avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Iron hollow cathode lamp.
4.2.2 Wavelength: 248.3 nm (primary); 248.8, 271.9, 302.1, 252.7,
or 372.0 nm (alternates).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g Iron wire (analytical
reagent grade) 1n 10 mL redistilled HNOs and Type II water and dilute to
1 liter with Type II water. Note that Iron passlvates 1n concentrated
HN03, and thus some water should be present. Alternatively, procure a
certified standard from a supplier and verify by comparison with a second
standard.
7380 - 1
Revision
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result In the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.3-5 mg/L with a wavelength of 248.3 nm.
Sensitivity: 0.12 mg/L.
Detection limit: 0.03 mg/L.
9.2 Precision and accuracy data are available In Method 236.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 236.1.
7380 - 2
Revision
Date September 1986
-------
METHOD 7380
IRON (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.O
Prepare
standards
7. 1
prepar
ct
sec
For
sample
atlon see
tapter 3.
tlon 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7380 - 3
Revision 0
Date September 1986
-------
METHOD 7420
LEAD (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Background correction 1s required at either wavelength.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Lead hollow cathode lamp.
4.2.2 Wavelength: 283.3 nm (primary); 217.0 nm (alternate).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.599 g of lead nitrate,
(analytical reagent grade), 1n Type II water, acidify with 10 mL
redistilled HN03, and dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify by
comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentration as will result 1n the sample to be analyzed after
processing.
7420 - 1
Revision 0
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 1-20 mg/L with a wavelength of 283.3 nm.
Sensitivity: 0.5 mg/L.
Detection limit: 0.1 mg/L.
9.2 For concentrations of lead below 0.2 mg/L, the furnace technique
(Method 7421) 1s recommended.
9.3 Precision and accuracy data are available 1n Method 239.1 of Methods
for Chemical Analysis of Water and Wastes.
9.4 The data shown In Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 239.1.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7420 - 2
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Wastewater treatment sludge 3050 450, 404 ug/g
Emission control dust 3050 42,500, 63,600 ug/g
7420 - 3
Revision
Date September 1986
-------
METHOD 7430
LEAD (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.O
Prepare
standards
7. 1
F
s<
preparat
chat
sect]
'OP
inple
ion see
)ter. 3.
on 3.S
7.3 j
Analyze using
Method 700O.
Section 7.2
( Stop J
7420 - 4
Revision 0
Date September 1986
-------
METHOD 7421
LEAD (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Background correction 1s required.
3.3 If poor recoveries are obtained, a matrix modifier may be necessary.
Add 10 uL of phosphoric add (Paragraph 5.3) to 1 mL of prepared sample 1n the
furnace sampler cup and mix well.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30*sec at 125*C.
4.2.2 Ashing time and temp: 30'sec at 500*C.
4.2.3 Atomizing time and temp: 10 sec at 2700*C.
4.2.4 Purge gas: Argon.
4.2.5 Wavelength: 283.3 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular Instrument manufacturer.
NOTE: The above concentration values and Instrument conditions are for a
Perkln-Elmer HGA-2100, based on the use of a 20-uL Injection,
continuous-flow purge gas, and nonpyrolytic graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomlzatlon can be operated using lower atomlzatlon temperatures
for shorter time periods than the above-recommended settings.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7421 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.599 g of lead nitrate, Pb(N03)2
(analytical reagent grade), 1n Type II water, acidify with 10 mi-
red! stilled HN03, and dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify by
comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentrations as in the sample after processing (0.5% v/v HMOs).
5.3 Phosphoric acid; Reagent grade.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given in Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 239.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
7421 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Lead by Flameless Atomic Absorption with Phosphate Matrix Modification,
Atomic Spectroscopy, 1^ (1980), no. 3, pp. 80-81.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7421 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation
Matrix Method
Contaminated soil
Paint primer
Lagoon soil
NBS SRM 1646 Estuarine sediment
NBS SRM 1085 Wear metals in
lubricating oil
Solvent extracted oily waste
3050
3050
3050
3050
3030
3030
Laboratory
Replicates
.163, 120 mg/g
0.55, 0.63 mg/g
10.1, 10.0 ug/g
23.7 ug/ga
274, 298 ug/gb
9, 18 ug/L
aBias of -16% from expected.
^Bias of -10 and -2% from expected, respectively.
7421 - 4
Revision 0
Date September 1986
-------
METHOD 7421
LEAD (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
f Start ]
s.o 1
Prepare
standards
7.1
f
si
preparat
chap
sectl
7. Z
or
imple
Ion see
>ter 3.
on 3.2
Analyze using
Method 7000.
Section 7.3.
calculation 7.4
f Stop J
7421 - 5
Revision 0
Date September 1986
-------
METHOD 7450
MAGNESIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 All elements forming stable oxyanlons (P, B, Si, Cr, S, V, Ti, Al,
etc.) will complex magnesium and Interfere unless lanthanum 1s added. (See
Method 7000, Paragraph 3.1.1.) Addition of lanthanum to prepared samples
rarely presents a problem because virtually all environmental samples contain
sufficient magnesium to require dilution to be in the linear range of the
method.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Magnesium hollow cathode lamp.
4.2.2 Wavelength: 285.2 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of magnesium metal
(analytical reagent grade) in 20 mL 1:1 HN03 and dilute to 1 liter with
Type II water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
7450 - 1
Revision 0
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing, Including 1 ml lanthanum solution per 10 ml solution (see
Paragraph 3.2).
5.2.3 Lanthanum chloride solution: Dissolve 29 g 13203 1n 250 ml
concentrated HC1 -
(CAUTION: REACTION IS VIOLENT!) -
and dilute to 500 ml with Type II water.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 0.02-0.05 mg/L with a wavelength of 285.2
nm.
Sensitivity: 0.007 mg/L.
Detection limit: 0.001 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 2.1 and 8.2
mg/L gave standard deviations of +0.1 and +0.2, respectively. Recoveries at
both of these levels were 100%.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 242.1.
7450 - 2
Revision
Date September 1986
-------
METHOD 7450
MAGNESIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7. I
- 1 For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 700O.
Section 7.2
f StOP J
7450 - 3
Revision 0
Date September 1986
-------
METHOD 7460
MANGANESE (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Background correction 1s required.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Manganese hollow cathode lamp.
4.2.2 Wavelength: 279.5 nm (primary); 403.1 nm (alternate).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Slightly oxidizing (slightly fuel-lean to
sto1ch1ometr1c).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards:
5.2.1 Stock solution: Dissolve 1.000 g manganese metal (analytical
reagent grade) 1n 10 mL redistilled HN03 and dilute to 1 liter with
Type II water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentration as will result 1n the sample to be analyzed after
processing.
7460 - 1
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Date September 1986
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6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.1-3 mg/L with a wavelength of 279.5 nm.
Sensitivity: 0.05 mg/L.
Detection limit: 0.01 mg/L.
9.2 Precision and accuracy data are available 1n Method 243.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 243.1.
7460 - 2
Revision
Date September 1986
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METHOO 7460
MANGANESE (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7. 1
prepar
cr
set
For
sample
ation see
lapter 3.
.tlon 3. z
7.2
Analyze using
Method 7000.
Section 7.3
( StOP J
7460 - 3
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Date September 1986
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METHOD 7470
MERCURY IN LIQUID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7470 1s a cold-vapor atomic absorption procedure approved for
determining the concentration of mercury in mobility-procedure extracts, aque-
ous wastes, and ground waters. (Method 7470 can also be used for analyzing
certain solid and sludge-type wastes; however, Method 7471 1s usually the
method of choice for these waste types.) All samples must be subjected to an
appropriate dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, the liquid samples must be prepared according to
the procedure discussed in this method.
2.2 Method 7470, a cold-vapor atomic absorption technique, is based on
the absorption of radiation at 253.7-nm by mercury vapor. The mercury is
reduced to the elemental state and aerated from solution in a closed system.
The mercury vapor passes through a cell positioned 1n the light path of an
atomic absorption spectrophotometer. Absorbance (peak height) Is measured as
a function of mercury concentration.
2.3 The typical detection limit for this method 1s 0.0002 mg/L.
3.0 INTERFERENCES
3.1 Potassium permanganate is added to eliminate possible Interference
from sulfide. Concentrations as high as 20 mg/L of sulflde as sodium sulfide
do not interfere with the recovery of added Inorganic mercury from Type II
water.
3.2 Copper has also been reported to Interfere; however, copper concen-
trations as high as 10 mg/L had no effect on recovery of mercury from spiked
samples.
3.3 Seawaters, brines, and Industrial effluents high 1n chlorides
require additional permanganate (as much as 25 mL) because, during the
oxidation step, chlorides are converted to free chlorine, which also absorbs
radiation of 253.7 nm. Care must therefore be taken to ensure that free
chlorine is absent before the mercury is reduced and swept Into the cell.
This may be accomplished by using an excess of hydroxylamlne sulfate reagent
(25 mL). In addition, the dead air space 1n the BOD bottle must be purged
before adding stannous sulfate. Both inorganic and organic mercury spikes
have been quantitatively recovered from seawater by using this technique.
7470 - 1
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Date September 1986
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3.4 Certain volatile organic materials that absorb at this wavelength
may also cause Interference. A preliminary run without reagents should
determine If this type of Interference 1s present.
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer or equivalent; Any atomic
absorption unit with an opensample presentationarea 1n which to mount the
absorption cell 1s suitable. Instrument settings recommended by the partic-
ular manufacturer should be followed. Instruments designed specifically for
the measurement of mercury using the cold-vapor technique are commercially
available and may be substituted for the atomic absorption spectrophotometer.
4.2 Mercury hollow cathode lamp or electrodeless discharge lamp.
4.3 Recorder; Any multlrange variable-speed recorder that 1s compatible
with the UV detection system 1s suitable.
4.4 Absorption cell; Standard spectrophotometer cells 10 cm long with
quartz end windows maybe used. Suitable cells may be constructed from
Plexlglas tubing, 1 1n. O.D. x 4.5 1n. The ends are ground perpendicular to
the longitudinal axis, and quartz windows (1 In. diameter x 1/16 1n.
thickness) are cemented 1n place. The cell 1s strapped to a burner for
support and aligned 1n the light beam by use of two 2-1n. x 2-1n. cards. One-
1n.-diameter holes are cut 1n the middle of each card. The cards are then
placed over each end of the cell. The cell 1s then positioned and adjusted
vertically and horizontally to give the maximum transmlttance.
4.5 Air pump; Any peristaltic pump capable of delivering 1 liter
a1r/m1n may be used. A Masterflex pump with electronic speed control has been
found to be satisfactory.
4.6 Flowmeter; Capable of measuring an air flow of 1 I1ter/m1n.
4.7 Aeration tubing; A straight glass frit with a coarse porosity.
Tygon tubing 1s used for passage of the mercury vapor from the sample bottle
to the absorption cell and return.
4.8 Drying tube; 6-1n. x 3/4-1n.-diameter tube containing 20 g of mag-
nesium perchlorate or a small reading lamp with 60-W bulb which may be used to
prevent condensation of moisture Inside the cell. The lamp should be posi-
tioned to shine on the absorption cell so that the air temperature 1n the cell
1s about 10*C above ambient.
4.9 The cold-vapor generator 1s assembled as shown 1n Figure 1.
4.9.1 The apparatus shown In Figure 1 Is a closed system. An open
system, where the mercury vapor Is passed through the absorption cell
only once, may be used Instead of the closed system.
7470 - 2
Revision 0
Date September 1986
-------
o
I
CO
-0-
Air Pump
d
Desiccant
Bubbler
Sample Solution
in BOD Bottle
O
Absorption Cell
D
Scrubber
Containing
a Mercury
Absorbing
Media
O 73
o> n>
oo o
fD 3
o
r+
O)
Figure 1. Apparatus for ftameless mercury determination.
VO
00
-------
4.9.2 Because mercury vapor 1s toxic, precaution must be taken to
avoid Its Inhalation. Therefore, a bypass has been Included 1n the
system either to vent the mercury vapor Into an exhaust hood or to pass
the vapor through some absorbing medium, such as:
1. Equal volumes of 0.1 M KMnCty and 10% t^SO/i; or
2. 0.25% Iodine 1n a 3% KI solution.
A specially treated charcoal that will adsorb mercury vapor 1s also
available from Barnebey and Cheney, East 8th Avenue and North Cassldy
Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Sulfurlc add (f^SO/i), concentrated: Reagent grade.
5.3 Sulfurlc acid, 0.5 N: Dilute 14.0 ml of concentrated sulfurlc add
to 1.0 liter.
5.4 N1 trie add (HNOs), concentrated: Reagent grade of low mercury
content^ If a high reagent blank 1s obtained, 1t may be necessary to
distill the nitric add.
5.5 Stannous sulfate; Add 25 g stannous sulfate to 250 ml of 0.5 N
H2S04^ This mixture 1s a suspension and should be stirred continuously
during use. (Stannous chloride may be used 1n place of stannous
sulfate.)
5.6 Sodium chloride-hydroxylarnlne sulfate solution; Dissolve 12 g of
sodium chloride and 12 g of hydroxy 1 ami ne sulfate 1n Type II water and
dilute to 100 ml. (Hydroxy 1 ami ne hydrochlorlde may be used 1n place of
hydroxy 1 ami ne sulfate.)
5.7 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate 1n 100 ml of Type II water.
5.8 Potassium persulfate, 5% solution (w/v): Dissolve 5 g of potassium
persulfate 1n 100 ml of Type II water.
5.9 Stock mercury solution; Dissolve 0.1354 g of mercuric chloride 1n
75 ml of Type II water. Add 10 ml of concentrated HN03 and adjust the
volume to 100.0 ml (1 ml = 1 mg Hg).
5.10 Mercury working standard; Make successive dilutions of the stock
mercury solution to obtain a working standard containing 0.1 g per ml.
This working standard and the dilutions of the stock mercury solution
should be prepared fresh dally. Acidity of the working standard should
be maintained at 0.15% nitric add. This add should be added to the
flask, as needed, before addition of the aliquot.
7470 - 4
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Date September 1986
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6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed 1n Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, acids, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH <2 with HN03. The
suggested maximum holding times for these samples are 38 days 1n glass
containers and 13 days in plastic containers.
6.4 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation; Transfer 100 mL, or an aliquot diluted to
100 mL, containing <1.0 g of mercury, to a 300-mL BOD bottle. Add 5 mL of
H?S04 and 2.5 mL of concentrated HNOs, mixing after each addition. Add 15 mL
of potassium permanganate solution to each sample bottle. Sewage samples may
require additional permanganate. Ensure that equal amounts of permanganate
are added to standards and blanks. Shake and add additional portions of
potassium permanganate solution, 1f necessary, until the purple color persists
for at least 15 m1n. Add 8 mL of potassium persulfate to each bottle and heat
for 2 hr 1n a water bath maintained at 95*C. Cool and add 6 mL of sodium
chloride-hydroxylamlne sulfate to reduce the excess permanganate. After a
delay of at least 30 sec, add 5 mL of stannous sulfate, Immediately attach the
bottle to the aeration apparatus, and continue as described 1n Paragraph 7.3.
7.2 Standard preparation; Transfer 0-, 0.5-, 1.0-, 2.0-, 5.0-, and
10.0-mL aliquots of themercury working standard, containing 0-1.0 ug of
mercury, to a series of 300-mL BOD bottles. Add enough Type II water to each
bottle to make a total volume of 100 mL. Mix thoroughly and add 5 mL of
concentrated ^04 and 2.5 mL of concentrated HN03 to each bottle. Add 15 mL
of KMn04 solution to each bottle and allow to stand at least 15 m1n. Add 8 mL
of potassium persulfate to each bottle and heat for 2 hr in a water bath
maintained at 95*C. Cool and add 6 mL of sodium chloride-hydroxylamlne
sulfate solution to reduce the excess permanganate. When the solution has
been decolorized, wait 30 sec, add 5 mL of the stannous sulfate solution,
immediately attach the bottle to the aeration apparatus, and continue as
described in Paragraph 7.3.
7.3 Analysis; At this point the sample 1s allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of 1 I1ter/m1n, 1s allowed to run continuously. The
absorbance will Increase and reach a maximum within 30 sec. As soon as the
recorder pen levels off (approximately 1 min), open the bypass valve and
7470 - 5
Revision 0
Date September 1986
-------
continue the aeration until the absorbance returns to Its minimum valve.
Close the bypass valve, remove the stopper and frit from the BOD bottle, and
continue the aeration.
7.4 Construct a calibration curve by plotting the absorbances of stan-
dards versus mlcrograms of mercury. Determine the peak height of the unknown
from the chart and read the mercury value from the standard curve.
7.5 Analyze all EP extracts, all samples analyzed as part of a del 1 sting
petition, and all samples that suffer from matrix Interferences by the method
of standard additions.
7.6 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.7 Calculate metal concentrations (1) by the method of standard
additions, or (2) from a calibration curve. All dilution or concentration
factors must be taken Into account. Concentrations reported for multlphased
or wet samples must be appropriately qualified (e.g., 5 ug/g dry weight).
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 or any memory effects are 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 1s a sample brought through the entire sample preparation and
analytical process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a del 1 sting petition, and whenever a new sample matrix 1s being
analyzed.
7470 - 6
Revision
Date September 1986
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9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 245.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 245.1.
7470 - 7
Revision
Date September 1986
-------
METHOD 7470
MERCURY (MANUAL COLO-VAPOR TECHNIQUE)
c
7.1 I
Prepare sample
7.3 For
1 ana lysis.
run circulating
pump
continuously.
aerate
7.2
Transfer allquots of
mercury working
standard to series of
bottles for standard
preparation
7.2
7.5
Construct
calibration
curve;determine
peak height and
mercury value
Add
Type II
water to each
bottle: mix; add
concen. HjSO*
and HMO,
7.2
7.6
Analyze
by method of
standard
additions
Add
KMnO< solution;
add potassium
persulf ate:
heat: cool
7.3
7.7
Routinely
1 analyze
duplicates.
spiked samples.
and check
standards
Reduce
xcesc
permanganate:
attach to
aeration
apparatus
7.8
Calculate metal
concentration*
( Stop J
7470 - 8
Revision 0
Date September 1986
-------
METHOD 7471
MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLD-VAPOR TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7471 is approved for measuring total mercury (organic and
inorganic) in soils, sediments, bottom deposits, and sludge-type materials.
All samples must be subjected to an appropriate dissolution step prior to
analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis, the solid or semi-solid samples must be prepared
according to the procedures discussed in this method.
2.2 Method 7471, a cold-vapor atomic absorption method, is based on the
absorption of radiation at the 253.7-nm wavelength by mercury vapor. The
mercury is reduced to the elemental state and aerated from solution in a
closed system. The mercury vapor passes through a cell positioned in the
light path of an atomic absorption spectrophotometer. Absorbance (peak
height) is measured as a function of mercury concentration.
2.3 The typical detection limit for this method is 0.0002 mg/L.
3.0 INTERFERENCES
3.1 Potassium permanganate is added to eliminate possible interference
from sulfide. Concentrations as high as 20 mg/L of sulfide as sodium sulfide
do not interfere with the recovery of added inorganic mercury from Type II
water.
3.2 Copper has also been reported to interfere; however, copper concen-
trations as high as 10 mg/L had no effect on recovery of mercury from spiked
samples.
3.3 Seawaters, brines, and industrial effluents high in chlorides
require additional permanganate (as much as 25 mL) because, during the
oxidation step, chlorides are converted to free chlorine, which also absorbs
radiation of 253 nm. Care must therefore be taken to ensure that free
chlorine is absent before the mercury is reduced and swept into the cell.
This may be accomplished by using an excess of hydroxy1 amine sulfate reagent
(25 mL). In addition, the dead air space in the BOD bottle must be purged
before adding stannous sulfate. Both inorganic and organic mercury spikes
have been quantitatively recovered from seawater by using this technique.
3.4 Certain volatile organic materials that absorb at this wavelength
may also cause interference. A preliminary run without reagents should
determine if this type of interference is present.
7471 - 1
Revision 0
Date September 1986
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4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer or equivalent; Any atomic
absorption unit with an opensample presentationarea 1n which to mount the
absorption cell 1s suitable. Instrument settings recommended by the partic-
ular manufacturer should be followed. Instruments designed specifically for
the measurement of mercury using the cold-vapor technique are commercially
available and may be substituted for the atomic absorption spectrophotometer.
4.2 Mercury hollow cathode lamp or electrode!ess discharge lamp.
4.3 Recorder; Any multlrange variable-speed recorder that 1s compatible
with the UV detection system 1s suitable.
4.4 Absorption cell; Standard spectrophotometer cells 10 cm long with
quartz end windowsmaybe used. Suitable cells may be constructed from
Plexlglas tubing, 1 1n. O.D. x 4.5 1n. The ends are ground perpendicular to
the longitudinal axis, and quartz windows (1 1n. diameter x 1/16 1n.
thickness) are cemented 1n place. The cell 1s strapped to a burner for
support and aligned 1n the light beam by use of two 2-1n. x 2-1n. cards. One-
1n.-diameter holes are cut 1n the middle of each card. The cards are then
placed over each end of the cell. The cell 1s then positioned and adjusted
vertically and horizontally to give the maximum transmlttance.
4.5 Air pump; Any peristaltic pump capable of delivering 1 L/m1n air
may be usecTA Masterflex pump with electronic speed control has been found
to be satisfactory.
4.6 Flowmeter; Capable of measuring an air flow of 1 L/m1n.
4.7 Aeration tubing; A straight glass frit with a coarse porosity.
Tygon tubing Is used for passage of the mercury vapor from the sample bottle
to the absorption cell and return.
4.8 Drying tube; 6-1n. x 3/4-1n.-diameter tube containing 20 g of
magnesium perchlorate or a small reading lamp with 60-W bulb which may be used
to prevent condensation of moisture Inside the cell. The lamp should be
positioned to shine on the absorption cell so that the air temperature In the
cell 1s about 10*C above ambient.
4.9 The cold-vapor generator 1s assembled as shown 1n Figure 1.
4.9.1 The apparatus shown 1n Figure 1 1s a closed system. An open
system, where the mercury vapor 1s passed through the absorption cell
only once, may be used Instead of the closed system.
4.9.2 Because mercury vapor Is toxic, precaution must be taken to
avoid Us Inhalation. Therefore, a bypass has been Included 1n the
7471 - 2
Revision 0
Date September 1986
-------
1 «
1
CO
J[
n
u
Air Pump
"I Desiccant 1
.1 ^^
Absorption Cell
[J 4-j Bubbler
Sample Solution
O
^JL. JL
Scriihhiir
«^
CO O
ft) 3
D
rt-
cr
n
-! 0
l->
IO
00
o>
Figure 1. Apparatus for f tameless mercury determination.
-------
system either to vent the mercury vapor Into an exhaust hood or to pass
the vapor through some absorbing medium, such as:
1. equal volumes of 0.1 M KMnCty and 10% ^04, or
2. 0.25% Iodine 1n a 3% KI solution.
A specially treated charcoal that will adsorb mercury vapor Is also
available from Barneby and Cheney, East 8th Avenue and North Cassldy
Street, Columbus, Ohio 43219, Cat. #580-13 or #580-22.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Aqua reqia; Prepare Immediately before use by carefully adding
three volumes of concentrated HC1 to one volume of concentrated HN03.
5.3 Sulfuric acid, 0.5 N: Dilute 14.0 ml of concentrated sulfurlc add
to 1 liter. ,
5.4 Stannous sulfate; Add 25 g stannous sulfate to 250 ml of 0.5 N
sulfurlc add. This mixture 1s a suspension and should be stirred
continuously during use. A 10% solution of stannous chloride can be
substituted for stannous sulfate. -
5.5 Sodium chlor1de-hydroxy1amine sulfate solution; Dissolve 12 g of
sodium chloride and 12 g of hydroxylamlnesulfate 1n Type II water and dilute
to 100 ml. Hydroxylamlne hydrochlorlde .may be used 1n place of hydroxylamlne
sulfate.
5.6 Potassium permanganate, mercury-free, 5% solution (w/v): Dissolve
5 g of potassium permanganate 1n 100 ml of Type II water.
5.7 Mercury stock solution; Dissolve 0.1354 g of mercuric chloride 1n
75 "mL of Type II water. A33 10 ml of concentrated nitric add and adjust the
volume to 100.0 ml (1.0 ml = 1.0 mg Hg).
5.8 Mercury working standard; Make successive dilutions of the stock
mercury solution to obtainaworking standard containing 0.1 ug/mL. This
working standard and the dilution of the stock mercury solutions should be
prepared fresh dally. Acidity of the working standard should be maintained at
0.15% nitric add. This add should be added to the flask, as needed, before
adding the aliquot.
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.
7471 - 4
Revision
Date September 1986
-------
6.2 All sample containers must be prewashed with detergents, adds, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH <2 with nitric add.
6.4 For sol Ids or sem1sol1ds, moisture may be driven off 1n a drying
oven at a temperature of 60*C.
7.0 PROCEDURE
7.1 Sample preparation; Weigh triplicate 0.2-g portions of untreated
sample and place In the bottom of a BOD bottle. Add 5 ml of Type II water and
5 ml of aqua regla. Heat 2 m1n In a water bath at 95*C. Cool; then add 50 ml
Type II water and 15 ml potassium permanganate solution to each sample bottle.
Mix thoroughly and place 1n the water bath for 30 m1n at 95*C. Cool and add 6
ml of sodium chlor1de-hydroxylam1ne sulfate to reduce the excess permanganate.
CAUTION: Do this addition under a hood, as Cl£ could be evolved1. Add
55 ml of Type II water. Treating each bottle Individually, add
5 ml of stannous sulfate and Immediately attach the bottle to
the aeration apparatus. Continue as described under step 7.4.
7.2 An alternate digestion procedure employing an autoclave may also be
used. In this method, 5 ml of concentrated H2SOA and 2 ml of concentrated
HNOs are added to the 0.2 g of sample. Add 5 ml of saturated KMn04 solution
and cover the bottle with a piece of aluminum foil. The samples are
autoclaved at 121*C and 15 Ib for 15 m1n. Cool, dilute to a volume of 100 ml
with Type II water, and add 6 ml of sodium chlor1de-hydroxylam1ne sulfate
solution to reduce the excess permanganate. Purge the dead air space and
continue as described under step 7.4.
7.3 Standard preparation; Transfer 0.0-, 0.5-, 1.0-, 2.0-, 5.0-, and
10-mL allquotsof themercury working standard, containing 0-1.0 ug of
mercury, to a series of 300-mL BOD bottles. Add enough Type II water to each
bottle to make a total volume of 10 ml. Add 5 ml of aqua regla and heat 2 min
In a water bath at 95*C. Allow the sample to cool; add 50 ml Type II water
and 15 ml of KMn04 solution to each bottle and return to the water bath for
30 m1n. Cool and add 6 ml of sodium chlorlde-hydroxylamlne sulfate solution
to reduce the excess permanganate. Add 50 ml of Type II water. Treating each
bottle Individually, add 5 ml of stannous sulfate solution, Immediately attach
the bottle to the aeration apparatus, and continue as described 1n
Step 7.4.
7.4 Analysis; At this point, the sample 1s allowed to stand quietly
without manual agitation. The circulating pump, which has previously been
adjusted to a rate of 1 L/m1n, 1s allowed to run continuously. The
absorbance, as exhibited either on the spectrophotometer or the recorder, will
Increase and reach maximum within 30 sec. As soon as the recorder pen levels
off (approximately 1 m1n), open the bypass valve and continue the aeration
until the absorbance returns to Its minimum value. Close the bypass valve,
remove the fritted tubing from the BOD bottle, and continue the aeration.
7471 - 5
Revision 0
Date September 1986
-------
7.5 Construct a calibration curve by plotting the absorbances of
standards versus mlcrograms of mercury. Determine the peak height of the
unknown from the chart and read the mercury value from the standard curve.
7.6 Analyze all EP extracts, all samples analyzed as part of a dellsting
petition, and all samples that suffer from matrix Interferences by the method
of standard additions (see Method 7000, Section 8.7).
7.7 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.8 Calculate metal concentrations: (1) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the instrument's
concentration read-out. All dilution or concentration factors must be taken
into account. Concentrations reported for multiphased or wet samples must be
appropriately qualified (e.g., 5 ug/g dry weight).
8.0 QUALITY CONTROL
8.1 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 or any memory effects are 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 entire sample preparation and
analytical process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a dellsting petition, and whenever a new sample matrix is being
analyzed.
9.0 METHOD PERFORMANCE
9.1 , Precision and accuracy data are available in Method 245.5 of Methods
for Chemical Analysis of Water and Wastes.
7471 - 6
Revision
Date September 1986
-------
9.2 The data shown 1n Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 245.5.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7471 - 7
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Emission control dust Not known 12, 12 ug/g
Wastewater treatment sludge Not known 0.4, 0.28 ug/g
7471 - 8
Revision
Date September 1986
-------
METHOD 7471
MERCURY IN SOLID OR SEMISOLIO WASTE (MANUAL COLD-VAPOR TECHNIQUE)
7. 1
For sample
preparation weigh 3
portions of dry
sample: add Type II
water and aqua regie
to each
7. 1
Use 1 of 2
digestion proced
for sample
prep.
7.2
I Add
cone. HtSCU and
cone. HNOj to
sample: add
KMnO solution
Heat:
cool: add
Type II water
and potassium
permanganate
solution
7 .Z
Autoclave
samples:
cool: dilute:
add sodium
chloride
hydroxylamlne
7.1
Heat:
cool: add
sodium chloride
hydroxylamine
sulfate and
Type II water
7.1
Add
stannous
sulfate to each
bottle: attach
to aeration
apparatus
7471 - 9
Revision o
Date September 1986
-------
METHOD 7471
MERCURY IN SOLID OR SEMISOLID WASTE (MANUAL COLO-VAPOR TECHNIQUE)
(Continued)
7.3
Transfer allquots of
mercury working
standard to series of
bottles for standard
preparation
7.4
For
analysis.
run circulating
pump
continuously.
aerate
7.3 I
1 Add
Type II
water and aqua
regla to each
bottle: heat
7.S
I Construct
calibration
curve:determine
peak height and
mercury value
7.3
. Cool: add Type II
water and KMnCU
solution: heat: cool:
add sodium chloride
hydroxylamlne sulfate
solution
7.6
Analyze
by method of
standard
additions
7.3
Add Type
I II water
and stannous
sulfate; attach
to aeration
apparatus
7.7
Routinely
i analyze
duplicates.
spiked samples.
and check
standards
7.8
Calculate metal
concentrations
f Stop 1
7471 - 10
Revision o
Date September 1986
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METHOD 7480
MOLYBDENUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Interferences 1n an air/acetylene flame from Ca, Sr, $04, and Fe are
severe. These Interferences are greatly reduced 1n the nitrous oxide flame
and by addition of 1,000 mg/L aluminum to samples and standards.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Molybdenum hollow cathode lamp.
4.2.2 Wavelength: 313.3 nm.
4.2.3 Fuel: Acetylene.
4.2.4 0x1dant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.840 g of ammonium molybdate,
(NH4)fiMo7024'4H20 (analytical reagent grade), 1n Type II water and dilute
to 1 liter; 1 mL = 1 mg Mo (1,000 mg/L). Alternatively, procure a
certified standard from a supplier and verify by comparison with a second
standard.
7480 - 1
Revision
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of "analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing. The samples and standards should also contain 1,000 mg/L
aluminum (see Paragraph 5.2.3).
5.2.3 Aluminum nitrate solution: Dissolve 139 g aluminum nitrate,
Al(N03)3'9H20, 1n 150 ml of Type II water; heat to effect solution.
Allow to cool and make up to 200 ml. To each 100 ml of standard and
sample alike, add 2 ml of the aluminum nitrate solution.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section S.O^of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 1-40 mg/L with a wavelength of 313.3 nm.
Sensitivity: 0.4 mg/L.
Detection limit: 0.1 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 0.3, 1.5, and
7.5 mg/L gave standard deviations of +0.007, +0.02, and +0.07, respectively.
Recoveries at these levels were 100%, 96%, and 95%, respectively.
9.3 For concentrations of molybdenum below 0.2 mg/L, the furnace
technique (Method 7481) 1s recommended.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 246.1.
7480 - 2
Revision 0
Date September 1986
-------
METHOD 748O
MOLYBDENUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7.1
1 For
sample
preparation see
chapter 3.
section 3.2
7.2 1
Analyze using
Method 7OOO.
Section 7.Z
f Stop J
7480 - 3
Revision 0
Date September 1986
-------
METHOD 7481
MOLYBDENUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Molybdenum 1s prone to carbide formation. Use a pyrolytically
coated graphite tube.
3.3 Memory effects are possible, and cleaning of the furnace may be
required after analysis of more concentrated samples or standards.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125*C.
4.2.2 Ashing time and temp: 30 sec at 1400'C.
4.2.3 Atomizing time and temp: 5 sec at 2800*C.
4.2.4 Purge gas: Argon (nitrogen should not be used).
4.2.5 Wavelength: 313.3 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular Instrument manufacturer.
4.2.8 Pyrolytlcally coated graphite tube.
NOTE: The above concentration values and Instrument conditions are
for a Perkln-Elmer HGA-2100, based on the use of a 20-uL
Injection, continuous-flow purge gas, and nonpyrolytic
graphite. Smaller sizes of furnace devices or those
employing faster rates of atomlzatlon can be operated using
lower atomlzatlon temperatures for shorter time periods than
the above-recommended settings.
7481 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.840 g of ammonium molybdate,
(NH4)6M07024*4H20 (analytical reagent grade), 1n Type II water and
dilute to 1 liter; 1 ml = 1 mg Mo (1,000 mg/L). Alternatively, procure a
certified standard from a supplier and verify by comparison with a second
standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentrations as 1n the sample after processing (0.5% v/v HN03).
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
Is given 1n Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
9.2 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 3-60 ug/L.
Detection limit: 1 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 246.2.
7481 - 2
Revision 0
Date September 1986
-------
METHOD 7481
MOLYBDENUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
C
1.0
Prepare
calibration
standard
7. 1
For sample
preparation see
Chapter Three:
Section 3.2
7.2
Met
Sec
calc
Sect
Analyze
using
.hod 7000.
tlon 7.3:
:ulatlons
.Ion 7.4
f Stop J
7481 - 3
Revision 0
Date September 1986
-------
METHOD 7520
NICKEL (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Background correction 1s required.
3.3 High concentrations of Iron, cobalt, or chromium may Interfere,
requiring either matrix matching or use of a nitrous-oxide/acetylene flame.
3.4 A nonresonance line of N1 at 232.14 nm causes nonlinear calibration
curves at moderate to high nickel concentrations, requiring sample dilution or
use of the 352.4-nm line.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Nickel hollow cathode lamp.
4.2.2 Wavelength: 232.0 nm (primary); 352.4 nm (alternate).
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g nickel metal (analytical
reagent grade) or 4.953 g nickel nitrate, N1(N03)2'6H20 (analytical
reagent grade), 1n 10 mL HNOs and dilute to 1 liter with Type II water.
7520 - 1
Revision 0
Date September 1986
-------
Alternatively, procure a certified standard from a supplier and verify by
comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.3-5 mg/L with a wavelength of 232.0 nm.
Sensitivity: 0.15 mg/L.
Detection limit: 0.04 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 0.2, 1.0, and
5.0 mg/L gave standard deviations of +0.011, +0.02, and +0.04, respectively.
Recoveries at these levels were 100%, 97%, and 93%, respectively.
9.3 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
7520 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 249.1
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7520 - 3
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Wastewater treatment sludge 3050 13,000, 10,400 ug/g
7520 - 4
Revision
Date September 1986
-------
METHOD 7520
NICKEL (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7. 1
prepar
cf
sec
For
sample
atlon see
apter 3.
tlon 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7520 - 5
Revision o
Date September 1986
-------
METHOD 7550
OSMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 Method 7550 is an atomic absorption procedure approved for
determining the concentration of osmium in wastes, mobility procedure
extracts, soils, and ground water. All samples must be subjected to an
appropriate dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7550, samples must be prepared for
direct aspiration. The method of sample preparation will vary according to
the sample matrix. Aqueous samples are subjected to the acid digestion
procedure discussed 1n this method. Sludge samples are prepared using the
procedure described in Method 3050. For samples containing oils, greases, or
waxes, the procedure described in Method 3040 may be applicable. Due to the
very volatile nature of some osmium compounds, the applicability of a method
to a sample must be verified by means of spiked samples or standard reference
materials, or both.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 1s aspirated Into a nitrous oxide/acetylene flame. The resulting
absorption of hollow cathode radiation will be proportional to the osmium
concentration. Background correction must be employed for all analyses.
2.3 The typical detection limit for this method is 0.3 mg/L; typical
sensitivity 1s 1 mg/L.
3.0 INTERFERENCES
3.1 Background correction is required because nonspecific absorption and
light scattering can be significant at the analytical wavelength.
3.2 Due to the volatility of osmium, standards must be made on a daily
basis, and the applicability of sample-preparation techniques must be verified
for the sample matrices of interest.
3.3 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
3.4 Osmium and its compounds are extremely toxic; therefore, extreme
care must be taken to ensure that samples and standards are handled properly
and that all exhaust gases are properly vented.
7550 - 1
Revision 0
Date September 1986
-------
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer; Single- or dual-channel,
single- ordouble-beam Instrumentwithagrating monochromator, photomul-
tlpller detector, adjustable slits, and provisions for background correction.
4.2 Osmium hollow cathode lamp.
4.3 Strip-chart recorder (optional).
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Concentrated nitric acid (HN03): Add should be analyzed to
determine levels of Impurities.IT" a method blank using the aclde 1s
-------
6.4 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation; Aqueous samples should be prepared according to
the procedure describedTnT Paragraph 7.2. Sludge-type samples should be
prepared according to Method 3050; samples containing oils, greases, or waxes
may be prepared according to Method 3040. The applicability of a sample
preparation technique to a new matrix type must be demonstrated by analyzing
spiked samples, relevant standard reference materials, or both.
7.2 Sample preparation of aqueous samples;
7.2.1 Transfer a representative 100-mL aliquot of the well-mixed
sample to a Griffin beaker and add 1 ml of concentrated HN03.
7.2.2 Place the beaker on a steam bath or hot plate and warm for 15
m1n. Cool the beaker and, If necessary, filter or centrifuge to remove
Insoluble material.
7.2.3 Add 1 ml of concentrated ^04 and adjust the volume back to
100 ml. The sample 1s now ready for analysis.
7.3 The 290.0-nm wavelength line and background correction shall be
employed.
7.4 A fuel-rich nitrous oxide/acetylene flame shall be used.
7.5 Follow the manufacturer's operating Instructions for all other
Instrument parameters.
7.6 Either (1) run a series of osmium standards and construct a
calibration curve by plotting the concentrations of the standards against the
absorbances, or (2) for the method of standard additions, plot added
concentration versus absorbance. For Instruments that read directly 1n
concentration, set the curve corrector to read out the proper concentration.
7.7 Analyze all EP extracts, all samples analyzed as part of a del 1 sting
petition, and all samples that suffer from matrix Interferences by the method
of standard additions.
7.8 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.9 Calculate metal concentrations: (1) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the Instrument's
concentration read-out. All dilution or concentration factors must be taken
Into account.
7550 - 3
Revision
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples 1f they are more concentrated than the highest
standard or 1f they fall on the plateau of a calibration curve.
8.4 Employ a minimum of one blank per sample batch to determine If
contamination or any memory effects are 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 1s a sample brought through the entire sample preparation and
analytical process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a del 1 sting petition, and whenever a new sample matrix 1s being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 252.1.
7550 - 4
Revision
Date September 1986
-------
METHOD 7550
OSMIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
Samples containing
oils, greases.
or waxes ^^ Type of
7.1]
Use Method 3O40
for sample
preparation
Sludge-type
samples
7.2.1
Transfer
aliquot of
sample to
beaker: add
cone. HNOj
7.3-5
Adjust
Instrument
parameters
Use Method 3050
7.2.2
Harm Beaker;
cool and filter
if necessary
7.6
Plot
calibration
curve
7.7
Analyze
by method of
standard
additions
7.B
Routinely
analyze
duplicates.
spiked samples
and check
tandards
7.9
Calculate metal
concentrations
f Stop J
7550 - 5
Revision 0
Date September 1986
-------
METHOD 7610
POTASSIUM (ATOMIC ABSORPTION, DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 In air/acetylene or other high-temperature flames (>2800*C), potas-
sium can experience partial ionization, which indirectly affects absorption
sensitivity. The presence of other alkali salts in the sample can reduce this
ionization and thereby enhance analytical results. The ionization-suppressive
effect of sodium is small if the ratio of Na to K is under 10. Any enhance-
ment due to sodium can be stabilized by adding excess sodium (1,000 ug/mL) to
both sample and standard solutions. If more stringent control of Ionization
is required, the addition of cesium should be considered. Reagent blanks
should be analyzed to correct for potassium impurities in the buffer stock.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Potassium hollow cathode lamp.
4.2.2 Wavelength: 766.5 nm.
4.2.3 Fuel: Acetylene.
4.2.4 0x1dant: Air.
4.2.5 Type of flame: Slightly oxidizing (fuel lean).
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
7610 - 1
Revision
Date September 1986
-------
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.907 g of potassium chloride, KC1
(analytical reagent grade), dried at 110°C 1n Type II water and dilute to
1 liter with Type II water. Alternatively, procure a certified standard
from a supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation: The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of inter-
ferences are:
Optimum concentration range: 0.1-2 mg/L with a wavelength of 766.5 nm.
Sensitivity: 0.04 mg/L.
Detection limit: 0.01 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 1.6 and 6.3
mg/L gave standard deviations of +0.2 and +0.5, respectively. Recoveries at
these levels were 103% and 102%, respectively.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 258.1.
7610 - 2
Revision
Date September 1986
-------
METHOD 761O
POTASSIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7.1
1 For
sample
preparation 'see
chapter 3.
section 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7610 - 3
Revision 0
Date September 1986
-------
METHOD 7740
SELENIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 Method 7740 1s an atomic absorption procedure approved for
determining the concentration of selenium 1n wastes, mobility-procedure
extracts, soils, and ground water. All samples must be subjected to an
appropriate dissolution step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7740, samples must be prepared 1n order
to convert organic forms of selenium to Inorganic forms, to minimize organic
Interferences, and to convert samples to suitable solutions for analysis. The
sample-preparation procedure varies, depending on the sample matrix. Aqueous
samples are subjected to the ac1d-d1gest1on procedure described 1n this
method. Sludge samples are prepared using the procedure described 1n Method
3050.
2.2 Following the appropriate dissolution of the sample, a representa-
tive aliquot 1s placed manually or by means of an automatic sampler Into a
graphite tube furnace. The sample aliquot 1s then slowly evaporated to
dryness, charred (ashed), and atomized. The absorption of lamp radiation
during atomlzatlon will be proportional to the selenium concentration.
2.3 The typical detection limit for this method 1s 2 ug/L.
3.0 INTERFERENCES
3.1 Elemental selenium and many of Its compounds are volatile;
therefore, samples may be subject to losses of selenium during sample
preparation. Spike samples and relevant standard reference materials should
be processed to determine 1f the chosen dissolution method 1s appropriate.
3.2 Likewise, caution must be employed during the selection of
temperature and times for the dry and char (ash) cycles. A nickel nitrate
solution must be added to all dlgestates prior to analysis to minimize
volatilization losses during drying and ashing.
3.3 In addition to the normal Interferences experienced during graphite
furnace analysis, selenium analysis can suffer from severe nonspecific
absorption and light scattering caused by matrix components during
atomlzatlon. Selenium analysis Is particularly susceptible to these problems
because of Its low analytical wavelength (196.0 nm). Simultaneous background
correction 1s required to avoid erroneously high results. High Iron levels
can give overcorrectlon with deuterium background. Zeeman background
correction can be useful In this situation.
7740 - 1
Revision 0
Date September 1986
-------
3.4 If the analyte 1s not completely volatilized and removed from the
furnace during atomlzatlon, memory effects will occur. If this situation 1s
detected, the tube should be cleaned by operating the furnace at full power at
regular Intervals 1n the analytical scheme.
3.5 Selenium analysis suffers Interference from chlorides (>800 mg/L)
and sulfate (>200 mg/L). The addition of nickel nitrate such that the final
concentration Is 1% nickel will lessen this Interference.
s.
4.0 APPARATUS AND MATERIALS
4.1 250-mL Griffin beaker.
4.2 10-mL volumetric flasks.
4.3 Atomic absorption spectrophptometer; Single- or dual-channel,
single- or double-beam Instrument with a grating monochromator, photomulti-
pHer detector, adjustable slits, a wavelength range of 190-800 nm, and
provisions for simultaneous background correction and Interfacing with a
strip-chart recorder.
4.4 Selenium hollow cathode lamp, or electrodeless discharge lamp (EDL):
EDLs provide better sensitivity for the analysis of Se.
4.5 Graphite furnace; Any graphite furnace device with the appropriate
temperature and timing control s .
4.6 Strip-chart recorder; A recorder 1s strongly recommended for
furnace work so that there will be a permanent record and so that any problems
with the analysis, such as drift, Incomplete atomlzatlon, losses during
charring, changes In sensitivity, etc., can easily be recognized.
4.7 Plpets; M1crol1ter with disposable tips. Sizes can range from
5 to 1,000 uL, as required.
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
impurities.
5.2 Concentrated nitric acid (HNOs): Acid should be analyzed to
determine levels of Impurities. If~a method blank made with the add is
-------
5.4 Selenium standard stock solution (1,000 mg/L): Either procure a
certified aqueous standard fromasupplier and verify by comparison with a
second standard, or dissolve 0.3453 g of selenlous add (actual assay 94.6%
H2Se03, analyt1caT~reagent grade) or equivalent 1n Type II water and dilute to
200 ml.
5.5 Nickel nitrate solution (5%): Dissolve 24.780 g of ACS reagent
grade N1(N03)2*6H20 or equivalent 1n Type II water and dilute to 100 ml.
5.6 Nickel nitrate solution (1%): Dilute 20 ml of the 5% nickel nitrate
to 100 ml with Type II water.~~
5.7 Selenium working standards; Prepare dilutions of the stock solution
to be used as calibration standards at the time of the analysis. Withdraw
appropriate aliquots of the stock solution, add 1 mL of concentrated HN03,
2 ml of 30% H202, and 2 ml of the 5% nickel nitrate solution. Dilute to
100 ml with Type II water.
5.8 Air: Cleaned and dried through a suitable filter to remove oil,
water, and other foreign substances. The source may be a compressor or a
cylinder of Industrial-grade compressed air.
5.9 Hydrogen; Suitable for Instrumental analysis.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 All samples must have been collected using a sampling plan that
addresses the considerations discussed In Chapter Nine of this manual.
6.2 All sample containers must be prewashed with detergents, adds, and
Type II water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used If very volatile selenium compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric add.
6.5 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation: Aqueous samples should be prepared 1n the
manner described InSteps7.1.1 to 7.1.3. Sludge-type samples should be
prepared according to Method 3050. The applicability of a sample-preparation
technique to a new matrix type must be demonstrated by analyzing spiked
samples and/or relevant standard reference materials.
7740 - 3
Revision
Date September 1986
-------
7.1.1 Transfer 100 ml of well-mixed sample to a 250-mL Griffin
beaker; add 2 ml of 30% ^2 and sufficient concentrated HN03 to result
in an acid concentration of 1% (v/v). Heat for 1 hr at 95'C or until the
volume is slightly less than 50 ml.
7.1.2 Cool and bring back to 50 ml with Type II water.
7.1.3 Pi pet 5 ml of this digested solution into a 10-mL volumetric
flask, add 1 ml of the 1% nickel nitrate solution, and dilute to 10 ml
with Type II water. The sample is now ready for injection into the
furnace.
/
7.2 The 196.0-nm wavelength line and a background correction system must
be employed. Follow the manufacturer's suggestions for all other spectropho-
tometer parameters.
7.3 Furnace parameters suggested by the manufacturer should be employed
as guidelines. Because temperature-sensing mechanisms and temperature
controllers can vary between instruments or with time, the validity of the
furnace parameters must be periodically confirmed by systematically altering
the furnace parameters while analyzing a standard. In this manner, losses of
analyte due to overly high temperature settings or losses in sensitivity due
to less than optimum settings can be minimized. Similar verification of
furnace parameters may be required for complex sample matrices.
7.4 Inject a measured uL-aliquot of sample into the furnace and atomize.
If the concentration found is greater than the highest standard, the sample
should be diluted in the same acid matrix and reanalyzed. The use of multiple
injections can improve accuracy and help detect furnace pipetting errors.
7.5 Analyze all EP extracts, all samples analyzed as part of a deli sting
petition, and all samples that suffer from matrix interferences by the method
of standard additions.
7.6 Run a check standard after approximately every 10 sample injections.
Standards are run in part to monitor the life and performance of the graphite
tube. Lack of reproducibility or significant change in the signal for the
standard indicates that the tube should be replaced.
7.7 Duplicates, spiked samples, and check standards should be analyzed
every 20 samples.
7.8 Calculate metal concentrations: (1) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the instrument's
concentration read-out. All dilution or concentration factors must be taken
into account.
7740 - 4
Revision 0
Date September 1986
-------
8.0 QUALITY CONTROL
8.1 All quality control data should be maintained and available for easy
reference or Inspection.
8.2 Calibration curves must be composed of a minimum of a blank and
three standards. A calibration curve should be made for every hour of
continuous sample analysis.
8.3 Dilute samples 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 or any memory effects are 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 1s a sample brought through the entire sample preparation and
analytical process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a deli sting petition, and whenever a new sample matrix is being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available in Method 270.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The data shown in Table 1 were obtained from records of state and
contractor laboratories. The data are intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 270.2.
2. Gaskill, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7740 - 5
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Emission control dust 3050 14, 11 ug/g
7740 - 6
Revision
Date September 1986
-------
METHOD 7740
SELENIUM (ATOMIC ABSORPTION. FURNACE METHOD)
Type of sample
for sample
preparation
Sludge-type
samples
of sample to
beaker: add 30X
HjOz and cone .
HNO,
heat
7.1.2
Cool: bring to
volume
7.1.3
Plpet
digested
solution
into flask: add
nickel nitrate
solution: dilute
7. 1
Prepare sample
according to
Method 3050
7740 - 7
Revision 0
Date September 1986
-------
METHOD 7740
SELENIUM (ATOMIC ABSORPTION FURNACE METHOD)
(Continued)
7.2
Set Instrument
parameters
Analyze
by method of
standard
addition
7.3 I
Periodically
check validity
of furnace
parameters
7.4
_7_U
Run
check standard
after 10 sample
Injections
Inject sample
Into furnace:
atomize
Is
concentration
> highest
standard?
Dilute sample
and reanalyze
7.7
Routinely
i analyze
duplicates.
spiked samples.
and check
standards
7.B
Calculate metal
concentrations
( Stop J
7740 - 8
Revision 0
Date September 1986
-------
METHOD 7741
SELENIUM (ATOMIC ABSORPTION. GASEOUS HYDRIDE)
1.0 SCOPE AND APPLICATION
1.1 Method 7741 1s an atomic absorption procedure that 1s approved for
determining the concentration of selenium 1n wastes, mobility-procedure
extracts, soils, and ground water, provided that the sample matrix does not
contain high concentrations of chromium, copper, mercury, silver, cobalt, or
molybdenum. All samples must be subjected to an appropriate dissolution step
prior to analysis. Spiked samples and relevant standard reference materials
are employed to determine applicability of the method to a given waste.
2.0 SUMMARY OF METHOD
2.1 Samples are prepared according to the nltric/sulfuric acid digestion
procedure described in this method. Next, the selenium 1n the dlgestate is
reduced to Se(IV) with tin chloride. The Se(IV) 1s then converted to a
volatile hydride with hydrogen produced from a zinc/HCl reaction.
2.2 The volatile hydride 1s swept Into an argon-hydrogen flame located
1n the optical path of an atomic absorption spectrophotometer; the resulting
absorbance is proportional to the selenium concentration.
2.3 The typical detection limit for this method is 0.002 mg/L.
3.0 INTERFERENCES
3.1 High concentrations of chromium, cobalt, copper, mercury, molyb-
denum, nickel, and silver can cause analytical Interferences.
3.2 Traces of nitric acid left following the sample work-up can result
1n analytical Interferences. Nitric add must be distilled off the sample by
heating the sample until fumes of $03 are observed.
3.3 Elemental selenium and many of Its compounds are volatile;
therefore, certain samples may be subject to losses of selenium during sample
preparation.
4.0 APPARATUS AND MATERIALS
4.1 100-mL beaker.
4.2 Electric hot plate.
4.3 A commercially available zinc slurry hydride generator or a
generator constructed from the following material (see Figure 1);
7741 - 1
Revision 0
Date September 1986
-------
Argon
Plow Meter
JM-3325
Medicine
Dropper in
Size "0"
Rubber
Stopper
> JM-5835
(Auxiliary Air)
Argon (Nebulizer Air)
Figure 1. Zinc slurry hydride generator apparatus set-up and AAS sample introduction system.
7741 - 2
Revision p
Date September 1986
-------
4.3.1 Medicine dropper: Fitted Into a size "0" rubber stopper
capable of delivering 1.5 ml.
4.3.2 Reaction flask: 50-mL, pear-shaped, with two 14/20 necks
(Scientific Glass, JM-5835).
4.3.3 Gas Inlet-outlet tube: Constructed from a micro cold-finger
condenser (JM-3325) by cutting the portion below the 14/20 ground-glass
joint.
4.3.4 Magnetic stlrrer: To homogenize the zinc slurry.
4.3.5 Polyethylene drying tube: 10-cm, filled with glass to
prevent particulate matter from entering the burner.
4.3.6 Flow meter: Capable of measuring 1 I1ter/m1n.
4.4 Atomic absorption spectrophotometer; Single or dual channel, sin-
gle- or double-beam instrument, witha grating monochromator, photomultiplier
detector, adjustable slits, a wavelength range of 190-800 nm, and provisions
for interfacing with a 'strip-chart recorder and simultaneous background
correction.
4.5 Burner; Recommended by the particular instrument manufacturer for
the argon-hydrogen flame.
4.6 Selenium hollow cathode lamp or electrode!ess discharge lamp.
4.7 Strip-chart recorder (optional).
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Concentrated nitric acid; Acid should be analyzed to determine
levels of impurities. If a method blank made with the acid 1s
-------
5.6 Potassium Iodide solution: Dissolve 20 g KI 1n 100 ml Type II
water. :
5.7 Stannous chloride solution; Dissolve 100 g SnCl2 1n 100 ml of
concentrated HC1.
j
5.8 Selenium standard stock solution; : 1,000 mg/L solution may be
purchased, or prepared as follows; Dissolve 0:3453 g of selenlous add (assay
94.6% of H?Se03) 1n Type II water. Add to a 200-mL volumetric flask and bring
to volume (1 ml = 1 mg Se). . i
i
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 sample containers must be prewashed with detergents, adds, and
Type II water. Plastic and glass containers are both suitable.
6.3 Special containers (e.g., containers used for volatile organic
analysis) may have to be used if very volatile selenium compounds are to be
analyzed.
6.4 Aqueous samples must be acidified to a pH of <2 with nitric add.
6.5 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible. '
i
7.0 PROCEDURE ;
i
7.1 Sample preparation;
7.1.1 To a 50-mL aliquot of digested sample (or, 1n the case of EP
extracts, a 50-mL sample) add 10 mL of concentrated HNOs and 12 mL of
18 N H2S04. Evaporate the sample on a hot plate until white $63 fumes
are observed (a volume of about 20 mL). Do not let 1t char. If 1t
chars, stop the digestion, cool, and add additional HNOs. Maintain an
excess of HN03 (evidence of brown fumes) and do not let the solution
darken because selenium may be reduced and lost. When the sample remains
colorless or straw yellow during evolution of 503 fumes, the digestion is
complete.
7.1.2 Cool the sample, add about 25 mL Type II water, and again
evaporate to $03 fumes just to expel oxides of nitrogen. Cool. Add
40 mL concentrated HC1 and bring to a volume of 100 mL with Type II
water.
7.2 Prepare working standards from the standard stock solutions. The
following procedures provide standards in the optimum range.
7741 - 4
Revision 0
Date September 1986
-------
7.2.1 To prepare a working stock solution, plpet 1 mL standard
stock solution (see Paragraph 5.8) Into a 1-Hter volumetric flask.
Bring to volume with Type II water containing 1.5 ml concentrated
HNOs/Hter. The concentration of this solution 1s 1 mg Se/L
(1 ml = 1 ug Se).
7.2.2 Prepare six working standards by transferring 0, 0.5, 1.0,
1.5, 2.0, and 2.5 ml of the working stock solution (see Paragraph 7.2.1)
Into 100-mL volumetric flasks. Bring to volume with diluent. The
concentrations of these working standards are 0, 5, 10, 15, 20, and
25 ug Se/L.
7.3 Standard additions;
7.3.1 Take the 15-, 20-, and 25-ug standards and transfer
quantitatively 25 ml from each Into separate 50-mL volumetric flasks.
Add 10 ml of the prepared sample to each. Bring to volume with Type II
water containing 1.5 ml HN03/l1ter.
7.3.2 Add 10 ml of prepared sample to a 50-mL volumetric flask.
Bring to volume with Type II water containing 1.5 mL HN03/11ter. This 1s
the blank.
7.4 Follow the manufacturer's Instructions for operating an argon-
hydrogen flame. The argon-hydrogen flame 1s colorless; therefore, 1t may be
useful to aspirate a low concentration of sodium to ensure that Ignition has
occurred.
7.5 The 196.0-nm wavelength shall be used for the analysis of selenium.
7.6 Transfer a 25-mL portion of the digested sample or standard to the
reaction vessel. Add 0.5 mL SnCl2 solution. Allow at least 10 m1n for the
metal to be reduced to Its lowest oxidation state. Attach the reaction vessel
to the special gas Inlet-outlet glassware. Fill the medicine dropper with
1.50 mL zinc slurry that has been kept 1n suspension with the magnetic
stlrrer. Firmly Insert the stopper containing the medicine dropper Into the
side neck of the reaction vessel. Squeeze the bulb to Introduce the zinc
slurry Into the sample or standard solution. The metal hydride will produce a
peak almost Immediately. When the recorder pen returns partway to the base
line, remove the reaction vessel.
7.7 Analyze all EP extracts, all samples analyzed as part of a del 1 sting
petition, and all samples that suffer from matrix interferences by the method
of standard additions.
7.8 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.9 Calculate metal concentrations: (1) by the method of standard
additions (2) from a calibration curve, or (3) directly from the Instrument's
concentration read-out. All dilution or concentration factors must be taken
7741 - 5
Revision 0
Date September 1986
-------
Into account. For example, 1f the method of standard additions was employed,
the analytical value will be one-tenth the concentration of the original
sample due to dilution during preparation.
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 or any memory effects are 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 1s a sample brought through the entire sample preparation and
analytical process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a dellstlng petition, and whenever a new sample matrix 1s being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 270.3 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 270.3.
7741 - 6
Revision
Date September 1986
-------
METHOD 7741
SELENIUM (ATOMIC ABSORPTION. GASEOUS HYDRIDE)
7.1.1
preparat
cone. 1-
HjSO* tc
and evi
For
ample
ion add
NOj and
sample
porate
Prepare
6 working
standards from
selenium stock
standard: bring
each to volume
Stop digestion;
cool: add HNOJ
7.6
Transfer portion of
digested sample to
reaction vessel: ado
SnClj solution: allow
to stand for 10 min
7.3.1
Transfer 3 portions
of standard to
flasks; add 10 ml of
sample to each: bring
to volume
Cool sample: add
Type II water;
evaporate: cool:
add cone. HC1:
Increase volume
7.2.1
7.6
1 Attach
vessel to
gas glassware;
Introduce zinc
lurry
7.3.2
To
I prepare
blank add
10 ml of sample
to a flask:
bring to volume
To
prepare
standards pipet
stock solution
into flask:
bring to volume
7 .
7.7
Analyze
by method of
standard
additions
Follow
instructions
for operating
an argon-
hydrogen flame
Use 196.0 nm
wavelength
7.8 (Routinely
I analyze
duplicates.
spiked samples
anO check
standards
7.9
Calculate metal
concentrations
f Stop J
7741 - 7
Revision 0
Date September 1986
-------
METHOD 7760
SILVER (ATOMIC ABSORPTION. DIRECT ASPIRATON)
1.0 SCOPE AND APPLICATION
1.1 Method 7760 1s an atomic absorption procedure approved for determin-
ing the concentration of silver 1n wastes, mobility procedure extracts, soils,
and ground water. All samples must be subjected to an appropriate dissolution
step prior to analysis.
2.0 SUMMARY OF METHOD
2.1 Prior to analysis by Method 7760, samples must be prepared for
direct aspiration. The method of sample preparation will vary according to
the sample matrix. Aqueous samples are subjected to the ac1d-d1gest1on
procedure described 1n this method.
2.2 Following the appropriate dissolution of the sample, a represen-
tative aliquot 1s aspirated Into an air/acetylene flame. The resulting
absorption of hollow cathode radiation will be proportional to the silver
concentration. Background correction must be employed for all analyses.
2.3 The typical detection limit for this method 1s 0.01 mg/L; typical
sensitivity 1s 0.06 mg/L.
3.0 INTERFERENCES
3.1 Background correction 1s required because nonspecific absorption and
light scattering may occur at the analytical wavelength.
3.2 Silver nitrate solutions are light-sensitive and have the tendency
to plate out on container walls. Thus silver standards should be stored 1n
brown bottles.
3.3 Silver chloride 1s Insoluble; therefore, hydrochloric add should be
avoided unless the silver 1s already 1n solution as a chloride complex.
3.4 Samples and standards should be monitored for viscosity differences
that may alter the aspiration rate.
4.0 APPARATUS AND MATERIALS
4.1 Atomic absorption spectrophotometer; Single- or dual-channel,
single- ordouble-beamInstrumentwith a grating monochromator,
photomultlpHer detector, adjustable slits, and provisions for background
correction.
7760 - 1
Revision
Date September 1986
-------
4.2 Silver hollow cathode lamp.
4.3 Strip-chart recorder (optional).
5.0 REAGENTS
5.1 ASTM Type II water (ASTM D1193): Water should be monitored for
Impurities.
5.2 Concentrated nitric add (HNOs); Add should be analyzed to
determine levels of Impurities. If Impurities are detected, all analyses
should be blank-corrected.
5.3 Concentrated ammonium hydroxide (NfyOH): Base should be analyzed to
determine levels of Impurities. I? Impurities are detected, all analyses
should be blank-corrected.
5.4 Silver standard stock solution (1,000 mg/L): Either procure a
certified aqueous standard from a supplier and verify by comparison with a
second standard, or dissolve 0.7874 g anhydrous silver nitrate (AgNOs),
analytical reagent grade, 1n Type II water. Add 5 ml concentrated HN03 and
bring to volume 1n a 500-mL volumetric flask (1 ml = 1 mg Ag).
5.5 Silver working standards; These standards should be prepared with
nitric add and at the same concentrations as the analytical solution.
5.6 Iodine solution, 1 N: Dissolve 20 g potassium Iodide (KI),
analytical reagent grade, 1n 50 ml Type II water. Add 12.7 g Iodine (12),
analytical reagent grade, and dilute to 100 ml. Place 1n a brown bottle.
5.7 Cyanogen Iodide solution; To 50 ml Type II water add 4.0 ml
concentrated NH^OH, 6.5 g KCN, and 5.0 ml of Iodine solution. Mix and dilute
to 100 ml with Type II water. Do not keep longer than 2 wk.
CAUTION: This reagent cannot be mixed with any acid solutions because
toxic hydrogen cyanide will be produced.
5.8 A1r; Cleaned and dried through a suitable filter to remove oil,
water, and otKer foreign substances. The source may be a compressor or a
cylinder of Industrial -grade compressed air.
5.9 Acetylene; Should be of high purity. Acetone, which 1s usually
present 1n acetylene cylinders, can be prevented from entering and affecting
flame conditions by replacing the cylinder before the pressure has fallen to
50 pslg.
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.
7760 - 2
Revision 0
Date September 1986
-------
6.2 All sample containers must be prewashed with detergents, adds, and
Type II water. Plastic and glass containers are both suitable.
6.3 Aqueous samples must be acidified to a pH <2 with nitric add.
6.4 When possible, standards and samples should be stored 1n the dark
and 1n brown bottles.
6.5 Nonaqueous samples shall be refrigerated, when possible, and
analyzed as soon as possible.
7.0 PROCEDURE
7.1 Sample preparation; Aqueous samples should be prepared according to
Paragraphs 7.2 and 7.3.THe applicability of a sample-preparation technique
to a new matrix type must be demonstrated by analyzing spiked samples and/or
relevant standard reference materials.
7.2 Preparation of aqueous samples;
7.2.1 Transfer a representative aliquot of the well-mixed sample to
a Griffin beaker and add 3 ml of concentrated HN03. Cover the beaker
with a watch glass. Place the beaker on a hot plate and cautiously
evaporate to near dryness, making certain that the sample does not boll.
DO NOT BAKE. Cool the beaker and add another 3-mL portion of
concentrated HN03. Re-cover the beaker with a watch glass and return to
the hot plate. Increase the temperature of the hot plate so that a
gentle reflux action occurs.
NOTE; If the sample contains thiosulfates, this step may result 1n
splatter of sample out of the beaker as the sample approaches
dryness. This has been reported to occur with certain
photographic types of samples.
7.2.2 Continue heating, adding additional acid, as necessary, until
the digestion 1s complete (generally Indicated when the dlgestate 1s
light 1n color or does not change 1n appearance with continued
refluxlng). Again, evaporate to near dryness and cool the beaker. Add a
small quantity of HN03 so that the final dilution contains 0.5% (v/v)
HN03 and warm the beaker to dissolve any precipitate or residue resulting
from evaporation.
7.2.3 Wash down the beaker walls and watch glass with Type II water
and, when necessary, filter the sample to remove silicates and other
Insoluble material that could clog the nebulizer. Adjust the volume to
some predetermined value based on the expected metal concentrations. The
sample 1s now ready for analysis.
7760 - 3
Revision 0
Date September 1986
-------
7.3 If plating out of AgCl 1s suspected, the precipitate can be
redlssolved by adding cyanogen Iodide to the sample.
CAUTION: This can be done only after digestion to prevent formation of
toxic cyanide under add conditions.
If cyanogen Iodide addition to the sample 1s necessary, then the standards
must be treated 1n the same manner.
CAUTION: Cyanogen Iodide must not be added to the acidified silver
standards.
New standards must be made, as directed in Paragraphs 5.4 and 5.5, except that
the add addition step must be omitted. Transfer 10 ml of stock solution to a
small beaker. Add Type II water to make about 80 ml. Make the solution basic
(pH above 7) with ammonium hydroxide. Rinse the pH meter electrodes Into the
solution with Type II water. Add 1 ml cyanogen iodide and allow to stand 1
hr. Transfer quantitatively to a 100-mL volumetric flask and bring to volume
with Type II water.
7.4 The 328.1-nm wavelength line and background correction shall be
employed.
7.5 An oxidizing air-acetylene flame shall be used.
7.6 Follow the manufacturer's operating Instructions for all other
spectrophotometer parameters.
7.7 Either (1) run a series of silver standards and construct a
calibration curve by plotting the concentrations of the standards against the
absorbances, or (2) for the method of standard additions, plot added
concentration versus absorbance. For Instruments that read directly 1n
concentration, set the curve corrector to read out the proper concentration.
7.8 Analyze all EP extracts, all samples analyzed as part of a del 1 sting
petition, and all samples that suffer from matrix interferences by the method
of standard additions.
7.9 Duplicates, spiked samples, and check standards should be routinely
analyzed.
7.10 Calculate metal concentrations: (!) by the method of standard
additions, (2) from a calibration curve, or (3) directly from the Instrument's
concentration read-out. All dilution or concentration factors must be taken
Into account.
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.
7760 - 4
Revision
Date September 1986
-------
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 or any memory effects are 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 1s a sample brought through the entire sample preparation and
analytical process.
8.7 The method of standard additions (see Method 7000, Section 8.7)
shall be used for the analysis of all EP extracts, on all analyses submitted
as part of a del 1 sting petition, and whenever a new sample matrix 1s being
analyzed.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 272.1 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The data shown 1n Table 1 were obtained from records of state and
contractor laboratories. The data are Intended to show the precision of the
combined sample preparation and analysis method.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 272.1.
2. Gasklll, A., Compilation and Evaluation of RCRA Method Performance Data,
Work Assignment No. 2, EPA Contract No. 68-01-7075, September 1986.
7760 - 5
Revision
Date September 1986
-------
TABLE 1. METHOD PERFORMANCE DATA
Sample Preparation Laboratory
Matrix Method Replicates
Wastewater treatment sludge 3050 2.3, 1.6 ug/g
Emission control dust 3050 1.8, 4.2 ug/g
7760 - 6
Revision
Date September 1986
-------
METHOD 7760
SILVER (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
Samples containing
oils, grease. .,
or waxes -/^ Type
7.1
I Prepare
sample
according to
Methods 3040
Sludge-type
samples
7.Z.1I Transfer
I sample
to beaker:
add cone HNOj:
evaporate to
near dryness
7.2. 1
7. 1
Prepare sample
according to
Method 3050
Cool:
add cone.
HMD,: heat so
gentle reflux
action occurs
7.2.2 Complete
'digestion
and evaporate
to near
dryness: cool:
add HNOj: warm
Filter sample:
adjust volume
7760 - 7
Revision o
Date September 1986
-------
METHOD 7760
SILVER (ATOMIC ABSORPTION. DIRECT ASPIRATION METHOD)
(Continued)
IB plating out
of AgCl
suspected?
Yes
7.3
Add cyanogen
Iodide to redlssolve
precipitate: treat
all standards the
same, except
acidified silver
standards
7.8
Analyze
By method of
standard
addltons
7.9
Routinely
i analyze
duplicates.
spiked samples.
and check
standards
7.4-61
Set spectre-
photometer
parameters
710
Calculate metal
concentrations
7.7
Construct
calibration
curve
f Stop J
o
7760 - 8
Revision 0
Date September 1986
-------
METHOD 7770
SODIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Ion1zat1on Interferences can affect analysis for sodium; therefore,
samples and standards must be matrix matched or an 1on1zation suppressant
employed.
3.3 Sodium Is a universal contaminant, and .great care should be taken to
avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Sodium hollow cathode lamp.
4.2.2 Wavelength: 589.6 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 2.542 g sodium chloride, NaCl
(analytical reagent grade), 1n Type II water, acidify with 10 mL
redistilled HN03, and dilute to 1 liter with Type II water.
Alternatively, procure a certified standard from a supplier and verify by
comparison with a second standard.
7770 - 1
Revision 0
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of Inter-
ferences are:
Optimum concentration range: 0.03-1 mg/L with a wavelength of 589.6 nm.
Sensitivity: 0.015 mg/L.
Detection limit: 0.002 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 8.2 and 52
mg/L gave standard deviations.of +0.1 and +0.8, respectively. Recoveries at
these levels were 102% and 100%, respectively.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 273.1.
7770 - 2
Revision
Date September 1986
-------
METHOD 7770
SODIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7.1
I For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 7OOO.
Section 7.3
f Stop J
7770 - 3
Revision 0
Date September 1986
-------
METHOD 7840
THALLIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
3.2 Background correction is required.
3.3 Hydrochloric acid should not be used.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Thallium hollow cathode lamp.
4.2.2 Wavelength: 276.8 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Air.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.303 g thallium nitrate,
(analytical reagent grade), 1n Type II water, acidify with 10 mL
concentrated HN03, and dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify by
comparison with a second standard.
7840 - 1
Revision
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentration as will result 1n the sample to be analyzed after
processing (0.5% v/v
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given In Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 1-20 mg/L with a wavelength of 276.8 nm.
Sensitivity: 0.5 mg/L.
Detection limit: 0.1 mg/L.
9.2 In a single laboratory, analysis of a mixed Industrial -domestic
waste effluent, digested with Method 3010, at concentrations of 0.6, 3, and 15
mg/L gave standard deviations of +0.018, +0.05, and +0.2, respectively.
Recoveries at these levels were 100%, 98%, and 98%, respectively.
9.3 For concentrations of thallium below 0.2 mg/L, the furnace technique
(Method 7841) 1s recommended.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 279.1.
7840 - 2
Revision
Date September 1986
-------
METHOD 784O
THALLIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
5.0
Prepare
standards
7.1
prepar
cf
sec
7. 2
For
sample
atiorv see
tapter 3.
tlon 3.3
1
Analyze using
Method 7000.
Section 7.2
f Stop J
7840 - 3
Revision 0
Date September 1986
-------
METHOD 7841
THALLIUM (ATOMIC ABSORPTION, FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Background correction 1s required.
3.3 Hydrochloric add or excessive chloride will cause volatilization of
thallium at low temperatures. Verification that losses are not occurring, by
spiked samples or standard additions, must be made for each sample matrix.
3.4 Palladium 1s a suitable matrix modifier for thallium analysis.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125*C.
4.2.2 Ashing time and temp: 30 sec at 400*C.
4.2.3 Atomizing time and temp: 10 sec at 2400°C.
4.2.4 Purge gas: Argon or nitrogen.
4.2.5 Wavelength: 276.8 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular instrument manufacturer.
NOTE: The above concentration values and Instrument conditions are for a
Perkin-Elmer HGA-2100, based on the use of a 20-uL Injection,
continuous-flow purge gas, and nonpyrolytic graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomizatlon can be operated using lower atomlzatlon temperatures
for shorter time periods than the above-recommended settings.
7841 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.303 g thallium nitrate, T1N03
(analytical reagent grade), In Type II water, acidify with 10 ml
concentrated HN03, and dilute to 1 liter with Type II water. Alterna-
tively, procure a certified standard from a supplier and verify by
comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentrations as 1n the sample after processing (0.5% v/v
5.3 Palladium chloride; Weigh 0.25 g of PdCl2 to the nearest 0.0001 g.
Dissolve 1n 10 ml of 1:1 HN03 and dilute to 1 liter with Type II water. Use
equal volumes of sample and palladium solution.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
Is given 1n Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are not available at this time.
9.2 The performance characteristics for an aqueous sample free of
Interferences are;
Optimum concentration range: 5-100 ug/L.
Detection limit: 1 ug/L.
7841 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Application of Matrix-Modification 1n Determination of Thallium 1n
Wastewater by Graphite-Furnace Atomic-Absorption Spectrometry, Talanta, 31(2)
(1984), pp. 150-152.
7841 - 3
Revision
Date September 1986
-------
METHOD 7841
THALLIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
5
.0 1
Prepare
standards
7. 1
1 For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 7000.
Section 7.2:
Calculation 7.4
f Stop J
7841 - 4
Revision 0
Date September 1986
-------
METHOD 7870
TIN (ATOMIC ABSORPTION, DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 if interferences are suspected.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Tin hollow cathode lamp.
4.2.2 Wavelength: 286.3 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxidant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Not required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g of tin metal (analytical
reagent grade) in 100 mL of concentrated HC1 and dilute to 1 liter with
Type II water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentration as will result in the sample to be analyzed after
processing.
7870 - 1
Revision 0
Date September 1986
-------
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 10-300 mg/L with a wavelength of 286.3 nm.
Sensitivity: 4 mg/L.
Detection limit: 0.8 mg/L.
9.2 In a single laboratory, analysis of a mixed industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 4, 20, and 60
mg/L gave standard deviations of +0.25, +0.5, and +0.5, respectively.
Recoveries at these levels were 96%, 101%, and 101%, respectively.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 282.1.
7870 - 2
Revision
Date September 1986
-------
METHOD 787O
TIN (ATOMIC ABSORPTION. DIRECT ASPIRATION)
f Start J
s
mHf^m
il
Prepare
standards
7.1 I
I For
sample
preparation see
chapter 3.
section 3.2
7.2
Analyze using
Method 7000.
Section 7.2
f Stop J
7870 - 3
Revision 0
Date September 1986
-------
METHOD 7910
VANADIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Background correction may be required.
3.3 High concentrations of aluminum or titanium, or the presence of Bi,
Cr, Co, Fe, acetic add, phosphoric acid, surfactants, detergents, or alkali
metals, may interfere. The Interference can be controlled by adding
1,000 mg/L aluminum to samples and standards.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Vanadium hollow cathode lamp.
4.2.2 Wavelength: 318.4 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: Nitrous oxide.
4.2.5 Type of flame: Fuel rich.
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.7854 g of vanadium pentoxide,
V20s (analytical reagent grade), in 10 mL of concentrated nitric acid and
dilute to 1 liter with Type II water. Alternatively, procure a certified
standard from a supplier and verify by comparison with a second standard.
7910 - 1
Revision
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of acid and at the same
concentration as will result 1n the sample to be analyzed after
processing. In addition, 2 ml of the aluminum nitrate solution described
in Paragraph 5.2.3 should be added to each 100 ml of standards and
samples.
5.2.3 Aluminum nitrate solution: Dissolve 139 g aluminum nitrate
(A1[N03]3'9H?0) In 150 ml Type II water; heat to complete dissolution.
Allow to cool and dilute to 200 ml with Type II water. All samples and
standards should contain 2 ml of this solution per 100 ml.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 2-100 mg/L with a wavelength of 318.4 nm.
Sensitivity: 0.8 mg/L.
Detection limit: 0.2 mg/L.
9.2 In a single laboratory), analysis of a mixed Industrial-domestic
waste effluent, digested with Method 3010, at concentrations of 2, 10, and 50
mg/L gave standard deviations of +0.1, +0.1, and +0.2, respectively.
Recoveries at these levels were 100%, 95%, and 97%, respectively.
9.3 For concentrations of vanadium below 0.5 mg/L, the furnace technique
(Method 7911) 1s recommended.
7910 - 2
Revision
Date September 1986
-------
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 286.1.
7910 - 3
Revision
Date September 1986
-------
METHOD 7910
VANADIUM (ATOMIC ABSORPTION. DIRECT ASPIRATION)
C
5.0
Prepare
standards
7. 1
prepar
cr
sec
For
sample
ation see
apter 3.
tlon 3. Z
7.2
Analyze
Methoc
Sectic
using
7OOO.
n 7.2
f StOP \
7910 - 4
Revision 0
Date September 1986
-------
METHOD 7911
VANADIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 Background correction 1s required.
3.3 Vanadium 1s refractory and prone to form carbides. Consequently,
memory effects are common, and care should be taken to clean the furnace
before and after analysis.
3.4 Nitrogen should not be used as a purge gas.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Drying time and temp: 30 sec at 125*C.
4.2.2 Ashing time and temp: 30 sec at 1400*C.
4.2.3 Atomizing time and temp: 15 sec at 2800*C.
4.2.4 Purge gas: Argon (nitrogen should not be used).
4.2.5 Wavelength: 318.4 nm.
4.2.6 Background correction: Required.
4.2.7 Other operating parameters should be set as specified by the
particular Instrument manufacturer.
NOTE: The above concentration values and Instrument conditions are for a
Perkln-Elmer HGA-2100, based on the use of a 20-uL Injection,
continuous-flow purge gas, and nonpyrolytlc graphite. Smaller
sizes of furnace devices or those employing faster rates of
atomlzatlon can be operated using lower atomlzatlon temperatures
for shorter time periods than the above-recommended settings.
7911 - 1
Revision
Date September 1986
-------
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards:
5.2.1 Stock solution: Dissolve 1.7854 g of vanadium pentoxlde,
V^Os (analytical reagent grade), 1n 10 mL of concentrated nitric add and
dilute to 1 liter with Type II water. Alternatively, procure a certified
standard from a supplier and verify by comparison with a second standard.
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same
concentrations as 1n the sample after processing (0.5% v/v
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING^
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given 1n Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.3, Furnace Procedure. The calculation
Is given in Method 7000, Paragraph 7.4.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 Precision and accuracy data are available 1n Method 286.2 of Methods
for Chemical Analysis of Water and Wastes.
9.2 The performance characteristics for an aqueous sample free of
Interferences are:
Optimum concentration range: 10-200 ug/L.
Detection limit: 4 ug/L.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 286.2.
7911 - 2
Revision 0
Date September 1986
-------
METHOD 7911
VANADIUM (ATOMIC ABSORPTION. FURNACE TECHNIQUE)
5.0
Prepare
standards
7.1
prepar
cr
sec
7.2
For
sample
atlon see
lapter 3.
tlon .3.2
Analyze using
Method 7000.
Section 7.2;
calculation 7.4
f Stop J
7911 - 3
Revision 0
Date September 1986
-------
METHOD 7950
ZINC (ATOMIC ABSORPTION. DIRECT ASPIRATION)
1.0 SCOPE AND APPLICATION
1.1 See Section 1.0 of Method 7000.
2.0 SUMMARY OF METHOD
2.1 See Section 2.0 of Method 7000.
3.0 INTERFERENCES
3.1 See Section 3.0 of Method 7000 1f Interferences are suspected.
3.2 High levels of silicon, copper, or phosphate may Interfere. Addi-
tion of strontium (1,500 mg/L) removes the copper and phosphate Interference.
3.3 Z1nc 1s a universal contaminant, and great care should be taken to
avoid contamination.
4.0 APPARATUS AND MATERIALS
4.1 For basic apparatus, see Section 4.0 of Method 7000.
4.2 Instrument parameters (general):
4.2.1 Z1nc hollow cathode lamp.
4.2.2 Wavelength: 213.9 nm.
4.2.3 Fuel: Acetylene.
4.2.4 Oxldant: A1r.
4.2.5 Type of flame: Oxidizing (fuel lean).
4.2.6 Background correction: Required.
5.0 REAGENTS
5.1 See Section 5.0 of Method 7000.
5.2 Preparation of standards;
5.2.1 Stock solution: Dissolve 1.000 g zinc metal (analytical
reagent grade) 1n 10 ml of concentrated nitric add and dilute to 1 liter
with Type II water. Alternatively, procure a certified standard from a
supplier and verify by comparison with a second standard.
7950 - 1
Revision
Date September 1986
-------
5.2.2 Prepare dilutions of the stock solution to be used as
calibration standards at the time of analysis. The calibration standards
should be prepared using the same type of add and at the same concentra-
tion as will result In the sample to be analyzed after processing.
6.0 SAMPLE COLLECTION, PRESERVATION, AND HANDLING
6.1 See Chapter Three, Section 3.1.3, Sample Handling and Preservation.
7.0 PROCEDURE
7.1 Sample preparation; The procedures for preparation of the sample
are given In Chapter Three, Section 3.2.
7.2 See Method 7000, Paragraph 7.2, Direct Aspiration.
8.0 QUALITY CONTROL
8.1 See Section 8.0 of Method 7000.
9.0 METHOD PERFORMANCE
9.1 The performance characteristics for an aqueous sample free of
interferences are:
Optimum concentration range: 0.05-1 mg/L with a wavelength of 213.9 nm.
Sensitivity: 0.02 mg/L.
Detection limit: 0.005 mg/L.
9.2 For concentrations of zinc below 0.01 mg/L, the furnace technique
(Method 7951) is recommended.
9.3 Precision and accuracy data are available 1n Method 289.1 of Methods
for Chemical Analysis of Water and Wastes.
10.0 REFERENCES
1. Methods for Chemical Analysis of Water and Wastes, EPA-600/4-82-055,
December 1982, Method 289.1.
7950 - 2
Revision
Date September 1986
-------
METHOD 79SO
ZINC (ATOMIC ABSORPTION. DIRECT ASPIRATION)
s.o
Prepare
standards
7.1
1 For
sample
preparation see
chapter 3.
section 3.2
7.2 |
Analyze using
Method 7OOO.
Section 7.2
( StOP J
7950 - 3
Revision 0
Date September 1986
-------
APPENDIX
COMPANY REFERENCES
The following listing of frequently-used addresses Is provided for the
convenience of users of this manual. No endorsement 1s Intended or Implied.
Ace Glass Company
1342 N.W. Boulevard
P.O. Box 688
Vlneland, 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. Cassldy Street
P.O. Box 2526
Columbus, OH 43219
(614) 258-9501
Bio - Rad Laboratories
2200 Wright Avenue
Richmond, CA 94804
(415) 234-4130
Burdlck & 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
-------
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 - Manvllle Corporation
P.O. Box 5108
Denver, CO 80217
Kontes Glass Company
8000 Spruce Street
Vineland, NJ 08360
Mlllipore Corporation
80 Ashby Road
Bedford, MA 01730
(617) 275-9200
(800) 225-1380
COMPANIES - 2
Revision 0
Date September 1986
-------
National Bureau of Standards
U.S. Department of Commerce
Washington, DC 20234
(202) 921-1000
Pierce Chemical Company
Box 117
Rockford, IL 61105
(815) 968-0747
Scientific Glass and Instrument, Inc.
7246 - T Wynnwood
P.O. Box 6
Houston, TX 77001
(713) 868-1481
Scientific Products Company
1430 Waukegon Road
McGaw Park, IL 60085
(312) 689-8410
Spex Industries
3880 - T and Park Avenue
Edison, NJ 08820
Waters Associates
34 - T Maple Street
Mllford, MA 01757
(617) 478-2000
(800) 252-4752
Whatman Laboratory Products, Inc.
Clifton, NJ 07015
(201) 773-5800
COMPANIES - 3
Revision
Date September 1986
U.S. GOVERNMENT PRINTING OFFICE : 1987 0 - 169-930
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